ORCID Profile
0000-0001-6373-6582
Current Organisation
University of Tasmania
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Publisher: Elsevier BV
Date: 02-2020
DOI: 10.1016/J.CHROMA.2019.460669
Abstract: The development and application of non-porous and porous sorptive rods, comprised of polydimethylsiloxane-microdiamond (PDMS-MD) composites, is reported. The PDMS-MD composites were made porous using inorganic salt (NaCl and NaHCO
Publisher: Elsevier BV
Date: 12-2008
DOI: 10.1016/J.CHROMA.2008.08.049
Abstract: The selectivity, retention and separation of transition metals on a short (2 mm x 50 mm) column packed with a poly-iminodiacetic acid functionalised polymer 10 microm resin (Dionex ProPac IMAC-10) are presented. This stationary phase, typically used for the separation of proteins, is composed of long chain poly-iminodiacetic acid groups grafted to a hydrophilic layer surrounding a 10 microm polymeric bead. Through the use of a combination of a multi-step pH and picolinic acid gradient, the separation of magnesium, iron, cobalt, cadmium, zinc, lead and copper was possible, followed by post-column reaction with 4-(2-pyridylazo) resorcinol (PAR) and absorbance detection at 510 nm using a novel and inexpensive optical detector, comprised of two light emitting diodes with one acting as a light source and the other as a detector. Column efficiency for selective transition metals was in excess of N=10,000, with the baseline separation of seven metal cations in <3 min possible under optimised conditions. Detection limits of between 5 and 81 microg/L were possible based upon a 50 microL injection volume.
Publisher: Elsevier BV
Date: 10-2016
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B803349H
Abstract: The use of on-column capacitively coupled contactless conductivity detection for the accurate non-invasive visualisation of the pH dependence of covalently bound boronic acid groups within a monolithic polymeric capillary column is demonstrated.
Publisher: Elsevier BV
Date: 03-2020
Publisher: American Chemical Society (ACS)
Date: 05-06-2019
DOI: 10.1021/ACS.ANALCHEM.9B01288
Abstract: Distance-based detection methods, as used in development of microfluidic paper analytical devices (μPADs), rely on the dynamic formation of a colored band along the length of the paper microfluidic channels. The color change is driven by the reaction of chromogenic reagents (typically water-insoluble) that are bound to the paper, thus not subject to being washed away by the s le flow along the detection channel. Here, we introduce the use of an anion-exchange filter paper (as a replacement for standard, unmodified filter paper) for distance-based detection in μPADs, in order to immobilize the water-soluble anionic reagents upon the paper detection channels based on ion-exchange interactions of the oppositely charged paper (protonated tertiary amine groups) and the anionic groups of the reagents. The ion-exchange (IE) paper was initially characterized and its properties were compared with standard cellulose paper. The IE paper was shown to be capable of strong retention of anionic reagents exhibiting acidic functional groups (carboxylic, sulfonic), which become deprotonated and negatively charged when in contact with the IE paper. The effect of the ionic strength (10-250 mM Cl
Publisher: American Chemical Society (ACS)
Date: 14-01-2019
DOI: 10.1021/ACSCOMBSCI.8B00126
Abstract: Novel approaches that incorporate electrofluidic and microfluidic technologies are reviewed to illustrate the translation of traditional enclosed structures into open and accessible textile based platforms. Through the utilization of on-fiber and on-textile microfluidics, it is possible to invert the typical enclosed capillary column or microfluidic "chip" platform, to achieve surface accessible efficient separations and fluid handling, while maintaining a microfluidic environment. The open fiber/textile based fluidics approach immediately provides new possibilities to interrogate, manipulate, redirect, extract, characterize, and quantify solutes and target species at any point in time during such processes as on-fiber electrodriven separations. This approach is revolutionary in its simplicity and provides many potential advantages not otherwise afforded by the more traditional enclosed platforms.
Publisher: Elsevier BV
Date: 07-1999
DOI: 10.1016/S0021-9673(99)00143-0
Abstract: A method for the simultaneous separation and determination of Nb(V) and Ta(V) as ternary complexes formed with 4-(2-pyridylazo)resorcinol (PAR) and citrate was developed using ion-interaction reversed-phase high-performance liquid chromatography on a C18 column. Method parameters, such as pre-column complex formation conditions and composition of the complexes were investigated using spectrophotometry and HPLC. Under the optimum conditions, the Nb(V) and Ta(V) complexes were eluted within 12 min with a mobile phase of methanol-water (32:68, v/v) containing 5 mM acetate, 5 mM TBABr and 5 mM citrate buffer at pH 6.5, with detection at 540 nm. A typical separation efficiency was 33,000 and 20,000 theoretical plates per metre for Nb(V) and Ta(V), respectively. The relative standard deviation of retention times for the Nb(V) and Ta(V) complexes were 0.16% and 0.17% and for peak areas were 0.28% and 1.36%, respectively. The detection limits (signal-to-noise ratio = 3) for Nb(V) and Ta(V) were 0.4 ppb and 1.4 ppb, respectively. Results obtained for standard reference rock s les agreed well with certified values and results obtained by inductively coupled plasma MS.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1LC00538C
Abstract: Wireless bipolar electrochemistry on a surface-accessible textile-based electrofluidic 3D construct.
Publisher: Elsevier BV
Date: 03-2023
Publisher: Elsevier BV
Date: 03-2019
DOI: 10.1016/J.ACA.2018.11.033
Abstract: In this study, the separation of inorganic mono and alent cations using multi-lumen silica capillaries (MLCs) of 126 channels, each with either 4 or 8 μm inner diameter, was investigated using capillary electrophoresis and on-capillary capacitively coupled contactless conductivity detection (CE-C
Publisher: Springer Science and Business Media LLC
Date: 05-1996
DOI: 10.1007/BF02290287
Publisher: Elsevier BV
Date: 02-2022
DOI: 10.1016/J.ACA.2021.338810
Abstract: A thread-based isotachophoresis method coupled with desorption electrospray ionization mass spectrometry (TB-ITP-DESI-MS) was developed and applied for clean-up, preconcentration, and determination of alkaloids in biological fluids. This simple approach enables the focusing and rapid analysis of analytes of interest in complex matrices that are otherwise challenging using direct ambient mass spectrometry. The TB-ITP platform components were rapidly and reproducibly fabricated at low-cost using 3D printing. A single string of nylon 6 thread was used as the electrophoresis substrate and a cotton knot, tied to the nylon thread, was used as the trapping zone of the ITP focused model analytes (coptisine, berberine and palmatine). The trapping efficiency was evaluated upon different commercially available threads with different chemical properties and cotton was selected as the best material due to its highest trapping efficiency and subsequent DESI-MS ionization efficiency. Up to 11.6-fold increase in signal to noise ratio (S/N) was obtained using the proposed method compared to direct DESI-MS detection, due to the reduced matrix interference and focusing. The results demonstrated that the TB-ITP-DESI-MS approach is a viable solution for the analysis of complicated biological fluid s les.
Publisher: Elsevier BV
Date: 1998
Publisher: Elsevier BV
Date: 02-1998
Publisher: Elsevier BV
Date: 07-2010
Publisher: Elsevier BV
Date: 11-1998
Publisher: Informa UK Limited
Date: 30-06-2001
DOI: 10.1081/AL-100104925
Publisher: Elsevier BV
Date: 05-2006
DOI: 10.1016/J.ACA.2006.01.038
Abstract: The development of a rapid method for the determination of perchlorate in rain and drinking waters is presented. In the optimised method, an on-line preconcentration technique was employed utilising a 10 mm x 4.6 mm Phenomenex Onyx monolithic guard cartridge coated with (N-dodecyl-N,N-dimethylammonio)undecanoate for selective preconcentration, with subsequent elution into a fixed volume injection loop ('heart-cut' of the concentrator column eluate) and separation using an IonPac AS16 (250 mm x 2mm) anion exchange column and a potassium hydroxide concentration gradient. Off-line optimisation studies showed that the coated monolith displayed near quantitative recovery up to 50 microg/L perchlorate level from standards prepared in reagent water. On-line preconcentration of perchlorate obtained detection limits down to 56 ng/L in reagent water, between 70 and 80 ng/L in rainwater s les and 2.5 microg/L in non-pretreated drinking water. After an additional s le sulphate/carbonate removal step, low ng/L perchlorate concentrations could also be observed in drinking water. The complete on-line method exhibited reproducibility for n=10 replicate runs of R.S.D.< or =3% for peak height/area and R.S.D.=0.08% for retention time. The optimised method, of 20 min total duration, was applied to the determination of perchlorate by standard addition in 10 rainwater s les and one drinking water s le. Concentrations of perchlorate present ranged from below the detection limit for four rainwater s les, with another three s les showing perchlorate present at between 70 and 100 ng/L, and one s le showing perchlorate present at 2.8 microg/L. Levels of 1.1 microg/L in the drinking water s le were also recorded.
Publisher: Informa UK Limited
Date: 27-12-2004
DOI: 10.1081/AL-200032011
Publisher: Elsevier BV
Date: 11-2011
Publisher: Elsevier BV
Date: 11-2019
Publisher: Springer Science and Business Media LLC
Date: 19-10-2023
Publisher: Elsevier BV
Date: 05-2011
DOI: 10.1016/J.CHROMA.2011.03.021
Abstract: An investigation into the preparation of monolithic separation media utilising a cyanine dye sensitiser/triphenylbutylborate/N-methoxy-4-phenylpyridinium tetrafluoroborate initiating system activated by 660 nm light emitting diodes is reported. The work demonstrates multiple uses of red-light initiated polymerisation in the preparation of monolithic stationary phases within polyimide and polyimide coated channels and the modification of monolithic materials with molecules which absorb strongly in the UV region. This initiator complex was used to synthesise poly(butyl methacrylate-co-ethylene dimethacrylate) and poly(methyl methacrylate-co-ethylene dimethacrylate) monolithic stationary phases in polyimide coated fused silica capillaries of varying internal diameters, as well as within polyimide micro-fluidic chips. The repeatability of the preparation procedure and resultant monolithic structure was demonstrated with a batch of poly(butyl methacrylate-co-ethylene dimethacrylate) monoliths in 100 μm i.d. polyimide coated fused silica capillary, which were applied to the separation of a model protein mixture (ribonuclease A, cytochrome C, myoglobin and ovalbumin). Taking an average from 12 chromatograms originating from each batch, the maximum relative standard deviation of the retention factor (k) for the protein separations was recorded as 0.53%, the maximum variance for the selectivity factor (α) was 0.40% while the maximum relative standard deviation in peak resolution was 8.72%. All maxima were recorded for the Ribonuclease A/Cytochrome C peaks. Scanning electron microscopy confirmed the success of experiments in which poly(butyl methacrylate-co-ethylene dimethacrylate) monoliths were prepared using the same initiation approach in capillary and micro-fluidic chips, respectively. The initiating system was also applied to the photo-initiated grafting of a chromophoric monomer onto poly(butyl methacrylate-co-ethylene dimethacrylate) monoliths within poly(tetrafluoroethylene) coated fused silica capillaries.
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3AY00278K
Abstract: This work describes a fast, simple, and environmentally friendly method based on ultrasound probe extraction (UPS) and IC-MS analysis for the quantitation of levoglucosan and its isomers in sediments.
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B406355B
Abstract: Ion chromatography (IC) has a proven track record in the determination of inorganic and organic anions and cations in complex matrices. Recently, application of IC to the separation and determination of bio-molecules such as amino acids, carbohydrates, nucleotides, proteins and peptides has also received much attention. The key to the determination of all of the above species in the most analytically challenging complex matrices is the ability to manipulate selectivity through control of stationary phase chemistry, mobile phase chemistry and the choice of detection method. This Tutorial Review summarises some of the most significant recent advances made in IC stationary phase technology. In particular, the review details stationary phases specifically designed for ion analysis in complex s le matrices, and considers in which direction future stationary phase development might proceed.
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B802693A
Abstract: For the first time photopolymerisation of polymer monoliths has been realised with UV-light emitting diodes (LEDs) as light source and demonstrated with polymethacrylate monoliths created in fused silica capillaries and plastic chips.
Publisher: American Chemical Society (ACS)
Date: 30-09-2019
DOI: 10.1021/ACSSENSORS.9B01583
Abstract: A facile one-step method was used to create a selective and sensitive electrode for dopamine (DA) detection based upon a stainless steel (SS) filament substrate and reduced graphene oxide (rGO). The electrode successfully and selectively detects DA in the presence of uric acid and ascorbic acid without the need for a Nafion coating. The proposed electrode is easy to fabricate, low-cost, flexible, and strong. The rGO-SS electrode could also be incorporated into a three-dimensional braided structure enabling DA detection in a two-electrode fiber system. The sensor is an excellent candidate for production of an affordable, robust, and flexible wearable and portable sensor and expands the application of textiles in point of care diagnostic devices.
Publisher: Elsevier BV
Date: 07-1999
DOI: 10.1016/S0021-9673(99)00735-9
Abstract: The retention mechanism of aliphatic and aromatic carboxylic acids in ion-exclusion chromatography has been investigated with consideration of simultaneous electrostatic repulsion effects and hydrophobic adsorption effects. A mathematical relationship between the retention factor of the analyte and the mobile-phase composition (sulfuric acid concentration and percentage of methanol), the type of analyte (pKa and hydrophobicity) and some physical characteristics of the stationary phase has been derived. Thirteen carboxylic acids (comprising mono- and alent, aliphatic and aromatic acids) were chosen and used to acquire retention data on three different cation-exchange stationary phases (in which the sulfonate functional groups are bound to polystyrene- inylbenzene, polymethacrylate or silica) using 14 mobile-phase compositions of varying pH and percent methanol. These retention data were used to derive the parameters necessary to solve the retention model using non-linear regression. In this way, a quantitative measure of the effects of adsorption phenomena on analyte retention were obtained. The model was then used to optimise the separation of nine carboxylic acids.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0AN01344G
Abstract: Efficient ‘on-thread’ isoelectric focusing of proteins, with direct on-thread detection using desorption electrospray ionisation mass spectrometry.
Publisher: Elsevier BV
Date: 08-2014
DOI: 10.1016/J.CHROMA.2014.06.044
Abstract: The idea of using diamond and diamond containing materials in separation sciences has attracted a strong interest in the past decade. The combination of a unique range of properties, such as chemical inertness, mechanical, thermal and hydrolytic stability, excellent thermal conductivity with minimal thermal expansion and intriguing adsorption properties makes diamond a promising material for use in various modes of chromatography. This review summarises the recent research on the preparation of diamond and diamond based stationary phases, their properties and chromatographic performance. Special attention is devoted to the dominant retention mechanisms evident for particular diamond containing phases, and their subsequent applicability to various modes of chromatography, including chromatography carried out under conditions of high temperature and pressure.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1LC00452B
Abstract: Fused filament fabrication (FFF)-3D printed polylactic acid capillary structure base on “body centre cubic (BCC)” log-pile like filament arrangements utilising the negative print space technique.
Publisher: American Chemical Society (ACS)
Date: 19-01-2016
DOI: 10.1021/ACS.ANALCHEM.5B03181
Abstract: We describe a new process for preparing porous solid phase microextraction (SPME) coatings by the sputtering of silicon onto silica fibers. The microstructure of these coatings is a function of the substrate geometry and mean free path of the silicon atoms, and the coating thickness is controlled by the sputtering time. Sputtered silicon structures on silica fibers were treated with piranha solution (a mixture of concd H2SO4 and 30% H2O2) to increase the concentration of silanol groups on their surfaces, and the nanostructures were silanized with octadecyldimethylmethoxysilane in the gas phase. The attachment of this hydrophobic ligand was confirmed by X-ray photoelectron spectroscopy and contact angle goniometry on model, planar silicon substrates. Sputtered silicon coatings adhered strongly to their surfaces, as they were able to pass the Scotch tape adhesion test. The extraction time and temperature for headspace extraction of mixtures of alkanes and alcohols on the sputtered fibers were optimized (5 min and 40 °C), and the extraction performances of SPME fibers with 1.0 or 2.0 μm of sputtered silicon were compared to those from a commercial 7 μm poly(dimethylsiloxane) (PDMS) fiber. For mixtures of alcohols, aldehydes, amines, and esters, the 2.0 μm sputtered silicon fiber yielded signals that were 3-9, 3-5, 2.5-4.5, and 1.5-2 times higher, respectively, than those of the commercial fiber. For the heavier alkanes (undecane-hexadecane), the 2.0 μm sputtered fiber yielded signals that were approximately 1.0-1.5 times higher than the commercial fiber. The sputtered fibers extracted low molecular weight analytes that were not detectable with the commercial fiber. The selectivity of the sputtered fibers appears to favor analytes that have both a hydrophobic component and hydrogen-bonding capabilities. No detectable carryover between runs was noted for the sputtered fibers. The repeatability (RSD%) for a fiber (n = 3) was less than 10% for all analytes tested, and the between-fiber reproducibility (n = 3) was 0-15%, generally 5-10%, for all analytes tested. The repeatabilities of our sputtered fibers and the commercial 7 μm PDMS fiber are essentially the same. Fibers could be used for at least 300 extractions without loss of performance. More than 50 compounds were identified in a gas chromatography-mass spectrometry headspace analysis of a real world botanical s le with the 2.0 μm fiber.
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B618386G
Abstract: A robust, compact, on-chip, electro-osmotic micro-pump (EOP) for micro-flow analysis, based on parallel, encased, 10 x 0.1 mm I.D. monolithic silica capillary columns has been developed. A 15 x 40 x 2 mm poly(methyl methacrylate) (PMMA) chip, containing a total of nine parallel EOP systems was fabricated, allowing the use of single, double or triple monolithic columns to produce increased flow as required. The monolithic silica was compatible with both aqueous and organic solvents without swelling or shrinking problems, with the triple column EOP capable of generating flow of up to 0.6 microL min(-1) under zero pressure load and over 0.1 microL min(-1) with an applied pressure of ca. 2.4 bar using an applied voltage of just 2 kV. Current generated at the 2 kV applied voltage for a 2 mM acetate buffer solution (pH 4.5) was under 4 microA, allowing stable, bubble-free flow. The developed triple column EOP was incorporated within a micro-fluidic chip (5.0 x 2.0 x 0.4 cm) integrated with a second single 10 x 0.1 mm column EOP, for combined s le injection and simple on-chip micro-flow analysis.
Publisher: WIT Press
Date: 18-05-2006
DOI: 10.2495/AIR06054
Publisher: Elsevier BV
Date: 08-2004
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B925915P
Publisher: American Chemical Society (ACS)
Date: 10-09-2020
Publisher: IEEE
Date: 08-2007
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B924152C
Abstract: Gold nanoparticles have been immobilised on a methacrylate monolith via grafted polymer chains terminated with amine groups, resulting in a homogenous and dense surface coverage.
Publisher: Springer Science and Business Media LLC
Date: 07-03-2016
Publisher: Springer Science and Business Media LLC
Date: 31-10-2013
Publisher: Elsevier BV
Date: 11-2018
DOI: 10.1016/J.ACA.2018.06.005
Abstract: A new high sensitivity deep-UV LED photometric detector with a z-type flow cell (45 nL or 180 nL) for miniaturised and portable capillary liquid chromatography (LC) was designed and fabricated to overcome sensitivity limitations due to short pathlength in on-capillary detectors. The new detector has a 10 mm geometric pathlength and uses high intensity light-emitting diodes (LED) as light sources in the deep-UV range (254 nm and 280 nm). No optical reference was necessary due to the low drift in the signal. Stray light was minimized by the use of an adjustable slit with a 0.5 mm pinhole. The direct relationship between absorbance and concentration was obtained using dichromate to evaluate the sensitivity and the linearity range of the detector. Performance of the miniaturised version was compared with that obtained from a commercial benchtop detector for capillary LC under the same conditions using the same optical z-cell. The miniaturised version exhibited a superior performance across all parameters, including 3 times higher effective pathlength, 4 times higher upper limit of detector linearity, and 2-5 times lower stray light levels. An application of the new detector was shown with the detection of l-dopa, l-tyrosine, norfenefrine, phenylephrine and tyramine, separated using capillary LC. The baseline noise level recorded was as low as 3.9 μAU. Further, the detector was applied in a miniaturised capillary LC for the indirect detection of common inorganic anions. In comparison to an on-capillary LED detector applied under similar chromatographic conditions, there was a 50 times higher signal to noise (S/N) ratio.
Publisher: Elsevier BV
Date: 07-2019
DOI: 10.1016/J.ACA.2019.02.048
Abstract: Chloride (Cl
Publisher: Elsevier BV
Date: 10-2002
DOI: 10.1016/S0021-9673(02)01193-7
Abstract: An investigation into the use of zwitterionic ion chromatography for the determination of inorganic anions in water s les was carried out. When using an ODS stationary phase precoated with Zwittergent 3-14 and a pure water mobile phase, the stability of the adsorbed coating was insufficient for quantitative work. Recycling of the water mobile phase was used to stabilise the zwitterionic coating, and resulted in improved retention time precision (15.2% RSD down to 2.4% RSD for nitrate). Post-detection cation- and anion-exchange columns in acid and hydroxide form removed s le ions from the recycling mobile phase, with the desorbed Zwittergent 3-14 passing through unretained and passing back through the pump to the analytical column. A 200-ml volume of mobile phase was recycled over a 3-week period with retention times for sulphate, chloride and nitrate standards injected at the start and end of the period varying less than 2.5%. The same system was then used with a mobile phase containing 2 mM Zwittergent 3-14. This resulted in further improvements in retention time (0.2-0.5% RSD, n = 10) and peak area precision (2.6-6.0% RSD, 1 mM standards) and improved peak efficiencies (2421-4047 N). The developed method was applied to water s les, and results compared to those obtained using anion-exchange chromatography. All s le cations were exchanged to sodium using an off-line cation-exchange procedure prior to injection.
Publisher: Elsevier BV
Date: 10-2018
DOI: 10.1016/J.CHROMA.2018.08.021
Abstract: The selectivity for 15 biogenic amines and amino acids shown by three capillary cation-exchange columns, IonPac CS19, CS12A and CS17 (250 × 0.4 mm ID, all from Thermo Fisher Scientific), exhibiting medium, medium low and ultra-low hydrophobicity, and either carboxylic or mixed carboxylic hosphonic acid functional groups, was investigated. A mixed mode retention mechanism was revealed with ion-exchange, hydrophobic and hydrogen bonding interactions contributing to retention of polar organic molecules on these phases. The relative impact of these interactions was evaluated via the effect of concentration and pH of the eluent (methanesulfonic acid) on the retention of fifteen structurally similar biogenic amines and amino acids. Strong hydrogen bonding interactions were observed between the solute amino acid carboxylic groups and cation-exchange groups from the ion-exchangers. This is the first time retention data correlated with logP data has revealed clustering of the solutes in two groups, according to the presence or absence of a carboxylic acid functional group. In addition, stronger retention behaviour was found for the IonPac CS12A cation-exchanger, containing both carboxylic and phosphonic functional groups. Further assessment of the orthogonality plots of retention factors for the three stationary phases revealed that the columns exhibited different complimentary selectivity that can be utilised to achieve specific separations.
Publisher: Royal Society of Chemistry (RSC)
Date: 1992
DOI: 10.1039/AP9922900399
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B702799K
Abstract: A solid phase extraction (SPE) method has been developed and applied in conjunction with a previously reported liquid chromatography tandem mass spectrometry (LC-MS-MS) procedure for the determination of illicit drugs and abused pharmaceuticals in treated wastewater and surface water s les at the ng L(-1) level. A full method validation was also performed and determined levels of analytical sensitivity were found to lie in the 1-10 ng L(-1) range using river water as a test s le matrix and a s le size of 500 mL. The developed procedure was successfully applied for the determination of the chosen analytes in wastewater treatment plants in Dublin, Ireland and rapidly expanding commuter towns in the surrounding counties. Cocaine was detected in 70% of the collected s les in the range of 25-489 ng L(-1), its primary metabolite, benzoylecognine (BZE) was also detected in the range of 22-290 ng L(-1). Other substances detected included morphine, Tempazepam and the primary metabolite of methadone.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4EM00631C
Abstract: This letter discusses the origins of certain components of dissolved organic matter.
Publisher: Wiley
Date: 30-06-2014
Abstract: Liquid chromatographic assays were developed using a mixed-mode column coupled in sequence with a hydrophilic interaction liquid chromatography column to allow the simultaneous comprehensive analysis of inorganic/organic anions and cations, active pharmaceutical ingredients, and excipients (carbohydrates). The approach utilized dual s le injection and valve-mediated column switching and was based upon a single high-performance liquid chromatography gradient pump. The separation consisted of three distinct sequential separation mechanisms, namely, (i) ion-exchange, (ii) mixed-mode interactions under an applied dual gradient (reversed-phase/ion-exchange), and (iii) hydrophilic interaction chromatography. Upon first injection, the Scherzo SS C18 column (Imtakt) provided resolution of inorganic anions and cations under isocratic conditions, followed by a dual organic/salt gradient to elute active pharmaceutical ingredients and their respective organic counterions and potential degradants. At the top of the mixed-mode gradient (high acetonitrile content), the mobile phase flow was switched to a preconditioned hydrophilic interaction liquid chromatography column, and the standard/s le was reinjected for the separation of hydrophilic carbohydrates, some of which are commonly known excipients in drug formulations. The approach afforded reproducible separation and resolution of up to 23 chemically erse solutes in a single run. The method was applied to investigate the composition of commercial cough syrups (Robitussin®), allowing resolution and determination of inorganic ions, active pharmaceutical ingredients, excipients, and numerous well-resolved unknown peaks.
Publisher: Elsevier BV
Date: 02-1999
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5OB01573A
Abstract: Polygodial, was efficiently extracted and isolated in gram-scale quantities (3.3% w/w) from Tasmannia lanceolata (Tasmanian native pepper) using a pressurised hot water extraction (PHWE) technique that utilises an unmodified household espresso machine.
Publisher: Elsevier BV
Date: 04-2005
DOI: 10.1016/J.CHROMA.2005.02.062
Abstract: Both particle packed (25 cm x 0.46 cm I.D. SUPELCOSIL 5 microm C18) and monolithic type (10 cm x 0.46 cm I.D. Merck Chromolith Performance C18) reversed-phase substrates were dynamically coated with a carboxybetaine type zwitterionic surfactant ((dodecyldimethyl-amino) acetic acid) and investigated as stationary phases for use in zwitterionic ion chromatography (ZIC). Investigations into eluent concentration and pH were carried out using KCl eluents containing 0.2 mM of the carboxybetaine surfactant to stabilise the column coatings. It was found that eluent concentration decreased anion retention whilst simultaneously increasing peak efficiencies, which may be due to the dissociation of intra- and inter-molecular salts of the carboxybetaine surfactant under higher ionic strength conditions. The Effect of eluent pH was an increase in anion retention with decreased eluent pH due to the increased protonation of the weak acid terminal group of the carboxybetaine, causing both a relative increase in the positive charge of the stationary phase and less repulsion of the anions by the dissociated weak acid group. The carboxybetaine-coated monolithic phase was applied to rapid anion separations using elevated flow rates and flow rate gradients.
Publisher: Elsevier BV
Date: 05-1997
Publisher: Wiley
Date: 12-12-2013
Abstract: Normal-phase high-performance counter-current chromatography (HPCCC) is used to obtain a preliminary fractionation of components in dissolved organic matter (DOM) from a freshwater source. The HPCCC solvent system involved a normal-phase approach with water/methanol (1:1) as the lower stationary phase and hexane/ethyl acetate (1:1) as the upper mobile phase. The critical experiment parameters were optimised: revolution speed 1800 rpm and flow rate 0.15 mL/min. Under these conditions 50 μL of a 0.50 mg/mL DOM solution was loaded. The detection wavelength was monitored at 330 nm in order to isolate the main portion of DOM, which includes substances such as carboxyl-rich alicyclic molecules. By optimising this system it was possible to isolate materials that, according to GC-MS, can be related to molecules with an analogous structural background. Where fraction analysis was not suitable for GC-MS, RP-HPLC with UV absorbance detection was used, showing unique chromatograms for each fraction at both 210 and 330 nm.
Publisher: Wiley
Date: 08-2009
Abstract: The application of scanning capacitively coupled contactless conductivity detection (SC 4 D) for the determination of pH dependant behaviour of two aminopolycarboxylates immobilised onto the surface of a monolithic capillary column is described. The use of SC 4 D to visualise changes in conductivity of the discrete zones of functional groups within monolithic capillary columns allows for the effects of immobilisation on the physicochemical properties of zones to be compared to that of the functional group in solution. The perturbation of the p K a values of the functional groups can be attributed to the change in chemical environment experienced by the functional group through the presence of local hydrogen bonding and surface induced effects. These bonds, both between adjacent functional groups and with the monolithic polymethacrylate scaffold, result in a modification of the electron density on the functional group and therefore a change in p K a . Changes in the p K a of N ‐(2‐acetamido)iminodiacetic acid (ADA) from 2.48 to 5.2 for one of the acidic protons, with little change in the p K a of the amine group, were observed, which correlates to similar changes in aggregated systems of aminopolycarboxylates. Similar results were obtained for the iminodiacetic acid (IDA) once immobilised onto the surface of the monolith. Furthermore, the ability to measure changes in the charge of such discrete zones of functional groups allows for the visualisation of complexation events occurring directly on‐column, where such complexes result in a change in charge of the functional group. This potentially useful technique is illustrated within for the formation of aminopolycarboxylate complexes with a selection of metal ions.
Publisher: Elsevier BV
Date: 09-2006
DOI: 10.1016/J.ACA.2006.05.101
Abstract: The use of a low pressure ion chromatograph based upon short (25 mm x 4.6 mm) surfactant coated monolithic columns and a low cost paired emitter-detector diode (PEDD) based detector, for the determination of alkaline earth metals in aqueous matrices is presented. The system was applied to the separation of magnesium, calcium, strontium and barium in less than 7min using a 0.15M KCl mobile phase at pH 3, with post-column reaction detection at 570 nm using o-cresolphthalein complexone. A comparison of the performance of the PEDD detector with a standard laboratory absorbance detector is shown, with limits of detection for magnesium and calcium using the low cost PEDD detector equal to 0.16 and 0.23 mg L(-1), respectively. Finally, the developed system was used for the determination of calcium and magnesium in a commercial spring water s le.
Publisher: Springer Science and Business Media LLC
Date: 24-06-2015
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1LC00179E
Abstract: A rapid, low-cost, and disposable microfluidic thread-based isotachophoresis method was developed for the purification and preconcentration of nucleic acids from biological s les, prior to their extraction and successful analysis using qPCR.
Publisher: Elsevier BV
Date: 06-2010
DOI: 10.1016/J.ACA.2010.04.033
Abstract: This review critically summarises recent novel and advanced achievements in the application of monolithic materials and related porous polymer gels in micro-fluidic devices appearing within the literature over the period of the last 5 years (2005-2010). The range of monolithic materials has developed rapidly over the past decade, with a erse and highly versatile class of materials now available, with each exhibiting distinct porosities, pore sizes, and a wide variety of surface functionalities. A major advantage of these materials is their ease of preparation in micro-fluidic channels by in situ polymerisation, leading to monolithic materials being increasingly utilised for a larger variety of purposes in micro-fluidic platforms. Applications of porous polymer monoliths, silica-based monoliths and related homogeneous porous polymer gels in the preparation of separation columns, ion-permeable membranes, preconcentrators, extractors, electrospray emitters, micro-valves, electrokinetic pumps, micro-reactors and micro-mixers in micro-fluidic devices are discussed herein. Procedures used in the preparation of monolithic materials in micro-channels, as well as some practical aspects of the micro-fluidic chip fabrication are addressed. Recent analytical/bioanalytical and catalytic applications of the final micro-fluidic devices incorporating monolithic materials are also reviewed.
Publisher: Elsevier BV
Date: 12-2013
DOI: 10.1016/J.JPBA.2013.08.003
Abstract: The comprehensive separation and detection of hydrophobic and hydrophilic active pharmaceutical ingredients (APIs), their counter-ions (organic, inorganic) and excipients, using a single mixed-mode chromatographic column, and a dual injection approach is presented. Using a mixed-mode Thermo Fisher Acclaim Trinity P1 column, APIs, their counter-ions and possible degradants were first separated using a combination of anion-exchange, cation-exchange and hydrophobic interactions, using a mobile phase consisting of a dual organic modifier/salt concentration gradient. A complementary method was also developed using the same column for the separation of hydrophilic bulk excipients, using hydrophilic interaction liquid chromatography (HILIC) under high organic solvent mobile phase conditions. These two methods were then combined within a single gradient run using dual s le injection, with the first injection at the start of the applied gradient (mixed-mode retention of solutes), followed by a second s le injection at the end of the gradient (HILIC retention of solutes). Detection using both ultraviolet absorbance and refractive index enabled the sensitive detection of APIs and UV-absorbing counter-ions, together with quantitative determination of bulk excipients. The developed approach was applied successfully to the analysis of a dry powder inhalers (Flixotide(®), Spiriva(®)), enabling comprehensive quantification of all APIs and excipients in the s le.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6RA05261D
Abstract: A low cost 3D stereolithography based printer has been used for a new polymer composite material with enhanced thermal properties containing 30 wt% micro-particulate diamond.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0AN90013C
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2AN35316D
Abstract: Polymer monolithic columns with controlled surface ligand density, providing stationary phase gradients within monolithic capillary columns, have been developed using photo-grafting through optical filters. Utilising commercially available cyclic olefin co-polymer (COC) films, the production of an optical filter capable of attenuating UV irradiation, in a tailored manner, was investigated. This novel optical filter was successfully applied to the surface modification of poly(BuMA-co-EDMA) monolithic columns in a multi-step grafting procedure. Fabricated columns were subjected to scanning capacitively coupled contactless conductivity (sC(4)D), to determine the distribution of the grafted functional groups, axially along the column. Further modification to produce a chelating stationary phase gradient of iminodiacetic acid (IDA) was demonstrated. To demonstrate the distribution of the IDA sites, a metal cation (Cu(2+)) was complexed to the IDA forming a chelate. Upon the formation of a complex of IDA with Cu(2+), an overall drop in conductive response was observed. The COC optical filter was also used in the fabrication of a grafted gradient of strong cation exchanger (SCX), sulphopropyl methacrylate (SPM) upon a polymer monolith, demonstrating the broader applicability of such a filter.
Publisher: Wiley
Date: 08-2009
Abstract: A glycidyl methacrylate‐ co ‐ethylene dimethacrylate monolith in capillary format (100 μm/id) has been grafted with chains of poly([2(methacryloyloxy)ethyl] trimethylammonium chloride (poly‐META) and applied to the ion‐chromatographic separation of selected inorganic anions. Grafting chains of META onto the generic monolithic scaffold resulted in a monolith with ‘electrolyte responsive flow permeability’, which manifested as increased permeability in the presence of electrolyte solutions. Using an eluent of 2 mM sodium benzoate and on‐column contactless conductivity detection, a test mixture of six common anions was isocratically separated and detected within 12 min, with the first four anions baseline resolved within a retention time window of 3.2 min. Retention time precision was ⪇1.2% for all anions tested. Separation efficiencies of 15 000 N/m were achieved for fluoride at 1 μL/min, with column efficiencies up to 29 500 N/m obtained at a lower flow rate of 100 nL/min. Furthermore, repeatability of the column modification procedure using photografting methods was acceptable, with retention times between replicate columns matching within 9%.
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C003584J
Abstract: The use of scanning capacitively coupled contactless conductivity detection for the evaluation of the structural homogeneity and density of both packed and monolithic stationary phases in micro-fluidic chips is presented here for the first time.
Publisher: Informa UK Limited
Date: 30-01-2020
Publisher: Elsevier BV
Date: 02-2002
DOI: 10.1016/S0378-4347(01)00557-6
Abstract: A simple and rapid chromatographic method for determination of nitrite, nitrate and thiocyanate is reported, and applied to the analysis of non-, medium and heavy smokers' urine s les. Ion-interaction liquid chromatography was carried out on a short 30 mm x 4.6 mm C18 column (3 microm particle size) with a mobile phase of 10 mM tetrabutylammonium phosphate in 20% MeOH. The chromatography was performed at an elevated temperature of 45 degrees C, at a flow-rate of 1 ml/min. Detection was by direct UV absorption at 230 nm. S le preparation involved centrifugation and dilution, followed by s le clean-up on a C18 solid-phase extraction cartridge. The developed method proved both precise (% RSD <2%) and sensitive (standard detection limits <0.1 mg/l), and yielded total run times of under 10 min when applied to urine analysis of smokers and non-smokers, with thiocyanate eluting in under 5 min.
Publisher: Elsevier BV
Date: 02-2020
DOI: 10.1016/J.ACA.2019.11.025
Abstract: A multi-material 3D printed microfluidic reactor with integrated heating is presented, which was applied within a manifold for the colorimetric determination of ammonium in natural waters. Graphene doped polymer was used to provide localised heating when connected to a power source, achieving temperatures of up to 120 °C at 12 V, 0.7 A. An electrically insulating layer of acrylonitrile butadiene styrene (ABS) polymer or a new microdiamond-ABS polymer composite was used as a heater coating. The microdiamond polymer composite provided higher thermal conductivity and uniform heating of the serpentine microreactor which resulted in greater temperature control and accuracy in comparison to pure ABS polymer. The developed heater was then applied and demonstrated using a modified Berthelot reaction for ammonium analysis, in which the microreactor was configured at a predetermined optimised temperature. A 5-fold increase in reaction speed was observed compared to previously reported reaction rates. A simple flow injection analysis set up, comprising the microfluidic heater along with an LED-photodiode based optical detector, was assembled for ammonium analysis. Two river water s les and two blind ammonium standards were analysed and estimated concentrations were compared to concentrations determined using benchtop IC. The highest relative error observed following the analysis of the environmental s les was 11% and for the blind standards was 5%.
Publisher: Springer Science and Business Media LLC
Date: 31-10-2019
Publisher: American Chemical Society (ACS)
Date: 28-09-2020
Publisher: Elsevier BV
Date: 04-2019
DOI: 10.1016/J.ACA.2018.10.066
Abstract: Electrochemical (EC) detection techniques in flow-based analytical systems such as flow injection analysis (FIA), capillary electrophoresis (CE), and liquid chromatography (LC) have attracted continuous interest over the last three decades, leading to significant advances in EC detection of a wide range of analytes in the liquid phase. In this context, the unique advantages of pulsed erometric detection (PAD) in terms of high sensitivity and selectivity, and electrode cleaning through the application of pulsed potential for noble metal electrodes (e.g. Au, Pt), have established PAD as an important detection technique for a variety of electrochemically active compounds. PAD is especially valuable for analytes not detectable by ultraviolet (UV) photometric detection, such as organic aliphatic compounds and carbohydrates, especially when used with miniaturised capillary and chip-based separation methods. These applications have been accomplished through advances in PAD potential waveform design, as well as through the incorporation of nanomaterials (NMs) employed as microelectrodes in PAD. PAD allows on-line pulsed potential cleaning and coupling with capillary or standard separation techniques. The NMs are largely employed in microelectrodes to speed up mass and electron transfer between electrode surfaces and to perform as reactants in EC analysis. These advances in PAD have improved the sensitive and selective EC detection of analytes, especially in biological s les with complex s le matrices, and detection of electro-inactive compounds such as aliphatic organic compounds (i.e., formic acid, acetic acid, maleic acids, and β-cyclodextrin complexes). This review addresses the fundamentals of PAD, the role of pulsed sequences in AD, the utilisation of different EC detectors for PAD, technological advancements in PAD waveforms, utilisation of microelectrodes in PAD techniques, advances in the use of NMs in PAD, the applications of PAD, and prospects for EC detection, with emphasis on PAD in flow-based systems.
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B414323J
Abstract: An ultra-short 1.0 x 0.46 cm carboxybetaine coated monolithic anion exchanger has been used with a new double gradient ion chromatography (DG-IC) technique. The novel monolithic column can be used with flow rate gradients giving excellent peak efficiencies, and retention times can be simultaneously reduced through combining flow gradients with an eluent pH gradient.
Publisher: Elsevier BV
Date: 07-2015
Publisher: Elsevier BV
Date: 04-2014
DOI: 10.1016/J.SCITOTENV.2013.12.123
Abstract: Reports concerning the quantitative analysis of pharmaceuticals in marine ecosystems are somewhat limited. It is necessary to determine pharmaceutical fate and assess any potential risk of exposure to aquatic species and ultimately, seafood consumers. In the work presented herein, analytical methods were optimised and validated for the quantification of pharmaceutical residues in wastewater effluent, receiving marine waters and marine mussels (Mytilus spp.). Selected pharmaceuticals included two non-steroidal anti-inflammatory drugs (NSAIDs) (diclofenac and mefenamic acid), an antibiotic (trimethoprim), an antiepileptic (carbamazepine) and a lipid regulator (gemfibrozil). This paper also presents the results of an in situ study in which caged Mytilus spp. were deployed at three sites on the Irish coastline over a 1-year period. In water s les, pharmaceutical residues were determined using solid phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The extraction of pharmaceuticals from mussel tissues used an additional pressurised liquid extraction (PLE) step prior to SPE and LC-MS/MS. Limits of quantification between 15 and 225 ng·L(-1) were achieved in wastewater effluent, between 3 and 38 ng·L(-1) in marine surface water and between 4 and 29 ng·g(-1) dry weight in marine mussels. Method linearity was achieved for pharmaceuticals in each matrix with correlation coefficients of R(2)≥0.976. All five selected pharmaceuticals were quantified in wastewater effluent and marine surface waters. This work has demonstrated the susceptibility of the Mytilus spp. to pharmaceutical exposure following the detection of pharmaceutical residues in the tissues of this mussel species at measurable concentrations.
Publisher: Elsevier BV
Date: 04-1997
Publisher: Informa UK Limited
Date: 20-08-2021
Publisher: Wiley
Date: 11-2007
Abstract: Capacitively coupled contactless conductivity detection (C4D) is presented as a novel and versatile means of visualising discrete zones of charged functional groups grafted onto polymer based monoliths. Monoliths were first formed within 100 microm UV-transparent fused silica capillaries. Photografting methods were subsequently used to graft a charged functional monomer, 2-acrylamido-2-methyl-1-propanesulfonic acid, onto discrete regions of the monolith using a photomask. Post-modification monolith evaluation involves scanning the C4D detector along the length of the monolith to obtain a profile of the exact spatial location of grafted charged functionalities with millimetre accuracy. The methodology was extended to the visualisation of several zones of immobilised protein (bovine serum albumin) using photografted azlactone groups to enable covalent attachment of the protein to the monolith at precise locations along its length. In addition, the extent of non-specific binding of protein to the ungrafted regions of the monolith due to hydrophobic interactions could be monitored as an increase in background conductivity of the stationary phase. Finally, the technique was cross-validated using digital photography in combination with a UV light source by immobilising green fluorescent protein in discrete zones and comparing the results obtained using both complementary techniques.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6RA11334F
Abstract: The formulation of new composite materials compatible with additive fabrication techniques is driving a revolution in the field of applied materials science.
Publisher: Elsevier BV
Date: 07-1996
Publisher: Elsevier BV
Date: 08-2001
DOI: 10.1016/S0021-9673(01)01095-0
Abstract: The optical characteristics of on-capillary photometric detectors for capillary electrophoresis were evaluated and five commercial detectors were compared. Plots of sensitivity (absorbance/concentration) versus absorbance obtained with a suitable testing solution yield both the linear range and the effective path length of the detector. The detector linearity is a crucial parameter when using absorbing electrolytes, such as for indirect photometric detection, and especially for highly absorbing electrolyte probe ions. The upper limits of the linear ranges (determined as 5% decline in sensitivity) for five commercial detectors ranged from 0.175 to 1.2 AU. The effective pathlength reflects the quality of the optical design of the detector and is equal to the capillary internal diameter only for a light beam passing exactly through the capillary centre, but becomes progressively shorter for imperfect optical designs. The determined effective pathlength for the five investigated detectors ranged from 49.7 to 64.6 microm for a 75 microm I.D. capillary.
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B502514A
Abstract: Significant deviations from classical van Deemter behaviour, indicative of turbulent flow liquid chromatography, has been recorded for mobile phases of varying viscosity on porous silica monolithic columns at elevated mobile phase flow rates.
Publisher: American Chemical Society (ACS)
Date: 22-08-2013
DOI: 10.1021/AM403222U
Abstract: The dynamic batch adsorption of methylene blue (MB), a widely used and toxic dye, onto nanocrystalline cellulose (NCC) and crushed powder of carbon monolith (CM) was investigated using the pseudo-first- and -second-order kinetics. CM outperformed NCC with a maximum capacity of 127 mg/g compared to 101 mg/g for NCC. The Langmuir isotherm model was applicable for describing the binding data for MB on CM and NCC, indicating the homogeneous surface of these two materials. The Gibbs free energy of -15.22 kJ/mol estimated for CM unravelled the spontaneous nature of this adsorbent for MB, appreciably faster than the use of NCC (-4.47 kJ/mol). Both pH and temperature exhibited only a modest effect on the adsorption of MB onto CM. The desorption of MB from CM using acetonitrile was very effective with more than 94 % of MB desorbed from CM within 10 min to allow the reusability of this porous carbon material. In contrast, acetonitrile was less effective than ethanol in desorbing MB from NCC. The two solvents were incapable of completely desorbing MB on commercial granular coal-derived activated carbon.
Publisher: Royal Society of Chemistry (RSC)
Date: 17-04-2003
DOI: 10.1039/B303467D
Abstract: Iminodiacetic acid has been covalently bonded to a bare silica monolith to produce the first reported high-performance monolithic chelating ion exchange column. Using the new column, separation and determination of traces of alkaline earth metal ions (low ppm) in high ionic strength s les (up to 2 M NaCl and KCl brines), could be achieved in under 40 s. At an eluent flow rate of 4 mL min(-1) retention time precision was < 1.2% (n = 9) for Mg(II) and Ca(II), with detector linearity (n = 5) over the range 2-10 mg L(-1) of between R2 = 0.985 and R2 = 0.995. In 1 M KCl and NaCl brine s les, detection limits of 0.2 mg L(-1) were possible.
Publisher: Royal Society of Chemistry (RSC)
Date: 1994
DOI: 10.1039/AN9941900937
Publisher: Trans Tech Publications Ltd
Date: 27-10-2010
DOI: 10.4028/WWW.SCIENTIFIC.NET/AST.76.100
Abstract: Spiropyran photochromic compounds can be switched using light exposure between a non-polar spiro form (SP) and a zwitterionic merocyanine form (MC) that is subject to protonation (MC-H+). It has recently been demonstrated by Walsh et al. that, under acidic conditions, electroosmotic flow (EOF) generated in vinyl based spiropyran monoliths can be modulated using light irradiation [1]. In this paper, we report a spiropyran-modified acrylate based monolith which is particularly sensitive to protonation in the MC form, producing a positively charged surface that converts to the unpolar SP form by exposure to white light. When the MC-H+ form is dominant, it produces a charged surface which enables a relatively high flow rate (up to 1.6 μl/min) to be generated under electroosmotic conditions. Upon exposure to white light, the concentration of MC-H+ decreases due to the photo-conversion to the uncharged SP form, with up to 20% reduction of the EOF. The process is reversible, and removal of the light source results in a flow increase back to the original rate. The ability to alter flow rates in micro-fluidic channels using light has very significant implications, as it could dramatically simplify the manner in which micro-flow systems are controlled.
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B901300H
Abstract: Capacitively coupled contactless conductivity detection (C4D) is utilised as a simple, rapid and non-invasive technique for the quantitative evaluation of the ion-exchange capacity of charged polymer monoliths in capillary format. A charged monomer, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) was photografted onto a 100 microm i.d. butyl methacrylate-co-ethylenedimethacrylate monolith in a number of discrete 10 mm zones. By varying the energy dose (J/cm2) during grafting of each zone, the grafting density and thus ion-exchange capacity could be precisely controlled. Ion-exchange capacity could be correlated with energy dose by measuring the conductive response of each grafted region using scanning C4D techniques. Repeatability of the scanning C4D method was excellent with % RSD values of 0.7% and 2.4% obtained for three replicate scans of the ungrafted and grafted regions of a single monolith, respectively. Repeatability of the photografting process on separate monoliths was also examined by comparison of C4D profiles. The spatial accuracy of photografting was probed using scanning C4D which could measure the conductive response of the monolith at measurement intervals as low as 1 mm along its entire length. Scanning C4D was also used for the real time visualisation of the equilibration of grafted zones to permit the optimisation of monolith washing procedures. Finally, scanning C4D was applied to the measurement of the ion-exchange capacity of butyl methacrylate-co-AMPS-co-ethylenedimethacrylate copolymers with a direct correlation between monolith conductive response and concentration of charged monomer in the polymerisation mixture. The longitudinal homogeneity of charge along the monolith was 0.3% RSD, demonstrating that the charged functional monomer was evenly dispersed throughout the bulk of the monolith. Ion-exchange capacity was cross validated chromatographically using breakthrough studies and found to closely correlate to within 1% of the measurements made by scanning C4D.
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B816958F
Abstract: The spatially controlled synthesis of poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolithic stationary phases in polyimide coated fused silica capillaries by visible light induced radical polymerisation using a three-component initiator and a 660 nm light emitting diode (LED) as a light source is presented here.
Publisher: American Chemical Society (ACS)
Date: 24-03-2017
DOI: 10.1021/ACS.ANALCHEM.7B00136
Abstract: Three-dimensional (3D) printing has emerged as a potential revolutionary technology for the fabrication of microfluidic devices. A direct experimental comparison of the three 3D printing technologies dominating microfluidics was conducted using a Y-junction microfluidic device, the design of which was optimized for each printer: fused deposition molding (FDM), Polyjet, and digital light processing stereolithography (DLP-SLA). Printer performance was evaluated in terms of feature size, accuracy, and suitability for mass manufacturing laminar flow was studied to assess their suitability for microfluidics. FDM was suitable for microfabrication with minimum features of 321 ± 5 μm, and rough surfaces of 10.97 μm. Microfluidic devices >500 μm, rapid mixing (71% ± 12% after 5 mm, 100 μL/min) was observed, indicating a strength in fabricating micromixers. Polyjet fabricated channels with a minimum size of 205 ± 13 μm, and a surface roughness of 0.99 μm. Compared with FDM, mixing decreased (27% ± 10%), but Polyjet printing is more suited for microfluidic applications where flow splitting is not required, such as cell culture or droplet generators. DLP-SLA fabricated a minimum channel size of 154 ± 10 μm, and 94 ± 7 μm for positive structures such as soft lithography templates, with a roughness of 0.35 μm. These results, in addition to low mixing (8% ± 1%), showed suitability for microfabrication, and microfluidic applications requiring precise control of flow. Through further discussion of the capabilities (and limitations) of these printers, we intend to provide guidance toward the selection of the 3D printing technology most suitable for specific microfluidic applications.
Publisher: Springer Science and Business Media LLC
Date: 06-1996
DOI: 10.1007/BF02267703
Publisher: Surface Science Society Japan
Date: 2009
Publisher: Elsevier BV
Date: 04-2000
DOI: 10.1016/S0021-9673(00)00196-5
Abstract: An ion-interaction reversed-phase liquid chromatographic method has been developed for the determination of cadmium at low microg/l concentrations in environmental water s les. Cadmium and other matrix metals were separated through on-column complexation with 8-hydroxyquinoline sulphonate, using an octadecylsilica column and a mobile phase containing 15% acetonitrile, 10-13 mM tetrabutylammonium hydroxide, 5 mM 8-hydroxyquinoline 5-sulphonic acid and 10 mM acetic acid-acetate buffer (pH 4.8-5.4). Under the above conditions Cd(II) could be easily resolved from excess concentrations of matrix metals and could be detected at concentrations as low as 2 microg/l using fluorescence detection at 500 nm (based upon a 100-microl injection). The method showed a slightly curved detector response over the range of interest [up to 1 mg/l Cd(II)] and was successfully applied to the determination of trace Cd(II) in water s les containing large excesses of Mg(II) and Zn(II) and other matrix metals.
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B400805G
Abstract: The progressive development of a micro-fluidic manifold for the chemiluminescent detection of copper in water s les, based on the measurement of light emitted from the Cu(ii) catalysed oxidation of 1,10-phenanthroline by hydrogen peroxide, is reported. Micro-fluidic manifolds were designed and manufactured from polymethylmethacrylate (PMMA) using three micro-fabrication techniques, namely hot embossing, laser ablation and direct micro-milling. The final laser ablated design incorporated a reagent mixing channel of dimensions 7.3 cm in length and 250 x 250 microm in width and depth (triangular cross section), and a detection channel of 2.1 cm in length and 250 x 250 microm in width and depth (total approx. volume of between 16 to 22 microL). Optimised reagents conditions were found to be 0.07 mM 1,10-phenanthroline, containing 0.10 M cetyltrimethylammonium bromide and 0.075 M sodium hydroxide (reagent 1 delivered at 0.025 mL min(-1)) and 5% hydrogen peroxide (reagent 2 delivered at 0.025 mL min(-1)). The s le stream was mixed with reagent 1 in the mixing channel and subsequently mixed with reagent 2 at the start of the detection channel. The laser ablated manifold was found to give a linear response (R(2) = 0.998) over the concentration ranges 0-150 microg L(-1) and be reproducible (% RSD = 3.4 for five repeat injections of a 75 microg L(-1) std). Detection limits for Cu(ii) were found to be 20 microg L(-1). Selectivity was investigated using a copper selective mini-chelating column, which showed common cations found in drinking waters did not cause interference with the detection of Cu(ii). Finally the optimised system was successfully used for trace Cu(ii) determinations in a standard reference freshwater s le (SRM 1640).
Publisher: Elsevier BV
Date: 11-2020
Publisher: Elsevier BV
Date: 2001
DOI: 10.1016/S0021-9673(00)01027-X
Abstract: The chromatographic behaviour of alkaline earth metals on iminodiacetic acid bonded silica was studied. It was found that the ionic strength of the eluent greatly affected both retention time and selectivity by controlling the extent to which either simple ion exchange or surface complexation was responsible for retention. With a 0.1 M KNO3 eluent, the retention order was Mg(II), Sr(II), Ca(II) and Ba(II), indicating a strong contribution to retention from ion exchange. However, when using a 1.5 M KNO3 eluent, Ba(II) was found to elute first, indicating complexation to be more dominant under these conditions (pH 4.2). The effect of the ionic strength of the s le was also studied and it was found that by matching the eluent cation with that of the s le matrix, efficient separations of alkaline earth metals in 1.0 M NaCl and KCl brines could be obtained without matrix system peaks. Using post-column reaction with o-cresolphthalein complexone, trace levels of Ca(II) and Mg(II) were determined in medicinal NaCl saline solution and laboratory-grade KCl.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9AN00329K
Abstract: This review covers advances and applications of open tubular capillary liquid chromatography (OT-LC) over the period 2007–2018.
Publisher: American Chemical Society (ACS)
Date: 06-01-2020
Abstract: Humidity sensing is of significant interest to monitor and control the moisture sensitive environments. Here, we developed a novel 3D printable composite consisting of boron-doped diamond (BDD) (60 wt %) and LiCl (2 wt %) in acrylonitrile butadiene styrene (ABS). SEM analysis of the composite material confirmed the uniform distribution of the BDD and presence of a thin layer of LiCl distributed throughout the matrix. The developed composite material was employed for simple and quick (∼2 min) fabrication of the humidity sensor using low cost fused deposition modeling (FDM) 3D printer. The unique composite material allowed the fabrication of one-piece 3D printed sensor in comparison to traditional multicomponent (e.g., support, sensitive film, and electrodes) humidity sensing devices. The resulting humidity sensor showed excellent sensitivity with up to 125-fold change in resistance for the range of 11-97% relative humidity. The quick response (60 s,
Publisher: American Chemical Society (ACS)
Date: 17-09-2018
DOI: 10.1021/ACS.ANALCHEM.8B02893
Abstract: Multimaterial 3D printing facilitates the rapid production of complex devices with integrated materials of varying properties and functionality. Herein, multimaterial fused deposition modeling (MM-FDM) 3D printing was applied to the fabrication of low-cost passive s ler devices with integrated porous membranes. Using MM-FDM 3D printing, the device body was produced using black polylactic acid, with Poro-Lay Lay-Felt filament used for the printing of the integrated porous membranes (rubber-elastomeric polymer, porous after removal of a water-soluble poly(vinyl alcohol) component). The resulting device consisted of two interlocking circular frames, each containing the integrated membrane, which could be efficiently sealed together without the need for additional O-rings, and prevented loss of enclosed microparticulate sorbent. Scanning electron microscopy (SEM) analysis of the purified composite filament confirmed the porous properties of the material, an average pore size of ∼30 nm. The printed passive s lers with various membrane thicknesses, including 0.5, 1.0, and 1.5 mm, were evaluated for their ability to facilitate the extraction of atrazine as the model solute onto the internal sorbent, under standard conditions. Gas chromatography-mass spectrometry was used to determine the uptake of atrazine by the device from standard water s les and also to evaluate any chemical leaching from the printed materials. The s ler with 0.5 mm thick membrane showed the best performance with 87% depletion and a s ling rate of 0.19 Ld
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B803038C
Abstract: A capacitively coupled contactless conductivity detector cell was designed and constructed suitable for standard HPLC 1.6 mm o.d. (1/16'') tubing and columns. Bode plots were acquired in order to determine the optimum input frequency for the new detector cell, with three feedback resistors of increasing resistance (1 MOmega, 3.3 MOmega and 4.7 MOmega) alternately fitted to maximize sensitivity. To evaluate the new detector geometry, a 190 mm x 0.381 mm i.d. (1.59 mm o.d.) column packed with Dionex OmniPac 8.5 microm PAX-100 anion exchange resin was used, with an eluent of 0.5 mM sodium benzoate containing 2% methanol, pumped at 20 microL min(-1), with detection taking place 'on-column'. Standard analytical performance criteria were used to compare the test detector with a commercially available TraceDec C(4)D capillary (360 microm o.d.) detector, with the new detector cell matching the performance of the commercial instrument in terms of linearity, sensitivity and reproducibility. In 'on-column' detection mode, the detector cell could be moved during (or between) chromatographic runs along the length of the packed column bed, to shorten the effective length of the column and thus reduce the retention time of strongly retained s le components, whilst maintaining the resolution of weakly retained components. In addition, the detector could also be applied to the evaluation of the stationary phase packing homogeneity by physically scanning the entire length of the micro-bore column with the moveable detector cell.
Publisher: American Chemical Society (ACS)
Date: 09-11-2017
DOI: 10.1021/ACS.ANALCHEM.7B03796
Abstract: Three main fabrication steps for microfluidic paper-based analytical devices (μPADs) were fully integrated with accurate geometrical alignment between the in idual steps in a simple and rapid manner. A wax printer for creating hydrophobic barriers was integrated with an inexpensive (ca. $300) electronic craft plotter/cutter for paper cutting, followed by colorimetric reagent deposition using technical pens. The principal shortcoming in the lack of accurate and precise alignment of the features created by these three in idual fabrication steps was addressed in this work by developing appropriate alignment procedures during the multistep fabrication process. The wax printing step was geometrically aligned with the following cutting and plotting (deposition) steps in a highly accurate and precise manner using optical scanning function of the plotter/cutter based on registration marks printed on the paper using the wax printer and scanned by the plotter/cutter. The accuracy and precision of alignment in a two-dimensional plane were quantified by cutting and plotting cross-shaped features and measuring their center coordinates relative to wax printed reference lines. The average accuracy along the X- and Y-axis was 0.12 and 0.16 mm for cutting and 0.19 and 0.17 mm for plotting, respectively. The potential of this approach was demonstrated by fabricating μPADs for instrument-free determination of cobalt in waters using distance-based readout, with excellent precision (%RSD = 5.7) and detection limit (LOD) of 2.5 ng and 0.5 mg/L (mass and concentration LODs, respectively).
Publisher: Springer Science and Business Media LLC
Date: 05-10-2013
DOI: 10.1007/S00216-013-7371-6
Abstract: An optimised and validated method for the determination of pharmaceutical residues in blue mussels (Mytilus spp.) is presented herein, as well as an investigation of the effect of cooking (by steaming) on any potential difference in human exposure risk. Selected pharmaceuticals included two non-steroidal anti-inflammatory drugs (diclofenac and mefenamic acid), an antibiotic (trimethoprim), an anti-epileptic (carbamazepine) and a lipid regulator (gemfibrozil). An in vivo exposure experiment was set up in the laboratory in which mussels were exposed either directly by injection (10 ng) or daily through spiked artificial seawater (ASW) over 96 h. In liquid matrices, pharmaceutical residues were either determined using liquid chromatography-tandem mass spectrometry (LC-MS/MS) directly, or in combination with solid-phase extraction (SPE) for analyte concentration purposes. The extraction of pharmaceuticals from mussel tissues used an additional pressurised liquid extraction step prior to SPE and LC-MS/MS. Limits of quantification of between 2 and 46 ng L(-1) were achieved for extracted cooking water and ASW, between 2 and 64 μg L(-1) for ASW in exposure tanks, and between 4 and 29 ng g(-1) for mussel tissue. Method linearities were achieved for pharmaceuticals in each matrix with correlation coefficients of R (2) > 0.975. A selection of exposed mussels was also cooked (via steaming) and analysed using the optimised method to observe any effect on detectable concentrations of parent pharmaceuticals present. An overall increase in pharmaceutical residues in the contaminated mussel tissue and cooking water was observed after cooking.
Publisher: American Chemical Society (ACS)
Date: 03-04-2023
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B407483A
Abstract: A 1.0 x 0.4 cm silica based monolithic anion exchanger has been produced and evaluated for use within a miniature gradient suppressed ion chromatography system based upon low-pressure micro-scale peristaltic pumps.
Publisher: Springer Science and Business Media LLC
Date: 05-07-2009
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B606942H
Abstract: The use of radial (across) capillary column capacitively coupled contactless conductivity detection is demonstrated as a simple and rapid technique for visualisation of stationary phase longitudinal coverage and coating stability in capillary ion exchange chromatography.
Publisher: Informa UK Limited
Date: 09-2006
Publisher: Elsevier BV
Date: 05-2011
Publisher: Elsevier BV
Date: 08-2020
Publisher: Elsevier BV
Date: 07-2011
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8AN01330F
Abstract: In this work we evaluated a novel microreactor prepared using a surface modified, high surface-to-volume ratio multi-lumen fused silica capillary (MLC).
Publisher: Elsevier BV
Date: 06-2010
DOI: 10.1016/J.CHROMA.2010.04.036
Abstract: Two rapid, sensitive and quantitative methods for the determination of the cysteine and cystine ratio in complex defined media feedstock using monolithic reversed-phase liquid chromatography (RPLC) and RPLC-MS are presented. Cysteine is pre-derivatised with purified 2-chloro-1-methylquinolinium tetrafluoroborate (CMQT) and separated from other derivatisation products on a narrow-bore 50mmx2mm I.D. monolithic C(18) column with UV detection at 355nm. For reversed-phase LC (RPLC) the separation is carried out isocratically using a mobile phase of 50mM trichloroacetic acid (TCA) adjusted to pH 2.5 with lithium hydroxide (LiOH) and acetonitrile (83:14) pumped at 1.5mL/min with an elevated column temperature. For RPLC-MS an ammonium acetate and acetonitrile gradient method was developed with a reduced flow rate of 0.3mL/min. The treatment of the s les consisted of iding them into two aliquots, the first aliquot is analysed for cysteine and the second aliquot is analysed for cystine after its quantitative reduction to cysteine using tris(2-carboxyethyl)phosphine (TCEP). Both methods are linear, with R(2)>0.999 for 0.25-500microM for cysteine and 0.25-250microM for cystine using the LC-UV method, sensitive, with detection limit of 36nM for cysteine, and precise, with < or =1.1% RSD for both retention time and peak area (n=6). S les (n=31) of an industry standard and supplied chemically defined media feedstock were analysed, finding cysteine ranging from 1.56 to 2.26microg/mL and cystine from 1062.02 to 1348.13microg/mL.
Publisher: Royal Society of Chemistry
Date: 2019
Publisher: Springer Science and Business Media LLC
Date: 22-08-2012
Publisher: Elsevier BV
Date: 08-2013
Publisher: Elsevier BV
Date: 07-2002
DOI: 10.1016/S0021-9673(02)00652-0
Abstract: The unusual selectivity of a methylene succinic (itaconic) acid modified polymeric column was investigated for the separation of alkali, alkaline earth, transition and heavy metals employing non-chelating inorganic eluents. The retention of selected metal ions on the column was investigated with simple HNO3 eluents and eluents prepared from KNO3 and KCl salts of varying pH (adjusted using HNO3). From these studies both the effect of eluent ionic strength and pH upon retention was evaluated for the itaconic acid stationary phase. The results obtained showed that despite slow exchange kinetics causing poor efficiencies, acceptable baseline separations of selected alkaline earth and transitions could be obtained under optimum conditions (the baseline separation of Mg(II), Ca(II), Mn(II), Cd(II), Zn(II) and Co(II) was possible using a 15 mM KNO3-5 mM KCl eluent at pH 3.50 in under 25 min). The use of an simple ionic strength step gradient was shown that facilitated the addition of Pb(II) to the above group of metal ions. An investigation into the effect of temperature upon peak efficiency and retention showed increased column temperature could be used to improve the resolution of closely eluting metal ions such as Ca(II) and Sr(II) and Ca(II) and Mn(II).
Publisher: Trans Tech Publications, Ltd.
Date: 2012
DOI: 10.4028/WWW.SCIENTIFIC.NET/AMR.445.436
Abstract: This paper presents a fast fabrication process of microfluidic channels with quartz substrates. Microchannels were ablated on the surface of quartz s les with a CO 2 laser. Double sided Pressure Sensitive Adhesive (PSA) was applied to bond the s les with scribed microchannels to flat glass sheets. Dimensions of the fabricated channels were characterised with optical microscopy and laser profilometry. The recorded data was modelled with a BoxBehnken experiment design using Response Surface Methodology. Characterisation included also the measurement of optical transmission through the processed glass and measurement of flow rate through the fabricated channels. With an average width of 165 µm and depth of 280µm, fabricated channels had appropriate dimensions for a range of microfluidic applications. A significant width of the laser processed channels provided 100% transmission for a wide range of the optical spectrum. These fabricated channels were also shown to not significantly retard the fluid flow rate thus making these channels applicable for integration into numerous detection systems for chemical separation applications.
Publisher: Elsevier BV
Date: 08-1997
Publisher: Bentham Science Publishers Ltd.
Date: 30-07-2015
Publisher: Springer Science and Business Media LLC
Date: 28-04-2020
DOI: 10.1038/S41598-020-63785-Z
Abstract: The delivery of bioactive molecules (drugs) with control over spatial distribution remains a challenge. Herein, we demonstrate for the first time an electrofluidic approach to controlled delivery into soft tissue models based on gelatin methacryloyl (GelMA) hydrogels. This was achieved using a surgical suture, whereby transport of bioactive molecules, including drugs and proteins, was controlled by imposition of an electric field. Commonly employed surgical sutures or acrylic threads were integrated through the hydrogels to facilitate the directed introduction of bioactive species. The platform consisted of two reservoirs into which the ends of the thread were immersed. The anode and cathode were placed separately into each reservoir. The thread was taken from one reservoir to the other through the gel. When current was applied, biomolecules loaded onto the thread were directed into the gel. Under the same conditions, the rate of movement of the biomolecules along GelMA was dependent on the magnitude of the current. Using 5% GelMA and a current of 100 µA, 2 uL of fluorescein travelled through the hydrogel at a constant velocity of 7.17 ± 0.50 um/s and took less than 8 minutes to exit on the thread. Small molecules such as riboflavin migrated faster (5.99 ± 0.40 μm/s) than larger molecules such as dextran (2.26 ± 0.55 μm/s with 4 kDa) or BSA (0.33 ± 0.07 μm/s with 66.5 kDa). A number of commercial surgical sutures were tested and found to accommodate the controlled movement of biomolecules. Polyester, polyglactin 910, glycolide/lactide copolymer and polyglycolic acid braided sutures created adequate fluid connection between the electrodes and the hydrogel. With a view to application in skin inflammatory diseases and wound treatment, wound healing, slow and controlled delivery of dexamethasone 21-phosphate disodium salt (DSP), an anti-inflammatory prodrug, was achieved using medical surgicryl PGA absorbable suture. After 2 hours of electrical stimulation, still 81.1% of the drug loaded was encapsulated within the hydrogel.
Publisher: Elsevier BV
Date: 10-1996
Publisher: American Chemical Society (ACS)
Date: 22-12-2018
DOI: 10.1021/ACS.ANALCHEM.7B03778
Abstract: Effect of column geometry on the liquid chromatographic separations using 3D printed liquid chromatographic columns with in-column polymerized monoliths has been studied. Three different liquid chromatographic columns were designed and 3D printed in titanium as 2D serpentine, 3D spiral, and 3D serpentine columns, of equal length and i.d. Successful in-column thermal polymerization of mechanically stable poly(BuMA-co-EDMA) monoliths was achieved within each design without any significant structural differences between phases. Van Deemter plots indicated higher efficiencies for the 3D serpentine chromatographic columns with higher aspect ratio turns at higher linear velocities and smaller analysis times as compared to their counterpart columns with lower aspect ratio turns. Computational fluid dynamic simulations of a basic monolithic structure indicated 44%, 90%, 100%, and 118% higher flow through narrow channels in the curved monolithic configuration as compared to the straight monolithic configuration at linear velocities of 1, 2.5, 5, and 10 mm s
Publisher: Springer Science and Business Media LLC
Date: 18-02-2020
Publisher: Inderscience Publishers
Date: 2010
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5EM00223K
Abstract: This review presents an overview of the separation techniques applied to the complex challenge of dissolved organic matter characterisation.
Publisher: American Chemical Society (ACS)
Date: 09-2009
DOI: 10.1021/ED086P1085
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2AN00287F
Abstract: This research describes a nanomaterial-assisted TB-ITP setup for the clean-up, preconcentration, and trapping of alkaloids in biological fluids, followed by their on-thread DESI-MS determination.
Publisher: Elsevier BV
Date: 09-2014
Publisher: Elsevier BV
Date: 10-2023
Publisher: American Chemical Society (ACS)
Date: 11-06-2019
DOI: 10.1021/ACS.ANALCHEM.9B01335
Abstract: Ultraviolet (UV)-light-emitting diodes (LEDs) are now widely used in analytical absorbance-based detectors as compared to conventional UV l s, they offer lower cost, faster response time, and higher photon conversion efficiency. However, current generation deep-UV-LEDs produce excess heat when operated at normal operating currents, which affects output stability and reduces their overall performance and lifespan. Herein a 3D printed liquid cooling interface has been developed for a deep-UV-LED-based optical detector, for capillary format flow-through detection. The interface consists of a circular channel that is tightly wrapped around the LED to provide active liquid cooling. The design also facilitates easy plug-and-play assembly of the various essential components of the detector: specifically, a 255 nm UV-LED, a capillary Z-cell, and a broadband UV photodiode (PD). The unique liquid cooling interface improved the performance of the detector by reducing the LED temperature up to 22 °C, increasing the spectral output up to 34%, decreasing the required stabilization time by up to 6-fold, and reducing the baseline noise and limits of detection (LODs) by a factor of 2. The detector was successfully used within a capillary HPLC system and could offer a miniaturized, rapidly stabilized, highly sensitive, and low-cost alternative to conventional UV detectors.
Publisher: Elsevier BV
Date: 10-2019
DOI: 10.1016/J.CHROMA.2019.05.036
Abstract: A low cost, UV absorbance detector incorporating a 235 nm light emitting diode (LED) for portable ion chromatography has been designed and fabricated to achieve rapid, selective detection of nitrite and nitrate in natural waters. The optical cell was fabricated through micromilling and solvent vapour bonding of two layers of poly (methyl methacrylate) (PMMA). The cell was fitted within a 3D printed housing and the LED and photodiode were aligned using 3D printed holders. Isocratic separation and selective detection of nitrite and nitrate was achieved in under 2.5 min using the 235 nm LED based detector and custom electronics. The design of the new detector assembly allowed for effective and sustained operation of the deep UV LED source at a low current (<10 mA), maintaining consistent and low LED temperatures during operation, eliminating the need for a heat sink. The detector cell was produced at a fraction of the cost of commercial optical cells and demonstrated very low stray light (0.01%). For retention time and peak area repeatability, RSD values ranged from 0.75 to 1.10 % and 3.06-4.19 %, respectively. Broad dynamic linear ranges were obtained for nitrite and nitrate, with limits of detection at ppb levels. The analytical performance of the IC set up with optical cell was compared to that of an ISO-accredited IC through the analysis of five various water s les. Relative errors not exceeding 6.86% were obtained for all s les. The detector was also coupled to a low pressure, low cost syringe pump to assess the potential for use within a portable analytical system. RSD values for retention time and peak area using this simple configuration were <1.15% and <3.57% respectively, highlighting repeatability values comparable to those in which a commercial HPLC pump was used.
Publisher: American Chemical Society (ACS)
Date: 04-12-2010
DOI: 10.1021/AC902376V
Abstract: This work for the first time combines three on-capillary detection methods, namely, capacitively coupled contactless conductometric (C(4)D), photometric (PD), and fluorimetric (FD), in a single (identical) point of detection cell, allowing concurrent measurements at a single point of detection for use in capillary electrophoresis, capillary electrochromatography, and capillary/nanoliquid chromatography. The novel design is based on a standard 6.3 mm i.d. fiber-optic SMA adapter with a drilled opening for the separation capillary to go through, to which two concentrically positioned C(4)D detection electrodes with a detection gap of 7 mm were added on each side acting simultaneously as capillary guides. The optical fibers in the SMA adapter were used for the photometric signal (absorbance), and another optical fiber at a 45 degrees angle to the capillary was applied to collect the emitted light for FD. Light emitting diodes (255 and 470 nm) were used as light sources for the PD and FD detection modes. LOD values were determined under flow-injection conditions to exclude any stacking effects: For the 470 nm LED limits of detection (LODs) for FD and PD were for fluorescein (1 x 10(-8) mol/L) and tartrazine (6 x 10(-6) mol/L), respectively, and the LOD for the C(4)D was for magnesium chloride (5 x 10(-7) mol/L). The advantage of the three different detection signals in a single point is demonstrated in capillary electrophoresis using model mixtures and s les including a mixture of fluorescent and nonfluorescent dyes and common ions, underivatized amino acids, and a fluorescently labeled digest of bovine serum albumin.
Publisher: Elsevier BV
Date: 08-2001
Publisher: Springer Science and Business Media LLC
Date: 17-12-2014
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B602846B
Abstract: A novel low power, low cost, highly sensitive, miniaturized light emitting diode (LED) based flow detector has been used as optical detector for the detection of s le components in high performance liquid chromatography (HPLC). This colorimetric detector employs two LEDs, one operating in normal mode as a light source and the other is reverse biased to work as a light detector. Instead of measuring the photocurrent directly, a simple timer circuit is used to measure the time taken for the photocurrent generated by the emitter LED (lambda(max) 500 nm) to discharge the detector LED (lambda(max) 621 nm) from 5 V (logic 1) to 1.7 V (logic 0) to give digital output directly without using an A/D converter. Employing a post-column reagent method, a Nucleosil 100-7 column (functionalized with iminodiacetic acid (IDA) groups) was used to separate a mixture of transition metal complexes, manganese(II) and cobalt(II) in 4-(2-pyridylazo)-resorcinol (PAR). All optical measurements were taken by using both the in-built HPLC variable wavelength detector and the proposed paired-emitter-detector-diode (PEDD) optical detector configured in-line for data comparison. The concentration range investigated using the PEDD was found to give a linear response to the Mn(II) and Co(II) PAR complexes. The effects of flow rate and emitter LED light source intensity were investigated. Under optimised conditions the PEDD detector offered a linear range of 0.9-100 microM and LOD of 0.09 microM for Mn-PAR complex. A linear range of 0.2-100 microM and LOD of 0.09 microM for Co-PAR complex was achieved.
Publisher: Elsevier BV
Date: 11-2006
DOI: 10.1016/J.CHROMA.2006.07.068
Abstract: A method has been developed for the determination of zinc pyrithione (ZnPT) in environmental water s les using monolithic reversed-phase silica columns for rapid on-line large volume solid phase extraction in tandem with on-line matrix removal using sacrificial strong anion exchange (SAX) columns. This is coupled with reversed-phase liquid chromatography with atmospheric pressure chemical ionisation mass spectrometric detection. Limits of detection in spiked river water s les, using a 200 mL preconcentration volume, were determined as 18 ng L(-1), with a limit of quantitation of 62 ng L(-1). The percentage recovery from spiked river water was found to be 72+/-9 (n=3 extractions), whilst overall method precision, following 10 repeat complete analyses was found to be 27% RSD at 1 microg L(-1). Linearity was determined over the concentration range of 0.25-10 microg L(-1) and the calculated regression coefficient was R(2)=0.9802. The method was used to investigate the environmental fate of zinc pyrithione in waters and its partition coefficient between sediment and water phases.
Publisher: Elsevier BV
Date: 04-2015
DOI: 10.1016/J.CHROMA.2015.02.069
Abstract: The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated in normal phase mode of high performance liquid chromatography. Purified nonporous irregular shape particles of average particles size 1.2 μm and specific surface area 5.1 m(2) g(-1) were used for packing 100×4.6 mm ID or 50×4.6 mm ID stainless steel columns. The retention behaviour of several classes of compounds including alkyl benzenes, polyaromatic hydrocarbons (PAH), alkylphenylketones, phenols, aromatic acids and bases were studied using n-hexane-2-propanol mixtures as mobile phase. The results are compared with those observed for microdispersed sintered detonation nanodiamond (MSDN) and porous graphitic carbon (PGC). HPHT diamond revealed distinctive separation selectivity, which is orthogonal to that observed for porous graphitic carbon while selectivities of HPHT diamond and microdispersed sintered detonation nanodiamonds are similar. Owing to non-porous particle nature, columns packed with high pressure high temperature diamond exhibited excellent mass transfer and produce separations with maximum column efficiency of 128,200 theoretical plates per meter.
Publisher: Elsevier BV
Date: 11-1997
Publisher: Wiley
Date: 07-2004
Abstract: A 10 cm silica monolith has been modified with iminodiacetic acid (IDA) groups and characterised for its selectivity toward alkali, alkaline earth, and selected transition metal cations. Physical characterisation of the modified monolith found non‐homogeneous modification along the length of the monolith, although sufficient capacity was achieved to facilitate significant retention of alkaline earth and transition/heavy metal ions over a range of eluent pH and ionic strength conditions. For alkaline earth and transition/heavy metal ions, selectivity of the 10 cm IDA monolith closely matched that seen with a 25 cm IDA modified silica gel particle packed column, although the separation of alkali metal ions was noticeably poorer on the monolithic column. Peak efficiencies for most metal ions were of a similar order for both column types, except for Zn(II), which showed significant peak broadening on the IDA monolithic column.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1AN15137A
Abstract: The in situ preparation of ethylene dimethacrylate porous polymer monoliths within 20 μL polypropylene pipette tips, bound via surface grafted methacrylate anchor sites, is reported. Gold nano-particles (AuNPs) were immobilised onto the monolith pore surface utilising azlactone chemistry and coverage verified using field emission scanning electron microscopy. Erythrina cristagalli lectin (ECL) was immobilised upon the attached AuNPs via a bio-functional linker. The ECL-modified tip was successfully applied for the enrichment of galactosylated protein (desialylated transferrin) versus a non-galactosylated protein (ribonuclease B) due to the specificity of ECL. Reversed-phase capillary HPLC was used to validate the efficiency and selectivity of the developed micro-extraction phase which resulted in an increase in extraction recovery of ∼95% due to the AuNP enhanced surface area. Further specificity of the ECL-modified tip was demonstrated with a complex mixture of non-glycosylated and glycosylated proteins with differing terminal sugar structures. Finally, the lectin affinity phase was applied to a galactosylated glycoproteins spiked Escherichia coli cell lysate to successfully demonstrate matrix tolerance.
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B810080B
Publisher: American Chemical Society (ACS)
Date: 09-02-2017
DOI: 10.1021/ACS.ANALCHEM.6B04546
Abstract: Through optimization of the printing process and orientation, a suitably developed surface area has been realized upon a 3D printed polymer substrate to facilitate chromatographic separations in a planar configuration. Using an Objet Eden 260VS 3D printer, polymer thin layer chromatography platforms were directly fabricated without any additional surface functionalization and successfully applied to the separation of various dye and protein mixtures. The print material was characterized using gas chromatography coupled to mass spectrometry and spectroscopic techniques such as infrared and Raman. Preliminary studies included the separation of colored dyes, whereby the separation performance could be visualized optically. Subsequent separations were achieved using fluorescent dyes and fluorescently tagged proteins. The separation of proteins was affected by differences in the isoelectric point (pI) and the ion exchange properties of the printed substrate. The simple chromatographic separations are the first achieved using an unmodified 3D printed stationary phase.
Publisher: Elsevier BV
Date: 06-2009
Publisher: Springer Science and Business Media LLC
Date: 31-10-2022
DOI: 10.1007/S10404-022-02603-6
Abstract: Textile-based microfluidics offer new opportunities for developing low-cost, open surface-assessable analytical systems for the electrophoretic analysis of complex chemical and biological matrixes. In contrast to electrophoretic fluidic transport in typical chip-based enclosed capillaries where direct access to the s le zone during analysis is a real challenge. Herein, we demonstrate that electrophoretic selectivity could be easily manipulated on these inverted low-cost bespoke textile substrates via a simple surface-functionalization to manipulate, redirect, extract, and characterize charged analytes. This simple approach enables significant improvement in the electrophoretic separation and isotachophoretic (ITP) preconcentration of charged solutes at the surface of open surface-accessible 3D textile constructs. In this work, polyester 3D braided structures have been developed using the conventional braiding technique and used as the electrophoretic substrates, which were modified by dip-coating with polycationic polymers such as chitosan and polyethyleneimine (PEIn). The surface functionalization resulted in the modulation of the electroosmotic flow (EOF) and electrophoretic mobilities of the charged solutes with respect to the unmodified substrates. Chitosan outperformed PEIn in terms of efficient electrophoretic separation and isotachophoretic stacking of an anionic solute. However, PEIn modification resulted in significant suppression of the EOF over a broad range of pH values from 3 to 9 and exhibited fast EOF at acidic pH compared to controlled polyester, which could be promising for the analysis of basic proteins. These findings suggest a great potential for the development of affordable surface-accessible textile-based analytical devices for controlling the specific migration, direction, analysis time, and separation and preconcentration of charged analytes. Graphical abstract
Publisher: Informa UK Limited
Date: 22-05-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 26-03-2003
DOI: 10.1039/B300340J
Abstract: The effect of column temperature upon the retention of metal ions on sulfonated and mono-, di-, and amino-carboxylated cation exchange columns has been investigated. The retention of alkali, alkaline earth and transition metal ions on each of the above types of cation exchanger was studied over the temperature range 19-65 degrees C. A major difference between the behaviour of mono- and alent metal ions was shown on each of the above stationary phases, with the monovalent alkali metals exhibiting clearly exothermic behaviour (a decrease in retention with increased temperature) under acidic eluent conditions and an apparent relationship between retention factor and the magnitude of the temperature effect. The effect of temperature upon alkaline earth metal ions was less defined, although strongly endothermic behaviour (increase in retention with temperature) could be seen on all stationary phases through correct choice of eluent. The transition metal ions studied showed endothermic behaviour on all four stationary phases, with the sulfonated column unexpectedly showing the largest increases in retention. The above behaviour can be partially explained through the dominance of the type of solute-stationary phase interaction governing retention. In several of the above columns, both ion-exchange and surface complexation interactions can occur, with the effects of temperature indicating which process dominates under specific eluent conditions.
Publisher: Elsevier BV
Date: 12-2006
DOI: 10.1016/J.TALANTA.2006.02.026
Abstract: A simplified preconcentration method for a range of ultra-trace level pharmaceuticals in natural waters has been developed. Solid phase extraction was performed on-line using a micro-reversed-phase monolithic silica column, allowing for very rapid trace enrichment from large volume (500ml) s les with minimal s le handling. Acceptable recoveries of >70% were obtained for the majority of compounds investigated and the monolithic columns could be washed and conditioned on-line with no s le carryover and used reproducibly for up to eight extractions each. The on-line SPE-LC-UV method was coupled to electrospray ionisation ion trap mass spectrometry (ESI-MS) to increase both selectivity and specificity. Detection limits were determined in spiked river and tap water s les and found to lie in the low ng/l region using s le volumes of 500ml, loaded at a flow rate of 10ml/min, and therefore, were suitable for ultra trace analysis.
Publisher: Elsevier BV
Date: 04-2005
Publisher: American Chemical Society (ACS)
Date: 09-01-2019
Abstract: A relative lack of printable materials with tailored functional properties limits the applicability of three-dimensional (3D) printing. In this work, a diamond-acrylonitrile butadiene styrene (ABS) composite filament for use in 3D printing was created through incorporation of high-pressure and high-temperature (HPHT) synthetic microdiamonds as a filler. Homogenously distributed diamond composite filaments, containing either 37.5 or 60 wt % microdiamonds, were formed through preblending the diamond powder with ABS, followed by subsequent multiple fiber extrusions. The thermal conductivity of the ABS base material increased from 0.17 to 0.94 W/(m·K), more than five-fold following incorporation of the microdiamonds. The elastic modulus for the 60 wt % microdiamond containing composite material increased by 41.9% with respect to pure ABS, from 1050 to 1490 MPa. The hydrophilicity also increased by 32%. A low-cost fused deposition modeling printer was customized to handle the highly abrasive composite filament by replacing the conventional (stainless-steel) filament feeding gear with a harder titanium gear. To demonstrate improved thermal performance of 3D printed devices using the new composite filament, a number of composite heat sinks were printed and characterized. Heat dissipation measurements demonstrated that 3D printed heat sinks containing 60 wt % diamond increased the thermal dissipation by 42%.
Publisher: Elsevier
Date: 2013
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B803010C
Abstract: A major Irish study, based upon more than 8000 s les collected over the measurement period of 22 years, for sulfur dioxide (SO2-S), sulfate (SO4-S) and nitrogen dioxide (NO2-N) concentrations (microg m(-3)) within air, and the ionic composition of precipitation s les based on sodium (Na+), potassium (K+), magnesium (Mg2+), calcium (Ca2+), chloride (Cl-), sulfate (SO4-S), non-sea salt sulfate (nssSO4-S), ammonium (NH4-N), and nitrate (NO3-N) weighted mean concentrations (mg l(-1)), has been completed. For the air s les, the sulfur dioxide and sulfate concentrations decreased over the s ling period (1980-2004) by 75% and 45%, respectively, whereas no significant trend was observed for nitrogen dioxide. The highest concentrations for sulfur dioxide, sulfate and nitrogen dioxide were associated with wind originating from the easterly and northeasterly directions i.e. those influenced by Irish and European sources. The lowest concentrations were associated with the westerly directions i.e. for air masses originating in the North Atlantic region. This was further verified with the use of backward (back) trajectory analysis, which allowed tracing the movement of air parcels using the European Centre for Medium range Weather Forecasting (ECMWF) ERA-40 re-analysis data. High non-sea salt sulfate levels were being associated with air masses originating from Europe (easterlies) with lower levels from the Atlantic (westerlies). With the precipitation data, analysis of the non-sea salt sulfate concentrations showed a decrease by 47% since the measurements commenced.
Publisher: Wiley
Date: 07-2004
Abstract: Short permanently coated reversed‐phase silica based monolithic columns have been investigated for the rapid separation of inorganic anions and cations. One 2.5×0.46 cm column was permanently coated with didodecyldimethylammonium (DDAB), for anion analysis and a second 5.0×0.46 cm column was coated with dioctylsulphosuccinnate (DOSS), for cation analysis. The use of a single combined eluent of 2.5 mM phthalate/1.5 mM ethylenediamine, at flow rates of between 4.0 and 8.0 mL/min, resulted in the rapid separation of 8 anions (in under 100 s) and 5 cations (in under 100 s) on the above columns when used in idually, with detection limits for common anions ranging from approximately 0.25 to 5 mg/L, and between 2.5 and 50 mg/L for alkaline earth metals, by direct and indirect conductivity detection, respectively. However, with both columns subsequently connected in parallel, with the eluent delivered using a flow splitter from a single isocratic pump, the simultaneous analysis of anions and cations was also possible, based on a single conductivity detector. The potential of this system for the rapid, complete screening of water s les for multiple common anions and cations is shown.
Publisher: Wiley
Date: 21-10-2015
Abstract: The surface of polymethacrylate monoliths was functionalized by a post-polymerization modification, by means of a novel photo-initiated graft procedure where the charged monomer, sulfopropyl methacrylate, was controllably grafted stepwise, i.e. with incremental graft energies. The grafting approach was optimized using scanning capacitively coupled contactless conductivity detection. The effect of the localized ion exchange capacity and resultant gradient stationary phase upon ion-exchange chromatographic retention, selectivity, and performance was investigated, and compared to a homogeneously grafted (isotropic) column. The gradient column provided reduced peak widths at half height for both cationic analytes, with a reduction of 34 and 33%, respectively, when compared to the isotropic column.
Publisher: Elsevier BV
Date: 07-2018
DOI: 10.1016/J.CHROMA.2018.04.042
Abstract: The total ion current chromatogram (TICC) obtained by liquid-chromatography-mass spectrometry (LC-MS) is often extremely complex and 'noisy' in appearance, particularly when an electrospray ionization source is used. Accordingly, meaningful qualitative and quantitative information can be obtained in LC-MS by data mining processes. Here, one or more higher-quality mass chromatograms can be identified/extracted/isolated and combined to form a TICC, wherein much of the background mass noise is eliminated, and quantitative data for chromatographic peaks can be obtained. Pattern Recognition Entropy (PRE) is a new application of Shannon's statistical concept of entropy. PRE is both a pattern recognition tool and a summary statistic that can be used to identify information-containing mass chromatograms, where higher quality data (higher signal-to-noise mass chromatograms) usually have lower PRE values. Reduced TICCs are obtained by first calculating the PRE values of the component mass chromatograms. A plot of PRE value vs. m/z for the mass chromatograms is then generated, and the resulting band of PRE values is fit to a piecewise spline polynomial. The distribution of the differences between the in idual PRE values and the spline fit is then used to select 'good' mass chromatograms. For the data set considered herein, best results were obtained with a threshold of 0.5 standard deviations below the average value (value of the spline). PRE reduces the number of component mass chromatograms significantly (by an order of magnitude) and at the same time preserves most of the chemical information that is collectively in them. It can also distinguish between mass chromatograms of chemically similar species. PRE is arguably a less computationally intensive alternative to the widely used CODA algorithm for variable reduction. It produces reduced TICCs of comparable if not higher quality, and it requires only a single user input for variable selection. Reduced TICCs generated by PRE can be smoothed to further improve their signal-to-noise ratios.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1AY00886B
Abstract: Utilising a smartphone-based miniaturized Raman spectrometer and machine learning for the fast identification and discrimination of adulterated essential oils.
Publisher: Elsevier BV
Date: 11-2020
Publisher: Elsevier BV
Date: 2002
DOI: 10.1016/S0021-9673(01)01358-9
Abstract: An investigation into the selectivity of an iminodiacetic acid (IDA) modified silica gel column for transition and heavy metal ions using non-chelating inorganic eluents has been carried out. A number of eluent parameters were investigated to determine the exact retention mechanism taking place and to control selectivity. The parameters studied were eluent ionic strength and the nature of the inorganic salt used, eluent pH and eluent temperature. The results obtained showed how despite certain metal ions exhibiting similar stability constants with the bonded IDA groups, careful control of each of the above parameters, in particular eluent chloride ion concentration and eluent temperature, could result in large changes in selectivity. Optimal conditions for the isocratic and gradient separation of Mg(II), Ca(II), Mn(II), Cd(II), Co(II), Zn(II) and Pb(II) were determined. An isocratic method using a 0.035 M KCl, 0.065 M KNO3 (pH 2.5) eluent was successfully applied to the determination of Mn(II), Cd(II), Co(II) and Zn(II) at concentrations between 20 and 121 microg/l in a freshwater certified reference material (NIST 1640).
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0AY00516A
Publisher: Wiley
Date: 08-12-2014
Abstract: In this study, citrate-stabilised iron oxide nano-particles (∼16 nm) have been immobilised on commercial silica monolithic centrifugal spin columns (MonoSpin) for the extraction of phosphorylated compounds. Two alternative strategies were adopted involving either direct electrostatic attachment to an aminated MonoSpin (single-layer method) in the first instance, or the use of a layer-by-layer method with poly(diallyldimethylammonium) chloride. Field-emission scanning electron spectroscopy and energy-dispersive X-ray spectroscopy was used for confirming notably higher coverage of nano-particles using the layer-by-layer method (2.49 ± 0.53 wt%) compared with the single-layer method (0.43 ± 0.30 wt%). The modified monolith was used for the selective separation/extraction of adenosine monophosphate, adenosine diphosphate and adenosine triphosphate with elution using a phosphate buffer. A reversed-phase liquid chromatographic assay was used for confirming that adenosine, as a non-phosphorylated control was not retained on the modified MonoSpin devices, whereas recovery of 80% for adenosine monophosphate, 86% for adenosine diphosphate and 82% for adenosine triphosphate was achieved.
Publisher: Elsevier BV
Date: 12-2015
Publisher: Elsevier BV
Date: 10-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B812612G
Abstract: The combination of post-column derivatisation and visible detection are regularly employed in ion chromatography (IC) to detect poorly absorbing species. Although this mode is often highly sensitive, one disadvantage is the increase in repeating baseline artifacts associated with out-of-sync pumping systems. The work presented here will demonstrate the use of a second generation design paired emitter-detector diode (PEDD-II) detection mode offering enhanced sensitivity to transition metals in IC by markedly reducing this problem and also by improving signal noise. First generation designs demonstrated the use of a single integrated PEDD detector cell as a simple, small (15 x 5 mm), highly sensitive, low cost photometric detector for the detection of metals in IC. The basic principle of this detection mode lies in the employment of two linear light emitting diodes (LEDs), one operating in normal mode as a light source and the other in reverse bias serving as a light detector. The second generation PEDD-II design showed increased sensitivity for Mn(II)- and Co(II)-2-(pyridylazo)resorcinol (PAR) complexes as a result of two simultaneously acquiring detection cells--one analytical PEDD cell and one reference PEDD cell. Therefore, the PEDD-II employs two wavelengths whereby one monitors the analyte reaction product and the second monitors a wavelength close to the isosbestic point. The optimum LED wavelength to be used for the analytical cell was investigated to maximise peak response. The fabrication process for both the analytical and reference PEDD cells was validated by determining the reproducibility of detectors within a batch. The reproducibility and sensitivity of the PEDD-II detector was then investigated using signals obtained from both intra- and inter-day chromatograms.
Publisher: Wiley
Date: 26-05-2014
Abstract: A new method for the characterisation of purified detonation nanodiamond (DND) using CZE has been developed. The influence of BGE conditions on electrophoretic mobility, peak shape and particle aggregation was investigated, with resultant observations supported by zeta potential approximations and particle size measurements. Sodium tetraborate (pH 9.3), Tris (pH 9.3) and sodium phosphate (pH 7) were used in studying the BGE concentration effect on a commercial source of chemically stabilised DND. The BGE concentration had a strong effect on the stability of DND in suspension. The formation of aggregates of various sizes was observed as BGE concentration increased. The effect of pH on the electromigration of DND was examined using sodium phosphate (pH 8 and 10). The CZE method was subsequently applied to four different DND s les, which had undergone different routes of purification following detonation synthesis. Each s le produced a unique electrophoretic peak or profile in sodium tetraborate buffer (pH 9.3), such that the actual separation of DND s les from different sources could be achieved.
Publisher: Elsevier BV
Date: 05-2001
DOI: 10.1016/S0021-9673(01)00686-0
Abstract: Ion-interaction chromatography on a short (30 x 4.6 mm) 3 microm ODS column has been investigated with the aim of developing fast chromatographic separations of selected inorganic anions. Tetrabutylammonium chloride (TBA-Cl) was used as the ion-interaction reagent in mobile phases that also contained up to 20% methanol. Separations of simple test mixtures of up to eight UV absorbing anions illustrated how excellent efficiencies (>50,000 plates/m) could be obtained under optimized conditions. The use of an optimised mobile phase containing 20 mM TBA-Cl and 20% methanol resulted in the baseline separation of five important anions (iodate, bromate, nitrite, bromide and nitrate) in a separation window of just 28 s, with a shortest total analysis time of 50 s. The method was briefly applied to the rapid analysis of nitrite and nitrate in both a drinking water and a river water s le with a view to future on-line monitoring.
Publisher: Elsevier BV
Date: 04-2005
DOI: 10.1016/J.CHROMA.2005.03.028
Abstract: Temperature programming was used to improve selectivity in the suppressed ion chromatographic (IC) separation of inorganic anions, haloacetic acids and oxyhalides in drinking water s les when using NaOH gradient elution. The programme exploited varying responses of these anions to changes in temperature. Heats of adsorption (deltaH, kJ/mol) for 17 anionic species were calculated from van't Hoff plots. For haloacetic acids, both the degree of substitution and log P (log of n-octanol-waterpartition coefficient) values correlated well with the magnitude of the temperature effect, with monochloro- and monobromoacetic acids showing the largest effect (deltaH= -10.4 to -10.7 kJ/mol), dichloro- and dibromoacetic acids showing a reduced effect (deltaH= -6.8 to -8.4 kJ/mol) and trichloro-, bromodichloro- and chlorodibromoacetic acids showing the least effect (deltaH= -4.7 to -2.4 kJ/mol). The effect of temperature on oxyhalides ranged from deltaH= 8.4 kJ/mol for perchlorate to deltaH= -9.1 kJ/mol for iodate. The effectiveness of two commercial column ovens was investigated for the application of temperature gradients during chromatographic runs, with the best system applied to improve the resolution of closely retained species at the start, middle and end of the separation obtained using a previously optimised hydroxide gradient, in a real drinking water s le matrix. Retention time reproducibility of the final method ranged from 0.62 to 3.18% RSD (n = 30) showing temperature programming is indeed a practically important parameter to manipulate resolution.
Publisher: Elsevier BV
Date: 10-2016
DOI: 10.1016/J.CHROMA.2016.09.076
Abstract: The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated under the conditions of hydrophilic interaction liquid chromatography (HILIC). A 50×4.6mm ID stainless steel column packed with HPHT particles of mean diameter 1.6μm and specific surface area 5.1m
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B916081G
Abstract: A 255 nm deep-UV-light-emitting diode (deep-UV-LED) is investigated as a novel light source for photometric detection in view of fundamental properties of UV-LEDs, in particular emission spectra and energy conversion. Its performance in on-capillary photometric detection in capillary electrophoresis (CE) is determined and the potential of deep-UV-LEDs in optical detection is discussed.
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B707773B
Abstract: A micro-fluidic chip, within which two monolithic electroosmotic pumps are utilised for s le preconcentration, injection and delivery is presented. The monolithic pumps were capable of producing stable and bubble free flow rates at applied voltages below 2 kV, with a current <10 microA. Electrokinetic (EK) s le injection, down to low nano-litre volumes, was quantitatively controlled through applied voltage and injection times, whilst the s le pump delivered a carrier solution to indirectly dispense the s le. A nano-flow sensor (NFS) was used to continuously monitor the flow rate stability of each pump, showing response times of <5-10 s for changes in applied voltage. A capacitively coupled contactless conductivity detector (C(4)D), as an off-chip on-capillary detector, was used to complete the micro-flow injection analysis (FIA) system. A monolithic electroosmotic pump (EOP), modified with an anionic surfactant, was used to demonstrate a novel approach to on-chip cation preconcentration and elution.
Publisher: Elsevier BV
Date: 05-1997
Publisher: Elsevier BV
Date: 04-2002
DOI: 10.1016/S0021-9673(02)00108-5
Abstract: Fast ion-exchange chromatography has been developed and applied to the separation of common inorganic anions. Using a didodecyldimethylammonium bromide (DDAB) coated short (30 mm x 4.6 mm) ODS analytical column (3-microm particle size) and a 5 mM phthalate eluent (pH 7.5) the isocratic separation of nine common anions in 160 s was possible, with the first seven anions, including phosphate, chloride and sulphate, separated within 65 s. Detection was achieved using indirect UV at 279 nm. The high capacity, highly hydrophobic ion-exchange coating demonstrated excellent stability over time, even at elevated temperatures (45 degrees C) and exhibited unusual selectivity for common anions (retention order=fluoride, carbonate, phosphate, chloride, bromate, nitrite, sulphate, bromide and nitrate). The developed chromatography was successfully applied to the rapid analysis of river water and seawater s les.
Publisher: Springer Science and Business Media LLC
Date: 27-10-2200
Publisher: Elsevier BV
Date: 04-2015
DOI: 10.1016/J.TALANTA.2014.12.048
Abstract: Cobalt magnetic nanoparticles surface functionalised with iminodiacetic acid were evaluated as a nano-particulate solid phase extraction absorbent for copper ions (Cu(2+)) from environmental water s les. Using an external magnetic field, the collector nanoparticles could be separated from the aqueous phase, and adsorbed ions simply decomplexed using dilute HNO3. Effects of pH, buffer concentration, s le and sorbent volume, extraction equilibrium time, and interfering ion concentration on extraction efficiency were investigated. Optimal conditions were then applied to the extraction of Cu(2+) ions from natural water s les, prior to their quantitation using high-performance chelation ion chromatography. The limits of detection (LOD) of the combined extraction and chromatographic method were ~0.1 ng ml(-1), based upon a 100-fold preconcentration factor (chromatographic performance LOD=9.2 ng ml(-1) Cu(2+)), analytical linear range from 20 to 5000 ng mL(-1), and relative standard deviations=4.9% (c=1000 ng ml(-1), n=7). Accuracy and precision of the combined approach was verified using a certified reference standard estuarine water s le (SLEW-2) and comparison of s le determinations with sector field inductively coupled plasma mass spectrometry. Recoveries from the addition of Cu(2+) to impacted estuarine and rain water s les were 103.5% and 108.5%, respectively. Coastal seawater s les, both with and without prior UV irradiation and dissolved organic matter removal were also investigated using the new methodology. The effect of DOM concentration on copper availability was demonstrated.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3AY41549J
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B714807K
Abstract: Up to ten in idual reversed-phase monolithic LC columns were efficiently coupled to equal a total column length of 1 m. The column generated up to 90,000 theoretical plates under optimum conditions with a peak capacity under gradient conditions of 244 peaks h(-1) at a total column backpressure of just 140 bar, directly coupled to ESI-MS.
Publisher: Elsevier BV
Date: 02-2016
DOI: 10.1016/J.ACA.2016.01.003
Abstract: A simple, high-performance counter-current chromatography method with sequential UV absorbance (254 nm) and evaporative light scattering detection (ELSD) was developed for the quantification of pre-extracted low molecular weight dissolved organic matter (DOM) extracted from natural waters. The method requires solid-phase extraction (SPE) extraction of only small volumes of water s les, here using poly(styrene inylbenzene)-based extraction cartridges (Varian PPL). The extracted and concentrated DOM was quantified using reversed-phase high-performance counter-current chromatography (HPCCC), with a water/methanol (5:5) mobile phase and hexane/ethyl acetate (3:7) stationary phase. The critical chromatographic parameters were optimised, applying a revolution speed of 1900 rpm and a flow-rate of 1 mL min(-1). Under these conditions, 50 μL of extracted DOM solution could be injected and quantified using calibration against a reference natural dissolved material (Suwannee River), based upon UV absorbance at 254 nm and ELSD detection. Both detection methods provided excellent linearity (R(2) > 0.995) for DOM across the concentration ranges of interest, with limits of detection of 4 μg ml(-1) and 7 μg ml(-1) for ELSD and UV absorbance, respectively. The method was validated for peak area precision ( 95% recovery). The developed method was applied to the determination of the concentration of DOM in seawater, based upon initial s le volumes as small as 20 mL.
Publisher: Royal Society of Chemistry (RSC)
Date: 15-11-2002
DOI: 10.1039/B210485G
Abstract: Light emitting diodes (LEDs) are known to be excellent light sources for detectors in liquid chromatography and capillary electromigration separation techniques, but to date only LEDs emitting in the visible range have been used. In this work, a UV LED was investigated as a simple alternative light source to standard mercury or deuterium l s for use in indirect photometric detection of inorganic anions using capillary electrophoresis with a chromate background electrolyte (BGE). The UV LED used had an emission maximum at 379.5 nm, a wavelength at which chromate absorbs strongly and exhibits a 47% higher molar absorptivity than at 254 nm when using a standard mercury light source. The noise, sensitivity and linearity of the LED detector were evaluated and all exhibited superior performance to the mercury light source (up to 70% decrease in noise, up to 26.2% increase in sensitivity, and over 100% increase in linear range). Using the LED detector with a simple chromate-diethanolamine background electrolyte, limits of detection for the common inorganic anions, Cl-, NO3-, SO4(2-), F- and PO4(3-) ranged from 3 to 14 microg L(-1), using electrostatic injection at -5 kV for 5 s.
Publisher: Wiley
Date: 04-07-2023
Abstract: Liquid chromatography is a prominent analytical technique in separation science and chemical analysis, applied across numerous fields of research and within industrial applications. Over the past few decades, there has been a growing interest in the miniaturization of this technique, which has been particularly enabled through new miniature and portable detection technologies for in‐field, at‐site, and point‐of‐need (collectively ‘out‐of‐lab’) analyses. Accordingly, significant advances have been made in recent years in the development of miniaturized liquid chromatography with photometric, electrochemical, and mass spectrometric detection, enabling the development of field‐deployable and portable instruments for various applications. Herein, recent developments in the miniaturization of detection systems for inclusion within, and/or coupling with, portable liquid chromatographic systems, are reviewed in detail together with critical comments and expected future trends in this area.
Publisher: Wiley
Date: 29-08-2012
Abstract: Polymer monolithic materials have found particularly utility in the field of bioanalysis, particularly in the area of separation science, for both enrichment and trapping of biomolecules and their analytical reparative separations. Nanoparticle-modified monoliths have recently emerged as a new class of substrate, with unique characteristics and structure, and with selectively tailored surface chemistries for target molecules. Although several reviews exist on the applications of nanoparticles in analytical science, this review is the first to specifically summarise the applications in bioanalysis of nanoparticle-modified polymer monolithic materials. The review covers the range of nanoparticles being utilised in this way, their specific applications and future trends.
Publisher: Royal Society of Chemistry (RSC)
Date: 1994
DOI: 10.1039/AI9943100209
Publisher: Springer Science and Business Media LLC
Date: 25-05-2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B711350A
Abstract: A capacitively-coupled contactless conductivity detector (C4D) has been utilised as an on-capillary detector within a capillary ion chromatograph, incorporating a reversed-phase monolithic silica capillary column semi-permanently modified with a suitable ionic surfactant. The monolithic capillary column (150 x 0.1 mm i.d.) was modified using sodium dioctyl sulfosuccinate (DOSS), an anionic surfactant, for the separation of small inorganic and organic cations. With the use of the on-capillary conductivity detector, the longitudinal homogeneity and temporal stability of the coating were investigated. The approach allowed a detailed non-invasive observation of the nature of the ion-exchange coating over time, and an ex le of an application of the technique to produce a longitudinal stationary-phase charge gradient is shown. An investigation of the basis of the measured on-capillary conductivity was carried out with a counter ion study, clearly showing the on-capillary detection technique could also distinguish between chemical forms of the immobilised ion exchanger. The above method was used to produce a stable and homogeneously-modified monolithic ion-exchange capillary column, for application to the separation of inorganic alkaline earth cations and amino acids.
Publisher: Elsevier BV
Date: 11-2005
Publisher: Wiley
Date: 2010
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2AN01856J
Abstract: A novel platform for direct transfer, separation, and pre-concentration of swabbed s les without elution into a solvent or a medium.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4AY02126F
Abstract: A new high performance chelation ion chromatography method for the simultaneous determination of trace magnesium and strontium in various calcium carbonate s les was developed.
Publisher: Elsevier BV
Date: 02-2007
DOI: 10.1016/J.CHROMA.2006.12.049
Abstract: A reversed-phase monolithic silica based capillary column (Onyx C(18), 150 mm x 0.1 mm) was modified with the hoteric surfactant, N-dodecyl-N,N-(dimethylammonio)undecanoate (DDMAU) and evaluated for the separation and determination of inorganic anions using on-column capacitively coupled contactless conductivity detection (C(4)D). The chromatographic performance of the column was evaluated and under optimal conditions separation efficiencies of 56,200 plates per meter or 7025 plates per column (at detection point) were observed (for iodide). Direct plumbing of the capillary column to the micro-injector and on-column detection eliminated extra-column band broadening, thus allowing accurate analysis of van Deemter curves obtained for the monolithic capillary column. The calculated value for the C-term in the obtained van Deemter curve was between 3 and 4 ms for inorganic anions, allowing for the utilisation of relatively high flow rates without significant losses in efficiency. The performance of the C(4)D detector was investigated and compared for detection on an open tubular capillary column and on the modified monolithic silica capillary column. The on-column detection approach did not result in any significant decrease in peak sensitivity for the monolith compared to responses recorded for open tubular capillary columns, and in addition meant the system could be applied to rapid separations by simple variation in apparent column length. The proposed chromatographic system allowed for detection of common anions at sub-ppm level with a 10 nL injection volume. Additionally, on-column detection allowed visualisation of the development of the separation at any point in time and evaluation of the longitudinal uniformity of the ion-exchange coating.
Publisher: Elsevier BV
Date: 11-2013
DOI: 10.1016/J.ACA.2013.03.063
Abstract: The nature and extent of mixed-mode retention mechanisms evident for three structurally related, agglomerated, particle-based stationary phases were evaluated. These three agglomerated phases were Thermo Fisher ScientificIon PacAS11-HC - strong anion exchange, Thermo Fisher Scientific IonPac CS10--strong cation-exchange PS-DVB, and the Thermo Fisher Scientific Acclaim Trinity P1silica-based substrate, which is commercially marketed as a mixed-mode stationary phase. All studied phases can exhibit zwitterionic and hydrophobic properties, which contribute to the retention of charged organic analytes. A systematic approach was devised to investigate the relative ion-exchange capacities and hydrophobicities for each of the three phases, together with the effect of eluent pH upon selectivity, using a specifically selected range of anionic, cationic and neutral aromatic compounds. Investigation of the strong anion-exchange column and the Trinity P1 mixed-mode substrate, in relation to ion-exchange capacity and pH effects, demonstrated similar retention behaviour for both the anionic and holytic solutes, as expected from the structurally related phases. Further evaluation revealed that the ion-exchange selectivity of the mixed-mode phase exhibited properties similar to that of the strong anion-exchange column, with secondary cation-exchange selectivity, albeit with medium to high anion-exchange and cation-exchange capacities, allowing selective retention for each of the anionic, cationic and holytic solutes. Observed mixed-mode retention upon the examined phases was found to be a sum of anion- and cation-exchange interactions, secondary ion-exchange and hydrophobic interactions, with possible additional hydrogen bonding. Hydrophobic evaluation of the three phases revealed logP values of 0.38-0.48, suggesting low to medium hydrophobicity. These stationary phases were also benchmarked against traditional reversed-phase substrates namely, octadecylsilica YMC-Pac Pro C18 and neutral μPS-DVB resin IonPac NS1-5u, yielding logP values of 0.57 and 0.52, respectively.
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B717453E
Abstract: An analytical method to determine a selection of 27 frequently prescribed and consumed pharmaceuticals in biosolid enriched soils and digested sludges is presented. Using a combination of pressurized liquid extraction, solid phase extraction and liquid chromatography with tandem mass spectrometry, it was possible to detect all analytes in each s le type at the low-sub ng g(-1) level. Solid phase extraction efficiencies were compared for 6 different sorbent types and it was found that Waters Oasis HLB cartridges offered enhanced selectivities with 20 analytes showing final method recoveries > or =60% in both soils and digested sludges. The method was validated for linearity, range, precision and limits of detection in both s le matrices. All analytes were then determined in sludge enriched soils as well as the precursor thermally dried sludge fertilizer produced from a primary wastewater treatment plant. Levels of the antibacterial agent triclosan were found to exceed 20 microg g(-1) in digested sludge and 5 microg g(-1) in thermally dried sludge cake. Significant traces of carbamazepine and warfarin were also detected in the above s les.
Publisher: Elsevier BV
Date: 10-2012
DOI: 10.1016/J.ACA.2012.04.029
Abstract: The practical application of rigid, macro-porous organic polymer and silica based monolithic stationary phases as separation media has been described in the literature since 1992 and 1996, respectively. Today these materials are extensively used in chromatography and electrochromatography and several detailed reviews appear annually describing these materials, their synthesis and application. To compliment these publications, this review focuses upon the less commonly utilised materials for monolith synthesis, both those that have already been applied within separation science, and those that have found applications elsewhere, such as catalysis and water filtration, but have the clear potential to be explored as novel stationary phases in the near future. For the purpose of the review monoliths formed from these various alternative materials will be termed 'Exotic Monoliths', as these new substrates in many cases have only just begun to be explored for chromatographic separations, and in many instances have unusual and highly selective surface chemistries, which are attractive in terms of broadening the choice of monolithic materials for separation science. An extensive range of monolithic materials based on the following elements and their compounds (mostly oxides) are covered: Zr, Ti, Al, Hf, C, Au, Ag, Ce, Ge and hydroxyapatite, together with their relevant properties, methods of synthesis, and current and potential applications in separation science.
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B615669J
Abstract: A study comparing recently available 100 x 3 mm id, 200 x 3 mm id monolithic reversed-phase columns with a 50 x 2.1 mm id, 1.8 microm particle packed reversed-phase columns was carried out to determine the most efficient approach (using traditional van Deemter analysis and a modern kinetic plot approach) for the rapid screening of s les for 16 illicit drugs and associated metabolites. A plot of column backpressure versus plate number (N) showed a significant advantage of using the monolithic phases, with the 20 cm monolithic column exhibiting a maximum 15,000 plates at a column backpressure of approximately 70 bar, compared to approximately 7000 plates at 150 bar for the 5 cm 1.8 microm particle packed column. Optimum linear velocities were found to be 0.40 mm s(-1), 0.52 mm s(-1) and 0.98 mm s(-1) for the three above columns, respectively. The 20 cm monolithic column was subsequently applied to the separation and determination of illicit drug contamination on Irish euro banknotes, using methanol extraction followed by LC-MS/MS. Method performance data showed that the new LC-MS/MS method was significantly more sensitive than previous GC-MS/MS based methods for this application, with detection limits in the pg note(-1) region, based upon a 20 microL standard injection. All of the notes examined tested positive for trace quantities of cocaine, with benzoylecgonine detected on 12 of the 45 notes s led. Traces of heroin were also detected on three of the 45 notes.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6AY02426B
Abstract: Development of low volume capillary ion chromatography to deliver anion records from Antarctic snow pit s les.
Publisher: Elsevier BV
Date: 09-2004
Publisher: Elsevier BV
Date: 12-2202
Publisher: Elsevier BV
Date: 04-2021
Publisher: Elsevier BV
Date: 05-2005
DOI: 10.1016/J.CHROMA.2005.03.126
Abstract: A 0.46 cm x 10.0 cm silica monolith column was modified through the in situ covalent attachment of lysine (2,6-diaminohexanoic acid) groups. Due to the zwitterionic nature of the resultant stationary phase, the modified monolithic column contained both cation and anion exchange capacity. In the case of cation exchange, the capacity was found to be relatively low at between 5 and 6.5 micromoles Me2+ per column. However, as expected, the lysine monolith exhibited a higher anion exchange capacity at 12-13 micromoles A- per column (at pH 3.0), which was found to be dependent upon column pH, due to the dissociation of the weak acid carboxylic acid groups. High-performance separations of transition metal cations and inorganic anions were achieved using the modified monolith, with the effects of eluent concentration, pH and flow rate evaluated. Using elevated flow rates of up to 5 mL/min the separation of nitrite, bromate, bromide, nitrate, iodide and thiocyanate was possible in approximately 100 s with peak efficiencies of between 50 and 100,000 N/m and retention time %RSD of under 0.3%.
Publisher: Elsevier BV
Date: 04-2019
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2AY01714H
Abstract: Electrophoretic separation of charged ions on a textile-braided structure.
Publisher: Elsevier BV
Date: 2019
DOI: 10.1016/J.ACA.2018.09.006
Abstract: The deposition of chemical reagent inks on paper is a crucial step in the development and fabrication of microfluidic paper-based analytical devices (μPADs). A pen-plotting approach, delivering chemical ink deposition using technical pens filled with reagents and inserted into a desktop electronic plotter, is shown herein to be a versatile, low-cost, simple, rapid, reproducible, and high-throughput solution. The volume of the deposited ink was quantified gravimetrically, confirming that nanoliter volumes of reagents can be deposited reproducibly (e.g. 7.55 ± 0.37 nL/mm for a plotting speed of 10 cm/s) in detection zones of μPADs, typically spatially defined using wax printing. This approach was further investigated with regard to deposition of reagents in different geometrical forms (circular and linear), so demonstrating its applicability for preparation of μPADs with flexible design and application. By adjusting the plotting speed for linear deposition, lines with a relatively large range of widths (≈628-1192 μm) were created. Circular deposition was also demonstrated via delivery of reagents within wax printed circular fluidic barriers of a range of diameters (inner diameter = 1.5-7 mm). These capabilities were practically demonstrated via the fabrication of μPADs, based upon differing detection principles for determination of aluminum in natural waters using Morin as the fluorescent reagent. Traditional μPADs based on digital image colorimetry (DIC) were produced using circular deposition, whilst distance-based μPADs exploited linear deposition. Both types of μPADs developed using this method showed excellent precision for determination of trace concentrations of aluminium (average RSDs = 3.38% and 6.45%, and LODs = 0.5 ng (0.25 ppm) and 2 ng (0.5 ppm), for traditional and distance-based detection, respectively).
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B817822D
Abstract: A comprehensive analytical investigation of the sorption behaviour of a large selection of over-the-counter, prescribed pharmaceuticals and illicit drugs to agricultural soils and freeze-dried digested sludges is presented. Batch sorption experiments were carried out to identify which compounds could potentially concentrate in soils as a result of biosolid enrichment. Analysis of aqueous s les was carried out directly using liquid chromatography-tandem mass spectrometry (LC-MS/MS). For solids analysis, combined pressurised liquid extraction and solid phase extraction methods were used prior to LC-MS/MS. Solid-water distribution coefficients (K(d)) were calculated based on slopes of sorption isotherms over a defined concentration range. Molecular descriptors such as log P, pK(a), molar refractivity, aromatic ratio, hydrophilic factor and topological surface area were collected for all solutes and, along with generated K(d) data, were incorporated as a training set within a developed artificial neural network to predict K(d) for all solutes within both s le types. Therefore, this work represents a novel approach using combined and cross-validated analytical and computational techniques to confidently study sorption modes within the environment. The logarithm plots of predicted versus experimentally determined K(d) are presented which showed excellent correlation (R(2) > 0.88), highlighting that artificial neural networks could be used as a predictive tool for this application. To evaluate the developed model, it was used to predict K(d) for meclofenamic acid, mefenamic acid, ibuprofen and furosemide and subsequently compared to experimentally determined values in soil. Ratios of experimental redicted K(d) values were found to be 1.00, 1.00, 1.75 and 1.65, respectively.
Publisher: Elsevier BV
Date: 15-05-2006
DOI: 10.1016/J.TALANTA.2005.10.032
Abstract: A new analytical procedure for the simultaneous determination of trace oxyhalides and haloacetic acids (HAs) in drinking water and aqueous soil extracts is described. The method uses micro-bore ion chromatography (IC) coupled with suppressed conductivity (SC) and electrospray ionization mass spectrometric detection (ESI-MS). The IC-SC-ESI-MS system included a secondary flow of 100% MeOH, which was added to the column eluate (post-suppressor) and resulted in a significant increase in sensitivity for all analytes. All ESI-MS parameters were optimized for HA analysis and sensitivity quantitatively compared to suppressed conductivity. Full analytical performance characteristics for the developed method are presented for monochloro-, monobromo-, dichloro-, dibromo-, trichloro-, bromochloro, chlorodifluoro-, trifluoro-, dichlorobromo- and dibromochloroacetic acid, as well as the oxyhalides iodate, bromate, chlorate and perchlorate. In the case of the HAs, an optimised 25-fold SPE preconcentration method meant all analytes could be readily detected well below the USEPA 60mug/L regulatory limit using conductivity and/or ESI-MS. The IC-ESI-MS method was applied to the determination of oxyhalides and HAs in both soil extracts and drinking water s les. Soil s les were extracted using ultra pure water with subsequent determination of perchlorate at 1.68mug/g of soil. A drinking water s le containing HAs was preconcentrated using LiChrolut EN solid phase extraction cartridges with subsequent sulphate and chloride removal. Total HAs were determined at 13mug/L.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6AY01381C
Abstract: A new and sensitive ion chromatographic method for the speciation of iodine in aquacultural seawater s les has been developed.
Publisher: Elsevier BV
Date: 05-2020
DOI: 10.1016/J.CHROMA.2020.460853
Abstract: Analyses of the complex essential oil s les using gas chromatography hyphenated with mass spectrometry (GC-MS) generate large three-way data arrays. Processing such large data sets and extracting meaningful information in the metabolic studies of natural products requires application of multivariate statistical techniques (MSTs). From the GC-MS raw data several different input data sets for the MSTs can be created, including total chromatogram average mass spectra (TCAMS), segmented average mass spectra (SAMS) and chemical composition. Herein, we compared the performance of MSTs on average mass spectrum based data sets, TCAMS and SAMS, against chemical composition and attenuated total reflectance - Fourier transformation infrared (ATR-FTIR) spectroscopy in the evaluation of quality of ylang-ylang essential oils, based on their grade, geographical origin and chemical composition, using principal component analysis (PCA), partial least squares regression (PLS) and discriminatory analysis (PLS-DA). PCA based on TCAMS, SAMS and chemical composition showed clear trends amongst the s les based on increase in grade (distillation time). PLS-DA applied to TCAMS, SAMS and ATR-FTIR discriminated between all geographical origins. Predicted relative abundances of the 18 most important compounds, using PLS regression models on TCAMS, SAMS and ATR-FTIR, were successfully applied to ylang-ylang essential oil quality assessment based on comparison with the ISO 3063:2004 standard, where the SAMS data set showed superior performance, compared to other data sets.
Publisher: Elsevier BV
Date: 07-2019
DOI: 10.1016/J.ACA.2019.02.014
Abstract: The significant advance of delivering high value multi-species data from sub-1 mL ice core s le volumes allows higher temporal resolution in deposition records of inorganic and low molecular weight organic anions and cations. The determination of these species is a fundamental strategic requirement in modern paleoclimate studies. Herein, for the first time, a dual capillary ion chromatography (Cap-IC) based method for the simultaneous separation of 17 organic and inorganic anions and cations in low volume Antarctic ice core s les is presented. The total amount of s le required for direct injection has been reduced to 190 μL, which is 35 times lower than the amount of s le required by standard ion chromatography methods. A dual Cap-IC system configured for the simultaneous determination of cations and anions was used throughout. A range of chromatographic parameters was optimised for both anion and cation systems to obtain baseline separations of all target analytes in a suitable run time and to minimise the amount of s le required. Baseline separation of matrix and trace 'marker' ions were achieved in less than 35 min, after injecting only 40 μL of s le in each IC system. Limits of detection (LODs) for all analytes determined were within a range similar to that achieved by previously published standard bore IC-based methods. Intra- and inter-day repeatability were evaluated, with both parameters being typically below 3% for peak area. In further validation of the method, a comparative analysis of a set of 420 ice core s les from Aurora Basin North site, Antarctica, previously analysed by standard IC, established that the proposed low s le volume technique was applicable as a routine measurement approach in ice core analysis projects.
Publisher: Elsevier BV
Date: 04-1998
Publisher: American Chemical Society (ACS)
Date: 26-08-2021
Publisher: Informa UK Limited
Date: 15-06-2006
Publisher: Elsevier BV
Date: 03-2003
DOI: 10.1016/S0021-9673(00)01242-5
Abstract: A selective and sensitive ion chromatographic method has been developed for the determination of beryllium in a number of water s les at low-microg/l concentrations. The separation was performed on a 250x4.0 mm I.D. iminodiacetic acid functionalised silica gel column. Chromatographed Be(II) was detected using visible detection at 590 nm following post-column reaction with chrome azurol S (CAS). The optimum separation and derivatisation conditions were studied in detail. The optimum eluent conditions were found to be 0.4 M KNO3, adjusted to pH 2.5 using HNO3, with optimum post-column detection being achieved using a solution containing 0.26 mM CAS, 2% Triton X-100, 50 mM 2-(N-morpholino)ethanesulfonic acid, pH 6.0. Under the above conditions, the concentration detection limit for Be(II) was found to be 3 microg/l in a standard solution and 4 microg/l in a typical tap water s le, using a 250 microl injection. The method was linear over the investigated range of 10 microg/l to 10 mg/l and highly reproducible. The method was successfully applied to a number of water s les of varying matrix complexity, including simulated seawater, and also to a natural freshwater certified reference material NIST 1640.
Publisher: Elsevier BV
Date: 06-2022
DOI: 10.1016/J.CHROMA.2022.463127
Abstract: Adsorption and chromatographic properties of oxidized and hydrogenated 'high pressure and high temperature' synthesised diamond (HPHT) are studied using high-performance liquid chromatography. The retention factors of organic cation (benzyltributylammonium chloride), weak base (aniline), weak acid (benzoic acid), strong acid (benzenesulfonic acid), hydrophobic toluene, and hydrophilic uracil are obtained at varied pH, organic solvent content, and ionic strength of mobile phase. Both adsorbents exhibited moderate polarity with a mixed-mode retention mechanism with a combination of electrostatic, hydrophobic and hydrophilic interactions. Unexpectedly, hydrogenated HPHT revealed significant anion-exchange properties under acidic conditions and cation-exchange properties under alkaline conditions, while only cation-exchange selectivity was noted for oxidized HPHT across the enntire pH range. The retention factors obtained for a set of model compounds including n-alkyl-, polymethyl-, nitro- and halogenated benzenes correlated well with their hydrophobicity (logP) values. The thermal stability of the adsorbent and immutability of retention mechanisms involved was confirmed by linear van't Hoff plots for the investigated compounds.
Publisher: American Chemical Society (ACS)
Date: 19-11-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2AY25299F
Publisher: Elsevier BV
Date: 07-2013
Publisher: Wiley
Date: 03-2010
Abstract: Polymeric monoliths in capillary formats have been fabricated incorporating a gradient of charged functional groups along their length. Scanning capacitively coupled contactless conductivity detection (sC 4 D) was then used to measure the conductive response of the stationary phase and characterise the relative axial distribution of functional groups along the column length. Gradients of 2‐acrylamido‐2‐methyl‐1‐propanesulphonic acid were prepared using either photografting methods or by filling a capillary column with segmented plugs of monomer mixtures each containing incrementally higher concentrations of the functional monomer. The utility of sC 4 D as a rapid and non‐invasive tool for assessing the slope of a variety of gradient configurations is demonstrated. Repeatability of the sC 4 D measurements was .7% RSD. Columns with a gradient of covalently bonded iminodiacetic acid were also produced. Changes in the gradient slope were observed after chelation of copper on the stationary phase via a reduction of the conductive response. The effect upon the observed gradient profile of changing the co‐monomer composition during column fabrication was studied.
Publisher: Springer Science and Business Media LLC
Date: 30-01-2014
Publisher: Elsevier BV
Date: 09-2010
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