ORCID Profile
0000-0002-3804-6421
Current Organisation
Umeå University
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Research Topics
In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Top 5 Research Topics
ANZSRC Field of Research (FoR)
Composite and Hybrid Materials | Physical Chemistry of Materials | Functional Materials | Transition Metal Chemistry | Inorganic Chemistry | Inorganic Green Chemistry | Materials Engineering
ANZSRC Socio-Economic Objective (SEO)
Expanding Knowledge in the Chemical Sciences | Climate Change Mitigation Strategies | Industrial Energy Conservation and Efficiency | Inorganic Industrial Chemicals | Plastic Products (incl. Construction Materials) |
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Publications
A High‐Pressure NMR Probe for Aqueous Geochemistry
Publisher: Wiley
Date: 02-07-2014
Abstract: A non-magnetic piston-cylinder pressure cell is presented for solution-state NMR spectroscopy at geochemical pressures. The probe has been calibrated up to 20 kbar using in situ ruby fluorescence and allows for the measurement of pressure dependencies of a wide variety of NMR-active nuclei with as little as 10 μL of s le in a microcoil. Initial (11)B NMR spectroscopy of the H3BO3-catechol equilibria reveals a large pressure-driven exchange rate and a negative pressure-dependent activation volume, reflecting increased solvation and electrostriction upon boron-catecholate formation. The inexpensive probe design doubles the current pressure range available for solution NMR spectroscopy and is particularly important to advance the field of aqueous geochemistry.
A Soluble Phosphorus‐Centered Keggin Polyoxoniobate with Bicapping Vanadyl Groups
Publisher: Wiley
Date: 27-02-2013
Abstract: A water-soluble tetramethylammonium (TMA) salt of a novel Keggin-type polyoxoniobate has been isolated as TMA9[PV2Nb12O42]·19H2O (1). This species contains a central phosphorus site and two capping vanadyl sites. Previously only a single ex le of a phosphorus-containing polyoxoniobate, [(PO2)3PNb9O34](15-), was known, which is a lacunary Keggin ion decorated with three PO2 units. However, that cluster was isolated as an insoluble structure consisting of chains linked by sodium counterions. In contrast, the [PV2Nb12O42](9-) cluster in 1 is stable over a wide pH range, as evident by (31)P and (51)V NMR, UV/Vis spectroscopy, and ESI-MS spectrometry. The ease of substitution of phosphate into the central tetrahedral position suggests that other oxoanions can be similarly substituted, promising a richer set of structures in this class.
pH-Dependent solution dynamics of a manganese(ii ) polyoxometalate, [Mn4(H2O)2(P2W15O56)2]16−, and [Mn
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT03138A
Abstract: The NMR-determined pH-dependent water–ligand exchange rate of a Mn( ii )-polyoxometalate varies by more than an order of magnitude, in contrast with those of a hexa-aqua ion.
Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates
Publisher: Elsevier BV
Date: 02-2012
Ion pumps as biological targets for decavanadate
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3DT50462J
Abstract: The putative applications of poly-, oligo- and mono-oxometalates in biochemistry, biology, pharmacology and medicine are rapidly attracting interest. In particular, these compounds may act as potent ion pump inhibitors and have the potential to play a role in the treatment of e.g. ulcers, cancer and ischemic heart disease. However, the mechanism of action is not completely understood in most cases, and even remains largely unknown in other cases. In the present review we discuss the most recent insights into the interaction between mono- and polyoxometalate ions with ion pumps, with particular focus on the interaction of decavanadate with Ca(2+)-ATPase. We also compare the proposed mode of action with those of established ion pump inhibitors which are currently in therapeutic use. Of the 18 classes of compounds which are known to act as ion pump inhibitors, the complete mechanism of inhibition is only known for a handful. It has, however, been established that most ion pump inhibitors bind mainly to the E2 ion pump conformation within the membrane domain from the extracellular side and block the cation release. Polyoxometalates such as decavanadate, in contrast, interact with Ca(2+)-ATPase near the nucleotide binding site domain or at a pocket involving several cytoplasmic domains, and therefore need to cross through the membrane bilayer. In contrast to monomeric vanadate, which only binds to the E2 conformation, decavanadate binds to all protein conformations, i.e. E1, E1P, E2 and E2P. Moreover, the specific interaction of decavanadate with sarcoplasmic reticulum Ca(2+)-ATPase has been shown to be non-competitive with respect to ATP and induces protein cysteine oxidation with concomitant vanadium reduction which might explain the high inhibitory capacity of V10 (IC50 = 15 μM) which is quite similar to the majority of the established therapeutic drugs.
Computational exploration of heterometal substitution into the decaniobate framework, [Nb10O28]6−
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1CP01092A
Abstract: The relative energetics of isomers of [M z Nb 9 O 28 ] 11−z− is investigated computationally new synthetic targets are identified, thermodynamic control is discussed, and prediction of spin state is investigated.
Photo-electrocatalytic H 2 evolution on poly(2,2′-bithiophene) at neutral pH
Publisher: Elsevier BV
Date: 10-2014
Computational prediction of Mg-isotope fractionation between aqueous [Mg(OH2)6]2+ and brucite
Publisher: Elsevier BV
Date: 04-2018
Protonation and water exchange kinetics in sandwich polyoxometalates
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8DT02342E
Abstract: The locus of protonation in a sandwich polyoxmetalate is determined and linked to observed reactivities the implications for reactions on protic metal oxide surfaces are discussed.
Oxygen isotopic exchange in an MnIIIMn3IV-oxo cubane
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B906169J
Abstract: The rate and activation parameters for oxygen exchange of the mu(3)-oxo bridges in a manganese tetranuclear cluster with H(2)(18)O have been measured by ESI-MS the observed DeltaS(double dagger) of -146 +/- 22 J K(-1.)mol(-1) is consistent with the expected associative mechanism of substitution.
A new titanoniobate ion—completing the series [Nb10O28]6−, [TiNb9O28]7− and [Ti2Nb8O28]8−
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B900465C
Abstract: A new water-soluble polyoxometalate, [TiNb9O28]7-, completes an isostructural and homologous decametalate series from the decaniobate to the dititano-octaniobate ion.
Rates of Water Exchange in 2,2′-Bipyridine and 1,10-Phenanthroline Complexes of CoII and MnII
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH16667
Abstract: The rates and activation parameters of water exchange at pH 3.0 have been determined using variable temperature 17O NMR spectroscopy for four CoII complexes and one MnII complex: [Co(bpy)(H2O)4]2+, [Co(bpy)2 (H2O)2]2+, [Co(phen)-(H2O)4]2+, [Co(phen)2 (H2O)2]2+, and [Mn(bpy)(H2O)4]2+ (bpy = 2,2′-bipyridyl and phen = 1,10-phenanthroline). Substitution of aquo ligands with 1,10-phenanthroline or 2,2′-bipyridyl leads to an increase in the rate of exchange in the manganese complexes, from k298 (1.8 ± 0.1) × 107 s−1 for [Mn(H2O)6]2+ to (7.2 ± 0.3) × 107 s−1 for [Mn(phen)2 (H2O)2]2+, whereas the trends are more complex for the cobalt complexes. We have used the new data in conjunction with literature data for similar complexes to analyse the effect of M–OH2 distance and degree of substitution.
Synthesis and Characterization of a Soluble Vanadium‐Containing Keggin Polyoxoniobate by ESI‐MS and 51V NMR: (TMA)9[V3Nb12O42]·18H2O
Publisher: Wiley
Date: 10-12-2012
Abstract: The vanadium‐containing heteropolyoxoniobate (TMA) 9 [V 3 Nb 12 O 42 ] · 18H 2 O was synthesised by hydrothermal reaction of V 2 O 5 and hydrous niobium oxide in tetramethylammonium hydroxide solution. The cluster has an α‐Keggin structure with a central VO 4 and two trans ‐bicapped VO 5 . The water‐soluble product was characterised by X‐ray crystallography, ESI‐MS and both liquid‐ and solid‐state 51 V NMR spectroscopy. The solid‐ and solution‐phase 51 V NMR spectra indicate two major peaks corresponding to one VO 4 and two VO 5 sites.
Rates of Water Exchange on the [Fe4(OH)2(hpdta)2(H2O)4]0 Molecule and Its Implications for Geochemistry
Publisher: American Chemical Society (ACS)
Date: 06-06-2012
DOI: 10.1021/IC300370Q
Abstract: The ammonium salt of [Fe(4)O(OH)(hpdta)(2)(H(2)O)(4)](-) is soluble and makes a monospecific solution of [Fe(4)(OH)(2)(hpdta)(2)(H(2)O)(4)](0)(aq) in acidic solutions (hpdta = 2-hydroxypropane-1,3-diamino-N,N,N',N'-tetraacetate). This tetramer is a diprotic acid with pK(a)(1) estimated at 5.7 ± 0.2 and pK(a)(2) = 8.8(5) ± 0.2. In the pH region below pK(a)(1), the molecule is stable in solution and (17)O NMR line widths can be interpreted using the Swift-Connick equations to acquire rates of ligand substitution at the four isolated bound water sites. Averaging five measurements at pH < 5, where contribution from the less-reactive conjugate base are minimal, we estimate: k(ex)(298) = 8.1 (±2.6) × 10(5) s(-1), ΔH(++) = 46 (±4.6) kJ mol(-1), ΔS(++) = 22 (±18) J mol(-1) K(-1), and ΔV(++) = +1.85 (±0.2) cm(3) mol(-1) for waters bound to the fully protonated, neutral molecule. Regressing the experimental rate coefficients versus 1/[H(+)] to account for the small pH variation in rate yields a similar value of k(ex)(298) = 8.3 (±0.8) × 10(5) s(-1). These rates are ∼10(4) times faster than those of the [Fe(OH(2))(6)](3+) ion (k(ex)(298) = 1.6 × 10(2) s(-1)) but are about an order of magnitude slower than other studied aminocarboxylate complexes, although these complexes have seven-coordinated Fe(III), not six as in the [Fe(4)(OH)(2)(hpdta)(2)(H(2)O)(4)](0)(aq) molecule. As pH approaches pK(a1), the rates decrease and a compensatory relation is evident between the experimental ΔH(++) and ΔS(++) values. Such variation cannot be caused by enthalpy from the deprotonation reaction and is not well understood. A correlation between bond lengths and the logarithm of k(ex)(298) is geochemically important because it could be used to estimate rate coefficients for geochemical materials for which only DFT calculations are possible. This molecule is the only neutral, oxo-bridged Fe(III) multimer for which rate data are available.
Geochemical kinetics via the Swift–Connick equations and solution NMR
Publisher: Elsevier BV
Date: 07-2011
Energetics of paramagnetic oxide clusters: the Fe(iii ) oxyhydroxy Keggin ion
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9CP05795A
Abstract: The full energy landscape of the iron( iii ) oxyhydroxy Keggin ion is explored through a combination of computation and predictive fitting.
Sarcoplasmic reticulum calcium ATPase interactions with decaniobate, decavanadate, vanadate, tungstate and molybdate
Publisher: Elsevier BV
Date: 02-2012
DOI: 10.1016/J.JINORGBIO.2011.10.010
Abstract: Over the last few decades there has been increasing interest in oxometalate and polyoxometalate applications to medicine and pharmacology. This interest arose, at least in part, due to the properties of these classes of compounds as anti-cancer, anti-diabetic agents, and also for treatment of neurodegenerative diseases, among others. However, our understanding of the mechanism of action would be improved if biological models could be used to clarify potential toxicological effects in main cellular processes. Sarcoplasmic reticulum (SR) vesicles, containing a large amount of Ca(2+)-ATPase, an enzyme that accumulates calcium by active transport using ATP, have been suggested as a useful model to study the effects of oxometalates on calcium homeostasis. In the present article, it is shown that decavanadate, decaniobate, vanadate, tungstate and molybdate, all inhibited SR Ca(2+)-ATPase, with the following IC(50) values: 15, 35, 50, 400 μM and 45 mM, respectively. Decaniobate (Nb(10)), is the strongest P-type enzyme inhibitor, after decavanadate (V(10)). Atomic-absorption spectroscopy (AAS) analysis, indicates that decavanadate binds to the protein with a 1:1 decavanadate:Ca(2+)-ATPase stoichiometry. Furthermore, V(10) binds with similar extension to all the protein conformations, which occur during calcium translocation by active transport, namely E1, E1P, E2 and E2P, as analysed by AAS. In contrast, it was confirmed that the binding of monomeric vanadate (H(2)VO(4)(2-) V(1)) to the calcium pump is favoured only for the E2 and E2P conformations of the ATPase, whereas no significant amount of vanadate is bound to the E1 and E1P conformations. Scatchard plot analysis, confirmed a 1:1 ratio for decavanadate-Ca(2+)-ATPase, with a dissociation constant, k(d) of 1 μM(-1). The interaction of decavanadate V(10)O(28)(6-) (V(10)) with Ca(2+)-ATPase is prevented by the isostructural and isoelectronic decaniobate Nb(10)O(28)(6-) (Nb(10)), whereas no significant effects were detected with ATP or with heparin, a known competitive ATP binding molecule, suggesting that V(10) binds non-competitively, with respect to ATP, to the protein. Finally, it was shown that decaniobate inhibits SR Ca(2+)-ATPase activity in a non competitive type of inhibition, with respect to ATP. Taken together, these data demonstrate that decameric niobate and vanadate species are stronger inhibitors of the SR calcium ATPase than simple monomeric vanadate, tungstate and molybdate oxometalates, thus affecting calcium homeostasis, cell signalling and cell bioenergetics, as well many other cellular processes. The ability of these oxometalates to act either as phosphate analogues, as a transition-state analogue in enzyme-catalysed phosphoryl group transfer processes and as potentially nucleotide-dependent enzymes modulators or inhibitors, suggests that different oxometalates may reveal different mechanistic preferences in these classes of enzymes.
Microwave Synthesis of Alkali‐Free Hexaniobate, Decaniobate, and Hexatantalate Polyoxometalate Ions
Publisher: Wiley
Date: 05-09-2019
Predicting 17O NMR chemical shifts of polyoxometalates using density functional theory
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5CP07766D
Abstract: We have investigated the computation of 17 O NMR chemical shifts of a wide range of polyoxometalates using density functional theory.
Adding reactivity to structure 2: Oxygen-isotope-exchange rates in three isostructural oxide ions
Publisher: American Journal of Science (AJS)
Date: 09-2010
DOI: 10.2475/07.2010.03
Electronic Structure Description of a [Co(III)3Co(IV)O4] Cluster: A Model for the Paramagnetic Intermediate in Cobalt-Catalyzed Water Oxidation
Publisher: American Chemical Society (ACS)
Date: 13-09-2011
DOI: 10.1021/JA202320Q
Abstract: Multifrequency electron paramagnetic resonace (EPR) spectroscopy and electronic structure calculations were performed on [Co(4)O(4)(C(5)H(5)N)(4)(CH(3)CO(2))(4)](+) (1(+)), a cobalt tetramer with total electron spin S = 1/2 and formal cobalt oxidation states III, III, III, and IV. The cuboidal arrangement of its cobalt and oxygen atoms is similar to that of proposed structures for the molecular cobaltate clusters of the cobalt-phosphate (Co-Pi) water-oxidizing catalyst. The Davies electron-nuclear double resonance (ENDOR) spectrum is well-modeled using a single class of hyperfine-coupled (59)Co nuclei with a modestly strong interaction (principal elements of the hyperfine tensor are equal to [-20(±2), 77(±1), -5(±15)] MHz). Mims (1)H ENDOR spectra of 1(+) with selectively deuterated pyridine ligands confirm that the amount of unpaired spin on the cobalt-bonding partner is significantly reduced from unity. Multifrequency (14)N ESEEM spectra (acquired at 9.5 and 34.0 GHz) indicate that four nearly equivalent nitrogen nuclei are coupled to the electron spin. Cumulatively, our EPR spectroscopic findings indicate that the unpaired spin is delocalized almost equally across the eight core atoms, a finding corroborated by results from DFT calculations. Each octahedrally coordinated cobalt ion is forced into a low-spin electron configuration by the anionic oxo and carboxylato ligands, and a fractional electron hole is localized on each metal center in a Co 3d(xz,yz)-based molecular orbital for this essentially [Co(+3.125)(4)O(4)] system. Comparing the EPR spectrum of 1(+) with that of the catalyst film allows us to draw conclusions about the electronic structure of this water-oxidation catalyst.
Rates of Water Exchange for Two Cobalt(II) Heteropolyoxotungstate Compounds in Aqueous Solution
Publisher: Wiley
Date: 17-03-2011
Abstract: Polyoxometalate ions are used as ligands in water-oxidation processes related to solar energy production. An important step in these reactions is the association and dissociation of water from the catalytic sites, the rates of which are unknown. Here we report the exchange rates of water ligated to Co(II) atoms in two polyoxotungstate sandwich molecules using the (17)O-NMR-based Swift-Connick method. The compounds were the [Co(4)(H(2)O)(2)(B-α-PW(9)O(34))(2)](10-) and the larger αββα-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-) ions, each with two water molecules bound trans to one another in a Co(II) sandwich between the tungstate ligands. The clusters, in both solid and solution state, were characterized by a range of methods, including NMR, EPR, FT-IR, UV-Vis, and EXAFS spectroscopy, ESI-MS, single-crystal X-ray crystallography, and potentiometry. For [Co(4)(H(2)O)(2)(B-α-PW(9)O(34))(2)](10-) at pH 5.4, we estimate: k(298)=1.5(5)±0.3×10(6) s(-1), ΔH(≠)=39.8±0.4 kJ mol(-1), ΔS(≠)=+7.1±1.2 J mol(-1) K(-1) and ΔV(≠)=5.6 ±1.6 cm(3) mol(-1). For the Wells-Dawson sandwich cluster (αββα-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-)) at pH 5.54, we find: k(298)=1.6(2)±0.3×10(6) s(-1), ΔH(≠)=27.6±0.4 kJ mol(-1) ΔS(≠)=-33±1.3 J mol(-1) K(-1) and ΔV(≠)=2.2±1.4 cm(3) mol(-1) at pH 5.2. The molecules are clearly stable and monospecific in slightly acidic solutions, but dissociate in strongly acidic solutions. This dissociation is detectable by EPR spectroscopy as S=3/2 Co(II) species (such as the [Co(H(2)O)(6)](2+) monomer ion) and by the significant reduction of the Co-Co vector in the XAS spectra.
The first peroxotitanoniobate cluster –
Publisher: Elsevier BV
Date: 12-2010
Solution, Solid‐State, and Computational Analysis of Agostic Interactions in a Coherent Set of Low‐Coordinate Rhodium(III) and Iridium(III) Complexes
Publisher: Wiley
Date: 28-02-2018
Highly soluble iron- and nickel-substituted decaniobates with tetramethylammonium countercations
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3DT50887K
Abstract: Iron- and nickel-substituted decaniobates, [H2Fe(III)Nb9O28](6-) and [H3Ni(II)Nb9O(28)](6-) were hydrothermally synthesized as tetramethylammonium salts and the structures were determined by X-ray crystallography. The highly soluble title compounds were characterized by ESI-MS, FT-IR and UV-Vis titration.
Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9SC03857D
Abstract: Fullerene C 60 reacts with dimagnesium( i ) compounds LMgMgL, where L is a monoanionic β-diketiminate ligand, to contact ion complexes [(LMg) n C 60 ], where n is predominantly 2, 4 or 6.
Structural insights into [Co4O4(C5H5N)4(CH3CO2)4]+, a rare Co(IV)-containing cuboidal complex
Publisher: Elsevier BV
Date: 11-2013
Heavier Group 13 Metal(I) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates: A Structurally Characterized Monomer–Dimer Pair For Gallium
Publisher: Wiley
Date: 02-12-2016
Abstract: We have synthesized and characterized the monomeric diiminophosphinate-stabilized Group 13 metal(I) complexes [
Reaction Dynamics and Solution Chemistry of Polyoxometalates by Electrospray Ionization Mass Spectrometry
Publisher: Wiley
Date: 30-12-2011
Abstract: Mass spectrometry both complements other analytical techniques and allows for types of analyses and experiments not possible with common analytical methods, such as NMR, IR, and UV/Vis spectroscopy. Electrospray constitutes one of the mildest forms of ionization, making it the preferred method for the analysis of large fragile or reactive ions. There is particular promise for mass spectrometry in aiding the characterization of polyoxometalates and their solutions, but caution must be taken in designing the experiments in order to yield reliable data and to avoid the temptation of over-interpreting the relevance of gas-phase data to solution chemistry.
Lindqvist Polyoxoniobate Ion-Assisted Electrodeposition of Cobalt and Nickel Water Oxidation Catalysts
Publisher: American Chemical Society (ACS)
Date: 27-07-2015
Abstract: A method has been developed for the efficient electrodeposition of cobalt and nickel nanostructures with the assistance of the Lindqvist ion [Nb6O19](8-). Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectrometry, and a range of electrochemical techniques have been used to characterize the morphology, composition, catalytic water oxidation activity and stability of the films in alkaline solution. SEM images show that films consisting of nanoparticles with diameters of ca. 30 to 40 nm are formed after 40-50 potential cycles of deposition. Nb and Co/Ni are detected in the films by EDX. ICP-MS results show an elemental ratio of 1:1 for Co:Nb and 1:3 for Ni:Nb, respectively. Raman spectra reveal the presence of both [Nb6O19](8-) and Co(OH)2/Ni(OH)2. The films exhibit excellent stability and efficiency for electrocatalytic water oxidation in alkaline solution. Turnover frequencies of 12.9 and 13.2 s(-1) were determined by rotating ring disk electrode voltammetry at an overpotential of 480 mV for Co and Ni films, respectively. Fourier transformed large litude alternating current (FTAC) voltammetry reveals an additional underlying oxidation process for Co under catalytic turnover conditions, which indicates that a Co(IV) species is involved in the efficient catalytic water oxidation reactions. FTAC voltammetric data also suggest that the Ni films undergoes a clear phase transformation upon aging in aqueous 1 M NaOH and the electrogenerated higher oxidation state Ni from β-NiOOH is the more active form of the catalyst.
Decavanadate, decaniobate, tungstate and molybdate interactions with sarcoplasmic reticulum Ca2+-ATPase: quercetin prevents cysteine oxidation by vanadate but does not reverse ATPase inhibition
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT31688A
Abstract: Recently we demonstrated that the decavanadate (V(10)) ion is a stronger Ca(2+)-ATPase inhibitor than other oxometalates, such as the isoelectronic and isostructural decaniobate ion, and the tungstate and molybdate monomer ions, and that it binds to this protein with a 1 : 1 stoichiometry. The V(10) interaction is not affected by any of the protein conformations that occur during the process of calcium translocation (i.e. E1, E1P, E2 and E2P) (Fraqueza et al., J. Inorg. Biochem., 2012). In the present study, we further explore this subject, and we can now show that the decaniobate ion, [Nb(10) = Nb(10)O(28)](6-), is a useful tool in deducing the interaction and the non-competitive Ca(2+)-ATPase inhibition by the decavanadate ion [V(10) = V(10)O(28)](6-). Moreover, decavanadate and vanadate induce protein cysteine oxidation whereas no effects were detected for the decaniobate, tungstate or molybdate ions. The presence of the antioxidant quercetin prevents cysteine oxidation, but not ATPase inhibition, by vanadate or decavanadate. Definitive V(IV) EPR spectra were observed for decavanadate in the presence of sarcoplasmic reticulum Ca(2+)-ATPase, indicating a vanadate reduction at some stage of the protein interaction. Raman spectroscopy clearly shows that the protein conformation changes that are induced by V(10), Nb(10) and vanadate are different from the ones induced by molybdate and tungstate monomer ions. Here, Mo and W cause changes similar to those by phosphate, yielding changes similar to the E1P protein conformation. The putative reduction of vanadium(V) to vanadium(IV) and the non-competitive binding of the V(10) and Nb(10) decametalates may explain the differences in the Raman spectra compared to those seen in the presence of molybdate or tungstate. Putting it all together, we suggest that the ability of V(10) to inhibit the Ca(2+)-ATPase may be at least in part due to the process of vanadate reduction and associated protein cysteine oxidation. These results contribute to the understanding and application of these families of mono- and polyoxometalates as effective modulators of many biological processes, particularly those associated with calcium homeostasis.
Electrochemical and Electrogenerated Chemiluminescent Studies of a Trinuclear Complex, [((phen)2Ru(dpp))2RhCl2]5+, and Its Interactions with Calf Thymus DNA
Publisher: American Chemical Society (ACS)
Date: 09-04-2009
DOI: 10.1021/AC900282Y
Abstract: The electrochemical behavior of a trinuclear ruthenium(II)-containing complex, [((phen)(2)Ru(dpp))(2)RhCl(2)](5+) (where phen = 1,10-phenanthroline, dpp = 2,3-bis(2-pyridyl)pyrazine), was studied in acetonitrile (MeCN) and aqueous solutions. In MeCN containing 0.10 M tetra-n-butylammonium perchlorate (TBAP), the complex displayed a reversible, overlapping Ru(II/III) redox process with E(1/2) = +1.21 V vs Ag/Ag(+) (10 mM), an irreversible reduction of Rh(III/I) at -0.73 V vs Ag/Ag(+), and two quasi-reversible dpp/dpp(-) couples with E(1/2) = -1.11 and -1.36 V vs Ag/Ag(+) at a Pt electrode with a scan rate of 50 mV s(-1). In 0.20 M Tris buffer solution (pH 7.4), an irreversible, overlapping Ru(II/III) oxidation at +1.48 V vs Ag/AgCl (3 M KCl), and an irreversible reduction of Rh(III/II) at -0.78 V vs Ag/AgCl were observed at a glassy carbon electrode with a scan rate of 50 mV/s. Investigations on the electrogenerated chemiluminescence (ECL) of the complex revealed that 2-(dibutylamino) ethanol (DBAE) was superior to tri-n-propylamine (TPrA) as an ECL coreactant within their entire concentration range of 10-100 mM in MeCN, and in aqueous media, as low as 1.0 nM of the complex can be detected using TPrA coreactant ECL. A maximum ECL emission of 640 nm, which is about 55 nm blue shift to its fluorescence, was observed in MeCN with DBAE as a coreactant. Interactions of the complex with calf thymus DNA (ctDNA) were conducted with a flow-cell based quartz-crystal microbalance, and a binding constant of 2.5 x 10(5) M(-1) was calculated on the basis of the Langmuir isotherm equation.
The [Ti12Nb6O44]10− Ion—A New Type of Polyoxometalate Structure
Publisher: Wiley
Date: 09-07-2008
Reaction Dynamics of the Decaniobate Ion [HxNb10O28](6−x)− in Water
Publisher: Wiley
Date: 09-06-2008
Re-Writable Multi-Domain Liquid Crystal Alignment Layers through Laser-Induced Micropatterning
Publisher: IOP Publishing
Date: 09-06-2006
DOI: 10.1143/JJAP.45.L591
One-pot synthesis of the decaniobate salt [N(CH3)4]6[Nb10O28]·6H2O from hydrous niobium oxide
Publisher: Elsevier BV
Date: 03-2009
Characterization of decavanadate and decaniobate solutions by Raman spectroscopy
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5DT04176G
Abstract: V 10 dissociates at most pH values into smaller tetrahedral vanadate oligomers such as V 4 and V 2 , whereas Nb 10 dissociates into Nb 6 under mildly or highly alkaline conditions.
The energetics of isomerisation in Keggin-series aluminate cations
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4DT01763C
Abstract: The energetics of the Keggin isomers of the trideca-aluminate ion and their interconversion via cap rotation is investigated using DFT.
Decavanadate in vitro and in vivo effects: facts and opinions
Publisher: Elsevier BV
Date: 08-2014
DOI: 10.1016/J.JINORGBIO.2014.05.002
Abstract: This review covers recent advances in the understanding of the in vitro and in vivo effects of decavanadate, (V10O28)(6-), particularly in mitochondria. In vivo toxicological studies involving vanadium rarely account for the fact that under physiological conditions some vanadium may be present in the form of the decavanadate ion, which may behave differently from ortho- and metavanadates. It has for ex le been demonstrated that vanadium levels in heart or liver mitochondria are increased upon decavanadate exposure. Additionally, in vitro studies have shown that mitochondrial depolarization (IC50, 40 nM) and oxygen consumption (IC50, 99 nM) are strongly affected by decavanadate, which causes reduction of cytochrome b (complex III). We review these recent findings which together suggest that the observed cellular targets, metabolic pathway and toxicological effects differ according to the species of vanadium present. Finally, the toxicological effects of decavanadate depend on several factors such as the mode of administration, exposure time and type of tissue.
27Al MQMAS of the δ-Al13-Keggin
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6DT04263E
Abstract: 27 Al-MQMAS spectra of the δ isomer of the Na[AlO 4 Al 12 (OH) 24 (OH 2 ) 12 ]·2,6-napthalene disulfonate salt.
Coordination Induced Atropisomerism in an NHC-Based Rhodium Macrocycle
Publisher: American Chemical Society (ACS)
Date: 18-02-2015
DOI: 10.1021/OM501292K
Heterogeneous dehalogenation of arylhalides in the presence of ionic liquids
Publisher: Wiley
Date: 30-01-2007
DOI: 10.1002/AOC.1194
The Pressure Dependence of Oxygen Isotope Exchange Rates Between Solution and Apical Oxygen Atoms on the [UO2(OH)4]2− Ion
Publisher: Wiley
Date: 06-04-2011
Cell directional migration and oriented division on three-dimensional laser-induced periodic surface structures on polystyrene
Publisher: Elsevier BV
Date: 05-2008
DOI: 10.1016/J.BIOMATERIALS.2007.12.047
Abstract: The extracellular matrix in animal tissues usually provides a three-dimensional structural support to cells in addition to performing various other important functions. In the present study, wavy submicrometer laser-irradiated periodic surface structures (LIPSS) were produced on a smooth polystyrene film by polarized laser irradiation with a wavelength of 266 nm. Rat C6 glioma cells exhibited directional migration and oriented ision on laser-irradiated polystyrene, which was parallel to the direction of LIPSS. However, rat C6 glioma cells on smooth polystyrene moved in a three-step invasion cycle, with faster migration speed than that on laser-irradiated polystyrene. In addition, focal adhesions examined by immunostaining focal adhesion kinase in human epithelial carcinoma HeLa cells were punctuated on smooth polystyrene, whereas dash-like on laser-irradiated polystyrene. We hypothesized that LIPSS on laser-irradiated polystyrene acted as an anisotropic and persistent mechanical stimulus to guide cell anisotropic spreading, migration and ision through focal adhesions.
Polyoxoniobates as molecular building blocks in thin films
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1DT03116C
Abstract: Crystallinity, thickness, and roughness can be controlled using polyoxoniobates as molecular building blocks in niobium oxide thin film synthesis.
Enhanced catalytic activity towards hydrogen evolution on polythiophene via microstructural changes
Publisher: Elsevier BV
Date: 2017
Oxygen-Isotope Exchange Rates for Three Isostructural Polyoxometalate Ions
Publisher: American Chemical Society (ACS)
Date: 19-03-2010
DOI: 10.1021/JA100490N
Abstract: We compare oxygen-isotope exchange rates for all structural oxygens in three polyoxoniobate ions that differ by systematic metal substitutions of Ti(IV) --> Nb(V). The [H(x)Nb(10)O(28)]((6-x)-), [H(x)TiNb(9)O(28)]((7-x)-), and [H(x)Ti(2)Nb(8)O(28)]((8-x)-) ions are all isostructural yet have different Brønsted properties. Rates for sites within a particular molecule in the series differ by at least approximately 10(4), but the relative reactivities of the oxygen sites rank in nearly the same relative order for all ions in the series. Within a single ion, most structural oxygens exhibit rates of isotopic exchange that vary similarly with pH, indicating that each structure responds as a whole to changes in pH. Across the series of molecules, however, the pH dependencies for isotope exchanges and dissociation are distinctly different, reflecting different contributions from proton- or base-enhanced pathways. The proton-enhanced pathway for isotope exchange dominates at most pH conditions for the [H(x)Ti(2)Nb(8)O(28)]((8-x)-) ion, but the base-enhanced pathways are increasingly important for the [H(x)TiNb(9)O(28)]((7-x)-) and [H(x)Nb(10)O(28)]((6-x)-) structures at higher pH. The local effect of Ti(IV) substitution could be assessed by comparing rates for structurally similar oxygens on each side of the [H(x)TiNb(9)O(28)]((7-x)-) ion and is surprisingly small. Interestingly, these nanometer-size structures seem to manifest the same general averaged hoteric chemistry that is familiar for other reactions affecting oxides in water, including interface dissolution by proton- and hydroxyl-enhanced pathways.
A new class of soluble and stable transition-metal-substituted polyoxoniobate: [Cr2(OH)4Nb10O30]8−
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT31760E
Abstract: Hydrothermal synthesis of [Cr(III)(2)(OH)(4)Nb(10)O(30)](8-) in gram-scale quantities leads to a new polyoxometalate ion composed of two CrNb(6)O(19) Lindqvist-type units that are fused via shared faces. The two Cr(III) atoms are located in the centre of the molecule and are bridged by two μ(4)-O atoms. Electronic transitions are calculated using density functional theory and compare well with the measured UV-Vis spectra.
Non-aqueous microwave-assisted syntheses of deca- and hexa-molybdovanadates
Publisher: Wiley
Date: 16-01-2017
Abstract: We report a new approach for the synthesis of heterohexa- and heterodecametalates via the use of non-aqueous, microwave-assisted reaction conditions. The two novel molybdovanadates have been isolated and characterized in the solid and solution states using single-crystal X-ray diffraction, FT-IR, UV/Vis, multinuclear NMR spectroscopy, and ESI-MS. The relative stabilities of the possible structural isomers were probed using dispersion-corrected DFT calculations for both polyoxometalate systems.
Mechanistic studies of the photo-electrochemical hydrogen evolution reaction on poly(2,2′-bithiophene)
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5CY01852H
Abstract: The realisation of poly(2,2′-bithiophene) (PBTh) as an effective photo-electrocatalyst for the hydrogen evolution reaction is a novel discovery [Ng et al. , Int. J. Hydrogen Energy , 2014, 39 , 18230] however, the underlying mechanism for this catalysis remains unknown.
Exploration and optimisation of poly(2,2′-bithiophene) as a stable photo-electrocatalyst for hydrogen production
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5TA00291E
Abstract: Polybithiophene as a HER catalyst is further explored, revealing longterm stability, high faradaic efficiency and successful operation at pH 11.
17O NMR and Computational Study of a Tetrasiliconiobate Ion, [H2+xSi4Nb16O56](14−x)−
Publisher: Wiley
Date: 07-2011
Abstract: Rates of oxygen-isotope exchange were measured in the tetrasiliconiobate ion [H(2+x)Si(4)Nb(16)O(56)]((14-x)-) to better understand how large oxide ions interact with water. The molecule has 19 nonequivalent oxygen sites and is sufficiently complex to evaluate hypotheses derived from our previous work on smaller clusters. We want to examine the extent to which in idual oxygen atoms react independently with particular attention given to the order of protonation of the various oxygen sites as the pH decreases from 13 to 6. As in our previous work, we find that the set of oxygen sites reacts at rates that vary over approximately 10(4) across the molecule at 6<pH<13 but with similar pH dependencies. There is NMR evidence of an intra- or intermolecular reaction at pH∼7, where new peaks began to slowly form without losing the (17)O isotopic tag, and at pH ≤ 6 these new peaks formed rapidly. The oxygen atoms bonded to silicon atoms began to isotopically exchange at pH 9 and below. The (17)O NMR peak positions also vary considerably with pH for some, but not all, nonequivalent oxygen sites. This variation could be only partly accounted by electronic calculations, which indicate that oxygen atoms should shift similarly upon protonation. Instead, we see that some sites change enormously with pH, whereas other, similarly coordinated oxygen atoms are less affected, suggesting that either some protons are exchanging so rapidly that the oxygen sites are seeing an averaged charge, or that counterions are modulating the effect of the coordinated protons.
Characterisation of a series of triarylmethane dyes as light harvesters for photo-electrochemical systems
Publisher: Elsevier BV
Date: 04-2015
Multinuclear NMR Study of the Pressure Dependence for Carbonate Exchange in the UO2(CO3)34−(aq) Ion
Publisher: Wiley
Date: 16-09-2011
Adding reactivity to structure--reaction dynamics in a nanometer-size oxide ion in water
Publisher: American Journal of Science (AJS)
Date: 10-2008
DOI: 10.2475/08.2008.03
The Performance-determining Role of Lewis Bases in Dye-Sensitized Solar Cells Employing Copper-Bisphenanthroline Redox Mediators
Publisher: Wiley
Date: 02-09-2020
Application of the Tris(acetylacetonato)iron(III)/(II) Redox Couple in p‐Type Dye‐Sensitized Solar Cells
Publisher: Wiley
Date: 28-01-2015
Abstract: An electrolyte based on the tris(acetylacetonato)iron(III)/(II) redox couple ([Fe(acac)3](0/1-)) was developed for p-type dye-sensitized solar cells (DSSCs). Introduction of a NiO blocking layer on the working electrode and the use of chenodeoxycholic acid in the electrolyte enhanced device performance by improving the photocurrent. Devices containing [Fe(acac)3](0/1-) and a perylene-thiophene-triphenylamine sensitizer (PMI-6T-TPA) have the highest reported short-circuit current (J(SC)=7.65 mA cm(-2)), and energy conversion efficiency (2.51%) for p-type DSSCs coupled with a fill factor of 0.51 and an open-circuit voltage V(OC)=645 mV. Measurement of the kinetics of dye regeneration by the redox mediator revealed that the process is diffusion limited as the dye-regeneration rate constant (1.7×10(8) M(-1) s(-1)) is very close to the maximum theoretical rate constant of 3.3×10(8) M(-1) s(-1). Consequently, a very high dye-regeneration yield (>99%) could be calculated for these devices.
PNacPNacE: (E = Ga, In, Tl) – monomeric group 13 metal(i ) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7DT04048B
Abstract: Monomeric group 13 metal( i ) complexes of gallium, indium and thallium stabilised by a sterically demanding bis(iminophosphoranyl)methanide ligand have been prepared and characterised.
Diverse composites of metal-complexes and PEDOT facilitated by metal-free vapour phase polymerization
Publisher: Elsevier BV
Date: 07-2017
Cytotoxicity of ionic liquids and precursor compounds towards human cell line HeLa
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B704503D
Enhanced Water Purification: A Single Atom Makes a Difference
Publisher: American Chemical Society (ACS)
Date: 03-06-2009
DOI: 10.1021/ES803683T
Abstract: The aluminum Keggin polycation (Al13) has been identified as an effective specie for neutralization and coagulation of anionic contaminants in water. In this study, we compare efficacy of the aluminum Keggin-ion to the analogues containing a single Ga-atom or single Ge-atom (GaAl12 and GeAl12, respectively) substituted into the center of the polycation in water-treatment studies. We investigated removal of bacteriophage (model viruses), Cryptosporidium, dissolved organic carbon (DOC), and turbidity. In every study, the order of contaminant removal efficacy trends GaAl12 > Al13 > GeAl12. By ESI MS (electrospray ionization mass spectrometry), we noted the GaAl12 deprotonates least of the three aluminum polycations, and thus probably carries the highest charge, and also optimal contaminant-neutralization ability. The ESI MS studies of the aluminum polycation solutions, as well as solid-state characterization of their resulting precipitates both reveal some conversion of Al13 to larger polycations, Al30 for instance. The GaAl12 does not show any evidence for this alteration that is responsible for poor shelf life of commercial prehydrolyzed aluminum coagulants such as polyaluminum chloride. Based on these studies, we conclude that substitution of a single Ga-atom in the center of the aluminum Keggin polycation produces an optimal water-treatment product due to enhanced shelf life and efficacy in neutralization of anionic contaminants.
Dual-functionalised ionic liquids: synthesis and characterisation of imidazolium salts with a nitrile-functionalised anion
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B408938C
Abstract: A series of 'dual-functionalised' ionic liquids, comprising imidazolium cations with various functionalities and the nitrile functionalised anion [CH3CH(BF3)CH2CN]- have been prepared some exhibit very low viscosities-a highly valuable property in many applications.
Introducing manganese complexes as redox mediators for dye-sensitized solar cells
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3CP54894E
Abstract: The abundance and low toxicity of manganese have led us to explore the application of manganese complexes as redox mediators for dye sensitized solar cells (DSCs), a promising solar energy conversion technology which mimics some of the key processes in photosynthesis during its operation. In this paper, we report the development of a DSC electrolyte based on the tris(acetylacetonato)manganese(iii)/(iv), [Mn(acac)3](0/1+), redox couple. PEDOT-coated FTO glass was used as a counter electrode instead of the conventionally used platinum. The influence of a number of device parameters on the DSC performance was studied, including the concentration of the reduced and oxidized mediator species, the concentration of specific additives (4-tert-butylpyridine, lithium tetrafluoroborate, and chenodeoxycholic acid) and the thickness of the TiO2 working electrode. These studies were carried out with a new donor-π-acceptor sensitizer K4. Maximum energy conversion efficiencies of 3.8% at simulated one Sun irradiation (AM 1.5 G 1000 W m(-2)) with an open circuit voltage (VOC) of 765 mV, a short-circuit current (JSC) of 7.8 mA cm(-2) and a fill factor (FF) of 0.72 were obtained. Application of the commercially available MK2 and N719 sensitizers resulted in an energy conversion efficiency of 4.4% with a VOC of 733 mV and a JSC of 8.6 mA cm(-2) for MK2 and a VOC of 771 mV and a JSC of 7.9 mA cm(-2) for N719. Both dyes exhibit higher incident photon to current conversion efficiencies (IPCEs) than K4.
CARBON DIOXIDE REDUCTION IN BIPHASIC AQUEOUS-IONIC LIQUID SYSTEMS BY PRESSURIZED HYDROGEN
Publisher: Informa UK Limited
Date: 09-2003
Isotope-Exchange Dynamics in Isostructural Decametalates with Profound Differences in Reactivity
Publisher: American Chemical Society (ACS)
Date: 06-08-2009
DOI: 10.1021/JA905166C
Abstract: Rates of oxygen-isotope exchange at all structural sites in two isostructural polyoxometalates, [H(x)Nb(10)O(28)]((6-x)-) and [H(x)Ti(2)Nb(8)O(28)]((8-x)-), show that small changes in structure have surprising and profound effects: a single-site substitution of Ti(IV) for Nb(V) inverts the pH dependencies for rates throughout the structures. Within a given structure, all oxygens exhibit similar pH dependencies although they react over a range greater than approximately 10(4), indicating that pathways involve concerted motions of the entire lattices. Profound sensitivity to changes in structure and composition suggests reaction pathways in polyoxometalate ions will be highly variable even within structural classes. The results also require new thinking about how ab initio simulations are used to understand reaction pathways involving extended structures, like the mineral-water interface. Our data indicate that reactions proceed via metastable intermediates and that the simulations must be structurally faithful or will miss the essential chemistry.
Solvent promoted reversible cyclometalation in a tethered NHC iridium complex
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3CC48015A
Abstract: Reaction of [Ir(COD)(py-I(t)Bu)](+) (py-I(t)Bu = 3-tert-butyl-1-picolylimidazol-2-ylidene) with acetonitrile results in reversible intramolecular C-H bond activation of the NHC ligand and formation of [Ir(η(2):η(1)-C8H13)(py-I(t)Bu')(NCMe)](+). Coordinated COD acts as an internal hydride acceptor and acetonitrile coordination offsets the otherwise unfavourable thermodynamics of the process.
Influence of physicochemical properties of laser‐modified polystyrene on bovine serum albumin adsorption and rat C6 glioma cell behavior
Publisher: Wiley
Date: 31-05-2006
DOI: 10.1002/JBM.A.30764
Abstract: Biomaterial surface modification is an efficient way of improving cell-material interactions. In this study, sub-micrometer laser-induced periodic surface structures (LIPSS) were produced on polystyrene by laser irradiation. FT-IR analysis confirmed that this treatment also led to surface oxidation and anisotropic orientation of the produced carbonyl groups. As a consequence, the surface energy of the laser-treated polystyrene was 1.45 times that of the untreated polystyrene, as measured by contact-angle goniometry. Protein adsorption and rat C6 glioma cell behavior on the two substrates were investigated, showing that the changed physicochemical properties of laser-modified polystyrene surface led to an increase in the quantity of adsorbed bovine serum albumin and significantly affected the behavior of rat C6 glioma cells. In the early stages of cell spreading, cells explored their microenvironment using filopodium as the main sensor. Moreover, cells actively aligned themselves along the direction of LIPSS gradually and cell attachment and proliferation were significantly enhanced.
Dissolution of insulating oxide materials at the molecular scale
Publisher: Springer Science and Business Media LLC
Date: 17-11-2009
DOI: 10.1038/NMAT2585
Abstract: Our understanding of mineral and glass dissolution has advanced from simple thermodynamic treatments to models that emphasize adsorbate structures. This evolution was driven by the idea that the best understanding is built at the molecular level. Now, it is clear that the molecular questions cannot be answered uniquely with dissolution experiments. At the surface it is unclear which functional groups are present, how they are arranged, and how they interact with each other and with solutes as the key bonds are activated. An alternative approach has developed whereby reactions are studied with nanometre-sized aqueous oxide ions that serve as models for the more complicated oxide interface. For these ions, establishing the structure is not a research problem in itself, and bond ruptures and dissociations can be followed with much confidence. We review the field from bulk-dissolution kinetics to the new isotope-exchange experiments in large oxide ions.
Borate Accelerates Rates of Steady Oxygen‐Isotope Exchange for Polyoxoniobate Ions in Water
Publisher: Wiley
Date: 29-07-2010
Rationalisation of Solvent Effects in the DielsAlder Reaction Between Cyclopentadiene and Methyl Acrylate in Room Temperature Ionic Liquids
Publisher: Wiley
Date: 02-2005
Abstract: The Diels–Alder reaction between cyclopentadiene and methyl acrylate in ionic liquids has been studied in detail. The effect of contamination of the ionic liquids by common impurities, viz. sodium and chloride ions, and water, on the selectivity has been investigated. The presence of high concentrations of chloride was found to decrease the selectivity. Anion and, in particular, cation effects have been investigated using an extensive series of air‐stable room temperature ionic liquids, and kinetic parameters have been determined. It has been found that strongly interacting groups, particularly electrophilic moieties on the cation, accelerate the formation of the endo products. Substrate solubility intimately connected to the selectivity was found to be mainly anion dependent. An NMR‐based solvent parameter scale and semi‐empirical models are used to analyse the results and provide a tool for the prediction of selectivities in ionic liquids.
Distinctly Different Reactivities of Two Similar Polyoxoniobates with Hydrogen Peroxide
Publisher: Wiley
Date: 09-10-2008
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