Peter Andrew Lay

Imaging metals in proteins by combining electrophoresis with rapid X-ray fluorescence mapping

Publisher: American Chemical Society (ACS)

Date: 27-04-2010

DOI: 10.1021/CB1000263

Abstract: Growing evidence points toward a very dynamic role for metals in biology. This suggests that physiological circumstance may mandate metal ion redistribution among ligands. This work addresses a critical need for technology that detects, identifies, and measures the metal-containing components of complex biological matrixes. We describe a direct, user-friendly approach for identifying and quantifying metal-protein adducts in complex s les using native- or SDS-PAGE, blotting, and rapid synchrotron X-ray fluorescence mapping with micro-XANES (X-ray absorption near-edge structure) of entire blots. The identification and quantification of each metal bound to a protein spot has been demonstrated, and the technique has been applied in two exemplary cases. In the first, the speciation of the in vitro binding of exogenous chromium to blood serum proteins was influenced markedly by both the oxidation state of chromium exposed to the serum proteins and the treatment conditions, which is of relevance to the biochemistry of Cr dietary supplements. In the second case, in vivo changes in endogenous metal speciation were examined to probe the influence of oxygen depletion on iron speciation in Shewanella oneidensis.

EPR characterisation of the CrV intermediates in the CrVI/V oxidations of organic substrates and of relevance to Cr-induced cancers

Publisher: Royal Society of Chemistry (RSC)

Date: 1995

DOI: 10.1039/FT9959101207

Mechanisms of murine cerebral malaria: Multimodal imaging of altered cerebral metabolism and protein oxidation at hemorrhage sites

Publisher: American Association for the Advancement of Science (AAAS)

Date: 04-12-2015

DOI: 10.1126/SCIADV.1500911

Abstract: Multimodal spectroscopic imaging resolved controversies on biochemical changes associated with cerebral malaria pathology.

Semiconductor properties and redox responses at a-C:N thin film electrochemical electrodes

Publisher: Elsevier BV

Date: 10-2009

DOI: 10.1016/J.DIAMOND.2009.04.003

Three-dimensional structure determination using multiple-scattering analysis of XAFS: Applications to metalloproteins and coordination chemistry

Publisher: Elsevier BV

Date: 2005

DOI: 10.1016/J.CCR.2004.10.008

Determination-of the Fe-ligand bond lengths and Fe-N-O bond angles in horse heart ferric and ferrous nitrosylmyoglobin using multiple-scattering XAFS analyses

Publisher: American Chemical Society (ACS)

Date: 10-1998

DOI: 10.1021/JA980253G

Chromium(V)−Sialic (Neuraminic) Acid Species Are Formed from Mixtures of Chromium(VI) and Saliva

Publisher: American Chemical Society (ACS)

Date: 11-2001

DOI: 10.1021/JA0160501

Vanadium(V) and -(IV) complexes of anionic polysaccharides: Controlled release pharmaceutical formulations and models of vanadium biotransformation products

Publisher: Elsevier BV

Date: 06-2015

DOI: 10.1016/J.JINORGBIO.2015.03.016

Abstract: Uncontrolled reactions in biological media are a main obstacle for clinical translation of V-based anti-diabetic or anti-cancer pro-drugs. We investigated the use of controlled-release pharmaceutical formulations to ameliorate this issue with a series of V(V) and (IV) complexes of anionic polysaccharides. Carboxymethyl cellulose, xanthan gum, or alginic acid formulations were prepared by the reactions of [VO4](3-) with one or two molar equivalents of biological reductants, L-ascorbic acid (AA) or L-cysteine (Cys), in the presence of excess polysaccharide at pH~7 or pH~4. XANES studies with the use of a previously developed library of model V(V), V(IV) and V(III) complexes showed that reactions in the presence of AA led mostly to the mixtures of five- and six-coordinate V(IV) species, while the reactions in the presence of Cys led predominantly to the mixtures of five- and six-coordinate V(V) species. The XANES spectra of some of these s les closely matched those reported previously for [VO4](3-) biotransformation products in isolated blood plasma, red blood cells, or cultured adipocytes, which supports the hypothesis that modified polysaccharides are major binders of V(V) and V(IV) in biological systems. Studies by EPR spectroscopy suggested predominant V(IV)-carboxylato binding in complexes with polysaccharides. One of the isolated products (a V(IV)-alginato complex) showed selective release of low-molecular-mass V species at pH~8, but not at pH~2, which makes it a promising lead for the development of V-containing formulations for oral administration that are stable in the stomach, but release the active ingredient in the intestines.

Search for nonresonant pair production of Higgs bosons in the bb

Publisher: American Physical Society (APS)

Date: 05-09-2023

DOI: 10.1103/PHYSREVD.108.052003

Light-induced electron-transfer reactions involving the tris(2,2′-bipyridine)ruthenium dication and related complexes. III†‡ Improved synthesis of 2,2′-Bipyridine4,4′- dicarboxylic acid and photoreduction of water by Bis(2,2′-bipyridine)(2, 2′-bipyridine4,4′-dicarboxylic acid) ruthenium(II)

Publisher: CSIRO Publishing

Date: 1986

DOI: 10.1071/CH9861053

Abstract: The oxidation of 4,4′-dimethyl-2,2′-bipyridine with potassium permanganate in water gives 2,2′-bipyridine-4,4′-dicarboxylic acid and 4′-methyl-2,2?-bipyridine-4-carboxylic acid. The latter acid is oxidized to the diacid by boiling nitric acid. Complexes of the type Ru ( bpy )2L2+ have been prepared where L is 2,2′-bipyridine-4,4′- dicarboxylic acid, diethyl 2,2′-bipyridine-4,4′-dicarboxylate, 4′- methyl-2,2′-bipyridine-4-carboxylic acid and ethyl 4′-methyl-2,2′- bipyridine-4-carboxylate. These complexes have been compared with [ Ru ( bpy )3]2+ as sensitizers for the photoreduction of water. Stern- Volmer analysis has been applied to the quenching of their luminescence by methylviologen (mv2+), [Co(sep)]3+ (sep is 1,3,6,8,10,13,16,19- octaazabicyclo [6.6.6] icosane ) and [Co( CLsar )]3+ ( CLsar is 1-chloro- 3,6,10,13,16,19-hexaazabicyclo[6.6.6] icosane ). Changes in the Stern-Volmer constants have been related to the free energy changes associated with the oxidative quenching and the overall charges of the ruthenium complexes. The rates of formation of hydrogen compared favourably in sacrificial cycles with the ruthenium complexes as sensitizers, mv2+, Co(sep)3+ as electron-transfer agents, platinum oly(vinyl alcohol) as catalyst, and ethylenediaminetetraacetic acid as electron donor. The results obtained have been discussed in terms of variations in the efficiencies of cage escape in the oxidative quenching and competition between electron transfer and energy transfer.

Synthesis and the photophysical and biological properties of tricarbonyl Re(i) diimine complexes bound to thiotetrazolato ligands

Publisher: Royal Society of Chemistry (RSC)

Date: 2023

DOI: 10.1039/D2DT03237F

Abstract: The structure, stability, composition, photochemistry, and biological properties of twelve rhenium tris-carbonyl diamine complexes containing tautomeric thiotetrazolato ligands have been examined for their use as potential bio-imaging agents.

Charge distribution in chromium and vanadium catecholato complexes: X-ray absorption spectroscopic and computational studies

Publisher: American Chemical Society (ACS)

Date: 17-05-2006

DOI: 10.1021/IC0603611

Abstract: Transition-metal complexes with redox-active catecholato ligands are of interest as models of bioinorganic systems and as potential molecular materials. This work expands our recent X-ray absorption spectroscopic (XAS) studies of Cr(V/IV/III) triscatecholato complexes (Levina, A. Foran, G. J. Pattison, D. I. Lay, P. A. Angew. Chem., Int. Ed. 2004, 43, 462-465) to a Cr(III) monocatecholato complex, [Cr(tren)(cat)]+ (tren = tris(2-aminoethyl)amine, cat = catecholato2-), and its oxidized analogue, as well as to a series of V(V/IV/III) triscatecholato complexes ([VL3]n-, where L = cat, 3,5-di-tert-butylcatecholato2-, or tetrachlorocatecholato2-, and n = 1-3). Various oxidation states of these complexes in solutions were generated by bulk electrolysis directly in the XAS cell. Increases in the edge energies and pre-edge absorbance intensities in XANES spectra, as well as decreases in the average M-O bond lengths (M = Cr or V) revealed by XAFS data analyses, are consistent with predominantly metal-based oxidations in both the Cr(V/IV/III) and V(V/IV/III) triscatecholato series, but the degree of electron delocalization between the metal ion and the ligands was higher in the case of Cr complexes. By contrast, oxidation of [Cr(III)(tren)(cat)]+ was mainly ligand-based and led to [Cr(III)(tren)(sq)]2+ (sq = semiquinonato-), as shown by the absence of significant changes in the pre-edge and edge features and by an increase in the average Cr-O bond length. The observed differences in electron-density distribution in various oxidation states of Cr and V mono- and triscatecholato complexes have been discussed on the basis of the results of density functional calculations. A crystal and molecular structure of (Et3NH)2[V(IV)(cat)3] has been determined at 25 K and the same complex with an acetonitrile of crystallization at 150 K.

Calibration of the light-flavour jet mistagging efficiency of the b-tagging algorithms with Z+jets events using 139 $$\textrm{fb}^{-1}$$ of ATLAS proton–proton collision data at $$\sqrt{s} = 13$$ TeV

Publisher: Springer Science and Business Media LLC

Date: 14-08-2023

DOI: 10.1140/EPJC/S10052-023-11736-Z

Abstract: The identification of b -jets, referred to as b -tagging, is an important part of many physics analyses in the ATLAS experiment at the Large Hadron Collider and an accurate calibration of its performance is essential for high-quality physics results. This publication describes the calibration of the light-flavour jet mistagging efficiency in a data s le of proton–proton collision events at $$\\sqrt{s}=13$$ s = 13 TeV corresponding to an integrated luminosity of 139 fb $$^{-1}$$ - 1 . The calibration is performed in a s le of Z bosons produced in association with jets. Due to the low mistagging efficiency for light-flavour jets, a method which uses modified versions of the b -tagging algorithms referred to as flip taggers is used in this work. A fit to the jet-flavour-sensitive secondary-vertex mass is performed to extract a scale factor from data, to correct the light-flavour jet mistagging efficiency in Monte Carlo simulations, while simultaneously correcting the b -jet efficiency. With this procedure, uncertainties coming from the modeling of jets from heavy-flavour hadrons are considerably lower than in previous calibrations of the mistagging scale factors, where they were dominant. The scale factors obtained in this calibration are consistent with unity within uncertainties.

Search for single production of vector-like T quarks decaying into Ht or Zt in pp collisions at $$ \sqrt{s} $$ = 13 TeV with the ATLAS detector

Publisher: Springer Science and Business Media LLC

Date: 23-08-2023

DOI: 10.1007/JHEP08(2023)153

Abstract: This paper describes a search for the single production of an up-type vector-like quark ( T ) decaying as T → Ht or T → Zt . The search utilises a dataset of pp collisions at $$ \\sqrt{s} $$ s = 13 TeV collected with the ATLAS detector during the 2015–2018 data-taking period of the Large Hadron Collider, corresponding to an integrated luminosity of 139 fb − 1 . Data are analysed in final states containing a single lepton with multiple jets and b -jets. The presence of boosted heavy resonances in the event is exploited to discriminate the signal from the Standard Model background. No significant excess above the Standard Model expectation is observed, and 95% CL upper limits are set on the production cross section of T quarks in different decay channels. The results are interpreted in several benchmark scenarios to set limits on the mass and universal coupling strength ( κ ) of the vector-like quark. For singlet T quarks, κ values above 0.53 are excluded for all masses below 2.3 TeV. At a mass of 1.6 TeV, κ values as low as 0.35 are excluded. For T quarks in the doublet scenario, where the production cross section is much lower, κ values above 0.72 are excluded for all masses below 1.7 TeV, and this exclusion is extended to κ above 0.55 for low masses around 1.0 TeV.

The crystal and molecular structure of (η⁵-pentaphenylcyclopentadienyl) (η⁵-cyclopentadienyl)iron(II), 1,2,3,4,5-pentaphenylferrocene, [Fe(C5Ph5)(C5H5)]

Publisher: Elsevier BV

Date: 08-1993

DOI: 10.1016/S0277-5387(00)81480-1

Redox chemistry and biological activities of chromium(III) complexes

Publisher: Elsevier

Date: 2007

DOI: 10.1016/B978-044453071-4/50012-6

Molecular mechanism of AHSP-mediated stabilization of α-hemoglobin

Publisher: Elsevier BV

Date: 11-2004

DOI: 10.1016/J.CELL.2004.11.025

Abstract: Hemoglobin A (HbA), the oxygen delivery system in humans, comprises two alpha and two beta subunits. Free alpha-hemoglobin (alphaHb) is unstable, and its precipitation contributes to the pathophysiology of beta thalassemia. In erythrocytes, the alpha-hemoglobin stabilizing protein (AHSP) binds alphaHb and inhibits its precipitation. The crystal structure of AHSP bound to Fe(II)-alphaHb reveals that AHSP specifically recognizes the G and H helices of alphaHb through a hydrophobic interface that largely recapitulates the alpha1-beta1 interface of hemoglobin. The AHSP-alphaHb interactions are extensive but suboptimal, explaining why beta-hemoglobin can competitively displace AHSP to form HbA. Remarkably, the Fe(II)-heme group in AHSP bound alphaHb is coordinated by the distal but not the proximal histidine. Importantly, binding to AHSP facilitates the conversion of oxy-alphaHb to a deoxygenated, oxidized [Fe(III)], nonreactive form in which all six coordinate positions are occupied. These observations reveal the molecular mechanisms by which AHSP stabilizes free alphaHb.

Disproportionation of a model chromium(V) complex causes extensive chromium(III)-DNA binding in vitro

Publisher: American Chemical Society (ACS)

Date: 13-07-2001

DOI: 10.1021/TX010077G

Abstract: The first direct evidence for the role of Cr(V) complexes in the formation of potentially mutagenic Cr(III)-DNA adducts has been obtained. A model complex for the stabilized Cr(V) species formed in Cr(VI)-treated cells, [Cr(V)O(ehba)(2)]-[ehba = 2-ethyl-2-hydroxybutanoato(2-)], rapidly disproportionates in HEPES buffers at pH 7.4 [3 Cr(V) --> 2 Cr(VI) + Cr(III)], and the formed Cr(III) species undergo efficient ionic binding to DNA, followed by slower covalent binding. The extent of Cr(III)-DNA binding significantly exceeds that caused by [Cr(III)(OH(2))(6)](3+) or by the Cr(III) products of Cr(VI) reductions under similar conditions. The Cr(III)-DNA binding can be dramatically reduced by the ability of the reaction medium (e.g., phosphate buffer) to form complexes with Cr(III) during and after the disproportionation reaction. A mechanism of Cr(III)-DNA binding caused by Cr(V) disproportionation has been proposed on the basis of stoichiometric and kinetic studies.

Synthesis, Characterization, and Crystal Structure of a Vanadium(V)-Vanadium(IV)-Vanadium(V) Mixed-Valence Trinuclear Complex with a Tridentate Quinato Ligand, (NH4)2{[V^v(O)2]2[V^IV(O)](μ-(−)-quinato(3−))2}·H2O

Publisher: American Chemical Society (ACS)

Date: 02-1995

DOI: 10.1021/IC00108A019

STABILIZATION OF COBALT CAGE CONFORMERS IN THE SOLID-STATE AND SOLUTION

Publisher: American Chemical Society (ACS)

Date: 09-1994

DOI: 10.1021/IC00098A023

Are sirtuins viable targets for improving healthspan and lifespan?

Publisher: Springer Science and Business Media LLC

Date: 06-2012

DOI: 10.1038/NRD3738

Sialoglycoprotein and carbohydrate complexes in chromium toxicity

Publisher: Elsevier BV

Date: 04-2003

DOI: 10.1016/S1367-5931(03)00017-6

Abstract: Chromium(VI) compounds are amongst the most widely encountered industrial carcinogens and are of increasing concern with respect to environmental exposure. Sialoglycoproteins and carbohydrates play a crucial role in stabilizing oxoCr(V) intermediates, which are produced by extracellular and intracellular reduction of chromium(VI). Recent research has addressed the molecular characterization of oxoCr(V)-sialoglycoprotein and -carbohydrate complexes and the roles that these species may play in Cr(VI) metabolism and carcinogenesis. Particular highlights include the role of oxoCr(V) complexes of extracellular sialoglycoproteins, intracellular D-glucose, and related species and their potential roles in Cr(VI)-induced genotoxicity.

Characterization of a ruthenium(III)/nami-a adduct with bovine serum albumin that exhibits a high anti-metastatic activity

Publisher: Wiley

Date: 17-02-2010

DOI: 10.1002/ANIE.200906079

A potential role for protein tyrosine phosphatase inhibition by a Ru ^III-edta complex (edta = ethylenediaminetetraacetate) in its biological activity

Publisher: Royal Society of Chemistry (RSC)

Date: 2008

DOI: 10.1039/B803261K

Abstract: [RuIII(edta)(OH2/OH)]1-/2- (edta = ethylenediaminetetraacetate) inhibits protein tyrosine phosphatase (PTP) at physiological pH values in a mechanism that involves binding of the Cys residue of the catalytic domain of the enzyme and similar interactions may be important in the anti-cancer properties of the active forms of many Ru pro-drugs.

Reactivity of chromium(III) nutritional supplements in biological media: An X-ray absorption spectroscopic study

Publisher: American Chemical Society (ACS)

Date: 23-04-2008

DOI: 10.1021/IC7024389

Abstract: Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3](+) (A), [Cr(pic)3] (pic=2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4](+) (CrCl3.6H2O C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of a library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid rotein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I. Levina, A. Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].

Chromium(V) complexes generated in Arthrobacter oxydans by simulation analysis of EPR spectra

Publisher: Elsevier BV

Date: 11-2006

DOI: 10.1016/J.JINORGBIO.2006.07.004

Abstract: Chromium(V) is an intermediate formed during the reduction of Cr(VI) to Cr(III) compounds by various bacteria. However, little is known about the nature, localization and reactivity of Cr(V) species in microbial systems. Electron paramagnetic resonance (EPR) spectroscopy was used to study the nature of Cr(V) complexes generated in basalt-inhabiting Gram-positive Arthrobacter oxydans bacteria after exposure to high concentrations of Cr(VI). Numerical simulations of the EPR spectroscopic data provide strong evidence for at least two different diolato-type oxoCr(V) complexes (I, g(iso)=1.9801 II, g(iso)=1.9796) involving bacterial cell wall macromolecules in the Cr(VI)-A. oxydans system. The relative concentrations of the two oxoCr(V)-diolato species differ when Cr(VI) is incubated with either untreated A. oxydans cells (I:II approximately 50:50) or lyophilized cells (I:II approximately 10:90). Based upon the magnitudes of the proton superhyperfine coupling constants ((1)H a(iso)) for species I and II, the EPR simulation model is unable to distinguish unambiguously whether the oxoCr(V)-diolato species are linear alkoxides or cyclic diols (carbohydrates). The oxygen-containing functional groups associated with teichoic acids are the most likely candidates for complexation with the Cr(V) ion.

Focal plane array IR imaging at the Australian Synchrotron

Publisher: Elsevier BV

Date: 11-2018

DOI: 10.1016/J.INFRARED.2018.06.022

Studies on the Biotransformations and Biodistributions of Metal-Containing Drugs Using X-Ray Absorption Spectroscopy

Publisher: Bentham Science Publishers Ltd.

Date: 03-2011

DOI: 10.2174/156802611794785217

Abstract: Most metal-based drugs are pro-drugs therefore, it is essential that methods are developed to follow their speciation in biological fluids, cells and tissues. This will lead to both a better understanding of the factors that affect their efficacies and toxicities and, consequently, to the design of new and superior drugs. The use of X-ray absorption spectroscopy on bulk s les, and X-ray microprobe techniques on cells and tissues, provides unprecedented information on the biotransformations and biodistributions of metal-containing drugs that is required for a better understanding of their pharmacology. Here the methodologies that have been used on a range of metal- or metalloid-containing drugs and dietary supplements are reviewed, with an emphasis on research conducted within our group. In particular, applications of these techniques to anti-cancer, anti-diabetic, and anti-inflammatory drugs are discussed.

Synthesis, characterization and in vitro anti-cancer activity of vanadium-doped nanocrystalline hydroxyapatite

Publisher: Royal Society of Chemistry (RSC)

Date: 2019

DOI: 10.1039/C9NJ03406D

Abstract: Nanocrystalline V( v )-doped hydroxyapatite and its reduced analogue (V( v ) and V( iv ) mixture) show promising in vitro cytotoxicity against cultured human bone cancer cells.

Comparison of inclusive and photon-tagged jet suppression in 5.02 TeV Pb+Pb collisions with ATLAS

Publisher: Elsevier BV

Date: 11-2023

DOI: 10.1016/J.PHYSLETB.2023.138154

Status of the X-ray Absorption Spectroscopy (XAS) beamline at the Australian synchrotron

Publisher: AIP

Date: 2007

DOI: 10.1063/1.2644692

Carcinogenic Chromium(VI) Compounds Formed by Intracellular Oxidation of Chromium(III) Dietary Supplements by Adipocytes

Publisher: Wiley

Date: 22-12-2016

DOI: 10.1002/ANGE.201509065

Speciation of metal drugs, supplements and toxins in media and bodily fluids controls in vitro activities

Publisher: Elsevier BV

Date: 12-2017

DOI: 10.1016/J.CCR.2017.01.002

Comparison of KP1019 and NAMI-A in tumour-mimetic environments

Publisher: Oxford University Press (OUP)

Date: 2016

DOI: 10.1039/C6MT00145A

Abstract: NAMI-A and KP1019 are Ru(III)-based anti-metastatic and cytotoxic anti-cancer drugs, respectively, and have been proposed to be activated by reduction to Ru(II). The potential reduction of NAMI-A and KP1019 in the hypoxic environment of a tumour model of neuroblastoma was examined. Normoxic, hypoxic and necrotic tumour tissues were modelled by multicellular spheroids of SH-SY5Y human neuroblastoma cells of various diameters (50-800 μm). The variation in spheroid environment was confirmed with pimonidazole staining. Laser-ablation inductively-coupled plasma mass spectrometry showed KP1019 and NAMI-A penetration into the spheroid hypoxic region. XANES showed that the speciation of NAMI-A biotransformation products did not change significantly as hypoxia levels increased. KP1019 metabolites showed a correlation between the degree of spheroid hypoxia and the Ru K-edge energy consistent with either partial reduction of Ru(III) to Ru(II) in tumour microenvironments, increased S/Cl coordination or a reduced fraction of polynuclear Ru species. EXAFS spectroscopy was undertaken in an attempt to distinguish between these scenarios but was inconclusive.

A tetranuclear polypyridylruthenium(ii) complex as a selective stain for extracellular vesicle penetration through brain microvascular endothelium

Publisher: Royal Society of Chemistry (RSC)

Date: 2023

DOI: 10.1039/D2CC05827H

Abstract: A tetranuclear Ru dye for selective staining of extracellular vesicles for studies of in vitro blood–brain barrier permeability.

(Pentamethylcyclopentadienato)rhodium Complexes for Delivery of the Curcumin Anticancer Drug

Publisher: Wiley

Date: 16-02-2017

DOI: 10.1002/EJIC.201601331

Abstract: [Rh III (*Cp)Cl(X,Y)] n + complexes {X, Y = Cl, PTA, n = 0 ( 2 ) X, Y = en, n = 1 ( 3 , Cl – salt 4 , PF 6 – salt) X, Y = acac, n = 0 ( 5 ) X, Y = cur, n = 0 ( 6 ), where *Cp = pentamethylcyclopentadienato, curH = curcumin PTA = 1,3,5‐triaza‐7‐phosphatricyclo[3.3.1.1]decane en = 1,2‐ethanediamine acac = acetylacetonato = 2,4‐pentanedionato(1–)} were synthesized from [Rh(*Cp)(µ‐Cl)Cl] 2 ( 1 ). While 2 – 5 were inactive against human epithelial A549 lung‐cancer cells in assays of cytotoxicity, and antimetastatic and proapoptotic behaviors, 6 had a cytotoxic activity similar to that of curH over 72 h, but at 24 h in real‐time cell migration assays, it was less active, showing slow release of curH. All complexes underwent ligand‐exchange reactions with biomolecules and cells within the timeframes of the assays (X‐ray absorption spectroscopy). Intracellular elemental distributions (X‐ray fluorescence microscopy) showed that 6 effectively delivered curH to cells, where it was released. Other elemental distributions and caspase activities were consistent with preapoptotic activities. As such, 6 is a promising delivery agent for bioactive ligands, such as curH. However, pure curcumin itself showed a previously unrecognized ability to promote migration of A549 cells at subtoxic concentrations in the presence of endothelial growth factor, which may be a concern for its widespread use as a nutritional supplement and as a potential drug. This aspect warrants further research.

Toll-like receptors 2 and 4 modulate autonomic control of heart rate and energy metabolism

Publisher: Elsevier BV

Date: 02-2014

DOI: 10.1016/J.BBI.2013.10.013

Post-translational regulation of human indoleamine 2,3-dioxygenase activity by nitric oxide

Publisher: Elsevier BV

Date: 08-2007

DOI: 10.1074/JBC.M700669200

Erratum: High resolution nuclear and X-ray microprobes and their applications in single cell analysis (Nuclear Instruments and Methods in Physics Research, Section B: Beam Interactions with Materials and Atoms (2001) 181 (715-722) PII: S0168583X01005419)

Publisher: Elsevier BV

Date: 12-2002

DOI: 10.1016/S0168-583X(02)01471-4

Solvent effects on the electronic spectrum of C60

Publisher: American Chemical Society (ACS)

Date: 04-1995

DOI: 10.1021/J100016A015

Hard X-ray microprobe studies of chromium (VI)-treated V79 Chinese hamster lung cells: Intracellular mapping of the biotransformation products of a chromium carcinogen

Publisher: Springer Science and Business Media LLC

Date: 26-02-2002

DOI: 10.1007/S00775-002-0343-5

Abstract: The uptake of carcinogenic and mutagenic Cr compounds and the intracellular distribution of their biotransformation products in V79 Chinese hamster lung cells were studied by synchrotron-radiation-induced X-ray emission (SRIXE). SRIXE analysis was performed on whole cells that had been treated with either Cr(III) or Cr(V) 1,10-phenanthroline complexes, or Cr(VI). The high spatial resolution (0.3 microm) and elemental sensitivity (~10(-15) g Cr/cell) of the technique provided detailed maps of Cr and other cellular elements in thin sections prepared from Cr(VI)-treated cells. The Cr carcinogen concentrated in P-rich regions corresponding to the nucleus, as well as other areas of the cell that are likely to correspond to organelles. This is the first study that has enabled the determination of the localization of the biotransformation products of Cr(VI) carcinogens in a target lung cell.

Controversial Role of Transferrin in the Transport of Ruthenium Anticancer Drugs

Publisher: MDPI AG

Date: 18-09-2022

DOI: 10.3390/BIOM12091319

Abstract: Ruthenium complexes are at the forefront of developments in metal-based anticancer drugs, but many questions remain open regarding their reactivity in biological media, including the role of transferrin (Tf) in their transport and cellular uptake. A well-known anticancer drug, KP1019 ((IndH)[RuIIICl4(Ind)2], where Ind = indazole) and a reference complex, [RuIII(nta)2]3− (nta = nitrilotriacetato(3−)) interacted differently with human apoTf, monoFeTf, or Fe2Tf. These reactions were studied by biolayer interferometry (BLI) measurements of Ru–Fe–Tf binding to recombinant human transferrin receptor 1 (TfR1) in conjunction with UV-vis spectroscopy and particle size analysis. Cellular Ru uptake in human hepatoma (HepG2) cells was measured under the conditions of the BLI assays. The mode of Tf binding and cellular Ru uptake were critically dependent on the nature of Ru complex, availability of Fe(III) binding sites of Tf, and the presence of proteins that competed for metal binding, particularly serum albumin. Cellular uptake of KP1019 was not Tf-mediated and occurred mostly by passive diffusion, which may also be suitable for treatments of inoperable cancers by intratumoral injections. High cellular Ru uptake from a combination of [RuIII(nta)2]3− and Fe2Tf in the absence of significant Ru–Tf binding was likely to be due to trapping of Ru(III) species into the endosome during TfR1-mediated endocytosis of Fe2Tf.

Preparation and characterization of dinuclear copper-indomethacin anti-inflammatory drugs

Publisher: Elsevier BV

Date: 11-2001

DOI: 10.1016/S0020-1693(01)00570-9

Reactivity and Speciation of Anti-Diabetic Vanadium Complexes in Whole Blood and Its Components: The Important Role of Red Blood Cells

Publisher: American Chemical Society (ACS)

Date: 31-07-2015

DOI: 10.1021/ACS.INORGCHEM.5B00665

Abstract: Reactions with blood components are crucial for controlling the antidiabetic, anticancer, and other biological activities of V(V) and V(IV) complexes. Despite extensive studies of V(V) and V(IV) reactions with the major blood proteins (albumin and transferrin), reactions with whole blood and red blood cells (RBC) have been studied rarely. A detailed speciation study of Na3[V(V)O4] (A), K4[V(IV)2O2(citr)2]·6H2O (B citr = citrato(4-)) [V(IV)O(ma)2] (C ma = maltolato(-)), and (NH4)[V(V)(O)2(dipic)] (D dipic = pyridine-2,6-dicarboxylato(2-)) in whole rat blood, freshly isolated rat plasma, and commercial bovine serum using X-ray absorption near-edge structure (XANES) spectroscopy is reported. The latter two compounds are potential oral antidiabetic drugs, and the former two are likely to represent their typical decomposition products in gastrointestinal media. XANES spectral speciation was performed by principal component analysis and multiple linear regression techniques, and the distribution of V between RBC and plasma fractions was measured by electrothermal atomic absorption spectroscopy. Reactions of A, C, or D with whole blood (1.0 mM V, 1-6 h at 310 K) led to accumulation of ∼50% of total V in the RBC fraction (∼10% in the case of B), which indicated that RBC act as V carriers to peripheral organs. The spectra of V products in RBC were independent of the initial V complex, and were best fitted by a combination of V(IV)-carbohydrate (2-hydroxyacid moieties) and/or citrate (65-85%) and V(V)-protein (15-35%) models. The presence of RBC created a more reducing environment in the plasma fraction of whole blood compared with those in isolated plasma or serum, as shown by the differences in distribution of V(IV) and V(V) species in the reaction products of A-D in these media. At physiologically relevant V concentrations (<50 μM), this role of RBC may promote the formation of V(III)-transferrin as a major V carrier in the blood plasma. The results reported herein have broad implications for the roles of RBC in the transport and speciation of metal pro-drugs that have broad applications across medicine.

Syntheses and characterization of anti-inflammatory dinuclear and mononuclear zinc indomethacin complexes. Crystal structures of [Zn2(indomethacin)4(L)2] (L = N,N-dimethylacetamide, pyridine, 1-methyl-2-pyrrolidinone) and [Zn(indomethacin)2(L1)2] (L1 = ethanol, methanol)

Publisher: American Chemical Society (ACS)

Date: 26-07-2000

DOI: 10.1021/IC991477I

Abstract: The syntheses and spectral and structural characterizations of Zn(II) indomethacin [1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid = IndoH] complexes, as different solvent adducts, have been studied. The complexes are unusual in that both monomeric and dimeric complexes are formed and that this is the first ex le of the same carboxylato ligand binding via both carboxylate oxygen atoms in monomeric and dimeric Zn(II) complexes. The crystal structures of Zn-Indo complexes with N,N-dimethylacetamide (DMA), pyridine (Py), 1-methyl-2-pyrrolidinone (NMP), EtOH, and MeOH as solvent ligands, [Zn2(Indo)4(DMA)2].2DMA, 1, [Zn2(Indo)4(Py)2].2H2O, 2b, [Zn2(Indo)4(NMP)2], 3, cis-[Zn(Indo)2(EtOH)2], 4, and cis-[Zn(Indo)2(MeOH)2], 5, were determined. Complexes 1, 2b, and 3 crystallize in the triclinic space group P1 (No. 2): a = 13.628(2) A, b = 17.462(2) A, c = 11.078(1) A, alpha = 99.49(1) degrees, beta = 108.13(1) degrees, gamma = 110.10(1) degrees for 1 a = 13.347(3) A, b = 16.499(5) A, c = 10.857(1) A, alpha = 99.48(2) degrees, beta = 108.25(2) degrees, gamma = 106.24(2) degrees for 2 a = 14.143(3) A, b = 14.521(2) A, c = 11.558(2) A, alpha = 109.07(1) degrees, beta = 90.80(2) degrees, gamma = 116.40(1) degrees for 3. The three complexes exhibit dinuclear paddle-wheel structures with a Zn...Zn distance of 2.9686(6) A, Zn-ORCOO distances of 2.035(2)-2.060(2) A, and a Zn-ODMA distance of 1.989(2) A in 1, a Zn...Zn distance of 2.969(1) A, Zn-ORCOO distances of 2.020(3)-2.049(3) A, and a Zn-NPy distance of 2.036(3) A in 2, and a Zn...Zn distance of 2.934(1) A, Zn-ORCOO distances of 2.009(3)-2.051(3) A, and a Zn-ONMP distance of 1.986(3) A in 3. In these cases, the zinc ions are offset along the z direction such that the L-Zn...Zn-L moiety is nonlinear, unlike the Cu analogues. Each Zn has a square-pyramidal geometry bridged by four carboxylato ligands in the basal plane with the solvent ligands containing an O- or N-donor atom at the apex. Complexes 4 and 5 are isostructural, with space group C2/c (No. 15). For 4, a = 30.080(2) A, b = 5.3638(6) A, c = 24.739(2) A, beta = 90.342(7) degrees, and for 5, a = 29.419(2) A, b = 5.320(2) A, c = 24.461(2) A, beta = 90.840(4) degrees. The Zn resides on a 2-fold axis and the complexes have a distorted cis octahedral structure with Zn-ORCOO bond lengths of 2.183(3) and 2.169(3) A, a Zn-OEtOH bond length of 2.015(3) A in 4, Zn-ORCOO bond lengths of 2.195(2) and 2.151(2) A, and a Zn-OMeOH bond length of 2.022(3) A in 5.

Mechanistic studies of relevance to the biological activities of chromium

Publisher: Elsevier BV

Date: 02-2005

DOI: 10.1016/J.CCR.2004.02.017

Electrochemistry of the quasi-reversible bis[2-ethyl-2-hydroxybutanoato(2-)]-oxochromate-(V) and -(IV) and bis[2-hydroxy-2-methylbutanoato(2-)]oxochromate-(V) and -(IV) redox couples and the crystal and molecular structure of sodium bis[2-ethyl-2-hydroxybutanoato(2-)]oxochromate(V)sesquihydrate

Publisher: Royal Society of Chemistry (RSC)

Date: 1989

DOI: 10.1039/DT9890002205

Search for a light charged Higgs boson in t → H±b decays, with H± → cb, in the lepton+jets final state in proton-proton collisions at $$ \sqrt{s} $$ = 13 TeV with the ATLAS detector

Publisher: Springer Science and Business Media LLC

Date: 09-2023

DOI: 10.1007/JHEP09(2023)004

Transferrin Cycle and Clinical Roles of Citrate and Ascorbate in Improved Iron Metabolism

Publisher: American Chemical Society (ACS)

Date: 11-04-2019

DOI: 10.1021/ACSCHEMBIO.8B01100

Abstract: Fe(III) delivery from blood plasma to cells via the transferrin (Tf) cycle was studied intensively due to its crucial role in Fe homeostasis. Tf-cycle disruptions are linked to anemia, infections, immunodeficiency, and neurodegeneration. Biolayer interferometry (BLI) enabled direct kinetic and thermodynamic measurements for all Tf-cycle steps in a single in vitro experiment using Tf within blood serum or released into the medium by cultured liver cells. In these media, known Tf cycle features were reproduced, and unprecedented insights were gained into conditions of rapid endosomal (pH 5.6) Fe(III) release from the Tf-Tf receptor 1 (TfR1) adduct. This release occurred via synergistic citrate and ascorbate effects, which pointed to respective roles as the likely elusive Fe chelator and reductant within the Tf cycle. These results explain enhanced cellular Fe uptake by ascorbate, the clinical efficacy of anemia treatment with Fe citrate and ascorbate, and dietary effects associated with loss of Fe homeostasis, including the large health burden of infections and neurodegeneration.

In Situ Fe K-edge X-ray Absorption Spectroscopy of a Nitrosyl Iron(II) Porphyrin Adduct Adsorbed on a High-Area Carbon Electrode in Aqueous Electrolytes

Publisher: American Chemical Society (ACS)

Date: 30-05-2001

DOI: 10.1021/IC001460W

Chromium(V) Complexes of Hydroxamic Acids:  Formation, Structures, and Reactivities

Publisher: American Chemical Society (ACS)

Date: 19-03-2005

DOI: 10.1021/IC048317D

Abstract: A new family of relatively stable Cr(V) complexes, [Cr(V)O(L)(2)](-) (LH(2) = RC(O)NHOH, R = Me, Ph, 2-HO-Ph, or HONHC(O)(CH(2))(6)), has been obtained by the reactions of hydroxamic acids with Cr(VI) in polar aprotic solvents. Similar reactions in aqueous solutions led to the formation of transient Cr(V) species. All complexes have been characterized by electron paramagnetic resonance spectroscopy and electrospray mass spectrometry. A Cr(V) complex of benzohydroxamic acid (1, R = Ph) was isolated in a pure form (as a K(+) salt) and was characterized by X-ray absorption spectroscopy and analytical techniques. Multiple-scattering analysis of X-ray absorption fine structure spectroscopic data for 1 (solid, 10 K) point to a distorted trigonal-bipyramidal structure with trans-oriented Ph groups and Cr-ligand bond lengths of 1.58 A (Cr-O), 1.88 A (Cr-O(C)), and 1.98 A (Cr-O(N)). Under ambient conditions, 1 is stable for days in aprotic solvents but decomposes within minutes in aqueous solutions (maximal stability at pH approximately 7), which leads predominantly to the formation of Cr(III) complexes. Complex 1 readily undergoes ligand-exchange reactions with biological 1,2-diols, including D-glucose and mucin, in neutral aqueous solutions. It differs from most other types of Cr(V) complexes in its biological activity, since no oxidative cleavage of plasmid DNA in vitro and no significant bacterial mutagenicity (in the TA 102 strain of Salmonella typhimurium) was observed for 1. In natural systems, stabilization of Cr(V) by hydroxamato ligands from bacterial-derived siderophores (followed by ligand-exchange reactions with more abundant carbohydrate ligands) may occur during the biological reduction of Cr(VI) in contaminated soils.

Raman excitation profiles of C70 in benzene solution. Assignment of the electronic spectrum in the 380-510-nm region

Publisher: American Chemical Society (ACS)

Date: 05-1997

DOI: 10.1021/JA963426F

Multiple protective activities of neuroglobin in cultured neuronal cells exposed to hypoxia re-oxygenation injury

Publisher: Wiley

Date: 09-02-2009

DOI: 10.1111/J.1471-4159.2008.05846.X

Abstract: Oxidative stress is associated with the pathology of acute and chronic neurodegenerative disease. We have cloned a human neuroglobin (Nb) construct and over-expressed this protein in cultured human neuronal cells to assess whether Nb ameliorates the cellular response to experimental hypoxia-reoxygenation (H/R) injury. Parental cells transfected with a blank (pDEST40) vector responded to H/R injury with a significant decrease in cellular ATP at 5 and 24 h after insult. This was coupled with increases in the cytosolic Ca(2+), and the transition metals iron (Fe), copper (Cu), and zinc (Zn) within the cell body, as monitored simultaneously using X-ray fluorescence microprobe imaging. Parental cell viability decreased over the same time period with a approximately 4 to 5-fold increase in cell death (maximum approximately 25%) matched by an increase in caspase 3/7 activation (peaking at a 15-fold increase after 24 h) and condensation of beta-actin along axonal processes. Over-expression of Nb inhibited ATP loss and except for significant decreases in the sulfur (S), chlorine (Cl), potassium (K) and Ca(2+) contents, maintained cellular ion homeostasis after H/R insult. This resulted in increased cell viability, significantly diminished caspase activation and maintenance of the beta-actin cytoskeletal structure and receptor-mediated endocytosis. These data indicate that bolstering the cellular content of Nb inhibits neuronal cell dysfunction promoted by H/R insult through multiple protective actions including: (i) maintenance of cellular bioenergetics (ii) inhibition of Ca(2+) influx (iii) a reduction in cellular uptake of Fe, Cu and Zn at the expense of S, Cl and K and (iv) an enhancement of cell viability through inhibiting necrosis and apoptosis.

Stabilities and Biological Activities of Vanadium Drugs: What is the Nature of the Active Species?

Publisher: Wiley

Date: 13-06-2017

DOI: 10.1002/ASIA.201700463

Abstract: Diverse biological activities of vanadium(V) drugs mainly arise from their abilities to inhibit phosphatase enzymes and to alter cell signaling. Initial interest focused on anti-diabetic activities but has shifted to anti-cancer and anti-parasitic drugs. V-based anti-diabetics are pro-drugs that release active components (e.g., H

Recent Advances in Osmium Chemistry

Publisher: Elsevier

Date: 1991

DOI: 10.1016/S0898-8838(08)60008-2

Chemical properties and toxicity of chromium(III) nutritional supplements

Publisher: American Chemical Society (ACS)

Date: 02-2008

DOI: 10.1021/TX700385T

Abstract: The status of Cr(III) as an essential micronutrient for humans is currently under question. No functional Cr(III)-containing biomolecules have been definitively described as yet, and accumulated experience in the use of Cr(III) nutritional supplements (such as [Cr(pic) 3], where pic = 2-pyridinecarboxylato) has shown no measurable benefits for nondiabetic people. Although the use of large doses of Cr(III) supplements may lead to improvements in glucose metabolism for type 2 diabetics, there is a growing concern over the possible genotoxicity of these compounds, particularly of [Cr(pic) 3]. The current perspective discusses chemical transformations of Cr(III) nutritional supplements in biological media, with implications for both beneficial and toxic actions of Cr(III) complexes, which are likely to arise from the same biochemical mechanisms, dependent on concentrations of the reactive species. These species include: (i) partial hydrolysis products of Cr(III) nutritional supplements, which are capable of binding to biological macromolecules and altering their functions and (ii) highly reactive Cr(VI/V/IV) species and organic radicals, formed in reactions of Cr(III) with biological oxidants. Low concentrations of these species are likely to cause alterations in cell signaling (including enhancement of insulin signaling) through interactions with the active centers of regulatory enzymes in the cell membrane or in the cytoplasm, while higher concentrations are likely to produce genotoxic DNA lesions in the cell nucleus. These data suggest that the potential for genotoxic side-effects of Cr(III) complexes may outweigh their possible benefits as insulin enhancers, and that recommendations for their use as either nutritional supplements or antidiabetic drugs need to be reconsidered in light of these recent findings.

Biomedical applications of X-ray absorption and vibrational spectroscopic microscopies in obtaining structural information from complex systems

Publisher: Elsevier BV

Date: 02-2010

DOI: 10.1016/J.RADPHYSCHEM.2009.03.068

Competition between 1,2-Diol and 2-Hydroxy Acid Coordination in Cr(V)-Quinic Acid Complexes:  Implications for Stabilization of Cr(V) Intermediates of Relevance to Cr(VI)-Induced Carcinogenesis

Publisher: American Chemical Society (ACS)

Date: 12-08-1999

DOI: 10.1021/JA9909780

Synchrotron radiation induced X-ray emission studies of the antioxidant mechanism of the organoselenium drug ebselen

Publisher: Springer Science and Business Media LLC

Date: 11-02-2012

DOI: 10.1007/S00775-012-0879-Y

Abstract: Synchrotron radiation induced X-ray emission (SRIXE) spectroscopy was used to map the cellular uptake of the organoselenium-based antioxidant drug ebselen using differentiated ND15 cells as a neuronal model. The cellular SRIXE spectra, acquired using a hard X-ray microprobe beam (12.8-keV), showed a large enhancement of fluorescence at the K(α) line for Se (11.2-keV) following treatment with ebselen (10 μM) at time periods from 60 to 240 min. Drug uptake was quantified and ebselen was shown to induce time-dependent changes in cellular elemental content that were characteristic of oxidative stress with the efflux of K, Cl, and Ca species. The SRIXE cellular Se distribution map revealed that ebselen was predominantly localized to a discreet region of the cell which, by comparison with the K and P elemental maps, is postulated to correspond to the endoplasmic reticulum. On the basis of these findings, it is hypothesized that a major outcome of ebselen redox catalysis is the induction of cellular stress. A mechanism of action of ebselen is proposed that involves the cell responding to drug-induced stress by increasing the expression of antioxidant genes. This hypothesis is supported by the observation that ebselen also regulated the homeostasis of the transition metals Mn, Cu, Fe, and Zn, with increases in transition metal uptake paralleling known induction times for the expression of antioxidant metalloenzymes.

Dinuclear chromium(V) amino acid complexes from the reduction of chromium(VI) in the presence of amino acid ligands: XAFS characterization of a chromium(V) amino acid complex

Publisher: American Chemical Society (ACS)

Date: 24-08-2001

DOI: 10.1021/IC010377L

Abstract: The first synthesis and characterization of Cr(V) complexes of non-sulfur-containing amino acids are reported. The reduction of Cr(VI) in methanol in the presence of amino acids glycine, alanine, and 2-amino-2-methylpropanoic acid (alpha-aminoisobutyric acid, Aib) yielded several Cr(V) EPR signals. For the reaction involving glycine, the only Cr(V) EPR signals detected were those of the Cr(V)-intermediate methanol complexes, which were also observed in the absence of amino acids. The reaction involving alanine yielded one Cr(V) signal with a g(iso) value of 1.9754 (a(iso) = 4.88 x 10(-4) cm(-1) and A(iso)(53Cr) = 17.89 x 10(-4) cm(-1)). However, a solid product isolated from the reaction solution was EPR silent and was characterized as a dioxo-bridged dimeric species, [Cr(V)2(mu-O)2(O)2(Ala)2(OCH3)2](2-), by multiple-scattering XAFS analysis and electrospray mass spectrometry. The EPR spectrum of the reduction reaction of Cr(VI) in the presence of Aib showed several different Cr(V) signals. Those observed at lower g(iso) values (1.9765, 1.9806) were assigned to Cr(V)-methanol intermediates, while the relatively broad six-line signal at g(iso) = 2.0058 was assigned as being due to a Cr(V) complex with coupling to a single deprotonated amine group of the amino acid. This was confirmed by simplification of the superhyperfine coupling lines from six to three when the deuterated ligand was substituted in the reaction. The reduction of Cr(VI) with excess alanine or Aib ligands resulted in the formation of tris-chelate Cr(III) complexes, which were analytically identical to complexes formed via Cr(III) synthesis methods. The fac-[Cr(Aib)3] complex was characterized by single-crystal X-ray diffraction.

NMR Spectroscopic Characterization of Copper(II) and Zinc(II) Complexes of Indomethacin

Publisher: American Chemical Society (ACS)

Date: 31-03-2004

DOI: 10.1021/IC0352811

Abstract: Molecular diffusion constants were studied by NMR spectroscopy to provide information about the solution structures of a variety of Cu(II) and Zn(II) monomeric and dimeric complexes of indomethacin (IndoH). These studies showed that monomeric Zn(II)-Indo complexes substantially dimerize in DMF-d7 and DMSO-d6 solutions at room temperature, whereas the Cu(II) and Zn(II) dinuclear complexes remain largely intact in these solutions. There is evidence of an equilibrium between monomers and dimers for the Zn(II) complexes in solution, as shown by a reduced diffusion constant and lower average radius compared to the Cu(II) dimer. Such an equilibrium between monomers and dimers for the Zn(II) complexes is also consistent with previous results obtained from XAFS analysis of DMF solutions of such complexes. The greater lability and lower thermodynamic stability of the Zn(II) dimer complex compared to the Cu(II) analogue, as determined from the NMR experiments, is likely to result in the more ready release of free Indo in the GI tract. This is consistent with the previously observed higher GI toxicities of the Zn-Indo pharmaceutical preparations compared to the Cu(II)-Indo counterparts.

Development of a Novel CD26-Targeted Chimeric Antigen Receptor T-Cell Therapy for CD26-Expressing T-Cell Malignancies

Publisher: MDPI AG

Date: 14-08-2023

DOI: 10.3390/CELLS12162059

Abstract: Chimeric-antigen-receptor (CAR) T-cell therapy for CD19-expressing B-cell malignancies is already widely adopted in clinical practice. On the other hand, the development of CAR-T-cell therapy for T-cell malignancies is in its nascent stage. One of the potential targets is CD26, to which we have developed and evaluated the efficacy and safety of the humanized monoclonal antibody YS110. We generated second (CD28) and third (CD28/4-1BB) generation CD26-targeted CAR-T-cells (CD26-2G/3G) using YS110 as the single-chain variable fragment. When co-cultured with CD26-overexpressing target cells, CD26-2G/3G strongly expressed the activation marker CD69 and secreted IFNgamma. In vitro studies targeting the T-cell leukemia cell line HSB2 showed that CD26-2G/3G exhibited significant anti-leukemia effects with the secretion of granzymeB, TNFα, and IL-8, with 3G being superior to 2G. CD26-2G/3G was also highly effective against T-cell lymphoma cells derived from patients. In an in vivo mouse model in which a T-cell lymphoma cell line, KARPAS299, was transplanted subcutaneously, CD26-3G inhibited tumor growth, whereas 2G had no effect. Furthermore, in a systemic dissemination model in which HSB2 was administered intravenously, CD26-3G inhibited tumor growth more potently than 2G, resulting in greater survival benefit. The third-generation CD26-targeted CAR-T-cell therapy may be a promising treatment modality for T-cell malignancies.

Biotransformations of anticancer ruthenium(III) complexes: An X-ray absorption spectroscopic study

Publisher: Wiley

Date: 30-01-2013

DOI: 10.1002/CHEM.201203127

Abstract: An anti-metastatic drug, NAMI-A ((ImH)[Ru(III) Cl4 (Im)(dmso)] Im=imidazole, dmso=S-bound dimethylsulfoxide), and a cytotoxic drug, KP1019 ((IndH)[Ru(III) Cl4 (Ind)2 ] Ind=indazole), are two Ru-based anticancer drugs in human clinical trials. Their reactivities under biologically relevant conditions, including aqueous buffers, protein solutions or gels (e.g, albumin, transferrin and collagen), undiluted blood serum, cell-culture medium and human liver (HepG2) cancer cells, were studied by Ru K-edge X-ray absorption spectroscopy (XAS). These XAS data were fitted from linear combinations of spectra of well-characterised Ru compounds. The absence of XAS data from the parent drugs in these fits points to profound changes in the coordination environments of Ru(III) . The fits point to the presence of Ru(IV/III) clusters and binding of Ru(III) to S-donor groups, amine/imine and carboxylato groups of proteins. Cellular uptake of KP1019 is approximately 20-fold higher than that of NAMI-A under the same conditions, but it diminishes drastically after the decomposition of KP1019 in cell-culture media, which indicate that the parent complex is taken in by cells through passive diffusion.

Tapered monocapillary optics for synchrotron x-ray microfocusing

Publisher: SPIE

Date: 06-11-1998

DOI: 10.1117/12.330343

Frontispiz: A Short‐Lived but Highly Cytotoxic Vanadium(V) Complex as a Potential Drug Lead for Brain Cancer Treatment by Intratumoral Injections

Publisher: Wiley

Date: 07-09-2020

DOI: 10.1002/ANGE.202083761

An investigation of the chromium oxidation state of a monoanionic chromium tris(catecholate) complex by X-ray absorption and EPR spectroscopies

Publisher: American Chemical Society (ACS)

Date: 13-12-2001

DOI: 10.1021/IC000298U

Abstract: The well-known monoanionic Cr tris(3,5-di-tert-butylcatecholato) complex, [Cr(DTBC)3]-, has been studied by X-ray absorption spectroscopy. The multiple-scattering fit to the XAFS gave good correlation (R = 19.8%) and good values for all of the bond lengths, angles, and Debye-Waller factors. The principal bond lengths and angles around the metal center (Cr-O, 1.96 A O-C, 1.28 A O-Cr-O, 81.8 degrees Cr-O-C, 113.3 degrees) were most consistent with the XRD structure for [Cr(X4C6O2)3]- (X = Cl, Br), compared to those in other oxidation states, [Cr(DTBC)3], [Cr(Cl4C6O2)3], and [Cr(O2C6H4)3]3-. The XANES spectrum shows the main K edge at 6003.3 eV and a preedge peak at 5992.9 eV, which is approximately 8% of the intensity of the main K edge. The XANES data were compared to those for Cr-ehba complexes (ehbaH2 = 2-ethyl-2-hydroxybutanoic acid) of known oxidation states (III, IV, and V) and show, in conjunction with EPR spectroscopy and a reevaluation of XRD structures and theoretical calulations, that the complex is best described as a Cr(V) center with delocalization from the catechol ligands. The [Cr(catecholato)3]n+ (n = 1, 0) complexes have similar EPR spectroscopic and structural properties, respectively, to the 1- complex and are also best described as Cr(V) complexes. Such intermediates are important in the redox reactions of catechol(amine)s, and oxidized amino acids (e.g., DOPA), with carcinogenic Cr(VI) and may have relevance in Cr-induced cancers.

Permeability, cytotoxicity, and genotoxicity of Cr(III) complexes and some Cr(V) analogues in V79 chinese hamster lung cells

Publisher: American Chemical Society (ACS)

Date: 26-07-2000

DOI: 10.1021/TX0000116

Abstract: The permeabilities and genotoxicities of the Cr(III) complexes [Cr(en)(3)](3+), mer-[Cr(glygly)(2)](-), cis-[Cr(phen)(2)(OH(2))(2)](3+), and trans-[Cr(salen)(OH(2))(2)](+) and the Cr(V) analogues of cis-[Cr(phen)(2)(OH(2))(2)](3+) and trans-[Cr(salen)(OH(2))(2)](+) [en being 1,2-ethanediamine, glygly being glycylglycine, phen being 1,10-phenanthroline, and salen being N,N'-ethylenebis(salicylideneiminato)] have been studied in V79 Chinese hamster lung cells. Following exposure of approximately 10(6) cells to 0.4 mM Cr(III) for 4 h, the Cr uptake by single cells was less than 10(-)(14) g/cell (as determined by GFAAS analysis and as confirmed by PIXE analysis where the Cr concentration was below the limit of detection). Importantly, the Cr(V) analogue of cis-[Cr(phen)(2)(OH(2))(2)] was significantly more permeable than the Cr(III) complex. The cytotoxicity of the Cr(III) complexes increased in the following order: mer-[Cr(glygly)(2)](-) < [Cr(en)(3)](3+) approximately cis-[Cr(phen)(2)(OH(2))(2)](3+) < trans-[Cr(salen)(OH(2))(2)](+). No genotoxic effects were observed following exposure to mer-[Cr(glygly)(2)](-) or [Cr(en)(3)](3+) at concentrations up to 6 mM. The Cr(III) imine complexes trans-[Cr(salen)(OH(2))(2)](+) and cis-[Cr(phen)(2)(OH(2))(2)](3+), which could be oxidized to Cr(V) complexes, induced MN in vitro at rates of 13.6 and 3.3 MN/1000 BN cells/micromol of Cr, respectively. The comparative permeabilities and genotoxicities of trans-[Cr(salen)(OH(2))(2)](+) and [CrO(salen)](+) were similar due to the instability of the Cr(V) complex at physiological pH values (7.4). There was a substantial increase in the permeability of [Cr(O)(2)(phen)(2)](+), compared to that of the Cr(III) analogue, which was accompanied by a highly genotoxic response. Consequently, any Cr(III) complex that is absorbed by cells and can be oxidized to Cr(V) must be considered as a potential carcinogen. This has potential implications for the increased use of Cr(III) complexes as dietary supplements and highlights the need to consider the genotoxicities of a variety of Cr(III) complexes when determining the carcinogenic potential of Cr(III) particularly when "high" deliberately administered doses are concerned.

Binding of Chromium(III) to Transferrin Could Be Involved in Detoxification of Dietary Chromium(III) Rather than Transport of an Essential Trace Element

Publisher: Wiley

Date: 20-05-2016

DOI: 10.1002/ANIE.201602996

Abstract: Cr(III) binding to transferrin (Tf the main Fe(III) transport protein) has been postulated to mediate cellular uptake of Cr(III) to facilitate a purported essential role for this element. Experiments using HepG2 (human hepatoma) cells, which were chosen because of high levels of the transferrin receptor, showed that Cr(III) binding to vacant Fe(III) -binding sites of human Tf effectively blocks cellular Cr(III) uptake. Through bio-layer interferometry studies of the Tf cycle, it was found that both exclusion and efflux of Cr2 (III) Tf from cells was caused by 1) relatively low Cr2 Tf affinity to cell-surface Tf receptors compared to Fe2 Tf, and 2) disruption of metal release under endosomal conditions and post-endosomal Tf dissociation from the receptor. These data support mounting evidence that Cr(III) is not essential and that Tf binding is likely to be a natural protective mechanism against the toxicity and potential genotoxicity of dietary Cr through blocking Cr(III) cellular accumulation.

X-ray Absorption Spectroscopic and Electrochemical Studies of Tris(catecholato(2-)) chromate (V/IV/III) Complexes

Publisher: Wiley

Date: 14-01-2004

DOI: 10.1002/ANIE.200352418

Disproportionation and nuclease activity of bis[2-ethyl-2-hydroxybutanoato(2-)]oxochromate(V) in neutral aqueous solutions

Publisher: American Chemical Society (ACS)

Date: 13-01-2000

DOI: 10.1021/IC990729C

Abstract: Complex 1, [Cr(V)O(ehba)2]- (ehba = 2-ethyl-2-hydroxybutanoate(2-)) is the most studied model compound of relevance to the biological activity of Cr(V) with regard to Cr-induced cancers. The first detailed kinetic study of disproportionation of 1 under neutral pH conditions (pH 6.0-8.0, [NaClO4] = 1.0 M, 37 degrees C) is reported. Kinetic data were collected by stopped-flow and conventional UV-vis spectroscopies and processed by the global analysis method. The disproportionation, which follows the stoichiometry 3Cr(V) --> 2Cr(VI) + Cr(III) (1), leads to release of 5 mol of H+/3 mol of Cr(V). Reaction 1 is accelerated by phosphate, but is not affected by acetate, HEPES, or Tris buffers. Initial rates of Cr(V) decay are directly proportional to [Cr(V)]0 (0.020-1.0 mM) they increase with an increase in the pH values and decrease in the presence of a large excess of ehba ligand. The first direct evidence for the formation of Cr(IV) intermediates in reaction 1 has been obtained however, their UV-vis spectral properties were different from those of the well-characterized Cr(IV)-ehba complexes. The Cr(III) products of reaction I in phosphate buffers differ from those in the other buffers. A mechanism is proposed for reaction 1 on the basis of kinetic modeling. Influences of the reaction time and conditions on the extent of plasmid DNA cleavage induced by 1 have been studied under conditions corresponding to those of the kinetic studies. A comparison of the kinetic and DNA cleavage results has shown that direct interaction of 1 with the phosphate backbone of DNA is the most likely first step in the mechanism of DNA cleavage in neutral media. Small additions of Mn(II) ((0.01-0.1)[Cr(V)]0) did not affect the rate and stoichiometry of reaction 1, but suppressed the formation of Cr(IV) intermediates (presumably due to the catalysis of Cr(IV) disproportionation). However, much higher concentrations of Mn(II) ((0.1-1.0)[Cr(V)]0) were required to inhibit DNA cleavage induced by 1. Thus, contrary to previous reports (Sugden, K. D. Wetterhahn, K. E. J. Am. Chem. Soc. 1996, 118, 10811-10818), inhibition by Mn(II) does not indicate a key role of Cr(IV) in Cr(V)-induced DNA cleavage.

High resolution nuclear and X-ray microprobes and their applications in single cell analysis

Publisher: Elsevier BV

Date: 07-2001

DOI: 10.1016/S0168-583X(01)00541-9

Negative Regulation of STAT3 Protein-mediated Cellular Respiration by SIRT1 Protein

Publisher: Elsevier BV

Date: 06-2011

DOI: 10.1074/JBC.M110.200311

EXAFS and EPR Studies of the Alkene Oxidation Catalyst Species trans-[Cr^III(bpb)(L)<inf>2</inf>]ⁿ⁺ and Cr^V Oxidation Products (bpb=N,N′-Bis(2-pyridinecarboxamido)-1,2-benzene)

Publisher: CSIRO Publishing

Date: 2015

DOI: 10.1071/CH14532

Abstract: The structures of trans-[CrIII(bpb)(OH2)2]+ and trans-[CrIII(bpb)(OH2)Cl] (bpb = N,N′-bis(2-pyridinecarboxamido)-1,2-benzene) have been determined by multiple-scattering analysis of their extended X-ray absorption fine structure (EXAFS) spectra. This is the first reported structural characterizations of these complexes, which have been used as catalysts in the oxidation of alkenes and the industrially important coupling reaction of epoxides with CO2. The formation of CrV species, which are likely catalytic intermediates, was observed when trans-[CrIII(bpb)(OH2)Cl] was treated with oxidants: PbO2, iodosylbenzene, or tert-butylhydroperoxide. The intermediates in these reactions were studied using X-band and Q-band electron paramagnetic resonance (EPR) spectroscopy to probe the ability of the bpb ligand to stabilize CrV–oxido complexes. Several CrV species were generated in such oxidation reactions that may be the reason for the lack of selectivity when the CrIII species are used as oxidation catalysts in the presence of oxidants.

Search for pair-produced vector-like top and bottom partners in events with large missing transverse momentum in pp collisions with the ATLAS detector

Publisher: Springer Science and Business Media LLC

Date: 10-08-2023

DOI: 10.1140/EPJC/S10052-023-11790-7

Abstract: A search for pair-produced vector-like quarks using events with exactly one lepton ( e or $$\\mu $$ μ ), at least four jets including at least one b -tagged jet, and large missing transverse momentum is presented. Data from proton–proton collisions at a centre-of-mass energy of $$\\sqrt{s}=$$ s = 13 $$\\text {TeV}$$ TeV , recorded by the ATLAS detector at the LHC from 2015 to 2018 and corresponding to an integrated luminosity of 139 fb $$^{-1}$$ - 1 , are analysed. Vector-like partners T and B of the top and bottom quarks are considered, as is a vector-like X with charge $$+5/3$$ + 5 / 3 , assuming their decay into a W , Z , or Higgs boson and a third-generation quark. No significant deviations from the Standard Model expectation are observed. Upper limits on the production cross-section of T and B quark pairs as a function of their mass are derived for various decay branching ratio scenarios. The strongest lower limits on the masses are 1.59 $$\\text {TeV}$$ TeV assuming mass-degenerate vector-like quarks and branching ratios corresponding to the weak-isospin doublet model, and 1.47 $$\\text {TeV}$$ TeV (1.46 $$\\text {TeV}$$ TeV ) for exclusive $$T \\rightarrow Zt$$ T → Z t ( $$B/X \\rightarrow Wt$$ B / X → W t ) decays. In addition, lower limits on the T and B quark masses are derived for all possible branching ratios.

Reactivity and Transformation of Antimetastatic and Cytotoxic Rhodium(III)–Dimethyl Sulfoxide Complexes in Biological Fluids: An XAS Speciation Study

Publisher: American Chemical Society (ACS)

Date: 04-2019

DOI: 10.1021/ACS.INORGCHEM.8B03477

Abstract: Rhodium(III) anticancer drugs can exert preferential antimetastatic or cytotoxic activities, which are dependent on subtle structural changes. In order to delineate factors affecting the biotransformations and speciation, mer,cis-[RhCl

Spectroelectrochemical evidence for communication within a laterally-bridged dimanganese(iii) bis-porphyrin

Publisher: Royal Society of Chemistry (RSC)

Date: 2006

DOI: 10.1039/B607748J

Abstract: Electronic coupling between the porphyrin units of a laterally-bridged dimanganese(III) bis-porphyrin 2 is explored using electrochemistry, spectroelectrochemistry and resonance-Raman spectroscopy. It is found that strong electronic interactions between the manganese(III) ion and the porphyrin macrocycle enhance the perturbations experienced by these bis-porphyrin systems when compared to related monomer porphyrin systems. In turn this leads to effective electronic communication between the manganese ions in the bis-porphyrin. This finding has importance in the design of molecular wires based on laterally-bridged oligo-metallo-porphyrins.

Metformin improves healthspan and lifespan in mice

Publisher: Springer Science and Business Media LLC

Date: 30-07-2013

DOI: 10.1038/NCOMMS3192

Reactivity-activity relationships of oral anti-diabetic vanadium complexes in gastrointestinal media: An X-ray absorption spectroscopic study

Publisher: Oxford University Press (OUP)

Date: 2014

DOI: 10.1039/C4MT00146J

Abstract: X-ray absorption near edge structure (XANES) speciation of vanadium pro-drugs in artificial digestive juices has delineated biotransformations after oral administration.

Correlation between film structures and potential limits for hydrogen and oxygen evolutions at a-C:N film electrochemical electrodes

Publisher: Elsevier BV

Date: 04-2008

DOI: 10.1016/J.CARBON.2008.01.022

Carcinogenic Chromium(VI) Compounds Formed by Intracellular Oxidation of Chromium(III) Dietary Supplements by Adipocytes

Publisher: Wiley

Date: 22-12-2016

DOI: 10.1002/ANIE.201509065

Abstract: Chromium(III) nutritional supplements are widely consumed for their purported antidiabetic activities. X-ray fluorescence microscopy (XFM) and X-ray absorption near-edge structure (XANES) studies have now shown that non-toxic doses of [Cr3 O(OCOEt)6 (OH2 )3 ](+) (A), a prospective antidiabetic drug that undergoes similar H2 O2 induced oxidation reactions in the blood as other Cr supplements, was also oxidized to carcinogenic Cr(VI) and Cr(V) in living cells. Single adipocytes treated with A had approximately 1 μm large Cr hotspots containing Cr(III) , Cr(V) , and Cr(VI) (primarily Cr(VI) thiolates) species. These results strongly support the hypothesis that the antidiabetic activity of Cr(III) and the carcinogenicity of Cr(VI) compounds arise from similar mechanisms involving highly reactive Cr(VI) and Cr(V) intermediates, and highlight concerns over the safety of Cr(III) nutritional supplements.

Some cobalt(III) complexes with coordinated dioxygen and multidentate and cyclic amine ligands

Publisher: Elsevier BV

Date: 1979

DOI: 10.1016/0022-1902(79)80137-2

Searches for exclusive Higgs and Z boson decays into a vector quarkonium state and a photon using 139 fb$$^{-1}$$ of ATLAS $$\sqrt{s}=13$$ TeV proton–proton collision data

Publisher: Springer Science and Business Media LLC

Date: 05-09-2023

DOI: 10.1140/EPJC/S10052-023-11869-1

Determination of the structures of antiinflammatory copper(II) dimers of indomethacin by multipie-scattering analyses of X-ray absorption fine structure data

Publisher: American Chemical Society (ACS)

Date: 13-02-2001

DOI: 10.1021/IC0007815

Abstract: Copper K-edge X-ray absorption spectroscopic (XAS) measurements were recorded for the veterinary antiinflammatory Cu(II) complexes of indomethacin (1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid = IndoH), of the general formula [Cu(2)(Indo)(4)L(2)] (L = N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), and water), and [Cu(2)(OAc)(4)(OH(2))(2)] at room temperature and 10 K. The bond lengths and bridging O-C-O angles of the dimeric Cu(II) cage (Cu(2)O(10)C(8)) obtained from the multiple-scattering (MS) fitting of the X-ray absorption fine structure (XAFS) using a centrosymmetric model of [Cu(2)(Indo)(4)(DMF)(2)] gave Cu.Cu = 2.62(2) A, mean Cu-O(Ac) = 1.95(2) A, Cu-O(L) = 2.15(2) A, bridging O-C-O = 125(1) degrees, Cu displacement from plane 0.19 A compared with the XRD data Cu.Cu = 2.630(1) A, mean Cu-O(Ac) = 1.959 A, Cu-O(L) = 2.143(5) A, bridging O-C-O angles = 123.2(5) degrees, Cu displacement from plane 0.20 A. The excellent agreement between the XAFS- and XRD-derived data allowed the structures of related [Cu(2)(Indo)(4)L(2)] (L = DMA, NMP) complexes to be determined. All display a similar Cu(2)O(10)C(8) coordination geometry, which is independent of the nature of the axial ligand. While XAFS analysis of [Cu(2)(Indo)(4)(OH(2))(2)] and [Cu(2)(OAc)(4)(OH(2))(2)] indicates a coordination geometry similar to that of [Cu(2)(Indo)(4)L(2)] (L = DMF, DMA, NMP), removal of symmetry restraints in the MS model is required to obtain axial bond lengths comparable to those derived in the XRD structures of the acetate complex. For the Indo complex, the fitted bond lengths with the lower symmetry model give a mean Cu-L(OH2) bond distance within experimental errors of the value for [Cu(2)(Indo)(4)(DMSO)(2)] (2.16(2) A) (XRD). The difficulty in refining the Cu-O(OH2) distance of [Cu(2)(OAc)(4)(OH(2))(2)] and [Cu(2)(Indo)(4)(OH(2))(2)] using a centrosymmetric MS model is attributed to a symmetry reduction due to hydrogen-bonding effects characteristic of the aqua adducts, as is observed in the XRD structure of the acetate complex.

Vanadium Chloro-Substituted Schiff Base Catecholate Complexes are Reducible, Lipophilic, Water Stable, and Have Anticancer Activities

Publisher: American Chemical Society (ACS)

Date: 15-12-2022

DOI: 10.1021/ACS.INORGCHEM.2C02557

A Molecular Probe for the Detection of Polar Lipids in Live Cells

Publisher: Public Library of Science (PLoS)

Date: 23-08-2016

DOI: 10.1371/JOURNAL.PONE.0161557

(η⁵-Pentaphenylcyclopentadienyl){1-(η⁶-phenyl)-2,3,4,5-tetraphenylcyclopentadienyl} iron(II), [Fe(η⁵-C₅Ph₅){(η⁶-C6

Publisher: Royal Society of Chemistry (RSC)

Date: 1990

DOI: 10.1039/C39900000408

Recent developments on the mechanisms of substitution reactions of octahedral coordination complexes

Publisher: Elsevier BV

Date: 10-1991

DOI: 10.1016/0010-8545(91)80006-Y

Vanadium(V/IV)–Transferrin Binding Disrupts the Transferrin Cycle and Reduces Vanadium Uptake and Antiproliferative Activity in Human Lung Cancer Cells

Publisher: American Chemical Society (ACS)

Date: 24-06-2020

DOI: 10.1021/ACS.INORGCHEM.0C00926

XAFS Studies of Anti-Inflammatory Dinuclear and Mononuclear Zn(II) Complexes of Indomethacin

Publisher: American Chemical Society (ACS)

Date: 14-11-2003

DOI: 10.1021/IC034049S

Abstract: Zinc K-edge X-ray absorption fine structure (XAFS) experiments were performed in the solid and solution states at low temperature (10 K), on dimeric and monomeric anti-inflammatory Zn(II) complexes of indomethacin [1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid=IndoH] of the formula [Zn2(Indo)4L2] [L=pyridine (Py), N,N-dimethylacetamide (DMA)], [Zn(Indo)2L2] [L=ethanol (EtOH), methanol (MeOH)], and Zn(II) acetate dihydrate [Zn(OAc)2(OH2)2]. The bond distances and angles obtained from multiple-scattering fits to the XAFS data of the Zn(II) dimeric complexes in the solid and solution states exhibit excellent correspondence with those obtained from single crystal diffraction studies. The Zn...Zn separations of 2.97 and 2.96 A and carboxylate group O-C-O angles of 125 degrees for powdered [Zn2(Indo)4(Py)2] and [Zn2(Indo)4(DMA)2] agree well with the XRD values of 2.969(1) and 2.9686(6) A and 125.8(4) degrees and 126.1(2) degrees, respectively. The calculated Zn-O(RCOO) and Zn-L bond distances of 2.03 and 2.04 A, or 2.02 and 1.98 A for Py or DMA complexes, respectively, also agree well with crystallographic data. The X-ray powder diffraction data on s les of the monomers exhibited additional reflections apart from those due to the crystallographically characterized cis-[Zn(eta2-O,O'-Indo)2L2], but microanalyses were consistent with this formulation. Therefore, mixed models that contained the cis complex and a second component consisting of a trans-six-coordinate complex, a five-coordinate complex, or a four-coordinate complex were used to model the XAFS. The best fits to the XAFS data were obtained with a mixture of the cis-six-coordinate complex and a four-coordinate complex containing two monodentate Indo ligands. The bond lengths for the six-coordinate structure were consistent with those determined on a single crystal, and those for the four-coordinate complexes were consistent with related four-coordinate structures with two monodentate carboxylate ligands. Dissolution of the dimer (DMA adduct) in DMF resulted in a mixture of dimer and monomer species as shown by MS XAFS fitting. This is the first time that solution structures have been determined for anti-inflammatory Zn(II) complexes, and this is an important first step in understanding the pharmacology of the complexes.

FTIR Imaging of Brain Tissue Reveals Crystalline Creatine Deposits Are an ex Vivo Marker of Localized Ischemia during Murine Cerebral Malaria: General Implications for Disease Neurochemistry

Publisher: American Chemical Society (ACS)

Date: 25-09-2012

DOI: 10.1021/CN300093G

EPR studies of chromium(V) intermediates generated via reduction of chromium(VI) by DOPA and related catecholamines: Potential role for oxidized amino acids in chromium-induced cancers

Publisher: American Chemical Society (ACS)

Date: 31-05-2000

DOI: 10.1021/IC991443A

Abstract: The reductions of K2Cr2O7 by catecholamines, DOPA, DOPA-beta,beta-d2, N-acetyl-DOPA, alpha-methyl-DOPA, dopamine, adrenaline, noradrenaline, catechol, 1,2-dihydroxybenzoic acid (DHBA), and 4-tert-butylcatechol (TBC), produce a number of Cr(V) electron paramagnetic resonance (EPR) signals. These species are of interest in relation to the potential role of oxidized proteins and amino acids in Cr-induced cancers. With excess organic ligand, all of the substrates yield Cr species with signals at g(iso) approximately 1.972 (Aiso(53Cr) > 23.9 x 10(-4) cm(-1)). These are similar to signals reported previously but have been reassigned as octahedral Cr(V) species with mixed catechol-derived ligands, [CrV(semiquinone)2(catecholate)]+. Experiments with excess K2Cr2O7 show complex behavior with the catecholamines and TBC. Several weak Cr(V) signals are detected after mixing, and the spectra evolve over time to yield relatively stable substrate-dependent signals at g(iso) approximately 1.980. These signals have been attributed to [Cr(O)L2](L = diolato) species, in which the Cr is coordinated to two cyclized catecholamine ligands and an oxo ligand. Isotopic labeling studies with DOPA (ring or side chain deuteration or enrichment with 15N), and simulation of the signals, show that the superhyperfine couplings originate from the side chain protons, confirming that the catecholamine ligands are cyclized. At pH 3.5, a major short-lived EPR signal is observed for many of the substrates at g(iso) approximately 1.969, but the species responsible for this signal was not identified. Several other minor Cr signals are detected, which are attributed (by comparison with isoelectronic V(IV) species) to Cr(V) complexes coordinated by a single catecholamine ligand (and auxiliary ligands e.g. H2O), or to [Cr(O)L2]- (L = diolato) species with a sixth ligand (e.g. H2O). Addition of catalase or deoxygenation of the solutions did not affect the main EPR signals. When the substrates were in excess (pH > 4.5), primary and secondary (cyclized) semiquinones were also detected. Semiquinone stabilization by Zn(II) complexation yielded stronger EPR signals (g(iso) approximately 2.004).

D-term Scattering in the Resonance Raman Spectrum of C60

Publisher: American Chemical Society (ACS)

Date: 12-1994

DOI: 10.1021/JA00105A075

Light and heavy ion beam analysis of thin biological sections

Publisher: Elsevier BV

Date: 07-2013

DOI: 10.1016/J.NIMB.2012.11.045

The SIRT1 Activator SRT1720 Extends Lifespan and Improves Health of Mice Fed a Standard Diet

Publisher: Elsevier BV

Date: 03-2014

DOI: 10.1016/J.CELREP.2014.01.031

Measurements of differential cross sections of Higgs boson production through gluon fusion in the $$H\rightarrow WW^{*}\rightarrow e\nu \mu \nu $$ final state at $$\sqrt{s} = 13$$ TeV with the ATLAS d

Publisher: Springer Science and Business Media LLC

Date: 09-2023

DOI: 10.1140/EPJC/S10052-023-11873-5

Synthesis of a Pyridinium Bis[citrato(2−)]oxochromate(V) Complex and Its Ligand-Exchange Reactions

Publisher: American Chemical Society (ACS)

Date: 10-09-2003

DOI: 10.1021/IC034146L

Abstract: The reaction of citric acid (caH(4)) with pyridinium dichromate (PDC) in anhydrous acetone yields pyridinium bis[citrato(2-)]oxochromate(V), pyH[CrO(caH(2))(2)], as a mixed salt with the Cr(III) product. The compound persists in the solid state for months, is highly soluble in water (pH 4.0), and gives a sharp electron paramagnetic resonance (EPR) signal in solution (g(iso) = 1.9781, A(iso)(Cr) = 17.1 x 10(-4) cm(-1)), which is characteristic of d(1) Cr(V). The presence of [Cr(V)O(caH(2))(2)](-) in the solid state was confirmed by electrospray mass spectroscopy, X-ray absorption near-edge structure (XANES), and EPR spectroscopy. Solid-state EPR spectroscopy, XANES, and a spectrophotometric assay showed that the solid is a mixture of [Cr(V)O(caH(2))(2)](-) and a Cr(III)-citrate complex. The structures of the [Cr(V)O(caH(2))(2)](-) and [Cr(III)(caH(2))(2)](-) components of the mixture were established by multiple-scattering MS analysis of the X-ray absorption fine structure data. The structure of [Cr(V)O(caH(2))(2)](-) is similar to that of other 2-hydroxy acid complexes with Cr=O, Cr-O(alcoholato), and Cr-O(carboxylato) bond lengths of 1.59, 1.81, and 1.90 A, respectively. The Cr(III) complex has bond lengths typical for ligands with deprotonated carboxylate and protonated alcohol donors with distances of 1.90 and 1.99 A, respectively, for the Cr-O(carboxylato) and Cr-O(alcohol) bond lengths. In aqueous solution, [CrO(caH(2))(2)](-) is short lived, but it is a convenient starting material for ligand-exchange reactions. It has been used to generate short-lived mixed-ligand Cr(V) complexes with citrate and picolinate, iminodiacetate, 2,2'-bipyridine, or 1,10-phenanthroline, which were characterized by EPR spectroscopy. The g values are between 1.971 and 1.974. For the picolinate, 2,2'-bipyridine, and 1,10-phenanthroline mixed-ligand complexes, there is hyperfine coupling (2.2 x 10(-4) to 2.4 x 10(-4) cm(-1)) to a single proton of the citrate ligand.

Binding of chromium(VI) to histones: Implications for chromium(VI)-induced genotoxicity

Publisher: Springer Science and Business Media LLC

Date: 15-12-2006

DOI: 10.1007/S00775-005-0068-3

Abstract: The first evidence has been obtained for Cr(VI) (chromate) binding to isolated calf thymus (CT) histones under physiological conditions (pH 7.4, Cl(-) concentration 152 mM, 310 K). No significant Cr(VI) binding under the same conditions was observed for other extracellular and intracellular proteins, including albumin, apo-transferrin and G-actin, as well as for CT DNA. The mode of Cr(VI) binding to histones was studied by vibrational, electronic and X-ray absorption (X-ray absorption near-edge structure and X-ray absorption fine structure) spectroscopies and molecular mechanics calculations. A proposed binding mechanism includes electrostatic interactions of CrO(4) (2-) with protonated Lys and Arg residues of histones, as well as the formation of hydrogen bonds with the protein backbone. Similarly, Cr(VI) can bind to nuclear localization signals (typically, Lys- and Arg-rich fragments) of other nuclear proteins. Selective binding of Cr(VI) to newly synthesized nuclear proteins (including histones) in the cytoplasm is likely to be responsible for the active transport of Cr(VI) into the nuclei of living cells.

Isolation, Characterization, and Nuclease Activity of Biologically Relevant Chromium(V) Complexes with Monosaccharides and Model Diols. Likely Intermediates in Chromium-Induced Cancers

Publisher: American Chemical Society (ACS)

Date: 26-03-2013

DOI: 10.1021/IC3022408

Abstract: The stabilization of Cr(V) by biological 1,2-diolato ligands, including carbohydrates, glycoproteins, and sialic acid derivatives, is likely to play a crucial role in the genotoxicity of Cr(VI) and has also been implicated in the antidiabetic effect of Cr(III). Previously, such complexes have been observed by electron paramagnetic resonance (EPR) spectroscopy in living cells or animals, treated with carcinogenic Cr(VI), as well as in numerous model systems, but attempts to isolate them have been elusive. Recently, the first crystal structure of a Cr(V) complex with cis-1,2-cyclohexanediol (1, a close structural analogue of carbohydrates) has been reported. In this work, Cr(V) complexes of the general formula [Cr(V)OL2](-) [where LH2 = 1, cis-1,2-cyclopentanediol (2), D-glucose (3), D-mannose (4), D-galactose (5), and D-ribose (6)] have been isolated from light-catalyzed reactions of Cr(VI) (anhydrous Na2Cr2O7) with slight molar excesses of the corresponding ligands in N,N-dimethylformamide. The complexes were characterized by elemental analyses, electrospray mass spectrometry (ESMS), and EPR spectroscopy. Studies by electronic absorption spectroscopy have shown that the solids isolated from reactions of Cr(VI) with 3-6 contained mixtures of Cr(V) complexes (40-65 mol %) and Cr(III) species (probably complexes with oxidized ligands), while those from reactions with 1 and 2 were practically pure Cr(V). The first isolation of solids containing significant proportions of chromium(V) monosaccharide complexes led to the definitive assignment of their general formula ([Cr(V)OL2](-), based on ESMS), in agreement with the earlier EPR spectroscopic data. The first direct comparison of the decomposition rates of Cr(V) complexes with 1-6, made possible by isolation of the solids, have shown that the complexes with five-membered-ring ligands (2 and 6) are more stable at pH ∼ 7 compared with their six-membered-ring counterparts (1 and 3-5). This finding emphasizes the likely biological roles of chromium(V) pentose complexes, e.g., those with sugar residues of RNA, ATP, or NAD(P)H. Finally, the first direct evidence for the ability of these Cr(V) complexes to cause oxidative DNA damage in the absence of added reductants or oxidants has been obtained. These data support significant roles for chromium(V) 1,2-diolato complexes in the erse biological activities of Cr(VI) and Cr(III).

Food Intake, Life Style, Aging and Human Longevity

Publisher: Springer Netherlands

Date: 2010

DOI: 10.1007/978-90-481-8556-6_2

Ruthenium(II)–Arene Thiocarboxylates: Identification of a Stable Dimer Selectively Cytotoxic to Invasive Breast Cancer Cells

Publisher: Wiley

Date: 12-12-2019

DOI: 10.1002/CBIC.201900676

Abstract: Ru

Hydrophobicity may enhance membrane affinity and anti-cancer effects of Schiff base vanadium(v) catecholate complexes

Publisher: Royal Society of Chemistry (RSC)

Date: 2019

DOI: 10.1039/C9DT00601J

Abstract: Hydrophobicity may increase the hydrolytic stability of vanadium( v ) catecholate complexes enabling rapid cellular uptake of the intact complex exhibiting potent anti-cancer activity.

Use of dry-matter intake recorded at multiple time periods during lactation increases the accuracy of genomic prediction for dry-matter intake and residual feed intake in dairy cattle

Publisher: CSIRO Publishing

Date: 29-05-2023

DOI: 10.1071/AN23022

Abstract: Context Feed is the largest expense on a dairy farm, therefore improving feed efficiency is important. Recording dry-matter intake (DMI) is a prerequisite for calculating feed efficiency. Genetic variation of feed intake and feed efficiency varies across lactation stages and parities. DMI is an expensive and difficult-to-measure trait. This raises the question of which time periods during lactation would be most appropriate to measure DMI. Aims The aim was to evaluate whether sequence variants selected from genome-wide association studies (GWAS) for DMI recorded at multiple lactation time periods and parities would increase the accuracy of genomic estimated breeding values (GEBVs) for DMI and residual feed intake (RFI). Methods Data of 2274 overseas lactating cows were used for the GWAS to select sequence variants. GWAS was performed using the average of the DMI phenotypes in a 30-day window of six different time periods across the lactation. The most significant sequence variants were selected from the GWAS at each time period for either first or later parities. GEBVs for DMI and RFI in Australian lactating cows were estimated using BayesRC with 50 k single nucleotide polymorphisms (SNPs) and selected GWAS sequence variants. Key results There were differences in DMI genomic correlations and heritabilities between first and later parities and within parity across lactation time periods. Compared with using 50 k single-nucleotide polymorphisms (SNPs) only, the accuracy of DMI GEBVs increased by up to 11% by using the 50 k SNPs plus the selected sequence variants. Compared with DMI, the increase in accuracy for RFI was lower (by 6%) likely because the sequence variants were selected from GWAS for DMI not RFI. The accuracies for DMI and RFI GEBVs were highest by using selected sequence variants from the DMI GWAS in the mid- to late-lactation periods in later parity. Conclusions Our results showed that DMI phenotypes in late lactation time periods could capture more genetic variation and increase genomic prediction accuracy through the use of custom genotype panels in genomic selection. Implications Collecting DMI at the optimal time period(s) of lactation may help develop more accurate and cost-effective breeding values for feed efficiency in dairy cattle.

Metal Carcinogens

Publisher: Elsevier

Date: 2013

DOI: 10.1016/B978-0-08-097774-4.00333-8

INSTRUMENTAL CONFIGURATIONS FOR THE DETERMINATION OF SUBMICROMOLAR CONCENTRATIONS OF ELECTROACTIVE SPECIES WITH CARBON, GOLD AND PLATINUM MICRODISK ELECTRODES IN STATIC AND FLOW-THROUGH CELLS

Publisher: Elsevier BV

Date: 1986

DOI: 10.1016/S0003-2670(00)82899-8

Biotransformations of Antidiabetic Vanadium Prodrugs in Mammalian Cells and Cell Culture Media: A XANES Spectroscopic Study

Publisher: American Chemical Society (ACS)

Date: 23-04-2015

DOI: 10.1021/IC5028948

Nuclear magnetic resonance analysis of indomethacin-induced gastric ulcers

Publisher: American Chemical Society (ACS)

Date: 19-01-2005

DOI: 10.1021/TX049806T

Abstract: Acetonitrile extracts of ulcerated and control rat stomachs were studied by various NMR techniques in an attempt to understand how indomethacin, a common and powerful nonsteroidal antiinflammatory drug (NSAID), induces ulcers in the stomach. One- (1D) and two-dimensional (2D) NMR spectra of extracts of ulcerated and control stomachs revealed that glycolytic and Krebs cycle enzymes were partially inhibited in the ulcerated stomach as shown by the lactate/glucose ratio. The (total choline)/lactate ratio was also higher in the extract from the control stomach than in the ulcerated stomach. Glycerophosphoethanolamine and glycerophosphocholine concentrations were higher in the ulcerated stomach extract as compared with the control stomach extract. These results explain the gastrointestinal protective effect of D-glucose and Krebs cycle intermediates on NSAID-induced ulceration.

High cytotoxicity of vanadium(IV) complexes with 1,10-phenanthroline and related ligands is due to decomposition in cell culture medium

Publisher: Springer Science and Business Media LLC

Date: 03-04-2017

DOI: 10.1007/S00775-017-1453-4

Abstract: Cytotoxic effects of Metvan (cis-[V

Age-Related Pseudocapillarization of the Liver Sinusoidal Endothelium Impairs the Hepatic Clearance of Acetaminophen in Rats

Publisher: Oxford University Press (OUP)

Date: 07-02-2011

DOI: 10.1093/GERONA/GLQ221

Determination of the Nature of the Heme Environment in Nitrosyl Indoleamine 2,3-Dioxygenase Using Multiple-Scattering Analyses of X-ray Absorption Fine Structure

Publisher: American Chemical Society (ACS)

Date: 09-04-2004

DOI: 10.1021/BI049645S

Abstract: Multiple-scattering analysis of X-ray absorption fine structure data on the NO adducts of indoleamine 2,3-dioxygenase (IDO) and analysis of X-ray absorption near-edge structure (XANES) have provided the first direct structural information about the iron center for this ubiquitous mammalian metalloprotein. The IDO(II)NO adduct, which is likely to play a physiological role in the immune system, differs from similar adducts such as Mb(II)NO and Lb(II)NO in that the Fe-His bond is essentially broken. At 10 K, the Fe-N(p)(av) bond length = 2.00(2) A, Fe-NO bond length = 1.75 A, and angle = 140 degrees, which are typical of five-coordinate Fe(II)NO species. The XANES is also closer to that of five-coordinate model complexes than six-coordinate species. In addition to the Fe(II)NO species, there was a minor component of the Fe(III)NO adduct because of incomplete reduction of the Fe(II) species. This was also a five-coordinate center and consists of a linear Fe(II)NO(+) moiety with the Fe-N(p)(av) bond length = 2.00(2) A, Fe-NO bond length = 1.63(3) A, and angle = 179 degrees. The results indicate that both the blocking of the heme site to O(2) binding and conformational changes induced by breaking the Fe-N(epsilon) bond may be important mechanisms by which NO inhibits IDO in vitro and in vivo.

Chromium(VI) reduction by catechol(amine)s results in DNA cleavage in vitro: Relevance to chromium genotoxicity

Publisher: American Chemical Society (ACS)

Date: 26-04-2001

DOI: 10.1021/TX000229S

Abstract: Catechols are found extensively in nature both as essential biomolecules and as the byproducts of normal oxidative damage of amino acids and proteins. They are also present in cigarette smoke and other atmospheric pollutants. Here, the interactions of reactive species generated in Cr(VI)/catechol(amine) mixtures with plasmid DNA have been investigated to model a potential route to Cr(VI)-induced genotoxicity. Reduction of Cr(VI) by 3,4-dihydroxyphenylalanine (DOPA) (1), dopamine (2), or adrenaline (3) produces species that cause extensive DNA damage, but the products of similar reactions with catechol (4) or 4-tert-butylcatechol (5) do not damage DNA. The Cr(VI)/catechol(amine) reactions have been studied at low added H(2)O(2) concentrations, which lead to enhanced DNA cleavage with 1 and induce DNA cleavage with 4. The Cr(V) and organic intermediates generated by the reactions of Cr(VI) with 1 or 4 in the presence of H(2)O(2) were characterized by EPR spectroscopy. The detected signals were assigned to Cr(V)-catechol, Cr(V)-peroxo, and mixed Cr(V)-catechol-peroxo complexes. Oxygen consumption during the reactions of Cr(VI) with 1, 2, 4, and 5 was studied, and H(2)O(2) production was quantified. Reactions of Cr(VI) with 1 and 2, but not 4 and 5, consume considerable amounts of dissolved O(2), and give extensive H(2)O(2) production. Extents of oxygen consumption and H(2)O(2) production during the reaction of Cr(VI) with enzymatically generated 1 and N-acetyl-DOPA (from the reaction of Tyr and N-acetyl-Tyr with tyrosinase, respectively) were correlated with the DNA cleaving abilities of the products of these reactions. The reaction of Cr(VI) with enzymatically generated 1 produced significant amounts of H(2)O(2) and caused significant DNA damage, but the N-acetyl-DOPA did not. The extent of in vitro DNA damage is reduced considerably by treatment of the Cr(VI)/catechol(amine) mixtures with catalase, which shows that the DNA damage is H(2)O(2)-dependent and that the major reactive intermediates are likely to be Cr(V)-peroxo and mixed Cr(V)-catechol-peroxo complexes, rather than Cr(V)-catechol intermediates.

ATLAS flavour-tagging algorithms for the LHC Run 2 pp collision dataset

Publisher: Springer Science and Business Media LLC

Date: 31-07-2023

DOI: 10.1140/EPJC/S10052-023-11699-1

Abstract: The flavour-tagging algorithms developed by the ATLAS Collaboration and used to analyse its dataset of $$\\sqrt{s} = 13$$ s = 13 TeV pp collisions from Run 2 of the Large Hadron Collider are presented. These new tagging algorithms are based on recurrent and deep neural networks, and their performance is evaluated in simulated collision events. These developments yield considerable improvements over previous jet-flavour identification strategies. At the 77% b -jet identification efficiency operating point, light-jet (charm-jet) rejection factors of 170 (5) are achieved in a s le of simulated Standard Model $$t\\bar{t}$$ t t ¯ events similarly, at a c -jet identification efficiency of 30%, a light-jet ( b -jet) rejection factor of 70 (9) is obtained.

Microprobe X-ray absorption spectroscopic determination of the oxidation state of intracellular chromium following exposure of V79 Chinese hamster lung cells to genotoxic chromium complexes

Publisher: American Chemical Society (ACS)

Date: 05-1997

DOI: 10.1021/TX970010M

Role of tyrosine-103 in myoglobin peroxidase activity: Kinetic and steady-state studies on the reaction of wild-type and variant recombinant human myoglobins with H2O2

Publisher: American Chemical Society (ACS)

Date: 30-08-2002

DOI: 10.1021/BI025835W

Abstract: Myoglobin (Mb) catalyzes a range of oxidation reactions in the presence of hydrogen peroxide (H(2)O(2)) through a peroxidase-like cycle. C110A and Y103F variants of human Mb have been constructed to assess the effects of removing electron-rich oxidizable amino acids from the protein on the peroxidase activity of Mb: a point mutation at W14 failed to yield a viable protein. Point mutations at C110 and Y103 did not result in significant changes to structural elements of the heme pocket, as judged by low-temperature electron paramagnetic spectroscopy (EPR) studies on the ground-state ferric proteins. However, compared to the native protein, the yield of globin radical (globin*) was significantly decreased for the Y103F but not the C110A variant Mb upon reaction of the respective proteins with H(2)O(2). In contrast with our expectation that inhibiting pathways of intramolecular electron transfer may lead to enhanced Mb peroxidase activity, mutation of Y103 marginally decreased the rate constant for reaction of Mb with H(2)O(2) (1.4-fold) as judged by stopped-flow kinetic analyses. Consistent with this decrease in rate constant, steady-state analyses of Y103F Mb-derived thioanisole sulfoxidation indicated decreased V(max) and increased K(m) relative to the wild-type control. Additionally, thioanisole sulfoxidation proceeded with lower stereoselectivity, suggesting that Y103 plays a significant role in substrate binding and orientation in the heme pocket of Mb. Together, these results show that electron transfer within the globin portion of the protein is an important modulator of its stability and catalytic activity. Furthermore, the hydrogen-bonding network involving the residues that line the heme pocket of Mb is crucial to both efficient peroxidase activity and stereospecificity.

X-ray absorption and EPR spectroscopic studies of the biotransformations of chromium(VI) in mammalian cells. Is chromodulin an artifact of isolation methods?

Publisher: American Chemical Society (ACS)

Date: 13-01-2007

DOI: 10.1021/JA063792R

Abstract: Very different biological activities are usually ascribed to Cr(VI) (a toxin and carcinogen) and Cr(III) (an antidiabetic agent), although recent evidence suggests that both these types of actions are likely to arise from cellular uptake of varying concentrations of Cr(VI). The first systematic study of XANES spectra of Cr(III) complexes formed in Cr(VI)-treated mammalian cells (A549, HepG2, V79, and C2C12 cell lines), and in subcellular fractions of A549 cells, has been performed using a library of XANES spectra of model Cr(III) complexes. The results of multiple linear regression analyses of XANES spectra, in combination with multiple-scattering fits of XAFS spectra, indicate that Cr(III) formed in Cr(VI)-treated cells is most likely to bind to carboxylato, amine, and imidazole residues of amino acids, and to a lesser extent to hydroxo or aqua ligands. A combination of XANES and EPR spectroscopic data for Cr(VI)-treated cells indicates that the main component of Cr(III) formed in such cells is bound to high-molecular-mass ligands (>30 kDa, probably proteins), but significant redistribution of Cr(III) occurs during the cell lysis, which leads to the formation of a low-molecular-mass (<30 kDa) Cr(III)-containing fraction. The spectroscopic (XANES, XAFS, and EPR) properties of this fraction were strikingly similar to those of the purported natural Cr(III)-containing factor, chromodulin, that was reported to be isolated from the reaction of Cr(VI) with liver. These data support the hypothesis that a chromodulin-like species, which is formed from such a reaction, is an artifact of the reported isolation procedure.

X-ray absorption spectroscopic studies of chromium nitroso complexes. Crystal and molecular structure of (Ph4P) 3[Cr(NO)(NCS)5]·2.4(CH3)2CO

Publisher: American Chemical Society (ACS)

Date: 23-07-2003

DOI: 10.1021/IC0340480

Abstract: X-ray absorption spectroscopy (XAS) provides a direct means of solving the controversy on Cr oxidation states in nitroso complexes. The first XAS studies of four known Cr-NO complexes, [Cr(NO)(OH(2))(5)](2+), [Cr(NO)(acac)(2)(OH(2))], [Cr(NO)(CN)(5)](3)(-), and [Cr(NO)(NCS)(5)](3)(-), have been performed, in comparison with the related Cr(III) complexes, [Cr(OH(2))(6)](3+), [Cr(acac)(3)], [Cr(CN)(6)](3)(-), and [Cr(NCS)(6)](3)(-). The X-ray absorption near-edge structure (XANES) spectra of the Cr-NO complexes are distinguished from those of the corresponding Cr(III) complexes by increased intensities of pre-edge absorbancies due to the 1s --> 3d transition, as well as with slight shifts (by 0.2-1.0 eV) of the edge positions to lower energies, with no major changes in the edge shape. These features, together with the available structural data on Cr-NO complexes, show that the effective Cr oxidation states in such complexes are close to Cr(III), due to the pi-back-bonding within the Cr-NO moiety. Multiple-scattering fitting of X-ray absorption fine structure (XAFS) spectra of [Cr(NO)(acac)(2)(OH(2))] supported the assignment of this complex as a trans-isomer (Keller, A. Jezovska-Trzebiatowska, B. Polyhedron 1985, 4, 1847-1852). The first crystal structure of a Cr nitroso-isothiocyanato complex, (Ph(4)P)(3)[Cr(NO)(NCS)(5)].2.4(CH(3))(2)CO, has been determined.

Vanadium(V) Pyridine‐Containing Schiff Base Catecholate Complexes are Lipophilic, Redox‐Active and Selectively Cytotoxic in Glioblastoma (T98G) Cells

Publisher: Wiley

Date: 24-10-2023

DOI: 10.1002/CHEM.202302271

Abstract: Two new series of complexes with pyridine‐containing Schiff bases, [VVO(SALIEP)L] and [VVO(Cl‐SALIEP)L] (SALIEP = N‐(salicylideneaminato)‐2‐(2‐aminoethylpyridine Cl‐SALIEP = N‐(5‐chlorosalicylideneaminato)‐2‐(2‐aminoethylpyridine, L = catecholato(2‐) ligand) were synthesized. Characterization by 1H and 51V NMR and UV‐Vis spectroscopies confirmed that: 1) most complexes form two major geometric isomers in solution, and [VVO(SALIEP)(DTB)] (DTB = di‐tert‐butylcatecholato(2‐)) forms two isomers that equilibrate in solution and 2) tert‐butyl substituents was necessary to stabilize the reduced V(IV) species (EPR spectroscopy and cyclic voltammetry). The pyridine moiety within the Schiff base ligands significantly changed their chemical properties with unsubstituted catecholate ligands compared with the parent HSHED (N‐(salicylideneaminato)‐Nˊ‐(2‐hydroxyethyl)‐1,2‐ethanediamine) Schiff base complexes. Immediate reduction to V(IV) occurred for the unsubstituted‐catecholato V(V) complexes on dissolution in DMSO. By contrast, the pyridine moiety within the Schiff base significantly improved the hydrolytic stability of [VVO(SALIEP)(DTB)] compared with [VVO(HSHED)(DTB)]. [VVO(SALIEP)(DTB)] had moderate stability in cell culture media. There was significant cellular uptake of the intact complex by T98g (human glioblastoma) cells and very good anti‐proliferative activity (IC50 6.7 ± 0.9 μM, 72 h), which was ~five‐fold higher compared with the non‐cancerous human cell line, HFF‐1 (IC50 34 ± 10 μM). This made it a potential drug candidate for the treatment of advanced gliomas by intracranial injections.

Synthesis and characterisation of pentaphenylcyclo-pentadienyliron arene sandwich complex cations [Fe(η⁵-C5Ph5)(arene)]⁺ and the X-ray crystal structure of the [Fe(η⁵-C5Ph5)(η⁶-C 6H5Me)]⁺ cation

Publisher: Royal Society of Chemistry (RSC)

Date: 1991

DOI: 10.1039/DT9910001499

SRT1720 improves survival and healthspan of obese mice

Publisher: Springer Science and Business Media LLC

Date: 18-08-2011

DOI: 10.1038/SREP00070

In Vitro Plasmid DNA Cleavage by Chromium(V) and -(IV) 2-Hydroxycarboxylato Complexes

Publisher: American Chemical Society (ACS)

Date: 25-03-1999

DOI: 10.1021/TX980229G

The endothelium-derived hyperpolarizing factor, H2O2, promotes metal-ion efflux in aortic endothelial cells: Elemental mapping by a hard X-ray microprobe

Publisher: American Chemical Society (ACS)

Date: 23-09-2006

DOI: 10.1021/BI0604375

Abstract: Hydrogen peroxide (H(2)O(2)) is a physiologic oxidant implicated in vascular cell signaling, although little is known about the biochemical consequences of its reaction with endothelial cells. Submicrometer-resolution hard X-ray elemental mapping of cultured porcine aortic endothelial cells (PAEC) has provided data on the global changes for intracellular elemental density within PAEC and indicates an efflux of metal ions and phosphorus from the cytoplasm after H(2)O(2) treatment. The synchrotron-radiation-induced X-ray emission experiments (SRIXE) show that H(2)O(2)-treated cells are irregularly shaped and exhibit blebbing indicative of increased permeability due to the damaged membrane. The SRIXE results suggest that H(2)O(2)-induced damage is largely restricted to the cell membrane as judged by the changes to membrane and cytoplasmic components rather than the cell nucleus. The SRIXE data also provide a mechanism for cell detoxification as the metal-ion efflux resulting from the initial H(2)O(2)-mediated changes to cell membrane potentially limits intracellular metal-mediated redox processes through Fenton-like chemistry. They may also explain the increased levels of these ions in atherosclerotic plaques, regardless of whether they are involved in plaque formation. Finally, the SRIXE data support the notion that cultured endothelial cells exposed to H(2)O(2) respond with enhanced cellular metal-ion efflux into the extracellular space.

Evidence for bond breaking substantially preceding bond making in the mechanisms of spontaneous aquations of penta-aminechloro-chromium(III), -cobalt(III), and -rhodium(III) complexes: Crystal and molecular structure of chloropentakis(methylamine)rhodium(III) chloride

Publisher: Royal Society of Chemistry (RSC)

Date: 1987

DOI: 10.1039/C39870000865

Physiological, Anthropometric, and Performance Characteristics of Rugby Sevens Players

Publisher: Human Kinetics

Date: 2013

DOI: 10.1123/IJSPP.8.1.19

Abstract: Although the characteristics of 15-a-side rugby union players have been well defined, there is little information on rugby sevens players. The authors profiled the anthropometric, physiological, and performance qualities of elite-level rugby sevens players and quantified relationships between these characteristics. Eighteen male international rugby sevens players undertook anthropometric (body mass, height, sum of 7 skinfolds, lean-mass index), acceleration and speed (40-m sprint), muscle-power (vertical jump), repeatedsprint- ability (6 × 30-m sprint), and endurance (Yo-Yo Intermittent Recovery test and treadmill VO 2max ) testing. Associations between measurements were assessed by correlation analysis. Rugby sevens players had anthropometric characteristics (body mass 89.7 ± 7.6 kg, height 1.83 ± 0.06 m, sum of 7 skinfolds 52.2 ± 11.5 mm mean ± SD) similar to those of backs in international 15-player rugby union. Acceleration and speed (40-m sprint 5.11 ± 0.15 s), muscle-power (vertical jump 66 ± 7 cm), and endurance (VO 2max 53.8 ± 3.4 mL · kg −1 · min −1 ) qualities were similar to, or better than, those of professional 15-a-side players. Coefficients of variation ranged from 2.5% to 22%. Relative VO 2max was largely correlated with Yo-Yo distance ( r = .60, .21−.82 90% confidence interval) and moderately correlated with 40-m sprint time ( r = −.46, −.75 to −.02) and repeated-sprint ability ( r = −.38, −.72 to .09). International rugby sevens players require highly developed speed, power, and endurance to tolerate the demands of competition. The small between-athletes variability of characteristics in rugby sevens players highlights the need for relatively uniform physical and performance standards in contrast with 15-a-side players.

Intracellular targeting and pharmacological activity of the superoxide dismutase mimics MnTE-2-PyP⁵⁺ and MnTnHex-2-PyP⁵⁺ regulated by their porphyrin ring substituents

Publisher: American Chemical Society (ACS)

Date: 03-04-2013

DOI: 10.1021/IC300700G

Abstract: Manganese porphyrin-based drugs are potent mimics of the enzyme superoxide dismutase. They exert remarkable efficacy in disease models and are entering clinical trials. Two lead compounds, MnTE-2-PyP(5+) and MnTnHex-2-PyP(5+), have similar catalytic rates, but differ in their alkyl chain substituents (ethyl vs n-hexyl). Herein we demonstrate that these changes in ring substitution impact upon drug intracellular distribution and pharmacological mechanism, with MnTnHex-2-PyP(5+) superior in augmenting menadione toxicity. These findings establish that both catalytic activity and intracellular distribution determine drug action.

Search for pairs of muons with small displacements in pp collisions at s

Publisher: Elsevier BV

Date: 11-2023

DOI: 10.1016/J.PHYSLETB.2023.138172

Response to Guzzi & Pigattos Comments on Migration of mercury from dental amalgam through human teeth by H. H. Harris et al. (2008). J. Synchrotron Rad. 15, 123-128

Publisher: International Union of Crystallography (IUCr)

Date: 17-03-2009

DOI: 10.1107/S0909049509005706

Synthesis, reactivities and anti-cancer properties of ruthenium(II) complexes with a thiaether macrocyclic ligand

Publisher: Elsevier BV

Date: 2017

DOI: 10.1016/J.ICA.2016.07.050

Determination of Fe-ligand bond lengths and the Fe-N-O bond angles in soybean ferrous and ferric nitrosylleghemoglobin a using multiple-scattering XAFS analyses

Publisher: American Chemical Society (ACS)

Date: 23-11-1999

DOI: 10.1021/BI990730N

Abstract: The NO adducts of leghemoglobin (Lb) are implicated in biological processes, but only the adduct with ferrous Lb (Lb(II)NO) has been characterized previously. We report the first characterization of ferric nitrosylleghemoglobin (Lb(III)NO) and XAS experiments performed on frozen aqueous solutions of Lb(II)NO and Lb(III)NO at 10 K. The XANES and electronic spectra of the NO adducts are similar in shape and energies to the myoglobin (Mb) analogues. The environment of the Fe atom has been refined using multiple-scattering (MS) analyses of the XAFS data. For Lb(II)NO, the MS analysis resulted in an averaged Fe-N(p)(pyrrole) distance of 2.02 A, an Fe-N(epsilon)(imidazole) distance of 1.98 A, an Fe-N(NO) distance of 1.77 A, and an Fe-N-O angle of 147 degrees. The Fe-N(NO) distance and Fe-N-O angle obtained from the analysis of Lb(II)NO are in good agreement with those determined crystallographically for [Fe(TPP)(NO)] (TPP, tetraphenylporphyrinato), with and without 1-methylimidazole (1-MeIm) as the sixth ligand, and the MS XAFS structures reported previously for the myoglobin (Mb(II)NO) analogue and [Fe(TPP)(NO)]. The MS analysis of Lb(III)NO yielded an average Fe-N(p) distance of 2.00 A, an Fe-N(epsilon) distance of 1.89 A, an Fe-N(NO) distance of 1.68 A, and an Fe-N-O angle of 173 degrees. These bond lengths and angles are consistent with those determined previously for the myoglobin analogue (Mb(III)NO) and the crystal structures of the model complexes, [Fe(III)(TPP)(NO)(OH(2))](+) and [Fe(OEP)(NO)](+) (OEP, octaethylporphyrinato). The final XAFS R values were 16.1 and 18.2% for Lb(II)NO and Lb(III)NO, respectively.

Recent developments in ruthenium anticancer drugs

Publisher: Oxford University Press (OUP)

Date: 2009

DOI: 10.1039/B904071D

Abstract: Interest in Ru anticancer drugs has been growing rapidly since NAMI-A ((ImH(+))[Ru(III)Cl(4)(Im)(S-dmso)], where Im = imidazole and S-dmso = S-bound dimethylsulfoxide) or KP1019 ((IndH(+))[Ru(III)Cl(4)(Ind)(2)], where Ind = indazole) have successfully completed phase I clinical trials and an array of other Ru complexes have shown promise for future development. Herein, the recent literature is reviewed critically to ascertain likely mechanisms of action of Ru-based anticancer drugs, with the emphasis on their reactions with biological media. The most likely interactions of Ru complexes are with: (i) albumin and transferrin in blood plasma, the former serving as a Ru depot, and the latter possibly providing active transport of Ru into cells (ii) collagens of the extracellular matrix and actins on the cell surface, which are likely to be involved in the specific anti-metastatic action of Ru complexes (iii) regulatory enzymes within the cell membrane and/or in the cytoplasm and (iv) DNA in the cell nucleus. Some types of Ru complexes can also promote the intracellular formation of free radical species, either through irradiation (photodynamic therapy), or through reactions with cellular reductants. The metabolic pathways involve competition among reduction, aquation, and hydrolysis in the extracellular medium binding to transport proteins, the extracellular matrix, and cell-surface biomolecules and diffusion into cells with the extent to which in idual drugs participate in various steps along these pathways being crucial factors in determining whether they are mainly anti-metastatic or cytotoxic. This ersity of modes of action of Ru anticancer drugs is also likely to enhance their anticancer activities and to reduce the potential for them to develop tumour resistance. New approaches to metabolic studies, such as X-ray absorption spectroscopy and X-ray fluorescence microscopy, are required to provide further mechanistic insights, which could lead to the rational design of improved Ru anticancer drugs.

New techniques for jet calibration with the ATLAS detector

Publisher: Springer Science and Business Media LLC

Date: 28-07-2021

DOI: 10.1140/EPJC/S10052-023-11837-9

Abstract: A determination of the jet energy scale is presented using proton–proton collision data with a centre-of-mass energy of $$\\sqrt{s}=13$$ s = 13 TeV, corresponding to an integrated luminosity of 140 fb $$^{-1}$$ - 1 collected using the ATLAS detector at the LHC. Jets are reconstructed using the ATLAS particle-flow method that combines charged-particle tracks and topo-clusters formed from energy deposits in the calorimeter cells. The anti- $$k_\\textrm{t}$$ k t jet algorithm with radius parameter $$R=0.4$$ R = 0.4 is used to define the jet. Novel jet energy scale calibration strategies developed for the LHC Run 2 are reported that lay the foundation for the jet calibration in Run 3. Jets are calibrated with a series of simulation-based corrections, including state-of-the-art techniques in jet calibration such as machine learning methods and novel in situ calibrations to achieve better performance than the baseline calibration derived using up to 81 fb $$^{-1}$$ - 1 of Run 2 data. The performance of these new techniques is then examined in the in situ measurements by exploiting the transverse momentum balance between a jet and a reference object. The b -quark jet energy scale using particle flow jets is measured for the first time with around 1% precision using $$\\gamma $$ γ +jet events.

Chromium(V) peptide complexes: Synthesis and spectroscopic characterization

Publisher: American Chemical Society (ACS)

Date: 25-01-2005

DOI: 10.1021/IC048322H

Abstract: A series of stable Cr(V) model complexes that mimic the binding of Cr(V) to peptide backbones at the C-terminus of proteins have been prepared for N,N-dimethylurea derivatives of the tripeptides Aib3-DMF, AibLAlaAib-DMF, and AibDAlaAib-DMF (Aib = 2-amino-2-methylpropanoic acid, DMF = N,N-dimethylformamide). The Cr(ll) precursor complexes were synthesized by the initial deprotonation of the amide and acid groups of the peptide ligands in DMF with potassium tert-butoxide in the presence of CrCl2. The Cr(II) intermediates thus formed were then immediately oxidized to Cr(V) using tert-butyl hydroperoxide. Spectroscopic and mass-spectrometric analyses of the Cr(V) complexes showed that a new metal-directed organic transformation of the ligand had occurred. This involved a DMF solvent molecule becoming covalently bound to the amine group of the peptide ligand, yielding a urea group, and a third coordinated deprotonated urea nitrogen donor. A metal-directed oxidative coupling has been proposed as a possible mechanism for the organic transformation. The Cr(V/IV) reduction potential was determined for the three Cr(V) complexes using cyclic voltammetry, and in all cases it was quasi-reversible. These are the first isolated and fully characterized Cr(V) complexes with non-sulfur-containing peptide ligands.

Solvent dependence, metal ion catalysis and base catalysis of nitrito to nitro linkage isomerization of pentaamminenitritocobalt (III)

Publisher: CSIRO Publishing

Date: 1982

DOI: 10.1071/CH9821561

Abstract: The spontaneous rate of nitrito to nitro isomerization of [(NH3),Co(ONO)]2+ spans two orders of magnitude for 16 solvents studied. The volume of activation is small and negative (from - 3.5 to -7 cm3 mol-1) for water, dimethyl sulfoxide, N-methylformamide and sulfolane. Combined with the observation of negligible competitive solvolysis, and of an isokinetic plot of ΔH‡ against ΔS‡, this indicates that isomerization is intramolecular in all solvents. The solvent dependence is interpreted in terms of a dual-parameter equation involving terms for the Lewis basicities (DN) and Lewis acidities and polarity (ET). By use of this approach both DN and ET of the solvents are shown to be major contributing factors to reactivity. Further studies on base-catalysed nitrito to nitro isomerizations reveal mild catalysis by F-, AcO- and Et3N in Me2SO. The metal ions HgZ+, Ag+ and Cd2+ also catalyse the isomerization in water [kHg 1.16 × dm3 mol-1 s-1, kAg 2.85 × dm3 mol-1 s-1, kCd 4.4 × 10-5 dm3 mol-1 s-1 ,μ 1.0 M (CIO4-), 25°C]. The lack of competition by AcO-, NO3- and H2O in the Hg2+-catalysed isomerization reaction also implicates an intramolecular process for this path. In acetone, the ions Hg2+, Ag+, Cd2+ and Zn2+ catalyse the isomerization reaction with a rate law of the form Kobs = Ks + Km[n+] except for Ag+, where the rate law takes the form Kobs = (ks + kK[Ag+])/(1 + K[Mn+]) with kAg = kK = 2.11 × dm3 mol-1 s-1, k = 1.74 × 10-4 s-1 and K = 12 ± 1 dm3 mol-1. The limiting rate is ascribed to a high stability constant for the silver adduct intermediate. The analogous RhIII and IrIII complexes also exhibit catalysis by Ag+ and Hg2+ in aqueous solution.

Frontispiece: A Short‐Lived but Highly Cytotoxic Vanadium(V) Complex as a Potential Drug Lead for Brain Cancer Treatment by Intratumoral Injections

Publisher: Wiley

Date: 07-09-2020

DOI: 10.1002/ANIE.202083761

Investigation of the mouse cerebellum using STIM and μ-PIXE spectrometric and FTIR spectroscopic mapping and imaging

Publisher: Elsevier BV

Date: 10-2011

DOI: 10.1016/J.NIMB.2011.02.034

Redox potentials of chromium(V)/(IV), -(V)/(III), and -(IV)/(III) complexes with 2-ethyl-2-hydroxybutanoato(2-/1-) ligands

Publisher: American Chemical Society (ACS)

Date: 1996

DOI: 10.1021/JA954047+

The Fe-heme structure of met-indoleamine 2,3-dioxygenase-2 determined by X-ray absorption fine structure

Publisher: Elsevier BV

Date: 07-2014

DOI: 10.1016/J.BBRC.2014.05.054

Abstract: Multiple-scattering (MS) analysis of EXAFS data on met-indoleamine 2,3-dioxygenase-2 (IDO2) and analysis of XANES have provided the first direct structural information about the axial donor ligands of the iron center for this recently discovered protein. At 10K, it exists in a low-spin bis(His) form with Fe-Np(av)=1.97Å, the Fe-NIm bond lengths of 2.11Å and 2.05Å, which is in equilibrium with a high-spin form at room temperature. The bond distances in the low-spin form are consistent with other low-spin hemeproteins, as is the XANES spectrum, which is closer to that of the low-spin met-Lb than that of the high-spin met-Mb. The potential physiological role of this spin equilibrium is discussed.

Surface-enhanced Raman spectroscopy of pentaammineosmium (III)/(II) and pentaammineruthenium (II) containing pyridine, pyrazine or 4,4′-bipyridine ligands at silver electrodes: vibrational assignments

Publisher: Elsevier BV

Date: 1984

DOI: 10.1016/0584-8539(84)80150-6

Solution Structures of Chromium(VI) Complexes with Glutathione and Model Thiols

Publisher: American Chemical Society (ACS)

Date: 05-12-2004

DOI: 10.1021/IC034901V

Abstract: Chromium(VI) complexes of the most abundant biological reductant, glutathione (gamma-Glu-Cys-Gly, I), are among the likely initial reactive intermediates formed during the cellular metabolism of carcinogenic and genotoxic Cr(VI). Detailed structural characterization of such complexes in solutions has been performed by a combination of X-ray absorption fine structure (XAFS) and X-ray absorption near-edge structure (XANES) spectroscopies, electrospray mass spectrometry (ESMS), UV-vis spectroscopy, and kinetic studies. The Cr(VI) complexes of two model thiols, N-acetyl-2-mercaptoethylamine (II) and 4-bromobenzenethiol (III), were used for comparison. The Cr(VI)-thiolato complexes were generated quantitatively in weakly acidic aqueous solutions (for I and II) or in DMF solutions (for II) or isolated as a pure solid (for III). Contrary to some claims in the literature, no evidence was found for the formation of relatively stable Cr(IV) intermediates during the reactions of Cr(VI) with I in acidic aqueous solutions. The Cr(VI) complexes of I-III exist as tetrahedral [CrO(3)(SR)](-) (IVa) species in the solid state, in solutions of aprotic solvents such as DMF, or in the gas phase (under ESMS conditions). In aqueous or alcohol solutions, reversible addition of a solvent molecule occurs, with the formation of five-coordinate species, [CrO(3)(SR)L](-) (IVb, probably of a trigonal bipyramidal structure, L = H(2)O or MeOH), with a Cr-L bond length of 1.97(1) A (determined by XAFS data modeling). Complex IVb (L = H(2)O) is also formed (in an equilibrium mixture with [CrO(4)](2)(-)) at the first stage of reduction of Cr(VI) by I in neutral aqueous solutions (as shown by global kinetic analysis of time-dependent UV-vis spectra). This is the first observation of a reversible ligand addition reaction in Cr(VI) complexes. The formation of IVb (rather than IVa, as thought before) during the reactions of Cr(VI) with I in aqueous solutions is likely to be important for the reactivity of Cr(VI) in cellular media, including DNA and protein damage and inhibition of protein tyrosine phosphatases.

Aging Biology and Novel Targets for Drug Discovery

Publisher: Oxford University Press (OUP)

Date: 21-06-2012

DOI: 10.1093/GERONA/GLR095

Electrochemistry of chlorinated ferrocenes: Stability of chlorinated ferrocenium ions

Publisher: Royal Society of Chemistry (RSC)

Date: 1993

DOI: 10.1039/DT9930000835

Reactivity of potential anti-diabetic molybdenum(VI) complexes in biological media: A XANES spectroscopic study

Publisher: Elsevier BV

Date: 11-2007

DOI: 10.1016/J.JINORGBIO.2007.07.016

Abstract: The application of Mo(VI) complexes as anti-diabetic agents is a subject of considerable recent interest. The stability and speciation of [Mo(VI)O(4)](2-) and three analogs of known anti-diabetic V(IV) complexes ([Mo(VI)O(2)L(2)] where LH=2,4-pentanedione, l-cysteine ethyl ester or N,N-diethyldithiocarbamic acid) in natural and simulated biological fluids (including blood and its components, cell culture media, and artificial digestion systems) were studied using MoK-edge XANES (X-ray absorption near-edge structure) spectroscopy of freeze-dried s les at 20K. All of the studied [MoO(2)L(2)] complexes decomposed extensively under simulated gastric and intestinal digestion conditions (3 h at 310 K), as well as in blood plasma or in cell culture medium (24 h at 310 K). The reaction products of [MoO(4)](2-) and [MoO(2)L(2)] with biological fluids could be satisfactorily modelled (using multiple linear regression analyses) as mixtures of tetrahedral and octahedral Mo(VI) species (with O-donor ligands) in various ratios, which were dependent on the nature of the medium rather than that of the initial Mo(VI) compounds. Red blood cells take up Mo(VI) predominantly in the form of [MoO(4)](2-). Implications of these results to the development of Mo(VI)-based anti-diabetics and to the mechanisms of natural uptake and metabolism of Mo(VI) are discussed.

Gastrointestinal toxicity, antiinflammatory activity, and superoxide dismutase activity of copper and zinc complexes of the antiinfiammatory drug indomethacin

Publisher: American Chemical Society (ACS)

Date: 10-12-2003

DOI: 10.1021/TX020078O

Abstract: Gastrointestinal (GI) toxicity is one of the major problems associated with antiinflammatory drugs. The complexation of the powerful antiinflammatory drug (IndoH) by metal ions, as a means of reducing GI toxicity, has been studied. The in vitro superoxide dismutase (SOD) activity, in vivo antiinflammatory activity, and gastrointestinal ulcerogenic properties of IndoH, [Cu2(Indo)4(DMF)2], and [Zn2(Indo)4(DMA)2] are reported. No SOD activity was observed for IndoH or [Zn2(Indo)4(DMA)2], but [Cu2(Indo)4(DMF)2] inhibited the reduction of nitroblue tetrazolium (NBT) at an IC50 value of 0.23 microM. All three compounds exhibited antiinflammatory activity in male Sprague-Dawley rats at an equivalent Indo dose of 10 mg/kg following oral administration of the drugs in 2% CMC solution. The severity of the toxicity (macroscopic ulcerations) in the stomach following oral dosing with [Zn2(Indo)4(DMF)2] was not significantly lower than that induced by IndoH (P = 0.78). Gastric ulcerations induced by [Cu2(Indo)4(DMF)2] were significantly lower than those induced by IndoH or [Zn2(Indo)4(DMA)2] (P = 0.0012 and P = 0.0175, respectively) but significantly greater than the control (P = 0.0013). The intestinal ulcerations induced by [Cu2(Indo)4(DMF)2] or [Zn2(Indo)4(DMA)2] were approximately 15 times lower than those of IndoH. A further indicator of gastrointestinal toxicity, caecal haemoglobin, increased in the following order: control < [Cu2(Indo)4(DMF)2] < [Zn2(Indo)4(DMA)2] < IndoH.[Cu2(Indo)4(DMF)2] exhibited the most promising results of the Indo complexes assayed, in that it exhibited SOD activity and the lowest gastrointestinal damage while also exhibiting antiinflammatory activity that was comparable to that for IndoH. Low-temperature EPR analyses also showed that the formulation used for [Cu2(Indo)4(DMF)2] administration was crucial to the integrity of the complex.

Native oxides and their effect on electrochemical characteristics of ta-C:N films

Publisher: Elsevier BV

Date: 08-2013

DOI: 10.1016/J.SURFCOAT.2012.05.010

Reduction of Bridgehead Halogens by an Intramolecular Electron Transfer Radical Mechanism

Publisher: American Chemical Society (ACS)

Date: 09-1995

DOI: 10.1021/JO00122A030

Imaging of Vanadium in Microfossils: A New Potential Biosignature

Publisher: Mary Ann Liebert Inc

Date: 11-2017

DOI: 10.1089/AST.2017.1709

Abstract: The inability to unambiguously distinguish the biogenicity of microfossil-like structures in the ancient rock record is a fundamental predicament facing Archean paleobiologists and astrobiologists. Therefore, novel methods for discriminating biological from nonbiological chemistries of microfossil-like structures are of the utmost importance in the search for evidence of early life on Earth. This, too, is important for the search for life on Mars by in situ analyses via rovers or s le return missions for future analysis here on Earth. Here, we report the application of synchrotron X-ray fluorescence imaging of vanadium, within thermally altered organic-walled microfossils of bona fide biological origin. From our data, we demonstrate that vanadium is present within microfossils of undisputable biological origin. It is well known in the organic geochemistry literature that elements such as vanadium are enriched and contained within crude oils, asphalts, and black shales that have been formed by diagenesis of biological organic material. It has been demonstrated that the origin of vanadium is due to the diagenetic alteration of precursor chlorophyll and heme porphyrin pigment compounds from living organisms. We propose that, taken together, microfossil-like morphology, carbonaceous composition, and the presence of vanadium could be used in tandem as a biosignature to ascertain the biogenicity of putative microfossil-like structures. Key Words: Microfossils-Synchrotron micro-X-ray fluorescence-Vanadium-Tetrapyrrole-Biosignature. Astrobiology 17, 1069-1076.

Resonance Raman spectra of C70 in benzene

Publisher: Elsevier BV

Date: 03-1995

DOI: 10.1016/0009-2614(95)00025-Y

Permeability, cytotoxicity, and genotoxicity of chromium(V) and chromium(VI) complexes in V79 chinese hamster lung cells

Publisher: American Chemical Society (ACS)

Date: 28-01-1998

DOI: 10.1021/TX9701541

SRT1720 improves survival and healthspan of obese mice (vol 1, 70, 2011)

Publisher: Springer Science and Business Media LLC

Date: 16-01-2013

DOI: 10.1038/SREP01131

Regio- and stereo-chemical oxidation of linoleic acid by human myoglobin and hydrogen peroxide: Tyr¹⁰³ affects rate and product distribution

Publisher: Portland Press Ltd.

Date: 06-07-2004

DOI: 10.1042/BJ20031924

Abstract: Mb (myoglobin) plus H2O2 catalyses the oxidation of various substrates via a peroxidase-like activity. A Y103F (Tyr103→Phe) variant of human Mb has been constructed to assess the effect of exchanging an electron-rich oxidizable amino acid on the peroxidase activity of human Mb. Steady-state analyses of reaction mixtures containing Y103F Mb, purified linoleic acid and H2O2 revealed a lower total yield of lipid oxidation products than mixtures containing the wild-type protein, consistent with the reported decrease in the rate constant for reaction of Y103F Mb with H2O2 [Witting, Mauk and Lay (2002) Biochemistry 41, 11495–11503]. Irrespective of the Mb employed, lipid oxidation yielded 9(R/S)-HODE [9(R,S)-hydroxy-10E,12Z-octadecadienoic acid] in preference to 13(R/S)-HODE [13(R,S)-hydroxy-9Z,11E-octadecadienoic acid], while 9- and 13-keto-octadecadienoic acid were formed in trace amounts. However, lipid oxidation by the Y103F variant of Mb proceeded with a lower Vmax value and an increased Km value relative to the wild-type control. Consistent with the increased Km, the product distribution from reactions with Y103F Mb showed decreased selectivity compared with the wild-type protein, as judged by the decreased yield of 9(S)-relative to 9(R)-HODE. Together, these data verify that Tyr103 plays a significant role in substrate binding and orientation in the haem pocket of human Mb. Also, the midpoint potential for the Fe(III)/(II) one-electron reduction was shifted slightly, but significantly, to a higher potential, confirming the importance of Tyr103 to the hydrogen-bonding network involving residues that line the haem crevice of human Mb.

Copper complexes of non-steroidal anti-inflammatory drugs: An opportunity yet to be realized

Publisher: Elsevier BV

Date: 10-2002

DOI: 10.1016/S0010-8545(02)00086-3

Evaluation of Resveratrol, Green Tea Extract, Curcumin, Oxaloacetic Acid, and Medium-Chain Triglyceride Oil on Life Span of Genetically Heterogeneous Mice

Publisher: Oxford University Press (OUP)

Date: 26-03-2012

DOI: 10.1093/GERONA/GLS070

Search for dark matter produced in association with a Higgs boson decaying to tau leptons at $$ \sqrt{s} $$ = 13 TeV with the ATLAS detector

Publisher: Springer Science and Business Media LLC

Date: 26-09-2023

DOI: 10.1007/JHEP09(2023)189

Biomimetic oxidation of chromium(III): Does the antidiabetic activity of chromium(III) involve carcinogenic chromium(VI)?

Publisher: Wiley

Date: 25-08-2004

DOI: 10.1002/ANIE.200460113

The influence of old age and poloxamer-407 on the hepatic disposition of diazepam in the isolated perfused rat liver

Publisher: S. Karger AG

Date: 2012

DOI: 10.1159/000341724

XAS spectroelectrochemistry: Reliable measurement of X-ray absorption spectra from redox manipulated solutions at room temperature

Publisher: International Union of Crystallography (IUCr)

Date: 14-04-2016

DOI: 10.1107/S1600577516005464

Abstract: The design and operation of a low-volume spectroelectrochemical cell for X-ray absorption spectroscopy (XAS) of solutions at room temperature is described. Fluorescence XAS measurements are obtained from s les contained in the void space of a 50 µL reticulated vitreous carbon (sponge) working electrode. Both rapid electrosynthesis and control of the effects of photoreduction are achieved by control over the flow properties of the solution through the working electrode, where a good balance between the rate of consumption of s le and the minimization of decomposition was obtained by pulsing the flow of the solution by 1–2 µL with duty cycle of ∼3 s while maintaining a small net flow rate (26–100 µL h −1 ). The performance of the cell in terms of control of the redox state of the s le and minimization of the effects of photoreduction was demonstrated by XAS measurements of aqueous solutions of the photosensitive Fe III species, [Fe(C 2 O 4 ) 3 ] 3− , together with that of the electrogenerated [Fe(C 2 O 4 ) 3 ] 4− product. The current response from the cell during the collection of XAS spectra provides an independent measure of the stability of the s le of the measurement. The suitability of the approach for the study of small volumes of m M concentrations of protein s les was demonstrated by the measurement of the oxidized and electrochemically reduced forms of cytochrome c .

Uncovering system-specific stress signatures in primate teeth with multimodal imaging

Publisher: Springer Science and Business Media LLC

Date: 04-01-2016

DOI: 10.1038/SREP18802

Abstract: Early life stress can disrupt development and negatively impact long-term health trajectories. Reconstructing histories of early life exposure to external stressors is h ered by the absence of retrospective time-specific biomarkers. Defects in tooth enamel have been used to reconstruct stress but the methods used are subjective and do not identify the specific biological systems impacted by external stressors. Here we show that external physical and social stressors impart biochemical signatures in primate teeth that can be retrieved to objectively reconstruct the timing of early life developmental disruptions. Using teeth from captive macaques, we uncovered elemental imprints specific to disruptions of skeletal growth, including major disruptions in body weight trajectory and moderate to severe illnesses. Discrete increases in heat shock protein-70 expression in dentine coincided with elemental signatures, confirming that elemental signals were associated with activation of stress-related pathways. To overcome limitations of conventional light-microscopic analysis, we used high resolution Raman microspectral imaging to identify structural and compositional alterations in enamel and dentine that coincided with elemental signatures and with detailed medical and behavioural data. Integrating these objective biochemical markers with temporal mapping of teeth enables the retrospective study of early life developmental disruptions and their ensuing health sequelae.

Assessment tools for microplastics and natural fibres ingested by fish in an urbanised estuary

Publisher: Elsevier BV

Date: 03-2018

DOI: 10.1016/J.ENVPOL.2017.11.085

Abstract: Microplastics and fibres occur in high concentrations along urban coastlines, but the occurrence of microplastic ingestion by fishes in these areas requires further investigation. Herein, the ingestion of debris (i.e., synthetic and natural fibres and synthetic fragments of various polymer types) by three benthic-foraging fish species Acanthopagrus australis (yellowfin bream), Mugil cephalus (sea mullet) and Gerres subfasciatus (silverbiddy) in Sydney Harbour, Australia has been quantified and chemically speciated by vibrational spectroscopy to identify the polymer type. Ingested debris were quantified using gut content analysis, and identified using attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Raman microspectroscopies in combination with principal component analysis (PCA). The occurrence of debris ingestion at the time of s ling ranged from 21 to 64% for the three species, and the debris number ranged from 0.2 to 4.6 items per fish for the different species, with ∼53% of debris being microplastic. There was a significant difference in the amount of debris ingested among species however, there was no difference among species when debris counts were standardised to fish weight or gut content weight, indicating that these species ingest a similar concentration of debris relative to their ingestion rate of other material. ATR-FTIR microspectroscopy successfully identified 72% of debris. Raman spectroscopy contributed an additional 1% of successful identification. In addition, PCA was used to non-subjectively classify the ATR-FTIR spectra resulting in the identification of an additional 9% of the debris. The most common microplastics found were polyester (PET), acrylic-polyester blend, and rayon (semi-synthetic) fibres. The potential of using Raman microspectroscopy for debris identification was investigated and provided additional information about the nature of the debris as well as the presence of specific dyes (and hence potential toxicity).

Vibrational spectroscopic mapping and imaging of tissues and cells

Publisher: Springer Science and Business Media LLC

Date: 23-06-2009

DOI: 10.1007/S12551-009-0012-9

The EPR pattern of CrV complexes of d-ribose derivatives

Publisher: Elsevier BV

Date: 06-2005

DOI: 10.1016/J.POLY.2005.02.025

Potential Applications of Vanadium-Based Anticancer Drugs for Intratumoral Injections

Publisher: MDPI

Date: 29-06-2022

DOI: 10.3390/BITAP-12783

Investigation of indoleamine 2,3-dioxygenase using synchrotron radiation techniques

Publisher: Elsevier BV

Date: 07-2003

DOI: 10.1016/S0162-0134(03)80546-9

A link between copper and dental caries in human teeth identified by X-ray fluorescence elemental mapping

Publisher: Springer Science and Business Media LLC

Date: 22-11-2008

DOI: 10.1007/S00775-007-0321-Z

Abstract: Quantitative X-ray fluorescence imaging of sections of human teeth revealed an increased concentration of copper and zinc in carious regions of dentine compared with unaffected portions of the tooth. Higher-resolution images provided strong evidence that the copper was transported and localized mainly in the dentinal tubules. While similar levels of zinc were found in these areas and concentrated in the tubules, zinc was also more evident in the hydroxyapatite, and the increase in zinc levels compared with the levels in background (normal) areas was less than that for copper. These results suggest a role for copper and zinc in the formation and progression of dental caries and present a potential point of intervention for treatment.

Bonding in HNO-Myoglobin as Characterized by X-ray Absorption and Resonance Raman Spectroscopies

Publisher: American Chemical Society (ACS)

Date: 31-12-2004

DOI: 10.1021/JA0433727

Abstract: The EXAFS and resonance Raman spectra on the HNO-myoglobin adduct, 1, are consistent with the presence of HNO bound to a heme center. The three-dimensional structure about the heme center of 1 obtained from multiple-scattering (MS) analysis of the EXAFS of the heme protein yielded an Fe-N-O bond angle of 131 degrees and an Fe-N bond length of 1.82 A, which compare well with published values for model complexes containing RNO ligands. Resonance Raman spectra identified the nu(N=O) stretch at 1385 cm-1 (confirmed by 15N labeling), which corresponds well with those reported for small molecule HNO complexes. The wavelength of the nu(Fe-N) at 636 cm-1 of 1 is significantly higher than those of MbIINO and MbIIINO (554 and 595 cm-1, respectively). The XAFS, XANES, and resonance Raman data are all consistent with the structure deduced from the NMR experiments, providing more detail on the bonding between HNO and the metal center.

Correlation of film structure and molecular oxygen reduction at nitrogen doped amorphous carbon thin film electrochemical electrodes

Publisher: Elsevier BV

Date: 09-2009

DOI: 10.1016/J.DIAMOND.2009.02.013

Extension of the Preparation of New Osmium Species to the cis-Tetraammine Moiety

Publisher: American Chemical Society (ACS)

Date: 08-1994

DOI: 10.1021/IC00095A004

A novel class of copper(II)- and zinc(II)-bound non-steroidal anti-inflammatory drugs that inhibits acute inflammation in vivo

Publisher: Springer Science and Business Media LLC

Date: 06-02-2016

DOI: 10.1186/S13578-016-0076-8

EPR spectroscopic studies of the reactions of Cr(VI) with L-ascorbic acid, L-dehydroascorbic acid, and 5,6-O-isopropylidene-L-ascorbic acid in water. Implications for chromium(VI) genotoxicity

Publisher: American Chemical Society (ACS)

Date: 1996

DOI: 10.1021/JA961824C

Erratum: X-ray absorption and EPR spectroscopic studies of the biotransformations of chromium(VI) in mammalian cells. Is chromodulin an artifact of isolation methods? (Journal of the American Chemical Society (2007) 129, (1065-1075))

Publisher: American Chemical Society (ACS)

Date: 17-07-2007

DOI: 10.1021/JA074677Z

The Evolution of Research on Ageing and Nutrition

Publisher: Oxford University Press (OUP)

Date: 10-09-2014

DOI: 10.1093/GERONA/GLT130

Metal-based anti-diabetic drugs: Advances and challenges

Publisher: Royal Society of Chemistry (RSC)

Date: 2011

DOI: 10.1039/C1DT10380F

Abstract: The current status and likely future directions of complexes of V(V/IV), Cr(III), Mo(VI), W(VI), Zn(II), Cu(II), and Mn(III) as potential oral drugs against type 2 diabetes are reviewed. We propose a unified model of extra- and intracellular mechanisms of anti-diabetic efficacies of V(V/IV), Mo(VI), W(VI), and Cr(III), centred on high-oxidation-state oxido eroxido species that inhibit protein tyrosine phosphatases (PTPs) involved in insulin signalling. The postulated oxidative mechanism of anti-diabetic activity of Cr(III) via carcinogenic Cr(VI/V) (which adds to safety concerns) is consistent with recent clinical trials on Cr(III) picolinate, where activity was apparent only in patients with poorly controlled diabetes (high oxidative stress), and the correlation between the anti-diabetic activities and ease of oxidation of Cr(III) supplements and their metabolites in vivo. Zn(II) and Cu(II) anti-diabetics act via different mechanisms and are unlikely to be used as specific anti-diabetics due to their erse and unpredictable biological activities. Hence, future research directions are likely to centre on enhancing the bioavailability and selectivity of V(V/IV), Mo(VI), or W(VI) drugs. The strategy of potentiating circulating insulin with metal ions has distinct therapeutic advantages over interventions that stimulate the release of more insulin, or use insulin mimetics, because of many adverse side-effects of increased levels of insulin, including increased risks of cancer and cardiovascular diseases.

A Short‐Lived but Highly Cytotoxic Vanadium(V) Complex as a Potential Drug Lead for Brain Cancer Treatment by Intratumoral Injections

Publisher: Wiley

Date: 11-08-2020

DOI: 10.1002/ANIE.202005458

Pentaammineiridium(III) and Hexaammineiridium(III) Complexes

Publisher: Wiley

Date: 2007

DOI: 10.1002/9780470132555.CH72

Pentaammineruthenium(III), pentaammineruthenium(II), and Binuclear decaamminediruthenium(III)/(II) complexes

Publisher: Wiley

Date: 2007

DOI: 10.1002/9780470132555.CH71

α-Hemoglobin-stabilizing Protein (AHSP) perturbs the proximal heme pocket of oxy-α-hemoglobin and weakens the iron-oxygen bond

Publisher: Elsevier BV

Date: 07-2013

DOI: 10.1074/JBC.M112.437509

Pentaammineosmium(III) and Hexaammineosmium(III) Complexes

Publisher: Wiley

Date: 2007

DOI: 10.1002/9780470132555.CH73

Strong Constraints on Jet Quenching in Centrality-Dependent p+Pb

Publisher: American Physical Society (APS)

Date: 16-08-2023

DOI: 10.1103/PHYSREVLETT.131.072301

Cis- and Trans-Bis(1,2-Ethanediamine)-Rhodium(III) Complexes

Publisher: Wiley

Date: 2007

DOI: 10.1002/9780470132555.CH76

Cis-Bis(2,2′-Bipyridine-N, N′) Complexes of Ruthenium(III)/(II) and Osmium(III)/(II)

Publisher: Wiley

Date: 2007

DOI: 10.1002/9780470132555.CH78

Cis-and Trans-Bis(1,2-Ethanediamine)-Iridium(III) Complexes

Publisher: Wiley

Date: 2007

DOI: 10.1002/9780470132555.CH77

Tris(1,2-ethanediamine) complexes of osmium(IV), osmium(III) and osmium(II): oxidative dehydrogenation reactions

Publisher: Elsevier BV

Date: 08-1992

DOI: 10.1016/S0020-1693(00)92389-2

Solvent/C60 interactions evidenced in the resonance Raman spectrum of C60

Publisher: Elsevier BV

Date: 1996

DOI: 10.1016/0009-2614(95)01311-3

(2,2′-Bipyridine-N, N′)(2,2′: 6′,2″-Terpyridine-N, N′, N′) Complexes of Ruthenium(III)/(II) and Osmium(III)/(II)

Publisher: Wiley

Date: 2007

DOI: 10.1002/9780470132555.CH79

Synthesis and characterization of a chromium(V) cis -1,2-cyclohexanediolato complex: A model of reactive intermediates in chromium-induced cancers

Publisher: American Chemical Society (ACS)

Date: 17-10-2012

DOI: 10.1021/IC301900Q

Abstract: Stabilization of chromium(V) by biological 1,2-diolato ligands, e.g., carbohydrates and glycoproteins, is postulated to be crucial for both the chromium(VI)-induced carcinogenicity and chromium(III) antidiabetic activities. Close structural mimics of biologically relevant chromium(V) 1,2-diolato complexes, M[Cr(V)O(chd)(2)] [chd = cis-1,2-cyclohexanediolato(2-)], were synthesized and characterized by X-ray crystallography (M = Na) or by spectroscopic techniques, including X-ray absorption spectroscopy (M = K). This is the first structurally characterized chromium(V) complex with a cyclic diolato ligand.

Response of chromium(V) to the diphenylcarbazide spectrophotometric method for the determination of chromium(VI)

Publisher: Elsevier BV

Date: 12-1991

DOI: 10.1016/0003-2670(91)85083-5

SIRT1 Is Required for AMPK Activation and the Beneficial Effects of Resveratrol on Mitochondrial Function

Publisher: Elsevier BV

Date: 05-2012

DOI: 10.1016/J.CMET.2012.04.003

Spectroscopic characterization of genotoxic chromium(V) peptide complexes: Oxidation of Chromium(III) triglycine, tetraglycine and pentaglycine complexes

Publisher: Elsevier BV

Date: 09-2016

DOI: 10.1016/J.JINORGBIO.2016.06.015

Abstract: Evidence is growing that metabolites of Cr(III) dietary supplements are partially oxidized to carcinogenic Cr(VI) and Cr(V) in vivo. Hence, we examined oxidations of Cr(III) peptide (triglycine, tetraglycine and pentaglycine) complexes to Cr(VI) and Cr(V) by PbO

Binding of Chromium(III) to Transferrin Could Be Involved in Detoxification of Dietary Chromium(III) Rather than Transport of an Essential Trace Element

Publisher: Wiley

Date: 20-05-2016

DOI: 10.1002/ANGE.201602996

Substitution Kinetics, Albumin and Transferrin Affinities, and Hypoxia All Affect the Biological Activities of Anticancer Vanadium(V) Complexes

Publisher: American Chemical Society (ACS)

Date: 20-10-2023

DOI: 10.1021/ACS.INORGCHEM.3C02561

Activation of molecular oxygen during the reactions of chromium(VI/V/IV) with biological reductants: Implications for chromium-induced genotoxicities

Publisher: American Chemical Society (ACS)

Date: 13-06-1998

DOI: 10.1021/JA974240Z

Calorie restriction, aging and longevity

Publisher: Springer Netherlands

Date: 2010

DOI: 10.1007/978-90-481-8556-6

Formation and reactivity of chromium(V)-thiolato complexes: A model for the intracellular reactions of carcinogenic chromium(VI) with biological thiols

Publisher: American Chemical Society (ACS)

Date: 07-06-2010

DOI: 10.1021/JA101675W

Abstract: The nature of the long-lived EPR-active Cr(V) species observed in cells and biological fluids exposed to carcinogenic Cr(VI) has been definitively assigned from detailed kinetic and spectroscopic analyses of a model reaction of Cr(VI) with p-bromobenzenethiol (RSH) in the presence or absence of cyclic 1,2-diols (LH(2)) in aprotic or mixed solvents. The first definitive structures for Cr(V) complexes with a monodentate thiolato ligand, [Cr(V)O(SR)(4)](-) (g(iso) = 1.9960, A(iso) = 14.7 x 10(-4) cm(-1)), [Cr(V)OL(SR)(2)](-) (g(iso) = 1.9854, A(iso) = (15.8-16.2) x 10(-4) cm(-1)) and [Cr(V)(O)(2)(SR)(2)](-) (g(iso) = 1.9828, A(iso) = 6.8 x 10(-4) cm(-1)) were assigned by EPR spectroscopy and electrospray mass spectrometry. The unusually low A(iso) ((53)Cr) value for the latter species is consistent with its rare four-coordinate, bis-oxido structure. The [Cr(V)OL(SR)(2)](-) species are responsible for the transient g(iso) approximately 1.986 EPR signals observed in living cells and animals treated with Cr(VI) (where RSH and LH(2) are biological thiols and 1,2-diols, respectively). For the first time, concentrations of Cr(V) intermediates formed during the reduction of Cr(VI) were determined by quantitative EPR spectroscopy, and a detailed reaction mechanism was proposed on the basis of stochastic simulations of the kinetic curves for Cr(V) species. A key feature of the proposed mechanism is the regeneration of Cr(V) species in the presence of Cr(VI) through the formation of organic free radicals, followed by the rapid reactions of the formed radicals with Cr(VI). The concentration of Cr(V) grows rapidly at the beginning of the reaction, reaches a steady-state level, and then drops sharply once Cr(VI) is spent. Similar mechanisms are likely to operate during the reduction of Cr(VI) in biological environment rich in reactive C-H bonds, including the oxidative DNA damage by Cr(V) intermediates.

Unprecedented staining of polar lipids by a luminescent rhenium complex revealed by FTIR microspectroscopy in adipocytes

Publisher: Royal Society of Chemistry (RSC)

Date: 2016

DOI: 10.1039/C6MB00242K

Abstract: Localisation of a neutral rhenium( i ) tricarbonyl phenanthroline species to regions of high polar lipid concentrations is demonstrated by Fourier transform infrared (FTIR) microspectroscopy.

Aging, Drugs, and Drug Metabolism

Publisher: Oxford University Press (OUP)

Date: 18-07-2012

DOI: 10.1093/GERONA/GLR084

13C N.M.R. Spectroscopic studies on the reactions of vanadium(v) with 13C2-Labeled oxalate in Aqueous and 50% v/v aqueous acetic acid solutions

Publisher: CSIRO Publishing

Date: 1995

DOI: 10.1071/CH9950763

Abstract: 13 C n.m.r, spectroscopy has been used to study the reactions of vanadate , H2VO4-, with 13C2-labelled oxalate in aqueous and 50% v/v aqueous acetic acid media. The results of the aqueous system corroborate the natural abundance oxalate 13C n.m.r. studies of Ehde and coworkers ( Ehde, P.M., Petterson , L., and Glaser, J., Acta Chem. Scand., 1991, 45, 998) who report the formation of both mono( oxalato )-, [VO2(ox)(OH2)] - , and bis(oxalato)-vanadium(V), cis-[VO2(ox)2]3-, complexes in solution. At 270 K, pH 3.3, and an n.m.r. operating frequency of 100.16 MHz, the former complex appears as a singlet (167.3 ppm ), while the latter resolves into an AB coupling pattern (169.6, 168.8, 166.6, 165.8 ppm Jc -c 85 Hz) owing to the inequivalence of carbons trans and cis to the oxo ligands . In 50% v/v aqueous acetic acid both the mono( oxalato ) singlet (166.8 ppm ) and the bis ( oxalato ) AB coupling pattern (169.2, 168.5, 166.2, 165.5 ppm Jc -c ≈ 75 Hz) are present but are somewhat broadened and shifted downfield, which is indicative of other species being present. There is also some resolution of new peaks within the broadened signals. These are believed to be due to the presence of the additional complexes, mainly [VO2(ox)( OAc )]2- and cis-[VO2(ox)( OAc )2]3-, generated in the acetic acid medium. At 298 K, the bis(oxalato) complex exhibits a single 13C peak for the inequivalent carbons at 167.6 ppm because of fluxional behaviour. The mono( oxalato ) complex is in rapid equilibrium with free oxalate, giving a second peak at lower value of 165.7 ppm that is pH-dependent. The mechanisms of the fluxionality of the different complexes are discussed.

Structure and reactivity of a chromium(V) glutathione complex

Publisher: American Chemical Society (ACS)

Date: 11-01-2003

DOI: 10.1021/IC020621O

Abstract: Chromium(V) glutathione complexes are among the likely reactive intermediates in Cr(VI)-induced genotoxicity and carcinogenicity. The first definitive structure of one such complex, [Cr(V)O(LH(2))(2)](3)(-) (I LH(5) = glutathione = GSH), isolated from the reaction of Cr(VI) with excess GSH at pH 7.0 (O'Brien, P. Pratt, J. Swanson, F. J. Thornton, P. Wang, G. Inorg. Chim. Acta 1990, 169, 265-269), has been determined by a combination of electrospray mass spectrometry (ESMS), X-ray absorption spectroscopy (XAS), EPR spectroscopy, and analytical techniques. In addition, Cr(V) complexes of GSH ethyl ester (gamma-Glu-Cys-GlyOEt) have been isolated and characterized by ESMS, and Cr(III) products of the Cr(VI) + GSH reaction have been isolated and characterized by ESMS and XAS. The thiolato and amido groups of the Cys residue in GSH are responsible for the Cr(V) binding in I. The Cr-ligand bond lengths, determined from multiple-scattering XAFS analysis, are as follows: 1.61 A for the oxo donor 1.99 A for the amido donors and 2.31 A for the thiolato donors. A significant electron withdrawal from the thiolato groups to Cr(V) in I was evident from the XANES spectra. Rapid decomposition of I in aqueous solutions (pH = 1-13) occurs predominantly by ligand oxidation with the formation of Cr(III) complexes of GSH and GSSG. Maximal half-lives of the Cr(V) species (40-50 s at [Cr] = 1.0 mM and 25 degrees C) are observed at pH 7.5-8.0. The experimental data are in conflict with a recent communication (Gaggelli, E. Berti, F. Gaggelli, N. Maccotta, A. Valensin, G. J. Am. Chem. Soc. 2001, 123, 8858-8859) on the formation of a Cr(V) dimer as a major product of the Cr(VI) + GSH reaction, which may have resulted from misinterpretation of the ESMS and NMR spectroscopic data.

Anti‐Migratory and Cytotoxic Activities of [Ga(8‐hydroxyquinolinato)₃]: Roles of Endogenous Cu(II) and Drug‐Induced Phenotypic Changes

Publisher: Wiley

Date: 28-08-2023

DOI: 10.1002/CHEM.202203323

Abstract: As shown by IncuCyte Zoom imaging proliferation assays, invasive triple‐negative human breast MDA‐MB‐231 cancer cells treated with sub‐toxic doses (5.0–20 μM, 72 h) of [GaQ 3 ] (Q=8‐hydroxyquinolinato) caused profound morphological changes and inhibition of cell migration, which were likely due to terminal cell differentiation or similar phenotypical change. This is the first demonstration of potential use of a metal complex in differentiation anti‐cancer therapy. Additionally, a trace amount of Cu(II) (0.20 μM) added to the medium dramatically increased [GaQ 3 ] cytotoxicity (IC 50 ~2 μM, 72 h) due to its partial dissociation and the action of the HQ ligand as a Cu(II) ionophore, as shown with electrospray mass spectrometry and fluorescence spectroscopy assays in the medium. Hence, cytotoxicity of [GaQ 3 ] is strongly linked to ligand binding of essential metal ions in the medium, for ex le, Cu(II). Appropriate delivery mechanisms of such complexes and their ligands could enable a powerful new triple therapeutic approach for cancer chemotherapy, including cytotoxicity against primary tumour, arrest of metastases, and activation of innate and adaptive immune responses.

Infrared spectroscopic characterization of monocytic microvesicles (microparticles) released upon lipopolysaccharide stimulation

Publisher: Wiley

Date: 17-03-2017

DOI: 10.1096/FJ.201601272R

EPR spectroscopic studies of the reduction of Chromium(VI) by methanol in the presence of peptides. Formation of long-lived Chromium(V) peptide complexes

Publisher: American Chemical Society (ACS)

Date: 07-12-2001

DOI: 10.1021/IC000299M

Abstract: The synthesis and characterization of the first Cr(V) complexes with non-sulfur-containing peptides, which may mimic the chemistry of the intermediates in the formation of Cr-induced peptide-DNA cross-links in vivo, are reported. The reduction of Cr(VI) with methanol in the presence of a number of non-sulfur-containing peptides produced relatively stable Cr(V)-peptide complexes, which were characterized by EPR spectroscopy and electrospray mass spectrometry. The reaction of Cr(VI) with methanol alone (in the absence of peptide ligands) resulted in the formation of two Cr(V)-methanol intermediates, with giso values of 1.9765 and 1.9687. The methanol reduction of Cr(VI) in the presence of the glycine peptides, triglycine, tetraglycine, and pentaglycine resulted in the formation of both Cr(V)-methanol and Cr(V)-peptide intermediates, while only the Cr(V)-peptide complexes were detected in the reactions with the alanine peptides trialanine, tetraalanine, and pentaalanine. Similar EPR signals were observed for all of the Cr(V)-peptide complexes with giso values between approximately 1.986 and approximately 1.979, and AN values of (2.1-2.6) x 10(-4) cm-1.

Comment on 'Genetic relationship between intrinsic Raman and infrared fundamental vibrations of the C60 and C70 fullerenes' [J. Mol. Struct. 378 (1996) 147]

Publisher: Elsevier BV

Date: 05-1997

DOI: 10.1016/S0022-2860(96)09725-6

A Short‐Lived but Highly Cytotoxic Vanadium(V) Complex as a Potential Drug Lead for Brain Cancer Treatment by Intratumoral Injections

Publisher: Wiley

Date: 07-08-2020

DOI: 10.1002/ANGE.202005458

Time-dependent uptake, distribution and biotransformation of chromium(VI) in individual and bulk human lung cells: Application of synchrotron radiation techniques

Publisher: Springer Science and Business Media LLC

Date: 16-02-2005

DOI: 10.1007/S00775-004-0617-1

Abstract: Chromium(VI) is a human carcinogen, primarily affecting the respiratory tract probably via active transport into cells, followed by the reduction to Cr(III) with the formation of DNA-damaging intermediates. Distribution of Cr and endogenous elements within A549 human lung adenocarcinoma epithelial cells, following treatment with Cr(VI) (100 microM, 20 min or 4 h) were studied by synchrotron-radiation-induced X-ray emission (SRIXE) of single freeze-dried cells. After the 20-min treatment, Cr was confined to a small area of the cytoplasm and strongly co-localized with S, Cl, K, and Ca. After the 4-h treatment, Cr was distributed throughout the cell, with higher concentrations in the nucleus and the cytoplasmic membrane. This time-dependence corresponded to approximately 100% or 0% clonogenic survival of the cells following the 20-min or 4-h treatments, respectively, and could potentially be explained by a new cellular protective mechanism. Such processes may also be important in reducing the potential hazards of Cr(III) dietary supplements, for which there is emerging evidence that they exert their anti-diabetic effects via biological oxidation to Cr(VI). The predominance of Cr(III) was confirmed by micro-XANES spectroscopy of intracellular Cr hotspots. X-ray absorption spectroscopy (XANES and EXAFS, using freeze-dried cells after the 0-4-h treatments) was used to gain insight into the chemical structures of Cr(III) complexes formed during the intracellular reduction of Cr(VI). The polynuclear nature of such complexes (probably with a combination of carboxylato and hydroxo bridging groups and O-donor atoms of small peptides or proteins) was established by XAFS data analyses.

X-ray-induced photo-chemistry and X-ray absorption spectroscopy of biological samples

Publisher: International Union of Crystallography (IUCr)

Date: 18-10-2012

DOI: 10.1107/S090904951203943X

Silicon nitride as a versatile growth substrate for microspectroscopic imaging and mapping of individual cells

Publisher: Royal Society of Chemistry (RSC)

Date: 2010

DOI: 10.1039/C001499K

Abstract: Herein is described a general s ling protocol that includes culture, differentiation and fixing of cells in their preferred morphology on the one s le substrate (Si(3)N(4)) to enable subsequent erse modern microspectroscopic analyses. The protocol enables unprecedented correlated and complementary information on the intracellular biochemistry of metabolic processes, diseases and their treatment, which offers the opportunity to revolutionize our understanding of cell and tissue biology at a molecular level. The culture of adherent cells onto inexpensive Si(3)N(4) membranes allows microspectroscopic analyses across the electromagnetic spectrum, from hard X-ray fluorescence (both XRF and XANES), through to visible and fluorescence light microscopies, and infrared microspectroscopy without substrate interference. Adherent mammalian cell lines (3T3-L1 adipocytes and H9c2 cardiac myocytes) illustrate the in vitro application of these protocols. The cells adhered strongly to Si(3)N(4) membranes and visually displayed normal proliferative and phenotypic growth more importantly, rapid alcohol fixation of cells did not affect their structural integrity for subsequent analyses.

CYCLIC VOLTAMMETRY AT MICROELECTRODES IN THE ABSENCE OF ADDED ELECTROLYTE USING A PLATINUM QUASI-REFERENCE ELECTRODE

Publisher: Elsevier BV

Date: 03-1986

DOI: 10.1016/0022-0728(86)80004-3

Inhibition of experimental colorectal cancer and reduction in renal and gastrointestinal toxicities by copper-indomethacin in rats

Publisher: Springer Science and Business Media LLC

Date: 25-12-2010

DOI: 10.1007/S00280-009-1220-5

Abstract: To evaluate, for the first time, the efficacy of copper-indomethacin in the inhibition of aberrant crypt foci formation using the azoxymethane-induced adenocarcinoma model, to examine cell viability in the HCT-116 colorectal cancer cell line, gastrointestinal permeability, mitochondrial oxidative damage, and renal toxicity in rat models. Azoxymethane-induced adenocarcinoma rats were dosed with indomethacin and copper-indomethacin for 28 days and aberrant crypt foci were evaluated. HCT-116 colorectal cancer cells were exposed to indomethacin and copper-indomethacin at 0-250 microg/mL (0-698 microM for indomethacin, and 0-147 microM for copper-indomethacin), and cell viability was measured. Acute gastrointestinal toxicity was measured using gastrointestinal permeability markers, gastrointestinal ulceration and bleeding, and measurement of an acute-phase protein haptoglobin. Effects of acute and chronic administration of indomethacin and copper-indomethacin on urinary electrolyte concentrations were examined. Both indomethacin and copper-indomethacin resulted in a significant reduction in aberrant crypt foci in azoxymethane-treated rats. In parallel, high concentrations of indomethacin and copper-indomethacin also reduced cell viability in HCT-116 colorectal cancer cells. However, copper-indomethacin was considerably safer in all measures of gastrointestinal toxicity compared to indomethacin. In addition, indomethacin reduced urinary electrolytes at an ulcerogenic dose of 10 mg/kg acutely and chronically at 3.0 mg/kg for 28 days, whereas copper-indomethacin at equimolar doses of indomethacin affected urine electrolytes after acute dosing but not after chronic dosing for 28 days. Copper-indomethacin has both gastrointestinal and renal sparing properties while maintaining efficacy in experimental adenocarcinoma.

Simultaneous biosynthesis of putrebactin, avaroferrin and bisucaberin by Shewanella putrefaciens and characterisation of complexes with iron(III), molybdenum(VI) or chromium(V)

Publisher: Elsevier BV

Date: 09-2015

DOI: 10.1016/J.JINORGBIO.2015.12.008

Analysis of the near-infrared spectra of C60^-

Publisher: Elsevier BV

Date: 12-1995

DOI: 10.1016/0009-2614(95)01207-3

Synthesis and characterization of a chromium(V) cis-dioxo bis(1,10-phenanthroline) complex and crystal and molecular structures of its chromium(III) precursor

Publisher: American Chemical Society (ACS)

Date: 28-10-2004

DOI: 10.1021/IC049008Q

Abstract: The first structurally characterized Cr(V) dioxo complex, cis-[CrV(O)2(phen)2](BF4) (2, phen=1,10-phenanthroline) has been synthesized by the oxidation of a related Cr(III) complex, cis-[Cr(III)(phen)2(OH2)2](NO3)3.2.5H2O (1, characterized by X-ray crystallography), with NaOCl in aqueous solutions in the presence of excess NaBF4, and its purity has been confirmed by electrospray mass spectrometry (ESMS), EPR spectroscopy, and analytical techniques. Previously reported methods for the generation of Cr(V)-phen complexes, such as the oxidation of 1 with PbO2 or PhIO, have been shown by ESMS to lead to mixtures of Cr(III), Cr(V), Cr(VI), and in some cases Cr(IV) species, 3. Species 3 was assigned as [CrIV(O)(OH)(phen)2]+, based on ESMS and X-ray absorption spectroscopy measurements. A distorted octahedral structure for 2 (CrO, 1.63 A Cr-N, 2.04 and 2.16 A) was established by multiple-scattering (MS) modeling of XAFS spectra (solid, 10 K). The validity of the model was verified by a good agreement between the results of MS XAFS fitting and X-ray crystallography for 1 (distorted octahedron Cr-O, 1.95 A Cr-N, 2.06 A). Unlike for the well-studied Cr(V) 2-hydroxycarboxylato complexes, 2 was equally or more stable in aqueous media (hours at pH=1-13 and 25 degrees C) compared with polar aprotic solvents. A stable Cr(III)-Cr(VI) dimer, [Cr(III)(Cr(VI)O4)(phen)2]+ (detected by ESMS), is formed during the decomposition of 2 in nonaqueous media. Comparative studies of the oxidation of 1 by NaOCl or PbO2 have shown that [Cr(V)(O)2(phen)2]+ was the active species responsible for the previously reported oxidative DNA damage, bacterial mutagenicity, and increased incidence of micronuclei in mammalian cells, caused by the oxidation products of 1 with PbO2. Efficient oxidation of 1 to a genotoxic species, [Cr(V)(O)2(phen)2]+, in neutral aqueous media by a biological oxidant, hypochlorite, supports the hypothesis on a significant role of reoxidation of Cr(III) complexes, formed during the intracellular reduction of Cr(VI), in Cr(VI)-induced carcinogenicity. Similar oxidation reactions may contribute to the reported adverse effects of a popular nutritional supplement, Cr(III) picolinate.

Studies of the muon momentum calibration and performance of the ATLAS detector with pp collisions at $$\sqrt{s}=13$$ TeV

Publisher: Springer Science and Business Media LLC

Date: 08-2023

DOI: 10.1140/EPJC/S10052-023-11584-X

Abstract: This paper presents the muon momentum calibration and performance studies for the ATLAS detector based on the pp collisions data s le produced at $$\\sqrt{s}$$ s = 13 TeV at the LHC during Run 2 and corresponding to an integrated luminosity of 139 $${\\textrm{fb}}^{-1}$$ fb - 1 . An innovative approach is used to correct for potential charge-dependent momentum biases related to the knowledge of the detector geometry, using the $$Z\\rightarrow \\mu ^{+}\\mu ^{-}$$ Z → μ + μ - resonance. The muon momentum scale and resolution are measured using s les of $$J/\\psi \\rightarrow \\mu ^{+}\\mu ^{-}$$ J / ψ → μ + μ - and $$Z\\rightarrow \\mu ^{+}\\mu ^{-}$$ Z → μ + μ - events. A calibration procedure is defined and applied to simulated data to match the performance measured in real data. The calibration is validated using an independent s le of $$\\Upsilon \\rightarrow \\mu ^{+}\\mu ^{-}$$ Υ → μ + μ - events. At the Z $$(J/\\psi )$$ ( J / ψ ) peak, the momentum scale is measured with an uncertainty at the 0.05% (0.1%) level, and the resolution is measured with an uncertainty at the 1.5% (2%) level. The charge-dependent bias is removed with a dedicated in situ correction for momenta up to 450 GeV with a precision better than 0.03 $${\\textrm{TeV}}^{-1}$$ TeV - 1 .

Tumor Antigen Expression in Melanoma Varies According to Antigen and Stage

Publisher: American Association for Cancer Research (AACR)

Date: 02-2006

DOI: 10.1158/1078-0432.CCR-05-1544

Abstract: Purpose: Melanoma cells express antigens that can induce T-cell and antibody responses. Obtaining a detailed understanding of antigen expression in primary and metastatic melanoma is essential if these molecules are to be useful targets for immunotherapy of melanoma. Experimental Design: Malignant melanomas (n = 586) from 426 patients were typed for antigen expression. Multiple s les were available from 86 in iduals, enabling analysis of antigen expression patterns over time. Paraffin-embedded s les were tested by immunohistochemistry for the presence of the differentiation antigens: gp100, Melan-A, tyrosinase, and the “cancer/testis” antigens MAGE-A1, MAGE-A4, and NY-ESO-1. Results: S les were primary tumors (n = 251), lymph node metastases (n = 174), s.c. metastases (n = 71), and distant metastases (n = 90). The differentiation antigens were strongly expressed in 93% to 95% of tumors regardless of stage. In contrast, the frequency of cancer/testis antigen expression in primary tumors for MAGE-A1, MAGE-A4, and NY-ESO-1 was lower (20%, 9%, and 45%, respectively). MAGE-A1 and MAGE-A4 were acquired with advancing disease (to 51% and 44% in distant metastases, respectively) but not NY-ESO-1, which remained positive in 45%. MAGE-A1 expression was twice as prevalent in ulcerated primaries as in nonulcerated primaries (30% versus 15% P = 0.006) and in thicker as opposed to thin melanomas (26% versus 10% P = 0.1). Conclusions: This large series describes patterns of antigen expression in melanoma and their evolution over time. This will help inform decisions about selection of patients and target antigens for melanoma immunotherapy clinical trials.

Measurements of the suppression and correlations of dijets in Xe+Xe collisions at s<

Publisher: American Physical Society (APS)

Date: 09-08-2023

DOI: 10.1103/PHYSREVC.108.024906

Parkinson's disease-linked human PARK9/ATP13A2 maintains zinc homeostasis and promotes α-Synuclein externalization via exosomes

Publisher: Oxford University Press (OUP)

Date: 06-03-2014

DOI: 10.1093/HMG/DDU099

Abstract: α-Synuclein plays a central causative role in Parkinson's disease (PD). Increased expression of the P-type ATPase ion pump PARK9/ATP13A2 suppresses α-Synuclein toxicity in primary neurons. Our data indicate that ATP13A2 encodes a zinc pump neurospheres from a compound heterozygous ATP13A2(-/-) patient and ATP13A2 knockdown cells are sensitive to zinc, whereas ATP13A2 over-expression in primary neurons confers zinc resistance. Reduced ATP13A2 expression significantly decreased vesicular zinc levels, indicating ATP13A2 facilitates transport of zinc into membrane-bound compartments or vesicles. Endogenous ATP13A2 localized to multi-vesicular bodies (MVBs), a late endosomal compartment located at the convergence point of the endosomal and autophagic pathways. Dysfunction in MVBs can cause a range of detrimental effects including lysosomal dysfunction and impaired delivery of endocytosed proteins/autophagy cargo to the lysosome, both of which have been observed in cells with reduced ATP13A2 function. MVBs also serve as the source of intra-luminal nanovesicles released extracellularly as exosomes that can contain a range of cargoes including α-Synuclein. Elevated ATP13A2 expression reduced intracellular α-Synuclein levels and increased α-Synuclein externalization in exosomes >3-fold whereas ATP13A2 knockdown decreased α-Synuclein externalization. An increased export of exosome-associated α-Synuclein may explain why surviving neurons of the substantia nigra pars compacta in sporadic PD patients were observed to over-express ATP13A2. We propose ATP13A2's modulation of zinc levels in MVBs can regulate the biogenesis of exosomes capable of containing α-Synuclein. Our data indicate that ATP13A2 is the first PD-associated gene involved in exosome biogenesis and indicates a potential neuroprotective role of exosomes in PD.

Investigation of the uptake of drugs, carcinogens and mutagens by individual mammalian cells using a scanning proton microprobe

Publisher: Elsevier BV

Date: 09-1995

DOI: 10.1016/0168-583X(95)00421-1

Biospectroscopy for studying the influences of anti-diabetic metals (V, Cr, Mo, and W) to the insulin signaling pathway

Publisher: Author(s)

Date: 2017

DOI: 10.1063/1.4978092

Chromium

Publisher: Elsevier

Date: 2004

DOI: 10.1016/B0-08-043748-6/03032-2

Search for Majorana neutrinos in same-sign WW scattering events from pp collisions at $$\sqrt{s}=13$$ TeV

Publisher: Springer Science and Business Media LLC

Date: 23-01-2118

DOI: 10.1140/EPJC/S10052-023-11915-Y

Introduction to trifluoromethanesulfonates and trifluoromethanesulfonato-O Complexes

Publisher: Wiley

Date: 2007

DOI: 10.1002/9780470132555.CH68

Measurements of $$W^{+}W^{-}$$ production in decay topologies inspired by searches for electroweak supersymmetry

Publisher: Springer Science and Business Media LLC

Date: 10-08-2023

DOI: 10.1140/EPJC/S10052-023-11508-9

Abstract: This paper presents a measurement of fiducial and differential cross-sections for $$W^{+}W^{-}$$ W + W - production in proton–proton collisions at $$\\sqrt{s}=13$$ s = 13 TeV with the ATLAS experiment at the Large Hadron Collider using a dataset corresponding to an integrated luminosity of 139 fb $$^{-1}$$ - 1 . Events with exactly one electron, one muon and no hadronic jets are studied. The fiducial region in which the measurements are performed is inspired by searches for the electroweak production of supersymmetric charginos decaying to two-lepton final states. The selected events have moderate values of missing transverse momentum and the ‘stransverse mass’ variable $$m_{\\textrm{T2}}$$ m T2 , which is widely used in searches for supersymmetry at the LHC. The ranges of these variables are chosen so that the acceptance is enhanced for direct $$W^{+}W^{-}$$ W + W - production and suppressed for production via top quarks, which is treated as a background. The fiducial cross-section and particle-level differential cross-sections for six variables are measured and compared with two theoretical SM predictions from perturbative QCD calculations.

Chemistry of Cobalt Acetate. 7. Electrochemical Oxidation of μ3-Oxo-Centered Cobalt(III) Acetate Trimers

Publisher: American Chemical Society (ACS)

Date: 07-11-2003

DOI: 10.1021/IC0345525

Abstract: Electrochemical and spectroelectrochemical properties of five cobalt(III) acetate complexes [CoIII3(mu3-O)(CH3CO2)5(OR)(py)3][PF6] are described, where py=pyridine and R=OCCH3 (A), H (B), CH3 (C), CH2CH=CH2 (D), and CH2C6H5 (E). Each is reduced irreversibly as observed by cyclic voltammetry at room temperature and at -40 degrees C in acetonitrile at scan rates up to 20 V s(-1), but oxidized reversibly to a mixed-valence Co(III)2Co(IV) species at approximately 1.23 V vs the ferrocenium/ferrocene couple. Controlled potential coulometry confirmed a one-electron-oxidation process. Spectroelectrochemical oxidation of A at 5 degrees C showed isosbestic points in the electronic absorption spectrum that showed the oxidized complex to be stable in solution for at least 1 h.

Studies on the genotoxicity of chromium: from the test tube to the cell

Publisher: Elsevier BV

Date: 06-2001

DOI: 10.1016/S0010-8545(00)00408-2

The Unusual Intensity Behavior of the 281-cm^-1 Resonance Raman Band of C₆₀:  A Complex Tale of Vibronic Coupling, Symmetry Reduction, Solvatochromism, and Jahn−Teller Activity

Publisher: American Chemical Society (ACS)

Date: 03-06-2004

DOI: 10.1021/JP036834W

SRT 2104 extends survival of male mice on a standard diet and preserves bone and muscle mass

Publisher: Wiley

Date: 16-06-2014

DOI: 10.1111/ACEL.12220

X-ray Absorption Spectroscopic Studies of Chromium(V/IV/III)-2-Ethyl-2-hydroxybutanoato(2-/1-) Complexes

Publisher: American Chemical Society (ACS)

Date: 07-01-2004

DOI: 10.1021/IC030239R

Abstract: Structures of the complexes [Cr(V)O(ehba)(2)](-), [Cr(IV)O(ehbaH)(2)](0), and [Cr(III)(ehbaH)(2)(OH(2))(2)](+) (ehbaH(2) = 2-ethyl-2-hydroxybutanoic acid) in frozen aqueous solutions (10 K, [Cr] = 10 mM, 1.0 M ehbaH(2)/ehbaH, pH 3.5) have been determined by single- and multiple-scattering fitting of X-ray absorption fine structure (XAFS) data. An optimal set of fitting parameters has been determined from the XAFS calculations for a compound with known crystal structure, Na[Cr(V)O(ehba)(2)] (solid, 10 K). The structure of the Cr(V) complex [Cr(V)O(ehba)(2)](-) does not change in solution in the presence of excess ligand. Contrary to the earlier suggestions made from the kinetic data (Ghosh, M. C. Gould, E. S. J. Chem. Soc., Chem. Commun. 1992, 195-196), the structure of the Cr(IV) complex (generated by the Cr(VI) + As(III) + ehbaH(2) reaction) is close to that of the Cr(V) complex (five-coordinate, distorted trigonal bipyramidal) and different from that of the Cr(III) complex (six-coordinate, octahedral). For both Cr(V) and Cr(IV) complexes, some disorder in the position of the oxo group is observed, which is consistent with but not definitive for the presence of geometric isomers. The structure of the Cr(IV) complex differs from that of Cr(V) by protonation of alcoholato groups of the ligands, which leads to significant elongation of the corresponding Cr-O bonds (2.0 vs 1.8 A). This is reflected in the different chemical properties reported previously for the Cr(IV) and Cr(V) complexes, including their reactivities toward DNA and other biomolecules in relation to Cr-induced carcinogenicity.

Sport and Society in the Global Age

Publisher: Macmillan Education UK

Date: 2012

DOI: 10.1007/978-0-230-35622-1

Reactions of Chromium(VI/V/IV) with bis(O-ethyl-L- cysteinato-N,S)zinc(II): A model for the action of carcinogenic chromium on zinc-finger proteins

Publisher: American Chemical Society (ACS)

Date: 16-06-2000

DOI: 10.1021/JA9944047

Declining NAD+ Induces a Pseudohypoxic State Disrupting Nuclear-Mitochondrial Communication during Aging

Publisher: Elsevier BV

Date: 12-2013

DOI: 10.1016/J.CELL.2013.11.037

Search for flavor-changing neutral-current couplings between the top quark and the Z boson with

Publisher: American Physical Society (APS)

Date: 30-08-2023

DOI: 10.1103/PHYSREVD.108.032019

Optical bistability for ZnO-Nb2O5-TeO2 glasses

Publisher: Elsevier BV

Date: 05-2004

DOI: 10.1016/J.OPTMAT.2003.10.004

The reactions of electrogenerated [ni(sacsac)2]: Biomimetic chemistry related to nickel enzymes

Publisher: CSIRO Publishing

Date: 1995

DOI: 10.1071/CH9950835

Abstract: The electrochemical reduction of [Ni( sacsac )2] ( sacsac = C5H7S2- = pentane-2,4-dithionate) has been investigated by cyclic voltammetry and controlled-potential electrolysis in acetone/tetra- butylammonium tetrafluoroborate (0.1 M). The reactions of the reduction product(s) with CO, CO2, CH3I, C12H25SH, light and water have been surveyed. At a scan rate of 100 mV s-1, [Ni( sacsac )2] (0.5 mM ) undergoes a quasi-reversible one-electron reduction (∆ Ep = 88 mV) at -1.543 V (v. Fc+/0) and an irreversible four-electron oxidation at +0.635 V. The oxidation generates the 3,5-dimethyl-1,2-dithiolium cation, as evidenced by the observation of the (known) reduction of this cation at -0.840 V. The initial product of the reduction of [Ni( sacsac )2] is a Lewis base, and reacts with light, water, CO, CO2, CH3I and C12H25SH. These reactions have been followed by electrochemical and spectroscopic methods. They appear to be biomimetic for a number of reactions observed for nickel enzymes.

Chemical alterations to murine brain tissue induced by formalin fixation: Implications for biospectroscopic imaging and mapping studies of disease pathogenesis

Publisher: Royal Society of Chemistry (RSC)

Date: 2011

DOI: 10.1039/C0AN00269K

Abstract: Understanding biochemical mechanisms and changes associated with disease conditions and, therefore, development of improved clinical treatments, is relying increasingly on various biochemical mapping and imaging techniques on tissue sections. However, it is essential to be able to ascertain whether the s ling used provides the full biochemical information relevant to the disease and is free from artefacts. A multi-modal micro-spectroscopic approach, including FTIR imaging and PIXE elemental mapping, has been used to study the molecular and elemental profile within cryofixed and formalin-fixed murine brain tissue sections. The results provide strong evidence that amino acids, carbohydrates, lipids, phosphates, proteins and ions, such as Cl(-) and K(+), leach from tissue sections into the aqueous fixative medium during formalin fixation of the sections. Large changes in the concentrations and distributions of most of these components are also observed by washing in PBS even for short periods. The most likely source of the chemical species lost during fixation is the extra-cellular and intra-cellular fluid of tissues. The results highlight that, at best, analysis of formalin-fixed tissues gives only part of the complete biochemical "picture" of a tissue s le. Further, this investigation has highlighted that significant lipid peroxidation/oxidation may occur during formalin fixation and that the use of standard histological fixation reagents can result in significant and differential metal contamination of different regions of tissue sections. While a consistent and reproducible fixation method may be suitable for diagnostic purposes, the findings of this study strongly question the use of formalin fixation prior to spectroscopic studies of the molecular and elemental composition of biological s les, if the primary purpose is mechanistic studies of disease pathogenesis.

A New Class of Layered Microporous Materials: Crystal Structure of Disodium Pentakis(trimethylphenylammonium) Bis[tris(oxalato(2-))chromate(III)] Chloride Pentahydrate

Publisher: American Chemical Society (ACS)

Date: 02-1995

DOI: 10.1021/IC00108A001

Search for displaced photons produced in exotic decays of the Higgs boson using 13 TeV pp

Publisher: American Physical Society (APS)

Date: 21-08-2023

DOI: 10.1103/PHYSREVD.108.032016

Rapamycin, But Not Resveratrol or Simvastatin, Extends Life Span of Genetically Heterogeneous Mice

Publisher: Oxford University Press (OUP)

Date: 25-10-2010

DOI: 10.1093/GERONA/GLQ178

Characterization and X-ray Absorption Spectroscopic Studies of Bis[quinato(2−)]oxochromate(V)¹

Publisher: American Chemical Society (ACS)

Date: 15-02-2000

DOI: 10.1021/IC990730B

Abstract: A new Cr(V) complex, K[CrVO(qaH3)2].H2O (Ia qaH3 = quinato = (1R,3R,4R,5R)-1,3,4,5-tetrahydroxycyclohexanecarboxylato(2-)), synthesized by the reaction of K2Cr2O7 with excess qaH5 in MeOH (Codd, R. Lay, P. A. J. Am. Chem. Soc. 1999, 121, 7864-7876), has been characterized by microanalyses, electrospray mass spectra, and UV-visible, CD, IR, EPR, and X-ray absorption spectroscopies. This complex is of interest because of its ability to act as both a structural and a biomimetic model for a range of Cr(V) species believed to be generated in vivo during the intracellular reduction of carcinogenic Cr(VI). The Na+ analogue of Ia (Ib) has also been isolated and characterized by microanalyses and IR and X-ray absorption spectroscopies. The reaction of Cr(VI) with MeOH in the presence of qaH5 that leads to I proceeds via a Cr(IV) intermediate (observed by UV-visible spectroscopy), and a mechanism for the formation of I has been proposed. DMF or DMSO solutions of I are stable for several days at 25 degrees C, while I in aqueous solution (pH = 4) disproportionates to Cr(VI) and Cr(III) in minutes. The likely structures in the solid state for Ia (14 K) and Ib (approximately 293 K) have been determined using both single-scattering (Ia,b) and multiple-scattering (Ia) analyses of XAFS data. These analyses have shown the following: (i) In agreement with the results from the other spectroscopic techniques, the quinato ligands are bound to Cr(V) by 2-hydroxycarboxylato moieties, with Cr-O bond lengths of 1.55, 1.82, and 1.94 A for the oxo, alcoholato, and carboxylato O atoms, respectively. (ii) The position of an oxo O atom is somewhat disordered. This is consistent with molecular mechanics modeling of the likely structures. The XAFS, EPR, and IR spectroscopic evidence points to the existence of hydrogen bonds between the oxo ligand and the 3,4,5-OH groups of the quinato ligands in the solid state of I.

Measurement of the inclusive tt¯

Publisher: American Physical Society (APS)

Date: 18-08-2023

DOI: 10.1103/PHYSREVD.108.032014

The Synthesis and Structure of Encapsulating Ligands: Properties of Bicyclic Hexamines

Publisher: CSIRO Publishing

Date: 1994

DOI: 10.1071/CH9940143

Abstract: Template syntheses based on tris (ethane-1,2-diamine)cobalt(III) lead to cobalt(III) complexes of cage hexamines of the ' sarcophagine ' type ( sarcophagine = sar = 3,6,10,13,16,19- hexaazabicyclo [6.6.6] icosane ) rapidly and in high yield. Reduction of these species to their cobalt(II) forms enables the ligands to be removed in concentrated acids at elevated temperatures, and in hot aqueous solutions containing excess cyanide ion. The free sarcophagine and 1,8-diaminosarcophagine [(NH2)2sar or diamsar] ligands are strong bases, accepting up to four and five protons, respectively, in aqueous solution. In chloride medium, I = 1.0, at 298 K, pK1 = 11.95, pK2 = 10.33, pK3 = 7.17, pK4 ≈ 0 for sarcophagine , and pK1 = 11.44, pK2 = 9.64, pK3 = 6.49, pK4 = 5.48, pK5 ≈ 0 for diaminosarcophagine , with very similar values being found for triflate medium. Crystal structure determinations for both free bases, the chloride, sulfate, perchlorate and nitrate salts of diamsar , the complex of zinc chloride with sar, and the magnesium nitrate complex with diamsar show remarkably small variations in the cavity defined by the bicyclic ligands, though relatively subtle bond length and bond angle changes can be rationalized in terms of the effects of proton and metal ion binding. Exhaustive methylation of sarcophagine produces the highly lipophilic, hexatertiary base hexamethylsarcophagine , which, in the solid state, adopts quite different conformations and nitrogen-atom configurations to those of sar itself. All the ligands rapidly form metal ion complexes of generally exceptional kinetic and thermodynamic stability.

Deposition of a-C:N films and evaluation of their robustness in electrochemical applications

Publisher: Elsevier BV

Date: 06-2008

DOI: 10.1016/J.TSF.2007.07.017

Dietary Restriction: Standing Up for Sirtuins

Publisher: American Association for the Advancement of Science (AAAS)

Date: 27-08-2010

DOI: 10.1126/SCIENCE.329.5995.1012

A review of necrophagous insects colonising human and animal cadavers in south-east Queensland, Australia

Publisher: Elsevier BV

Date: 12-2015

DOI: 10.1016/J.FORSCIINT.2015.07.053

Abstract: A review of insects collected from decomposing human remains in south-east Queensland yielded 32 species in three orders (Diptera, Coleoptera, Hymenoptera) and 11 families (Calliphoridae, Sarcophagidae, Muscidae, Phoridae, Sepsidae, Chironomidae, Dermestidae, Cleridae, Histeridae, Staphylinidae, Encyrtidae). There were 15 cases where remains were located indoors and five cases where remains were outdoors, in both terrestrial and aquatic environments. Coleoptera were strongly associated with outdoors remains, while dipteran species composition was similar in both indoor and outdoor habitats. Some Diptera were only associated with indoors remains, while others were similarly restricted to remains recovered outdoors. Hymenopteran parasitoids were active in both habitats. Comparative collections were made from other vertebrate remains, including road-kill and farmed animals throughout south-east Queensland (Qld) and northern New South Wales (NSW) during the same period.

In vitro DNA damage and mutations induced by a macrocyclic tetraamide chromium(v) complex: Implications for the role of cr(v) peptide complexes in chromium-induced cancers

Publisher: Oxford University Press (OUP)

Date: 1993

DOI: 10.1093/CARCIN/14.9.1875

Abstract: Electron paramagnetic resonance and electronic absorption spectroscopies have shown that unlike the bidentate Cr(V) complex [Cr(ehba)2O]- (ehba = 2-hydroxy-2-ethylbutanoato(2-)), I, the macrocyclic tetradentate complex, [Cr (m a-dcb)(O)]- (m a-dcb = 5,6-(4,5-dichlorobenzo)-3,8,11,13-tetraoxo-2,2,9,9-tetrameth yl-12,12-diethyl-1, 4,7,10-tetraazacyclotridecane), II, is substitutionally inert. Low levels of DNA strand cleavage were observed after treatment with II under physiological conditions (50 mM sodium phosphate, pH 7.4, 37 degrees C) at concentrations as high as 2 mM for periods as long as 2 days. II also induces a lower number of revertants in mutation assays with Salmonella typhimurium TA100 than I when identical Cr concentrations are applied. The slopes of the linear portion of the dose-response curves are parallel, however, indicating that the mutagenicity of II is comparable to I. II is stable toward ligand exchange, reduction and disproportionation in the mutagenicity test medium and also in the presence of bacteria and the common cell reductant, glutathione. This indicates that ligand exchange with DNA and/or reduction to Cr(IV) are not responsible for the mutagenicity of II (unlike I). It is believed that II reversibly but weakly intercalates with DNA placing the Cr(V) center in close proximity for hydrogen atom abstraction or oxo-transfer reactions to ensure. This tetraamide complex is a good structural and biomimetic model for non-sulfur-containing Cr(V) peptide species that may form in vivo from reactions of Cr(VI) with peptides. Hence, it is likely to be relevant to understanding one possible mechanism by which Cr(VI) causes cancer.

Influence of an anti-metastatic ruthenium(iii) prodrug on extracellular protein-protein interactions: studies by bio-layer interferometry

Publisher: Royal Society of Chemistry (RSC)

Date: 2014

DOI: 10.1039/C3QI00054K

Solid-state structural studies of chromium(III) nicotinato nutritional supplements

Publisher: American Chemical Society (ACS)

Date: 15-09-2014

DOI: 10.1021/IC501818W

Abstract: While Cr(III) dietary supplements are widely consumed, some commercial supplements have yet to be structurally characterized. X-ray absorption spectroscopy and other spectroscopic methods were used to characterize Cr(III) nicotinato nutritional supplements that have long been used in complementary medicine. Different ratios of nicotinic acid and CrCl3·6H2O (trans-[CrCl2(OH2)4]Cl·2H2O) at different pH values gave a range of products. The local structures of Cr(III) nicotinato complexes obtained at pH 7 and of the patented complex were characterized by performing multiple-scattering analysis of their EXAFS spectra as well as EPR, UV-vis, and IR spectroscopies. For the first time, these complexes have been definitively characterized as nicotinato-bridged polymers of dihydroxido-bridged dinuclear Cr(III) cores. In the patented complex used in commercial preparations, each Cr is octahedral with an additional terminal O-bound nicotinato ligand, two bridging nicotinato (one O and one N bound), and an aqua ligand. The other species also have two or three bridging nicotinato ligands and an aqua and, in some cases, a terminal hydroxido ligand, which is dependent upon the stoichiometry of the reactants and the pH value of the solution in which they are prepared.

The effect of metal ions on the electrochemistry of the antitumor antibiotic streptonigrin

Publisher: Elsevier BV

Date: 05-2004

DOI: 10.1016/J.JINORGBIO.2003.10.011

Migration of mercury from dental amalgam through human teeth

Publisher: International Union of Crystallography (IUCr)

Date: 19-02-2008

DOI: 10.1107/S0909049507061468

Dependence of the properties of cobalt(III) cage complex as a function of the derivatization of amine substituents

Publisher: CSIRO Publishing

Date: 2009

DOI: 10.1071/CH09368

Abstract: Control of redox properties of cobalt macrobicyclic hexaamine (cage) complexes by substituent modification is important for their use as electron-transfer agents, and the resultant derivatives can also change the lipophilicity of the complexes for a variety of biological and other applications. Such derivatization is also important for incorporating cage complexes into a range of redoxactive conjugates. Here, the derivatization of the amine groups in the 1 and 8 positions of [Co(sar)]3+ (sar = sarcophagine = 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) are reported. The synthesis and properties of methylamide (from the reactions with acetic anhydride), arylimine (from Schiff base reactions), benzylamine, phthalimido, and tosylate derivatives are described. These reactions provide synthons that have the potential to act as precursors for building a range of conjugates containing metal cage complexes, including dimers. The effects of the substituents on the ligand conformations, which affect other chemical and physical properties of the cage complexes, are discussed.

Vanadium speciation by XANES spectroscopy: A three-dimensional approach

Publisher: Wiley

Date: 08-2014

DOI: 10.1002/CHEM.201403993

Abstract: A library of X-ray absorption near-edge structure (XANES) spectroscopic data for V(V), V(IV) and V(III) complexes with a broad range of biologically relevant ligand has been used to demonstrate that three-dimensional plots of key XANES parameters (pre-edge and edge energies pre-edge and white line intensities) can be used for the prediction of V oxidation states and coordination numbers in biological or environmental matrices. The reliability of the technique has been demonstrated by re-analysis of the published XANES data for a V(V)-dependent bromoperoxidase.

Bournemouth University

Location: United Kingdom of Great Britain and Northern Ireland

View Organisation

FlyEvience

Location: United Kingdom of Great Britain and Northern Ireland

View Organisation

University Of Aberdeen

Location: United Kingdom of Great Britain and Northern Ireland

View Organisation

Andrew E. Whittington

Location: United Kingdom of Great Britain and Northern Ireland

View Organisation

United States Studies Centre, University Of Sydney

Location: No location found

View Organisation

United States Studies Centre, University Of Sydney

Location: Australia

View Organisation

University Of Melbourne

Location: Australia

View Organisation

Australian National University

Location: Australia

View Organisation

University Of Sydney

Location: Australia

View Organisation

Plymouth Marjon University

Location: United Kingdom of Great Britain and Northern Ireland

View Organisation

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0346515

Start Date: 01-2003

End Date: 12-2004

Amount: $507,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0344441

Start Date: 2003

End Date: 06-2005

Amount: $390,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0775598

Start Date: 10-2008

End Date: 11-2008

Amount: $1,000,000.00

Funder: Australian Research Council

Special Research Initiatives - Grant ID: SR0354630

Start Date: 11-2003

End Date: 12-2004

Amount: $20,000.00

Funder: Australian Research Council

Special Research Initiatives - Grant ID: SR0354691

Start Date: 01-2004

End Date: 11-2004

Amount: $30,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE200100043

Start Date: 05-2020

End Date: 12-2021

Amount: $389,000.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP210101632

Start Date: 03-2021

End Date: 02-2024

Amount: $600,000.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP0664706

Start Date: 02-2006

End Date: 11-2008

Amount: $342,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE150100001

Start Date: 2015

End Date: 12-2015

Amount: $410,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0560680

Start Date: 08-2005

End Date: 11-2006

Amount: $901,862.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0560685

Start Date: 2005

End Date: 06-2006

Amount: $451,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0237664

Start Date: 2001

End Date: 12-2002

Amount: $900,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0238898

Start Date: 2001

End Date: 12-2002

Amount: $352,000.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP160104172

Start Date: 2016

End Date: 06-2021

Amount: $495,700.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP0346162

Start Date: 03-2003

End Date: 02-2006

Amount: $276,000.00

Funder: Australian Research Council

Linkage Projects - Grant ID: LP170100313

Start Date: 12-2018

End Date: 08-2023

Amount: $786,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE110100174

Start Date: 12-2011

End Date: 12-2012

Amount: $800,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0989390

Start Date: 04-2009

End Date: 12-2013

Amount: $500,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0989759

Start Date: 2009

End Date: 12-2010

Amount: $360,000.00

Funder: Australian Research Council

Special Research Initiatives - Grant ID: SR0354474

Start Date: 01-2004

End Date: 12-2004

Amount: $30,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE130100146

Start Date: 10-2013

End Date: 12-2014

Amount: $860,000.00

Funder: Australian Research Council

Linkage - International - Grant ID: LX0776464

Start Date: 05-2007

End Date: 12-2010

Amount: $39,000.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP180102741

Start Date: 2018

End Date: 02-2021

Amount: $535,608.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP140100176

Start Date: 2014

End Date: 12-2017

Amount: $519,790.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP130103566

Start Date: 2013

End Date: 04-2016

Amount: $450,000.00

Funder: Australian Research Council

Special Research Initiatives - Grant ID: SR0354535

Start Date: 2004

End Date: 12-2004

Amount: $10,000.00

Funder: Australian Research Council

Special Research Initiatives - Grant ID: SR0354591

Start Date: 01-2004

End Date: 12-2003

Amount: $10,000.00

Funder: Australian Research Council

Research Networks - Grant ID: RN0460256

Start Date: 02-2005

End Date: 02-2010

Amount: $1,500,000.00

Funder: Australian Research Council

Research Networks - Grant ID: RN0460002

Start Date: 08-2004

End Date: 08-2009

Amount: $2,000,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0668439

Start Date: 11-2006

End Date: 11-2007

Amount: $730,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0668257

Start Date: 06-2006

End Date: 06-2007

Amount: $1,200,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0883030

Start Date: 09-2008

End Date: 01-2011

Amount: $450,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE0883036

Start Date: 01-2008

End Date: 10-2008

Amount: $400,000.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP1095310

Start Date: 01-2010

End Date: 12-2013

Amount: $450,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE100100125

Start Date: 06-2010

End Date: 12-2010

Amount: $330,000.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP0208409

Start Date: 10-2002

End Date: 09-2007

Amount: $982,302.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP0984722

Start Date: 01-2009

End Date: 12-2014

Amount: $995,000.00

Funder: Australian Research Council

Discovery Projects - Grant ID: DP0774173

Start Date: 01-2007

End Date: 01-2010

Amount: $394,000.00

Funder: Australian Research Council

Linkage Infrastructure, Equipment And Facilities - Grant ID: LE170100023

Start Date: 03-2017

End Date: 06-2018

Amount: $650,000.00

Funder: Australian Research Council

Linkage Projects - Grant ID: LP0453765

Start Date: 06-2004

End Date: 05-2008

Amount: $340,000.00

Funder: Australian Research Council