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Analytical and Bioanalytical Chemistry (v.401, #10)

Thanks to reviewers in 2011 (pp. 3019-3032).

Jürgen H. Gross: Mass spectrometry–A Textbook, 2nd ed. by Wolf Dieter Lehmann (pp. 3033-3034).

Vladimir M. Mirsky and Anatoly Yatsimirsky (Eds.): Artificial receptors for chemical sensors by Ryan J. White (pp. 3035-3036).

Eighth Advanced Study Course on Optical Chemical Sensors—ASCOS by A. Katrin Krieg; Sabrina Rau; Oliver Bleher; Felix Kolarov; Melanie Ewald (pp. 3037-3038).

2012 Bunsen-Kirchhoff Award for Analytical Spectroscopy by Detlef Günther (pp. 3039-3039).

Ambient aerosols and human health: working towards a combined analytical and toxicological approach by Ralf Zimmermann (pp. 3041-3044).

is Full Professor of Analytical Chemistry at the University of Rostock (UR) and also Head of the Cooperation Group “Comprehensive Molecular Analytics (CMA)” at the Helmholtz Zentrum München (HMGU). The Chair of Analytical Chemistry and the CMA together represent the Joint Mass Spectrometry Centre of UR and HMGU (JMSC, www.jmsc.de), which is also headed by Prof. Zimmermann. His research interests include instrumental development and application of photoionization mass spectrometry, comprehensive multidimensional chromatography, industrial process analysis, applied combustion research, metabolomics and aerosol analysis.

Understanding atmospheric organic aerosols via factor analysis of aerosol mass spectrometry: a review by Qi Zhang; Jose L. Jimenez; Manjula R. Canagaratna; Ingrid M. Ulbrich; Nga L. Ng; Douglas R. Worsnop; Yele Sun (pp. 3045-3067).

Organic species are an important but poorly characterized constituent of airborne particulate matter. A quantitative understanding of the organic fraction of particles (organic aerosol, OA) is necessary to reduce some of the largest uncertainties that confound the assessment of the radiative forcing of climate and air quality management policies. In recent years, aerosol mass spectrometry has been increasingly relied upon for highly time-resolved characterization of OA chemistry and for elucidation of aerosol sources and lifecycle processes. Aerodyne aerosol mass spectrometers (AMS) are particularly widely used, because of their ability to quantitatively characterize the size-resolved composition of submicron particles (PM₁). AMS report the bulk composition and temporal variations of OA in the form of ensemble mass spectra (MS) acquired over short time intervals. Because each MS represents the linear superposition of the spectra of individual components weighed by their concentrations, multivariate factor analysis of the MS matrix has proved effective at retrieving OA factors that offer a quantitative and simplified description of the thousands of individual organic species. The sum of the factors accounts for nearly 100% of the OA mass and each individual factor typically corresponds to a large group of OA constituents with similar chemical composition and temporal behavior that are characteristic of different sources and/or atmospheric processes. The application of this technique in aerosol mass spectrometry has grown rapidly in the last six years. Here we review multivariate factor analysis techniques applied to AMS and other aerosol mass spectrometers, and summarize key findings from field observations. Results that provide valuable information about aerosol sources and, in particular, secondary OA evolution on regional and global scales are highlighted. Advanced methods, for example a-priori constraints on factor mass spectra and the application of factor analysis to combined aerosol and gas phase data are discussed. Integrated analysis of worldwide OA factors is used to present a holistic regional and global description of OA. Finally, different ways in which OA factors can constrain global and regional models are discussed.

Keywords: Aerosol mass spectrometer (AMS); Positive matrix factorization (PMF); Bilinear factorization; Primary organic aerosol (POA); Secondary organic aerosol (SOA); Aerosol sources; Aerosol processes; Aerosol life cycle

Baltimore PM2.5 Supersite: highly time-resolved organic compounds—sampling duration and phase distribution—implications for health effects studies by Wolfgang F. Rogge; John M. Ondov; Anna Bernardo-Bricker; Orhan Sevimoglu (pp. 3069-3082).

As part of the Baltimore PM2.5 Supersite study, intensive three-hourly continuous PM2.5 sampling was conducted for nearly 4 weeks in summer of 2002 and as well in winter of 2002/2003. Close to 120 individual organic compounds have been quantified separately in filter and polyurethane foam (PUF) plug pairs for 17 days for each sampling period. Here, the focus is on (1) describing briefly the new sampling system, (2) discussing filter/PUF plugs breakthrough experiments for semi-volatile compounds, (3) providing insight into phase distribution of semi-volatile organic species, and (4) discussing the impact of air pollution sampling time on human exposure with information on maximum 3- and 24-h averaged ambient concentrations of potentially adverse health effects causing organic pollutants. The newly developed sampling system consisted of five electronically controlled parallel sampling channels that are operated in a sequential mode. Semi-volatile breakthrough experiments were conducted in three separate experiments over 3, 4, and 5 h each using one filter and three PUF plugs. Valuable insight was obtained about the transfer of semi-volatile organic compounds through the sequence of PUF plugs and a cut-off could be defined for complete sampling of semi-volatile compounds on only one filter/PUF plug pair, i.e., the setup finally used during the seasonal PM2.5 sampling campaign. Accordingly, n-nonadecane (C19) with a vapor pressure (vp) of 3.25 × 10⁻⁴ Torr is collected with > 95% on the filter/PUF pair. Applied to phenanthrene, the most abundant the PAH sampled, phenanthrene (vp, 6.2 × 10⁻⁵ Torr) was collected completely in wintertime and correlates very well with three-hourly PM2.5 ambient concentrations. Valuable data on the fractional partitioning for semi-volatile organics as a function of season is provided here and can be used to differentiate the human uptake of an organic pollutant of interest via gas- and particle-phase exposure. Health effects studies often relay on PM2.5 exposure measurements taken over 24 h or longer. We found that maximum 3-h concentrations are frequently two to five times higher than that found for maximum 24-h concentrations, an important aspect when considering that short-term exposure to higher air pollution levels are more likely to overpower defense mechanisms in the human lung with subsequent adverse effects even at lower pollutant levels.

Keywords: Multi-channel sampling system; Exposure to PM2.5; Semi-volatile organic compounds; Gas- and particle-phase partitioning; PM Supersite

Application of direct thermal desorption gas chromatography time-of-flight mass spectrometry for determination of nonpolar organics in low-volume samples from ambient particulate matter and personal samplers by Jürgen Schnelle-Kreis; Jürgen Orasche; Gülcin Abbaszade; Klaus Schäfer; David P. Harlos; Anthony D. A. Hansen; Ralf Zimmermann (pp. 3083-3094).

Direct thermal desorption and in-situ derivatization thermal desorption methods in conjunction with gas chromatography time-of-flight mass spectrometry have been characterized and evaluated for analysis of trace components from filters loaded with ambient particulate matter (PM). The limits of quantification were in the range of 7–24 pg for n-alkanes, 20 pg for hopanes, and 4–22 pg for polycyclic aromatic hydrocarbons (PAH). The limit of quantification was defined as the minimum amount of substance that conforms to the minimum distinguishable signal plus 9 times the standard deviation of this background signal from PM-loaded filters. The method has been successfully applied to low-volume samples from ambient PM collected with stationary and personal samplers. Stationary samples were collected in winter 2008 and 2010 in Augsburg, Germany. Sample aliquots of 0.2-0.3 m³ from stationary sampling were analyzed. High diurnal variation in concentration and source contribution was found especially during periods with low wind speed and low mixing layer height. High contributions of solid fuel combustion (wood and coal) were found in evening and nighttime samples, leading to peak PAH concentrations at midnight more than 10 times higher than at noon. Finally, the method was applied to samples collected by means of a personal sampler, i.e. a micro aethalometer, in Xi’an, China. Quantitative data on n-alkanes, hopanes, and PAH were obtained from sample volumes of 17 and 24 l. The impact of different sources such as vehicular and biogenic emissions could be distinguished. Figure Left side: “personal sampling” with Micro Aethalometer (microAeth® Model AE51, Magee Scientific, USA), right: section of the chromatograms from low volume personal samples showing mass trace m/z= 276.

Keywords: Thermal desorption; Gas chromatography–mass spectrometry; Polycyclic aromatic hydrocarbons; Ambient particulate matter; Personal sample

Characterisation of airborne particles and associated organic components produced from incense burning by Hsiao-Chi Chuang; Tim Jones; Yang Chen; Jennifer Bell; John Wenger; Kelly BéruBé (pp. 3095-3102).

Airborne particles generated from the burning of incense have been characterized in order to gain an insight into the possible implications for human respiratory health. Physical characterization performed using field-emission scanning electron microscopy showed incense particulate smoke mainly consisted of soot particles with fine and ultrafine fractions in various aggregated forms. A range of organic compounds present in incense smoke have been identified using derivatisation reactions coupled with gas chromatography–mass spectrometry analysis. A total of 19 polar organic compounds were positively identified in the samples, including the biomass burning markers levoglucosan, mannosan and galactosan, as well as a number of aromatic acids and phenols. Formaldehyde was among 12 carbonyl compounds detected and predominantly associated with the gas phase, whereas six different quinones were also identified in the incense particulate smoke. The nano-structured incense soot particles intermixed with organics (e.g. formaldehyde and quinones) could increase the oxidative capacity. When considering the worldwide prevalence of incense burning and resulting high respiratory exposures, the oxygenated organics identified in this study have significant human health implications, especially for susceptible populations.

Keywords: Carbonyl; Combustion; Incense; Joss sticks; Polar organic; Quinone

An advanced LC-MS (Q-TOF) technique for the detection of amino acids in atmospheric aerosols by Shar Samy; James Robinson; Michael D. Hays (pp. 3103-3113).

Methodology for detection of native (underivatized) amino acids (AA) in atmospheric aerosols has been developed. This article describes the use of LC-MS (Q-TOF) and microwave-assisted gas phase hydrolysis for detection of free and combined amino acids in aerosols collected in a Southeastern U.S. forest environment. Accurate mass detection and the addition of isotopically labeled surrogates prior to sample preparation allows for sensitive quantitation of target AA in a complex aerosol matrix. A total of 16 native AA were detected above the reporting threshold as water-soluble free AA, with an average concentration of 22 ± 9 ng m⁻³ (N = 13). Following microwave-assisted gas phase hydrolysis, the total AA concentration in the forest environment increased significantly (70 ± 35 ng m⁻³) and additional compounds (methionine, isoleucine) were detected above the reporting threshold. The ability to quantify AA in aerosol samples without derivatization reduces time-consuming preparation procedures while providing the advancement of selective mass determination for important organic nitrogen (ON) species. Details on sample preparation that eliminates the freeze-drying approach typically practiced for water removal with biological samples, and vapor phase microwave hydrolysis parameters are provided. Method application for determination of atmospheric ON is discussed.

Keywords: Organic nitrogen; Atmospheric amino acids; Native amino acid detection; Water-soluble organic nitrogen; Atmospheric proteinaceous material; Water-soluble organic compounds

Development and validation of a selective HPLC-ESI-MS/MS method for the quantification of glyoxal and methylglyoxal in atmospheric aerosols (PM_2.5) by Christopher J. Kampf; Boris Bonn; Thorsten Hoffmann (pp. 3115-3124).

This study concerns the development and validation of a complete method for the analysis of two highly reactive α-dicarbonyl compounds, glyoxal (Gly) and methylglyoxal (Mgly), in atmospheric fine particulate matter (PM_2.5). Method development included optimization of sample preparation procedures, e.g., filter extraction, concentration of extracts, derivatization and solid-phase extraction (SPE) of derivatives, as well as reversed-phase liquid chromatography coupled to electrospray ion-trap mass spectrometry (HPLC-ESI-IT/MS/MS) measurement parameters. Selectivity of detection was enhanced using tandem mass spectrometric analysis in ESI positive ion mode via two multiple reaction monitoring channels, m/z 433 → m/z 250 and m/z 419 → m/z 236 for Mgly and Gly. Retention times were 9.5 and 12.5 min for Gly- and Mgly-bis-hydrazone derivatives. Calibration ranged from 0.5 to 50 ng/mL. Inter-batch precision, expressed as relative standard deviation, was <15%. The method was shown to be unaffected by the sample matrix and to have recoveries of 100% and 60% for Gly and Mgly, respectively. Improved instrumental detection limits of 0.51 and 0.62 ng/mL for Gly and Mgly were achieved using a SPE method for the purification of 2,4-dinitrophenylhydrazine derivatization reagent solutions. This permitted the method to be used for analysis of filter samples obtained during a field study at the Taunus Observatory (mount Kleiner Feldberg, Germany). PM_2.5 concentrations ranged from 0.81 to 1.18 ng/m³ for Gly and from 0.83 to 1.92 ng/m³ for Mgly. PM concentrations correlated to the concentration of NO with coefficients (R ²) of 0.67 (Gly) and 0.78 (Mgly).

Keywords: Glyoxal; Methylglyoxal; PM_2.5 ; DNPH; HPLC-MS/MS

Nonpolar organic compounds in fine particles: quantification by thermal desorption–GC/MS and evidence for their significant oxidation in ambient aerosols in Hong Kong by Jian Zhen Yu; X. H. Hilda Huang; Steven S. H. Ho; Qijing Bian (pp. 3125-3139).

Nonpolar organic compounds (NPOCs) in ambient particulate matter (PM) commonly include n-alkanes, branched alkanes, hopanes and steranes, and polycyclic aromatic hydrocarbons (PAHs). The recent development of thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) has greatly reduced time and labor in their quantification by eliminating the laborious solvent extraction and sample concentration steps in the traditional approach that relies on solvent extraction. The simplicity of the TD-GCMS methods has afforded us concentration data of NPOCs in more than 90 aerosol samples in two aerosol field studies and 20 vehicular emissions-dominated source samples in Hong Kong over the past few years. In this work, we examine the interspecies relationships between select NPOCs and their concentration ratios to elemental carbon (EC) among the ambient samples and among the source samples. Our analysis indicates that hopanes were mainly from vehicular emissions and they were significantly oxidized in ambient PM. The hopane/EC ratio in ambient samples was on average less than half of the ratio in vehicular emissions-dominated source samples. This highlights the necessity in considering oxidation loss in applying organic tracer data in source apportionment studies. Select PAH/EC ratio–ratio plots reveal that PAHs had diverse sources and vehicular emissions were unlikely a dominant source for PAHs in Hong Kong. Biomass burning and other regional sources likely dominated ambient PAHs in Hong Kong.

Keywords: Organic aerosols; Source apportionment; Molecular tracers; Atmospheric oxidation; Carbonaceous aerosol; Squalane

Quality assurance and quality control for thermal/optical analysis of aerosol samples for organic and elemental carbon by Judith C. Chow; John G. Watson; Jerome Robles; Xiaoliang Wang; L.-W. Antony Chen; Dana L. Trimble; Steven D. Kohl; Richard J. Tropp; Kochy K. Fung (pp. 3141-3152).

Accurate, precise, and valid organic and elemental carbon (OC and EC, respectively) measurements require more effort than the routine analysis of ambient aerosol and source samples. This paper documents the quality assurance (QA) and quality control (QC) procedures that should be implemented to ensure consistency of OC and EC measurements. Prior to field sampling, the appropriate filter substrate must be selected and tested for sampling effectiveness. Unexposed filters are pre-fired to remove contaminants and acceptance tested. After sampling, filters must be stored in the laboratory in clean, labeled containers under refrigeration (<4 °C) to minimize loss of semi-volatile OC. QA activities include participation in laboratory accreditation programs, external system audits, and interlaboratory comparisons. For thermal/optical carbon analyses, periodic QC tests include calibration of the flame ionization detector with different types of carbon standards, thermogram inspection, replicate analyses, quantification of trace oxygen concentrations (<100 ppmv) in the helium atmosphere, and calibration of the sample temperature sensor. These established QA/QC procedures are applicable to aerosol sampling and analysis for carbon and other chemical components. Figure Distributions of the 3,460 OC and EC replicate analyses of the IMPROVE filter samples collected between January 01, 2006 and December 31, 2011 using 11 DRI Model 2001 thermal/optical carbon analyzers

Keywords: Thermal/optical carbon analysis; IMPROVE_A protocol; Aerosol; Organic carbon; Elemental carbon; Pyrolysis; Quality assurance; Quality control

Hyphenation of a carbon analyzer to photo-ionization mass spectrometry to unravel the organic composition of particulate matter on a molecular level by Jana Grabowsky; Thorsten Streibel; Martin Sklorz; Judith C. Chow; John G. Watson; Athanasios Mamakos; Ralf Zimmermann (pp. 3153-3164).

The carbonaceous fraction of airborne particulate matter (PM) is of increasing interest due to the adverse health effects they are linked to. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions is often carried out by determining bulk parameters such as the overall content of organic compounds (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC), however, no information about the individual substances or substance classes, of which the single fractions consist can be obtained. In this work, a carbon analyzer and a photo-ionization time-of-flight mass spectrometer (PI-TOF-MS) were hyphenated to investigate individual compounds especially from the OC fractions. The carbon analyzer enables the stepwise heating of particle samples and provides the bulk parameters. With the PI-TOF-MS, it is possible to detect the organic compounds released during the single-temperature steps due to soft ionization and fast detection of the molecular ions. The hyphenation was designed, built up, characterized by standard substances, and applied to several kinds of samples, such as ambient aerosol, gasoline, and diesel emission as well as wood combustion emission samples. The ambient filter sample showed a strong impact of wood combustion markers. This was revealed by comparison to the product pattern of the similar analysis of pure cellulose and lignin and the wood combustion PM. At higher temperatures (450 °C), a shift to smaller molecules occurred due to the thermal decomposition of larger structures of oligomeric or polymeric nature comparable to lignocelluloses and similar oxygenated humic-like substances. Finally, particulate matter from gasoline and diesel containing 10% biodiesel vehicle exhaust has been analyzed. Gasoline-derived PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content. The detected pattern revealed a strong influence of the biodiesel content on the nature of the particulate organic material. Figure Two-dimensional REMPI/TOF-MS spectrum of a PM loaded filter from car emissions using diesel (10% biodiesel) as fuel

Keywords: Aerosols/particulates; Carbon analyzer; Mass spectrometry; Organic carbon; Diesel/gasoline; Photo-ionization

Characterization of surgical aerosols by the compact single-particle mass spectrometer LAMPAS 3 by K.-P. Hinz; E. Gelhausen; K.-C. Schäfer; Z. Takats; B. Spengler (pp. 3165-3172).

A new method is presented using an optical particle counter and the compact mobile laser mass spectrometer LAMPAS 3 for in situ analysis of single particles generated by electrosurgical dissection of biological tissues. The instrumental performance is demonstrated for analysing aerosol particles formed during rapid thermal evaporation of porcine liver and porcine kidney tissues. Particle number concentrations of up to 5,000 particles per cubic centimetre were detected during surgical dissection. Chemical analysis of tissue particles was performed by bipolar time-of-flight mass spectrometry. The application of an online mass spectrometric particle analysis for surgical aerosols is reported here for the first time.

Keywords: Mass spectrometry; Single-particle analysis; In situ tissue analysis; Surgical aerosols

First field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer for the on-line detection of particle-bound polycyclic aromatic hydrocarbons by Markus Oster; Michael Elsasser; Jürgen Schnelle-Kreis; Ralf Zimmermann (pp. 3173-3182).

The on-line analysis of single aerosol particles with mass spectrometrical methods is an important tool for the investigation of aerosols. Often, a single laser pulse is used for one-step laser desorption/ionisation of aerosol particles. Resulting ions are detected with time-of-flight mass spectrometry. With this method, the detection of inorganic compounds is possible. The detection of more fragile organic compounds and carbon clusters can be accomplished by separating the desorption and the ionisation in two steps, e.g. by using two laser pulses. A further method is, using a heated metal surface for thermal desorption of aerosol particles. If an ultraviolet laser is used for ionisation, a selective ionisation of polycyclic aromatic hydrocarbons (PAH) and alkylated PAH is possible via a resonance-enhanced multiphoton-ionisation process. Laser velocimetry allows individual laser triggering for single particles and additionally delivers information on aerodynamic particle diameters. It was shown that particles deriving from different combustion sources can be differentiated according to their PAH patterns. For example, retene, a C₄-alkylated phenanthrene derivative, is a marker for the combustion of coniferous wood. In this paper, the first field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer during a measurement campaign in Augsburg, Germany in winter 2010 is presented. Larger PAH-containing particles (i.e. with aerodynamic diameters larger than 1 μm), which are suspected to be originated by re-suspension processes of agglomerated material, were in the focus of the investigation. Due to the low concentration of these particles, an on-line virtual impactor enrichment system was used. The detection of particle-bound PAH in ambient particles in this larger size region was possible and in addition, retene could be detected on several particles, which allows to identify wood combustion as generic source of these particles. The observed diurnal distribution of these larger particles, however, support the origin by traffic induced re-suspension of sedimented/agglomerated material. Figure TD-REMPI mass spectrum of a single particle from ambient air exhibiting an aerodynamic diameter of 1.3 μm, showing typical PAH masses. The intense peak at m/z = 234 (retene) allows to identify wood combustion as a generic source of this particle

Keywords: Aerosol mass spectrometry; Instrument development; Mass spectrometry; Laser ionisation; Environmental chemistry; Aerosols; Single particle

A novel particle sampling system for physico-chemical and toxicological characterization of emissions by Jarno Ruusunen; Maija Tapanainen; Olli Sippula; Pasi I. Jalava; Heikki Lamberg; Kati Nuutinen; Jarkko Tissari; Mika Ihalainen; Kari Kuuspalo; Jorma Mäki-Paakkanen; Pasi Hakulinen; Arto Pennanen; Kimmo Teinilä; Ulla Makkonen; Raimo O. Salonen; Risto Hillamo; Maija-Riitta Hirvonen; Jorma Jokiniemi (pp. 3183-3195).

Several studies have shown that combustion-derived fine particles cause adverse health effects. Previous toxicological studies on combustion-derived fine particles have rarely involved multiple endpoints and a detailed characterization of chemical composition. In this study, we developed a novel particle sampling system for toxicological and chemical characterization (PSTC), consisting of the Dekati Gravimetric Impactor (DGI) and a porous tube diluter. Physico-chemical and toxicological properties of the particles emitted from various combustion sources were evaluated in two measurement campaigns. First, the DGI was compared with the High-Volume Cascade Impactor (HVCI) and to the Dekati Low-Pressure Impactor (DLPI), using the same dilution system and the same sampling conditions. Only small differences were observed in the mass size distributions, total particulate matter (PM), and particulate matter with diameter smaller than 1 um (PM₁) concentrations and geometric mass mean diameters (GMMD) between these three impactors. Second, the PSTC was compared with the HVCI sampling system, which has been optimal for collection of particulate samples for toxicological and chemical analyses. Differences were observed in the mass size distributions, total PM and PM₁ emissions, and GMMDs, probably due to the different sampling and dilution methods as well as different sampling substrates which affected the behavior of semi-volatile and volatile organic compounds. However, no significant differences were detected in the in vitro measurements of cytotoxicity between the samples collected with the PSTC and the HVCI systems. In measurements of genotoxicity, significant differences between the two sampling systems were seen only with the particles emitted from the sauna stove. In conclusion, due to compact size, PSTC is an applicable method for use in particle sampling as part of the toxicological and chemical characterization of particulate emissions from different combustion sources. It offers some advantages compared to the previously used high-volume sampling methods including compactness for field measurements, simple preparation of sample substrates and high extraction efficiency.

Keywords: Aerosols/particulates; Sampling; Physico-chemical; Toxicological; Emission

Anti-oxidative and inflammatory responses induced by fly ash particles and carbon black in lung epithelial cells by Silvia Diabaté; Britta Bergfeldt; Diana Plaumann; Caroline Übel; Carsten Weiss (pp. 3197-3212).

Combustion-derived nanoparticles as constituents of ambient particulate matter have been shown to induce adverse health effects due to inhalation. However, the components inducing these effects as well as the biological mechanisms are still not fully understood. The fine fraction of fly ash particles collected from the electrostatic precipitator of a municipal solid waste incinerator was taken as an example for real particles with complex composition released into the atmosphere to study the mechanism of early biological responses of BEAS-2B human lung epithelial cells. The studies include the effects of the water-soluble and -insoluble fractions of the fly ash and the well-studied carbon black nanoparticles were used as a reference. Fly ash induced reactive oxygen species (ROS) and increased the total cellular glutathione (tGSH) content. Carbon black also induced ROS generation; however, in contrast to the fly ash, it decreased the intracellular tGSH. The fly ash-induced oxidative stress was correlated with induction of the anti-oxidant enzyme heme oxygenase-1 and increase of the redox-sensitive transcription factor Nrf2. Carbon black was not able to induce HO-1. ROS generation, tGSH increase and HO-1 induction were only induced by the insoluble fraction of the fly ash, not by the water-soluble fraction. ROS generation and HO-1 induction were markedly inhibited by pre-incubation of the cells with the anti-oxidant N-acetyl cysteine which confirmed the involvement of oxidative stress. Both effects were also reduced by the metal chelator deferoxamine indicating a contribution of bioavailable transition metals. In summary, both fly ash and carbon black induce ROS but only fly ash induced an increase of intracellular tGSH and HO-1 production. Bioavailable transition metals in the solid water-insoluble matrix of the fly ash mostly contribute to the effects.

Keywords: Lung epithelial cells; Fly ash; Carbon black; Nanoparticles; Oxidative stress; Glutathione; Heme oxygenase-1

Analytical in vitro approach for studying cyto- and genotoxic effects of particulate airborne material by Michaela Aufderheide; Stefanie Scheffler; Niklas Möhle; Beat Halter; Dieter Hochrainer (pp. 3213-3220).

In the field of inhalation toxicology, progress in the development of in vitro methods and efficient exposure strategies now offers the implementation of cellular-based systems. These can be used to analyze the hazardous potency of airborne substances like gases, particles, and complex mixtures (combustion products). In addition, the regulatory authorities require the integration of such approaches to reduce or replace animal experiments. Although the animal experiment currently still has to provide the last proof of the toxicological potency and classification of a certain compound, in vitro testing is gaining more and more importance in toxicological considerations. This paper gives a brief characterization of the CULTEX® Radial Flow System exposure device, which allows the exposure of cultivated cells as well as bacteria under reproducible and stable conditions for studying cellular and genotoxic effects after the exposure at the air–liquid or air–agar interface, respectively. A commercial bronchial epithelial cell line (16HBE14o-) as well as Salmonella typhimurium tester strains were exposed to smoke of different research and commercial available cigarettes. A dose-dependent reduction of cell viability was found in the case of 16HBE14o- cells; S. typhimurium responded with a dose-dependent induction of revertants. The promising results recommend the integration of cellular studies in the field of inhalation toxicology and their regulatory acceptance by advancing appropriate validation studies.

Keywords: Inhalation toxicology; CULTEX® RFS module; Electrical deposition; Air–liquid interface; Cigarette smoke; Ames assay

A standard additions method reduces inhibitor-induced bias in quantitative real-time PCR by Stephen L. R. Ellison; Kerry R. Emslie; Zena Kassir (pp. 3221-3227).

A method of calibration for real-time quantitative polymerase chain reaction (qPCR) experiments based on the method of standard additions combined with non-linear curve fitting is described. The method is tested by comparing the results of a traditionally calibrated qPCR experiment with the standard additions experiment in the presence of 2 mM EDTA, a known inhibitor chosen to provide an unambiguous test of the principle by inducing an approximately twofold bias in apparent copy number calculated using traditional calibration. The standard additions method is shown to substantially reduce inhibitor-induced bias in quantitative real-time qPCR.

Keywords: Nucleic acids; Quantitative PCR; Calibration; Standard additions

Fluorescence polarization biosensor based on an aptamer enzymatic cleavage protection strategy by Anthony Kidd; Valérie Guieu; Sandrine Perrier; Corinne Ravelet; Eric Peyrin (pp. 3229-3234).

A novel fluorescence polarization (FP) aptasensing platform based on target-induced aptamer enzymatic cleavage protection is reported. The method relies on the FP analysis of the phosphodiesterase I mediated size variation of a dye-labeled aptamer. The tyrosinamide/antityrosinamide DNA aptamer couple was firstly tested as a model system to establish the proof-of-concept. In the absence of the target, the labeled aptamer was enzymatically cleaved into small DNA fragments, leading to a low FP signal. Upon tyrosinamide binding, the DNA substrate was partially protected against the enzymatic attack, leading to an increase in the fluorescence anisotropy response as a result of the higher average molecular volume of the weakly digested probe. The method was subsequently applied to two other systems, i.e., for the detection of ochratoxin A and adenosine. Such an approach was found to combine simplicity and general applicability features.

Keywords: Fluorescence polarization; Aptamer; Enzymatic cleavage protection; Small analyte; Sensing

A simple method for quantifying the humic content of commercial products by François Quentel; Montserrat Filella (pp. 3235-3238).

A method based on an analytical technique, initially developed for quantifying aquatic refractory organic matter (often called humics), has been applied to commercial samples claiming to contain humic-type substances. At present, no method exists for quantifying the humic content on this type of sample. The analytical method is based on measuring the peak current obtained by adsorptive stripping voltammetry of the complex formed by refractory organic matter in the presence of trace amounts of Mo(VI). The quantification procedure requires the response obtained for the unknown sample to be compared with the response obtained with International Humic Substance Society (IHSS) reference humic substances. A very simple procedure that enables the humic content of any sample to be expressed as IHSS standard equivalents is described in detail. The method is highly selective, reproducible and suitable for routine analysis.

Keywords: Humic commercial products; Quantification; Humic substances; Voltammetry

Bubble cell for magnetic bead trapping in capillary electrophoresis by Anne-Laure Gassner; Gaëlle Proczek; Hubert H. Girault (pp. 3239-3248).

A bubble cell capillary classically used to extend the optical path length for UV–vis detection is employed here to trap magnetic beads. With this system, a large amount of beads can be captured without inducing a strong pressure drop, as it is the case with magnetic beads trapped in a standard capillary, thereby having less effect on the experimental conditions. Using numerical simulations and microscopic visualizations, the capture of beads inside a bubble cell was investigated with two magnet configurations. Pressure-driven and electro-osmotic flow velocities were measured for different amounts of protein-A-coated beads or C18-functionalized beads (RPC-18). Solid-phase extraction of a model antibody on protein-A beads and preconcentration of fluorescein on RPC-18 beads were performed as proof of concept experiments. Figure Isovalues of the magnetic induction produced by two permanent magnets in attraction configuration with a capillary placed between them.

Keywords: Magnetic particle; Bubble cell; Solid-phase extraction; Numerical simulation; Finite element method

Quantitative profiling of tryptophan metabolites in serum, urine, and cell culture supernatants by liquid chromatography–tandem mass spectrometry by Wentao Zhu; Axel P. Stevens; Katja Dettmer; Eva Gottfried; Sabine Hoves; Marina Kreutz; Ernst Holler; André B. Canelas; Ido Kema; Peter J. Oefner (pp. 3249-3261).

A sensitive, selective, and comprehensive method for the quantitative determination of tryptophan and 18 of its key metabolites in serum, urine, and cell culture supernatants was developed. The analytes were separated on a C18 silica column by reversed-phase liquid chromatography and detected by electrospray ionization tandem mass spectrometry in positive ion multiple reaction monitoring (MRM) mode, except for indoxyl sulfate which was measured in negative ion MRM mode in a separate run. The limits of detection and lower limits of quantification were in the range of 0.1–50 and 0.5–100 nM, respectively. Fully ¹³C isotope-labeled and deuterated internal standards were used to achieve accurate quantification. The applicability of the method to analyze serum, urine, and cell culture supernatants was demonstrated by recovery experiments and the evaluation of matrix effects. Precision for the analysis of serum, urine, and cell culture supernatants ranged between 1.3% and 16.0%, 1.5% and 13.5%, and 1.0% and 17.4%, respectively. The method was applied to analyze changes in tryptophan metabolism in cell culture supernatants from IFN-γ-treated monocytes and immature or mature dendritic cells.

Keywords: Tryptophan metabolism; LC-MS/MS; Serum; Urine; Cell culture supernatant

Orientation of molecular groups of fibers in nonoriented samples determined by polarized ATR-FTIR spectroscopy by Karima Belbachir; Sophie Lecomte; Ha-Phuong Ta; Cyril Petibois; Bernard Desbat (pp. 3263-3268).

A method based on polarized attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy is proposed for determining the infrared dichroic absorption ratio of a single fiber from a sample deposited flat on a germanium crystal without the requirement of fiber orientation. The method shows its efficiency on cellulose fibers of paper and has been applied to protein fibers (type I collagen and β-amyloid) and polysaccharide fibers (cellulose and starch). The method gives access to the dichroic ratio of strong absorptions bands, which is not easily accessible with conventional absorption techniques. Then, the orientation of the molecular groups of organic fibers can be easily determined by polarized ATR-FTIR spectroscopy. By extension, this method will be useful to determine the molecular orientation of fibers in structured complex samples, such as biological tissues and plants. Spatially resolved information on the organization of the fiber network will be easily extracted by utilizing a focal plane array detector for imaging measurements. Figure Type I collagen and cellulose fibers orientation determined by polarized ATR-FTIR spectroscopy. Non-oriented fiber samples deposited on ATR crystal can be used to determine molecular groups orientation in fibers with p- an s-polarization spectra. The method can be extended to complex samples containing different fiber compounds.

Keywords: Fourier transform infrared spectroscopy; Fibers; Structural Biochemistry; Molecular orientation; Method

Multianalyte immunoassay chip for detection of tumor markers by chemiluminescent and colorimetric methods by Wei Wei; Chunyan Zhang; Jing Qian; Songqin Liu (pp. 3269-3274).

Most cancers developed an elevation of the level of at least two markers associated with their incidence. Simultaneous detection of multi-tumor markers associated with a particular type of cancer plays an important role in cancer diagnostic. Here, a multianalyte immunoassay chip for simple and sensitive detection of tumor markers with chemiluminescent and colorimetric methods was proposed, in which carcinoembryonic antigen (CEA) and carbohydrate antigen (CA19-9) that associated with colorectal cancer were detected as model. The immunoassay chip was fabricated by co-immobilization of CEA/CA19-9 antibody on a glass slide with γ-glycidoxypropyltrimethoxysilane as linkage. Through sandwiched immunoreactions, CEA, CA19-9, and their corresponding enzyme tracers, alkaline phosphatase-labeled anti-CEA and horseradish peroxidase-labeled anti-CA19-9, were introduced on the chip. Then, they were sequentially detected by chemiluminescent method in the range of 0.5–80 μg/L and 0.5–80 kU/L with the detection limits of 0.41 μg/L and 0.36 kU/L at 3σ for CEA and CA19-9, respectively. They could also be detected by colorimetric method in the range of 1–200 μg/L and 5–200 kU/L with the detection limits of 0.25 μg/L and 1.25 kU/L at 3σ for CEA and CA19-9, respectively. All these results demonstrated that the present work provided a promising analytical method for tumor markers’ analysis with the advantages of simple analytical procedure, small sample volume and lower cost, which made the proposed method potential for high-throughput detection. Figure The multianalyte immunoassay chip was fabricated for detection of tumor markers by co-immobilization of CEA/CA19-9 antibody on a glass slide with γ-glycidoxypropyltrimethoxysilane (GPMS) as linkage

Keywords: Multianalyte immunoassay; Tumor markers; Chemiluminescence; Colorimetric method; Chip

Optimization of dynamic pH junction for the sensitive determination of amino acids in urine by capillary electrophoresis by Y. H. Tak; G. W. Somsen; G. J. de Jong (pp. 3275-3281).

A capillary electrophoresis method with UV-absorbance detection was studied and optimized for the determination of underivatized amino acids in urine. To improve concentration sensitivity the utility of in-capillary analyte stacking via dynamic pH junction was investigated with phenylalanine (Phe) and tyrosine (Tyr) as model amino acids. Before sample injection, a plug of ammonium hydroxide solution was injected to enable analyte concentration. Samples were 1:1 (v/v) mixed with background electrolyte (1 M formic acid) prior to injection. The effect of the injected sample volume, and the injected ammonium hydroxide volume and concentration on analyte stacking and separation performance was investigated. The optimal volume of ammonium hydroxide depended on the injected sample volume. Using a dynamic pH junction good resolution (1.4) was obtained for a sample injection volume of 10% of the capillary (196 nl) with Phe and Tyr dissolved in water. Limits of detection (LODs) were 0.036 and 0.049 μM for Phe and Tyr, respectively. For urine samples, the optimized procedure comprised a 1.7-nl injection of 12.5% ammonium hydroxide, followed by a 196-nl injection of urine spiked with Phe and Tyr. Satisfactory resolution was obtained and amino acid peak widths at half height were only 1.6 s indicating efficient stacking. Calibration plots for Phe and Tyr in urine showed good linearity (R ² > 0.96) in the concentration range 10–175 μM, and LODs for Phe and Tyr were 0.054 and 0.019 μM, respectively. RSDs for peak area and migration time for Phe and Tyr were below 7.5% and 0.75%, respectively. Figure CE-UV of a mixture of phenylalanine and tyrosine using a dynamic pH junction applying a variable ammonium hydroxide volume.

Keywords: Amino acids; Capillary electrophoresis; Dynamic pH junction; In-capillary sample preconcentration; Urine

Fluoridized iron phosphate as a novel adsorbent for selective separation/isolation of cytochrome c by ShiSong Tang; WenJing Wang; XuWei Chen; JianHua Wang (pp. 3283-3292).

Fluoridized iron phosphate (F-FePO) is prepared via a hydrothermal protocol and characterized by means of ⁵⁷Fe Mössbauer spectra, Fourier transform infrared, and surface charge analysis. For the first time, F-FePO is used as an adsorbent for the adsorption of proteins, which exhibits favorable selectivity toward cytochrome c (cyt-c) in the presence of acidic and neutral proteins under controlled experimental conditions. At pH 10.5, an adsorption efficiency of 100% is achieved for 60 mg L⁻¹ cyt-c in 1.0 mL of sample solution using 6.0 mg F-FePO. The adsorption behavior is consistent with the Langmuir adsorption model, corresponding to a theoretical adsorption capacity of 37.59 μg mg⁻¹. The retained cyt-c on F-FePO could be readily collected by 0.1 mol L⁻¹ Na₂CO₃–NaHCO₃ buffer (pH 10.5), deriving a recovery of 100%. Circular dichroism spectra indicate no conformational change for cyt-c after the adsorption and desorption processes, demonstrating the favorable biocompatibility of the fluoridized iron phosphate. F-FePO is employed for the selective isolation of cyt-c from a spiked human whole blood, achieving satisfactory results by assay with SDS-polyacrylamide gel electrophoresis and native polyacrylamide gel electrophoresis.

Keywords: Fluoridized iron phosphate; Adsorption; Cytochrome c; Solid-phase extraction

Analysis of multi-class preservatives in leave-on and rinse-off cosmetics by matrix solid-phase dispersion by Lucia Sanchez-Prado; Gerardo Alvarez-Rivera; J. Pablo Lamas; Marta Lores; Carmen Garcia-Jares; Maria Llompart (pp. 3293-3304).

Matrix solid-phase extraction has been successfully applied for the determination of multi-class preservatives in a wide variety of cosmetic samples including rinse-off and leave-on products. After extraction, derivatization with acetic anhydride, and gas chromatography–mass spectrometry analysis were performed. Optimization studies were done on real non-spiked and spiked leave-on and rinse-off cosmetic samples. The selection of the most suitable extraction conditions was made using statistical tools such as ANOVA, as well as factorial experimental designs. The final optimized conditions were common for both groups of cosmetics and included the dispersion of the sample with Florisil (1:4), and the elution of the MSPD column with 5 mL of hexane/acetone (1:1). After derivatization, the extract was analyzed without any further clean-up or concentration step. Accuracy, precision, linearity and detection limits were evaluated to assess the performance of the proposed method. The recovery studies on leave-on and rinse-off cosmetics gave satisfactory values (>78% for all analytes in all the samples) with an average relative standard deviation value of 4.2%. The quantification limits were well below those set by the international cosmetic regulations, making this multi-component analytical method suitable for routine control. The analysis of a broad range of cosmetics including body milk, moisturizing creams, anti-stretch marks creams, hand creams, deodorant, shampoos, liquid soaps, makeup, sun milk, hand soaps, among others, demonstrated the high use of most of the target preservatives, especially butylated hydroxytoluene, methylparaben, propylparaben, and butylparaben. Figure MSPD GC-MS analysis of preservatives in cosmetics

Keywords: Matrix solid-phase dispersion; Cosmetics; Preservatives; Antioxidants; Personal-care products; Experimental design; Derivatization; GC-MS

Improved efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) from the National Institute of Standards and Technology (NIST) Standard Reference Material Diesel Particulate Matter (SRM 2975) using accelerated solvent extraction by Silvia Masala; Trifa Ahmed; Christoffer Bergvall; Roger Westerholm (pp. 3305-3315).

The efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) with molecular masses of 252, 276, 278, 300, and 302 Da from standard reference material diesel particulate matter (SRM 2975) has been investigated using accelerated solvent extraction (ASE) with dichloromethane, toluene, methanol, and mixtures of toluene and methanol. Extraction of SRM 2975 using toluene/methanol (9:1, v/v) at maximum instrumental settings (200 °C, 20.7 MPa, and five extraction cycles) with 30-min extraction times resulted in the following elevations of the measured concentration when compared with the certified and reference concentrations reported by the National Institute of Standards and Technology (NIST): benzo[b]fluoranthene, 46%; benzo[k]fluoranthene, 137%; benzo[e]pyrene, 103%; benzo[a]pyrene, 1,570%; perylene, 37%; indeno[1,2,3-cd]pyrene, 41%; benzo[ghi]perylene, 163%; and coronene, 361%. The concentrations of the following PAHs were comparable to the reference values assigned by NIST: indeno[1,2,3-cd]fluoranthene, dibenz[a,h]anthracene, and picene. The measured concentration of dibenzo[a,e]-pyrene was lower than the information value reported by the NIST. The measured concentrations of other highly carcinogenic PAHs (dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene) in SRM 2975 are also reported. Comparison of measurements using the optimized ASE method and using similar conditions to those applied by the NIST for the assignment of PAH concentrations in SRM 2975 indicated that the higher values obtained in the present study were associated with more complete extraction of PAHs from the diesel particulate material. Re-extraction of the particulate samples demonstrated that the deuterated internal standards were more readily recovered than the native PAHs, which may explain the lower values reported by the NIST. The analytical results obtained in the study demonstrated that the efficient extraction of PAHs from SRM 2975 is a critical requirement for the accurate determination of PAHs with high molecular masses in this standard reference material and that the optimization of extraction conditions is essential to avoid underestimation of the PAH concentrations. The requirement is especially relevant to the human carcinogen benzo[a]pyrene, which is commonly used as an indicator of the carcinogenic risk presented by PAH mixtures.

Keywords: Accelerated solvent extraction; ASE; Diesel particulate matter; SRM 2975; PAH; Benzo[a]pyrene; Dibenzo[a,l]pyrene; Dibenzo[a,e]pyrene; Dibenzo[a,i]-pyrene; Dibenzo[a,h]pyrene

“Dilute-and-shoot” triple parallel mass spectrometry method for analysis of vitamin D and triacylglycerols in dietary supplements by William Craig Byrdwell (pp. 3317-3334).

A method is demonstrated for analysis of vitamin D fortified dietary supplements that eliminates virtually all chemical pretreatment prior to analysis, which is referred to as a “dilute-and-shoot” method. Three mass spectrometers, in parallel, plus a UV detector, an evaporative light-scattering detector (ELSD), and a corona charged aerosol detector (CAD) were used to allow a comparison of six detectors simultaneously. Ultraviolet data were analyzed using internal standard, external standard, and response factor approaches. The contents of gelcaps that contained 2,000 IU (50 μg) vitamin D₃ in rice bran oil, diluted to 100 mL, were analyzed without the need for lengthy saponification and extraction. Vitamin D₃ was analyzed using UV detection, extracted ion chromatograms, selected ion monitoring (SIM) atmospheric pressure chemical ionization mass spectrometry (APCI-MS), and two transitions of multiple reaction monitoring (MRM) APCI-MS. The internal standard, external standard, and response factor methods gave values of 0.5870 ± 0.0045, 0.5893 ± 0.0041, and 0.5889 ± 0.0045 μg/mL, respectively, by UV detection. The values obtained by MS were 0.6117 ± 0.0140, 0.6018 ± 0.0244, and 0.5848 ± 0.0146 μg/mL by SIM and two transitions of MRM, respectively. The triacylglycerols in the oils were analyzed using full-scan APCI-MS, electrospray ionization (ESI) MS, up to MS⁴, an ELSD, and a CAD. The method proved to be very sensitive for vitamin D₃, as well as triacylglycerols (TAGs), allowing identification of intact TAGs containing fatty acids up to 28 carbons in length. LC-ESI-MS of glycerin polymers is also demonstrated.

Keywords: Vitamin D; Cholecalciferol; Ergocalciferol; Calciol; APCI-MS; ESI-MS

Development and validation of an UPLC-MS/MS method for the determination of ionophoric and synthetic coccidiostats in vegetables by N. Broekaert; C. Van Peteghem; E. Daeseleire; D. Sticker; C. Van Poucke (pp. 3335-3344).

In poultry farming, anticoccidial drugs are widely used as feed additives for the prevention and treatment of coccidiosis. Because coccidiostats and veterinary medicines, in general, are often poorly absorbed, manure from treated animals may contain high concentrations of these compounds. Experimental studies have shown that the uptake of veterinary medicines by plants from soil containing contaminated manure may occur. This leads to several questions regarding the impact on the environment, resistance problems, and public health and allergy issues. This work describes the development of a quantification method for coccidiostats in vegetables. Vegetables were spiked at 100 μg kg⁻¹ (dry weight) with coccidiostats (monensin, narasin, lasalocid A, salinomycin, diclazuril, and nicarbazin) in order to optimize the extraction and clean-up. Possible critical factors (e.g., extraction solvent) were statistically examined by linear regression with the use of Plackett–Burman and full factorial designs. Final extracts were analyzed with ultra-performance liquid chromatography tandem mass spectrometry operating in multiple-reaction monitoring mode. Both the synthetic and ionophoric coccidiostats could be determined in a single run with an analysis time of 5 min. The developed method was validated taking into account the requirements of the Commission Decision 2002/657/EC as a guideline. The method is regarded as applicable for its intended purposes with quantification limits between 0.30 and 2.98 μg kg⁻¹. This method could be used to establish possible maximum residue limits for coccidiostats in vegetables, as already exist for eggs, meat, and milk. Figure Chromatogram of a 10 μg kg⁻¹ spiked, freeze-dried carrot sample; X: Carrot-specific interference in the channel of dinitrocarbanilide (DNC); A: DNC; B: diclazuril; C: monensin; D: lasalocid A; E: salinomycin; F: narasin

Keywords: LC-MS/MS; Coccidiostats; Vegetables; Veterinary; Residue

Multi-wall carbon nanotube aqueous dispersion monitoring by using A4F-UV-MALS by Julien Gigault; Bruno Grassl; Gaëtane Lespes (pp. 3345-3353).

In this work, the potentiality of asymmetrical flow field-flow fractionation (A4F) hyphenated to UV detector and multi-angle light scattering (MALS) was investigated for accurately determining multi-walled carbon nanotube (MWCNT) length and its corresponding dispersion state in aqueous medium. Fractionation key parameters were studied to obtain a method robust enough for heterogeneous sample characterization. The main A4F conditions were 10⁻⁵ mL min⁻¹ NH₄NO₃, elution flow of 1 mL min⁻¹, and cross flow of 2 mL min⁻¹. The recovery was found to be (94 ± 2)%. Online MALS analysis of eluted MWCNT suspension was performed to obtain length distribution. The length measurements were performed with a 4% relative standard deviation, and the length values were shown to be in accordance with expected ones. The capabilities of A4F-UV-MALS to size characterize various MWCNT samples and differentiate them according to their manufacturing process were evaluated by monitoring ball-milled MWCNT and MWCNT dispersions. The corresponding length distributions were found to be over 150–650 and 150–1,156 nm, respectively. A4F-UV-MALS was also used to evaluate MWCNT dispersion state in aqueous medium according to the surfactant concentration and sonication energy involved in the preparation of the dispersions. More especially, the presence or absence of aggregates, number and size of different populations, as well as size distributions were determined. A sodium dodecyl sulfate concentration of 15 to 30 mmol L⁻¹ and a sonication energy ranged over 20–30 kJ allow obtaining an optimal MWCNT dispersion. It is especially valuable for studying nanomaterials and checking their manufacturing processes, size characterization being always of high importance.

Keywords: Field-flow fractionation; MWCNT; Light scattering; Length characterization; Dispersion state

Rapid automated method for on-site determination of sulfadiazine in fish farming: a stainless steel veterinary syringe coated with a selective membrane of PVC serving as a potentiometric detector in a flow-injection-analysis system by S. A. A. Almeida; L. R. Amorim; A. H. Heitor; M. C. B. S. M. Montenegro; J. Barbosa; L. C. Sá; M. G. F. Sales (pp. 3355-3365).

Sulfadiazine is an antibiotic of the sulfonamide group and is used as a veterinary drug in fish farming. Monitoring it in the tanks is fundamental to control the applied doses and avoid environmental dissemination. Pursuing this goal, we included a novel potentiometric design in a flow-injection assembly. The electrode body was a stainless steel needle veterinary syringe of 0.8-mm inner diameter. A selective membrane of PVC acted as a sensory surface. Its composition, the length of the electrode, and other flow variables were optimized. The best performance was obtained for sensors of 1.5-cm length and a membrane composition of 33% PVC, 66% o-nitrophenyloctyl ether, 1% ion exchanger, and a small amount of a cationic additive. It exhibited Nernstian slopes of 61.0 mV decade^-1 down to 1.0 × 10^-5 mol L^-1, with a limit of detection of 3.1 × 10^-6 mol L^-1 in flowing media. All necessary pH/ionic strength adjustments were performed online by merging the sample plug with a buffer carrier of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, pH 4.9. The sensor exhibited the advantages of a fast response time (less than 15 s), long operational lifetime (60 days), and good selectivity for chloride, nitrite, acetate, tartrate, citrate, and ascorbate. The flow setup was successfully applied to the analysis of aquaculture waters. The analytical results were validated against those obtained with liquid chromatography–tandem mass spectrometry procedures. The sampling rate was about 84 samples per hour and recoveries ranged from 95.9 to 106.9%.

Keywords: Sulfadiazine; Chemical sensor; Aquaculture; Flow-injection analysis; Potentiometry

Development of an enzyme-linked immunosorbent assay for the determination of 5-hydroxymethyl-2-furfural in food by Guozhen Fang; Yanyan Lv; Wei Sheng; Bing Liu; Xiaoxue Wang; Shuo Wang (pp. 3367-3373).

5-Hydroxymethyl-2-furfural (5-HMF) is considered to be an excellent indicator of quality deterioration due to excessive heating or storage for a wide range of carbohydrate-containing foods. To facilitate its analysis, a highly selective and sensitive enzyme-linked immunosorbent assay for determination of 5-HMF in food has been developed. A specific polyclonal antibody was produced against a conjugate of 5-HMF coupled to bovine serum albumin. The IC₅₀ and limit of method detection were 0.15 ± 0.012 mg L^-1 and 0.02 ± 0.002 mg L^-1, respectively. The proposed method was applied to detect 5-HMF in French mini bread, potato chips, French soft bread, and wheat chicken nuggets with recoveries ranging from 84.07 to 97.09% and relative standard deviation (n = 3) below 8.65% in all samples. The quantitative results were in good agreement with those obtained by the high-performance liquid chromatography method, which suggests that the method developed will be very useful for monitoring 5-HMF in food samples. Schematic figure of enzyme-linked immunosorbent assay for 5-HMF

Keywords: 5-Hydroxymethyl-2-furfural; Antibody; ELISA; Determination; Food

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Analytical and Bioanalytical Chemistry (v.401, #10)