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Analytical and Bioanalytical Chemistry (v.390, #3)

Experiences at a small startup by J. Fetzer (pp. 795-796).

is the author or coauthor of over 130 research articles, reviews, and book chapters. He is a member of the International Advisory Board of Analytical and Bioanalytical Chemistry. He worked for over 20 years as an analytical chemist for the Chevron Corporation and now runs his own consulting company, Fetzpahs Consulting, in Hercules, CA, USA. His book Career management for chemists—a guide to success in a chemistry career was published by Springer.

D. Brynn Hibbert: Quality Assurance for the Analytical Chemistry Laboratory by Katrice Lippa; John Sieber; David Duewer (pp. 797-798).

Microfluidics in cell analysis by Alexandra Ros (pp. 799-800).

is an assistant professor in the Chemistry and Biochemistry Department at Arizona State University. Her work focuses on bioanalysis in micro- and nanofluidic systems with emphasis on migration mechanisms of colloids and biomolecules as well as single cell analysis.

Cellular microarrays for use with capillary-driven microfluidics by Robert Lovchik; Corinne von Arx; Angelika Viviani; Emmanuel Delamarche (pp. 801-808).

We present a method for the facile arraying of cells on microstructured substrates which should be suitable for cellular assays in autonomous microfluidic capillary systems (CSs). The CSs, which were designed and microfabricated in Si, have various microfluidic functional elements including reaction chambers wherein cellular arrays are located. Two methods for arraying the cells were explored. In the first method, a hydrophobic alkanethiol was microcontact-printed on the bottom surface of a microfluidic reaction chamber. The subsequent adsorption of protein-repellent alkanethiols around the printed areas and the deposition from solution of fibronectin (FN) on the hydrophobic areas resulted in an adhesive pattern for the attachment of living human breast cancer cells. This method was limited by the formation of cellular clusters, which proved difficult to remove selectively. The second method employed a poly(dimethylsiloxane) elastomer having oval recessed microstructures. The selective coating of the inner walls of the ovals with FN and the blocking of the mesas around the ovals with bovine serum albumin (BSA) permitted single or multiple cells to be arrayed depending on the size of the ovals. The possibility of sealing CSs with cells arrayed on poly(dimethylsiloxane) may provide a versatile platform for high-throughput experimentation down to the single-cell level. Figure The deposition of one or a few living cells in fibronectin-coated poly(dimethylsiloxane) microstructures results in cellular arrays, which can be interfaced with capillary-driven microfluidics

Keywords: Microfluidics; Cellular arrays; Microcontact printing; Poly(dimethylsiloxane)

Growth cone response to ephrin gradients produced by microfluidic networks by Susanne Lang; Anne C. von Philipsborn; André Bernard; Friedrich Bonhoeffer; Martin Bastmeyer (pp. 809-816).

A microfluidic network (μFN) etched into a silicon wafer was used to deliver protein solutions containing different concentrations of the axonal guidance molecule ephrinA5 onto a silicone stamp. In a subsequent microcontact printing (μCP) step, the protein was transferred onto a polystyrene culture dish. In this way, stepwise substrate-bound concentration gradients of ephrinA5 were fabricated spanning a total distance of 320 μm. We tested the response of chick retinal ganglion cell (RGC) axons, which are guided in vivo by ephrin gradients, to these in vitro gradients. Temporal, but not nasal axons stop at a distinct zone in the gradient, which is covered with a certain surface density of substrate-bound ephrinA5. Within the temporal RGC population, all axons respond uniformly to the gradients tested. The position of the stop zone depends on the slope of the gradient with axons growing further into the gradient in shallow gradients than in steep gradients. However, axons stop at lower ephrinA5 concentrations in shallow gradients than in steep gradients, indicating that the growth cone can adjust its sensitivity during the detection of a concentration gradient of ephrinA5.

Keywords: Microfluidic network; Microcontact printing; Axon guidance; Retinotectal projection; Chick; Ephrin

Growth cone response to ephrin gradients produced by microfluidic networks by Susanne Lang; Anne C. von Philipsborn; André Bernard; Friedrich Bonhoeffer; Martin Bastmeyer (pp. 809-816).

Keywords: Microfluidic network; Microcontact printing; Axon guidance; Retinotectal projection; Chick; Ephrin

Micro- and nanometer-scale patterned surface in a microchannel for cell culture in microfluidic devices by Makiko Goto; Takehiko Tsukahara; Kiichi Sato; Takehiko Kitamori (pp. 817-823).

A novel microdevice which had a micro- and nanometer-scale patterned surface for cell adhesion in a microchip was developed. The surface had a metal pattern fabricated by electron-beam lithography and metal sputtering and a chemical pattern consisting of a self-assembled monolayer of alkanethiol. The metal patterned surface had a gold stripe pattern which was as small as 300 nm wide and 150 nm high and both topography and chemical properties could be controlled. Mouse fibroblast NIH/3T3 cells were cultured on the patterned surface and elongated along the gold stripes. These cells recognized the size of the pattern and the chemical properties on the pattern though it was much smaller than they were. There was satisfactory cell growth under fresh medium flow in the microchip. The combination of the patterned surface and the microchip provides cells with a novel environment for their growth and will facilitate many cellular experiments.

Keywords: Micro- and nanometer-scale patterned surface; Nanofabrication; Self-assembled monolayer; Cell adhesion; Cell elongation

Development of an osteoblast-based 3D continuous-perfusion microfluidic system for drug screening by Kihoon Jang; Kae Sato; Kazuyo Igawa; Ung-il Chung; Takehiko Kitamori (pp. 825-832).

In this work, we demonstrated that biological cells could be cultured in a continuous-perfusion glass microchip system for drug screening. We used mouse Col1a1GFP MC-3T3 E1 osteoblastic cells, which have a marker gene system expressing green fluorescent protein (GFP) under the control of osteoblast-specific promoters. With our microchip-based cell culture system, we realized automated long-term monitoring of cells and sampling of the culture supernatant system for osteoblast differentiation assay using a small number of cells. The system successfully monitored cells for 10 days. Under the 3D microchannel condition, shear stress (0.07 dyne/cm² at a flow rate of 0.2 μL/min) was applied to the cells and it enhanced the GFP expression and differentiation of the osteoblasts. Analysis of alkaline phosphatase (ALP), which is an enzyme marker of osteoblasts, supported the results of GFP expression. In the case of differentiation medium containing bone morphogenetic protein 2, we found that ALP activity in the culture supernatant was enhanced 10 times in the microchannel compared with the static condition in 48-well dishes. A combined system of a microchip and a cell-based sensor might allow us to monitor osteogenic differentiation easily, precisely, and noninvasively. Our system can be applied in high-throughput drug screening assay for discovering osteogenic compounds.

Keywords: Bioassays; Cell systems; Microfluidics; Osteoblast; Shear stress; Differentiation

Characterization of cellular chemical dynamics using combined microfluidic and Raman techniques by Xunli Zhang; Huabing Yin; Jon M. Cooper; Stephen J. Haswell (pp. 833-840).

The integration of a range of technologies including microfluidics, surface-enhanced Raman scattering and confocal microspectroscopy has been successfully used to characterize in situ single living CHO (Chinese hamster ovary) cells with a high degree of spatial (in three dimensions) and temporal (1 s per spectrum) resolution. Following the introduction of a continuous flow of ionomycin, the real time spectral response from the cell was monitored during the agonist-evoked Ca²⁺ flux process. The methodology described has the potential to be used for the study of the cellular dynamics of a range of signalling processes. Figure Spectral mapping of a single CHO cell

Keywords: Microfluidics; Chinese hamster ovary (CHO) cells; Confocal microspectroscopy; Surface-enhanced Raman scattering (SERS); Dynamic monitoring

Miniaturized planar lipid bilayer: increased stability, low electric noise and fast fluid perfusion by Tivadar Mach; Catalin Chimerel; Jürgen Fritz; Niels Fertig; Mathias Winterhalter; Claus Fütterer (pp. 841-846).

A microfluidic device was designed allowing the formation of a planar lipid bilayer across a micron-sized aperture in a glass slide sandwiched between two polydimethylsiloxane channel systems. By flushing giant unilamellar vesicles through a 500-μm-wide channel above the hole, we were able to form a planar lipid bilayer across the hole, resulting in a giga-seal. We demonstrate incorporation of biological nanopores into the bilayer. This miniaturized system offers noise recordings comparable to open headstage noise (under 1 pA RMS at 10 kHz), fast precision perfusion on each side of the membrane and the use of nanoliter analyte volumes. This technique shows a promising potential for automation and parallelization of electrophysiological setups.

Keywords: Microfluidics; Planar bilayer; Electrophysiology; Membrane channel

Performance impact of dynamic surface coatings on polymeric insulator-based dielectrophoretic particle separators by Rafael V. Davalos; Gregory J. McGraw; Thomas I. Wallow; Alfredo M. Morales; Karen L. Krafcik; Yolanda Fintschenko; Eric B. Cummings; Blake A. Simmons (pp. 847-855).

Efficient and robust particle separation and enrichment techniques are critical for a diverse range of lab-on-a-chip analytical devices including pathogen detection, sample preparation, high-throughput particle sorting, and biomedical diagnostics. Previously, using insulator-based dielectrophoresis (iDEP) in microfluidic glass devices, we demonstrated simultaneous particle separation and concentration of various biological organisms, polymer microbeads, and viruses. As an alternative to glass, we evaluate the performance of similar iDEP structures produced in polymer-based microfluidic devices. There are numerous processing and operational advantages that motivate our transition to polymers such as the availability of numerous innate chemical compositions for tailoring performance, mechanical robustness, economy of scale, and ease of thermoforming and mass manufacturing. The polymer chips we have evaluated are fabricated through an injection molding process of the commercially available cyclic olefin copolymer Zeonor 1060R. This publication is the first to demonstrate insulator-based dielectrophoretic biological particle differentiation in a polymeric device injection molded from a silicon master. The results demonstrate that the polymer devices achieve the same performance metrics as glass devices. We also demonstrate an effective means of enhancing performance of these microsystems in terms of system power demand through the use of a dynamic surface coating. We demonstrate that the commercially available nonionic block copolymer surfactant, Pluronic F127, has a strong interaction with the cyclic olefin copolymer at very low concentrations, positively impacting performance by decreasing the electric field necessary to achieve particle trapping by an order of magnitude. The presence of this dynamic surface coating, therefore, lowers the power required to operate such devices and minimizes Joule heating. The results of this study demonstrate that iDEP polymeric microfluidic devices with surfactant coatings provide an affordable engineering strategy for selective particle enrichment and sorting. Figure Model generated image (COMSOL) depicting the electric field gradient divided by the electric field that occurs within an array of insulating posts

Keywords: Microfluidics/microfabrication; Surfactants; Biological samples; Bioanalytical methods

Gravitation-driven stress-reduced cell handling by Michael Boettcher; Magnus Jaeger; Michael Kirschbaum; Torsten Mueller; Thomas Schnelle; Claus Duschl (pp. 857-863).

We present a simple lab-on-chip device for handling small samples of delicate cells, e.g. stem cells. It uses a combination of sedimentation and dielectrophoresis. The transport of cells is driven by gravitation. Dielectrophoresis uses radio-frequency electric fields for generating particle-selective forces dependent on size and polarisability. Electrodes along the channels hold particles and/or cells in a defined position and deflect them towards different outlets. The absence of external pumping and the integration of injection and sampling ports allow the processing of tiny sample volumes. Various functions are demonstrated, such as contact-free cell trapping and cell/particle sorting. Pairs of human cells and antibody-coated beads, as they are formed for T cell activation, are separated from unbound beads. The cells experience only low stress levels compared with the stress levels in dielectrophoresis systems, where transport depends on external pumping. Our device is a versatile yet simple tool that finds applications in cellular biotechnology, in particular when an economic solution is required. Figure A simple gravitation-driven lab-on-chip device for the separation of mixed populations of microparticles or cells by negative dielectrophoresis.

Keywords: Dielectrophoresis; Sedimentation; Microfluidics; Cell separation; Low-stress cell handling

Electrogeneration of polyluminol and chemiluminescence for new disposable reagentless optical sensors by Audrey Sassolas; Loïc J. Blum; Béatrice D. Leca-Bouvier (pp. 865-871).

A performant reagentless electrochemiluminescent (ECL) detection system for H₂O₂ is presented, based on an electropolymerized polyluminol film prepared under near-neutral conditions. Such an original polyluminol electrodeposition is reported for the first time and on a screen-printed electrode (SPE) surface. Electropolymerized luminol acts as an active luminophore of the electrochemiluminescent reaction, as the monomer does. Polymerization conditions have been optimized in order to obtain the best ECL responses to H₂O₂. By performing electrodeposition in a potentiostatic mode, at 425 mV vs. Ag|AgCl, in 0.1 mol L⁻¹ phosphate/0.1 mol L⁻¹ KCl pH 6 and 1 mmol L⁻¹ luminol, with a total charge of 0.5 mC, the linear range for H₂O₂ detection extends from 7.9 × 10⁻⁸ mol L⁻¹ to 1.3 × 10⁻³ mol L⁻¹. Such performant disposable reagentless easy-to-use miniaturized systems based on SPEs should be applicable to the electrochemiluminescent detection of many oxidase-substrate compounds. Figure An original polyluminol electrodeposition process on a screen-printed electrode surface is reported for the first time. The polymeric structure is demonstrated to behave as an electrochemiluminescent luminophore, allowing disposable reagentless easy-to-use optical sensors for hydrogen peroxide detection to be designed.

Keywords: Luminol; Electropolymerization; Electrochemiluminescence; Optical detection; Screen-printed electrode

Determination of estrogen presence in water by SPR using estrogen receptor dimerization by Denis Habauzit; Jean Armengaud; Benoit Roig; Joël Chopineau (pp. 873-883).

Estrogenic compounds are a class of pharmaceutical products harmful to animals and a cause of environmental damage. The biological activity of these compounds is high since they have been designed to act at low concentrations. Thus, even at the low concentrations found in the environment, they may produce deleterious effects on aquatic organisms as well as on humans, who might be contaminated in a number of ways (via drinking water or contaminated food, for example). We used the property of these compounds to bind a specific protein (estrogen receptor, ER) to develop a quantification method of these chemical entities. Estrogenic compound detection was performed using ER dimerization properties monitored by surface plasmon resonance (SPR). The ligand-activated ER dimer was detected by its interaction with a specific DNA consensus sequence estrogen response element. The concentration and the nature of the estrogenic compounds modified the SPR signal and were characteristic of the ligand-dependent homodimerization of ER. For 17β-estradiol, dimerization of ER was experimentally determined at an ER to 17β-estradiol ratio near 1:1. Estrogenic compounds (17β-estradiol, estriol, estrone, ethynyl estradiol) activated the dimerization process at different concentration levels, while some others (tamoxiphen, resveratrol, genistein, bisphenol A) did not seem to have any effects on it. We demonstrated that this method allows the direct detection of 17β-estradiol at concentrations above 1.4 μg/L (5 nM).

Keywords: Surface plasmon resonance; Estrogen analysis; Estrogen receptor; Dimerization

Estimation of bacterial biomass in subsurface sediments by quantifying intact membrane phospholipids by Klaus-G. Zink; Kai Mangelsdorf; Liba Granina; Brian Horsfield (pp. 885-896).

In an earlier study of deep subsurface sediments from Nankai Trough (ODP Leg 190, offshore Japan) we employed intact phospholipids (PLs) as molecular indicators of living microorganisms. The current study extends this work by quantifying absolute amounts of sedimentary PLs by liquid chromatography-mass spectrometry (LC-MS) and by converting PL data into cell numbers in order to improve methods to estimate the extent of bacterial life in the subsurface. Investigations were carried out on 90 cm short cores of Lake Baikal sediment. High amounts of identified intact PLs are interpreted as reflecting the constituents of living bacteria due to high organic matter decomposition and oxic mineralisation between the epilimnion and the sediment-water interface. Concentrations of ester-bound PLs reach up to 13,120 ng/g sediment dry weight. Predominance of ethanolamine and glycerol PL head groups confirms the bacterial origin. The most abundant side-chain pairs are combinations including 14:0 and 16:0 fatty acids and to a minor extent 15:0 and 16:1 fatty acids. Depth profiles of PL concentrations converted from conventional PL fatty acid analysis are of the same order of magnitude and show comparable trends as those for intact PLs. An approximate estimation of bacterial cell numbers is inferred from intact PL quantification using LC-MS.

Keywords: Intact phospholipids; Quantification; Liquid chromatography-mass spectrometry; Phospholipid fatty acids; Lake Baikal

Retention characteristics of a new butylimidazolium-based stationary phase. Part II: anion exchange and partitioning by David S. Van Meter; Yaqin Sun; Kevin M. Parker; Apryll M. Stalcup (pp. 897-905).

A surface-confined ionic liquid (SCIL) and a commercial quaternary amine silica-based stationary phase were characterized employing the linear solvation energy relationship (LSER) method in binary methanol/water mobile phases. The retention properties of the stationary phases were evaluated in terms of intermolecular interactions between 28 test solutes and the stationary phases. The comparison reveals a difference in the hydrophobic and hydrogen bond acceptance interaction properties between the two phases. The anion exchange retention mechanism of the SCIL phase was demonstrated using nucleotides. The utility of the SCIL phase in predicting logk _IL/water values by chromatographic methods is also discussed.

Keywords: Butylimidazolium bromide; LSER; Ion exchange HPLC; RP-HPLC; Ionic liquid; Retention mechanisms

Monolithic macroporous albumin/chitosan cryogel structure: a new matrix for enzyme immobilization by Martin Hedström; Fatima Plieva; Igor Yu. Galaev; Bo Mattiasson (pp. 907-912).

A novel monolithic macroporous material was developed by cross-linking hen egg albumin (HEA) and chitosan with glutaraldehyde at subzero temperatures. A macroporous cryogel structure allowed efficient mass transport of solutes within the material. In one application, albumin was partially replaced with active enzymes (glucose oxidase and horseradish peroxidase) resulting in the production of macroporous biocatalyst preparations suitable for flow-injection analysis of glucose in the low millimolar range. In another application, the proteolytic enzymes savinase and esperase were coupled to the macroporous structure via free amino groups on the pore walls using glutaraldehyde as cross-linker/spacer agent. The low hydraulic resistance of the matrix allowed for the development of a generic, high-performance online protein digestion system utilizing the wall-bound proteases.

Keywords: Chitosan; Macroporous; Cryogel; Scaffold; Staphylococcal enterotoxin B

Preparation of β-caryophyllene oxidation products and their determination in ambient aerosol samples by Jevgeni Parshintsev; Joonas Nurmi; Ilkka Kilpeläinen; Kari Hartonen; Markku Kulmala; Marja-Liisa Riekkola (pp. 913-919).

Oxidation of β-caryophyllene with ozone followed by reduction was carried out in dichloromethane. Reaction led to the formation of β-caryophyllene aldehyde (11%, purity 90.8%) and β-nocaryophyllone aldehyde (79%, purity 99%). Compounds were purified and separated by liquid–liquid extraction and flash chromatography. Identifications were achieved by electron-impact and electrospray ionization mass spectrometry, and precise structures were confirmed by one and two-dimensional nuclear magnetic resonance spectroscopy. The prepared compounds were used in the analysis of ambient aerosol samples collected during spring 2003 at Hyytiälä, Finland. β-Nocaryophyllone aldehyde was positively identified and quantified in ambient aerosol samples for the first time. The amount of quantified β-nocaryophyllone aldehyde of aerosol origin was 17.4 ± 1.0 ng m⁻³ of sampled air. Comparison with previous findings led to the conclusion that oxidation products of β-caryophyllene participate in biogenic aerosol formation over boreal forest during late spring.

Keywords: β-Caryophyllene; β-Caryophyllene aldehyde; β-Nocaryophyllone aldehyde; Oxidation; Ozonolysis; Aerosol particle; GC–MS

Molecular characterization of brominated persistent pollutants using extended X-ray absorption fine structure (EXAFS) spectroscopy by Magnus Bergknut; Per Persson; Ulf Skyllberg (pp. 921-928).

X-ray absorption fine structure (EXAFS) spectroscopy spectra were collected for three brominated persistent pollutants: 6-bromo-2,4,5-trichlorophenol (BrTriClP), pentabromophenol (PentaBrP) and 3,3′,5,5′-tetrabromobisphenol A (TBBA). The substances were selected to be symmetrical (BrTriClP and TBBA) or asymmetrical (PentaBrP) with respect to the atomic Br positions and to differ in the number of bromine and other halide atoms, as well as their relative positions. The asymmetrical PentaBrP was modelled with special detail as not all bromine atoms have identical coordination environments. The studied substances displayed unique EXAFS spectra, which could be used to determine the molecular structure in fair detail. We conclude that EXAFS spectroscopy is a suitable technique for molecular characterization of the comparatively complex molecules within the class of compounds of brominated organic persistent pollutants. A detailed understanding of the EXAFS spectra of the pure compounds opens up possibilities to study the interactions with soil and sediment matrices by means of EXAFS spectroscopy. Figure Brominated organic persistent pollutants are characterized by EXAFS spectroscopy

Keywords: EXAFS; Brominated; Organohalogens; Molecular structure; TBBA; BFR

Electrospun polymer nanofibers as a solid-phase extraction sorbent for the determination of trace pollutants in environmental water by Dongjin Qi; Xuejun Kang; Liqin Chen; Yiyun Zhang; Hongmei Wei; Zhongze Gu (pp. 929-938).

This paper describes the novel preparation of three kinds of nanofibers [poly(styrene-co-methacrylic acid), poly(styrene-co-p-styrene sulfonate), polystyrene] investigated as solid-phase extraction (SPE) sorbents to extract six compounds (nitrobenzene, 2-naphthol, benzene, n-butyl p-hydroxybenzoate, naphthalene, p-dichlorobenzene) in environmental water by high-performance liquid chromatography. Parameters affecting extraction efficiency were investigated in detail to explore the extraction mechanism of the nanofibers. Under optimized conditions, six compounds followed an excellent linear relationship in the range 10–5,000 ng mL⁻¹ with coefficients of determination (r ²) greater than 0.99. The repeatability (expressed as relative standard deviations) was from 3.0 to 7.0%, corresponding to 2.0 mL of water samples at 25 and 500 ng mL⁻¹ spiked levels for the six compounds. The limits of detection varied from 0.01 to 0.15 ng mL⁻¹ (signal-to-noise ratio of3). A comparison of the SPE using nanofibers as sorbents and the most commonly used octadecylsilica SPE cartridges was carried out in terms of absolute recovery, sensitivity, and reproducibility for the compounds investigated. Finally, the method was applied to four real water samples. The results highlighted the importance of functional groups, and the polarity of nanofibers in controlling sorption of target compounds, and clearly showed that the new method could be a viable and environmentally friendly technique for analyzing pollutants in environmental samples.

Keywords: Solid-phase extraction; Preconcentration; Electrospinning; Nanofibers; Aromatic hydrocarbons; Water samples

Electrochemical preparation of copper–dendrimer nanocomposites: picomolar detection of Cu²⁺ ions by Sheela Berchmans; T. Mary Vergheese; A. L. Kavitha; Manoj Veerakumar; V. Yegnaraman (pp. 939-946).

The present work describes, for the first time, in situ electrochemical preparation of dendrimer-encapsulated Cu nanoparticles using a self-assembled monolayer of fourth-generation amine-terminated polyamidoamine (PAMAM) dendrimer as the template. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) studies of the modified surface confirmed the presence of Cu nanoparticles entrapped in dendrimer film. Au electrode modified with a monolayer of the dendrimer enables preconcentration and subsequent voltammetric detection of Cu²⁺ at picomolar concentrations. Further, Cu nanoparticles in the dendrimer monolayer could be electrochemically derivatised to Cu hexacyanoferrate, which exhibits specific crystal planes, unlike the random distribution of crystal planes in bulk-formed Cu hexacyanoferrate, which is another catalytically active material for sensor applications. Figure Electrochemical preparation of copper–dendrimer nanocomposite

Keywords: PAMAM dendrimers; Copper–dendrimer nanocomposite; Trace analysis; Copper ions; Templated growth

High-throughput determination of pesticide residues in food commodities by use of ultra-performance liquid chromatography–tandem mass spectrometry by A. Garrido Frenich; J. L. Martínez Vidal; E. Pastor-Montoro; R. Romero-González (pp. 947-959).

A rapid, simple, and sensitive multiresidue method for analysis of 53 pesticides in fruit and vegetables by ultra-performance liquid chromatography (UPLC) coupled to triple-quadrupole tandem mass spectrometry (MS-MS) has been developed and validated. Prior to analysis, analytes were extracted by use of buffered QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without further cleanup for non fatty matrices. Chromatographic conditions were optimised in order to achieve a fast separation in multiple reaction monitoring (MRM) mode. Indeed, more than 50 pesticides can be separated in less then 10 min. Four common representative matrices (cucumber, orange, strawberry, and olive) were selected to investigate the effect of different matrices on recovery and precision. Mean recoveries ranged from 70 to 109% with relative standard deviations lower than 20% for all the pesticides assayed in the four selected matrices. The method has been applied to the analysis of 200 vegetable samples, and imidacloprid was the pesticide most frequently found, with concentrations ranging from 0.01 to 1.00 mg kg⁻¹. This methodology combines the advantages of both QuEChERS and UPLC-MS-MS producing a very rapid, sensitive, and reliable procedure which can be applied in routine analytical laboratories.

Keywords: UPLC; Sample throughput; Tandem mass spectrometry; QuEChERS; Vegetables; Pesticides

Differentiation of certified brands of origins of Spanish white wines by HS-SPME-GC and chemometrics by J. M. Jurado; O. Ballesteros; A. Alcázar; F. Pablos; M. J. Martín; J. L. Vilchez; A. Navalón (pp. 961-970).

A headspace solid-phase microextraction gas-chromatographic (HS-SPME-GC) procedure was used to determine the composition of the volatile fraction of white wine samples from several Spanish certified brands of origin (CBO). The compounds present were previously identified by gas chromatography−mass spectrometry (GC−MS) and quantitative determinations were carried out by GC-FID. Four CBO, Rueda, Ribeiro, Penedés, and Condado de Huelva, were studied. Rueda wines present the highest concentrations of ethyl acetate (55.86−125.27 μg mL⁻¹), isoamyl acetate (0.91−6.72 μg mL⁻¹), hexyl acetate (0.09−0.81 μg g mL⁻¹), and 2-phenethyl acetate (0.14−0.66 μg mL⁻¹). Compounds such as ethyl hexanoate (0.88−2.15 μg mL⁻¹) and ethyl decanoate (0.29−0.96 μg mL⁻¹) appeared in higher concentration in Ribeiro, Rueda, and Penedés samples. According to the results obtained and by applying pattern-recognition procedures differentiation of the considered CBO was attained. Principal-component analysis (PCA), linear discriminant analysis (LDA), and multilayer perceptrons neural networks (MLP-NN) were used as chemometric tools for pattern-recognition studies.

Keywords: Wine; Volatile compounds; Chemometrics; Gas chromatography; Solid-phase microextraction

An amperometric hydrogen peroxide biosensor based on immobilization of horseradish peroxidase on an electrode modified with magnetic dextran microspheres by Hai-Li Zhang; Guo-Song Lai; De-Yan Han; Ai-Min Yu (pp. 971-977).

A new kind of magnetic dextran microsphere (MDMS) with uniform shape and narrow diameter distribution has been prepared from magnetic iron nanoparticles and dextran. Horseradish peroxidase (HRP) was successfully immobilized on the surface of an MDMS-modified glassy-carbon electrode (GCE), and the immobilized HRP displayed excellent electrocatalytic activity in the reduction of H₂O₂ in the presence of the mediator hydroquinone (HQ). The effects of experimental variables such as the concentration of HQ, solution pH, and the working potential were investigated for optimum analytical performance. This biosensor had a fast response to H₂O₂ of less than 10 s and an excellent linear relationship was obtained in the concentration range 0.20 μmol L⁻¹–0.68 mmol L⁻¹, with a detection limit of 0.078 μmol L⁻¹ (S/N = 3) under the optimum conditions. The response showed Michaelis–Menten behavior at larger H₂O₂ concentrations, and the apparent Michaelis–Menten constant $$ K^{{app}}_{M} $$ was estimated to be 1.38 mmol L⁻¹. Moreover, the selectivity, stability, and reproducibility of the biosensor were evaluated, with satisfactory results. Figure Amperometric response of the biosensor to successive additions of H₂O₂ and the plot of amperometric response vs. H₂O₂ concentration

Keywords: Horseradish peroxidase; Hydrogen peroxide; Magnetic microspheres; Biosensor

A catalytic adsorptive stripping voltammetric procedure for trace determination of Cr(VI) in natural samples containing high concentrations of humic substances by Malgorzata Grabarczyk (pp. 979-986).

A simple and fast catalytic adsorptive stripping voltammetric procedure for trace determination of Cr(VI) in natural samples containing high concentrations of humic substances has been developed. The procedure for chromium determination in the presence of DTPA and nitrates was employed as the initial method. In order to enhance the selectivity vs. Cr(III) the measurements were performed at 40°C. Interference from dissolved organic matter such as humic and fulvic acids was drastically decreased by adding Amberlite XAD-7 resin to the voltammetric cell before the deaeration step. The whole procedure was applied to a single cell, which allowed monitoring of the voltammetric scan. Optimum conditions for removing humic and fulvic acids due to their adsorption on XAD-7 resin were evaluated. The use of XAD-7 resin also minimize interferences from various cationic, anionic, and nonionic surfactants. The calibration graph for Cr(VI) for an accumulation time of 30 s was linear in the range 5 × 10⁻¹⁰ to 5 × 10⁻⁸ mol L⁻¹. The relative standard deviation for determination of Cr(VI) at a concentration of 1 × 10⁻⁸ mol L⁻¹ was 3.5% (n = 5). The detection limit estimated from 3 times the standard deviation for low Cr(VI) concentrations and an accumulation time of 30 s was about 1.3 × 10⁻¹⁰ mol L⁻¹. The proposed method was successfully applied to Cr(VI) determination at trace levels in soil samples.

Keywords: Hexavalent chromium; Determination; Voltammetry; Humic substances

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Analytical and Bioanalytical Chemistry (v.390, #3)