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A new miniaturized liquid extraction cartridge equipped with a functional porous polytetrafluoroethylene membrane was developed for the determination of formaldehyde in gaseous samples. The functional polytetrafluoroethylene membrane allows gas to pass through while repelling both water‐based and organic‐based liquids. A derivatization reagent for formaldehyde, 2,4‐dinitrophenylhydrazine, was placed in the cartridge and gaseous samples are collected through the cartridge at 20 ml/min for 30 min. Formaldehyde in the gaseous sample is captured as the corresponding 2,4‐dinitrophenylhydrazine hydrazone, and an aliquot of the sample collection solution can be directly subjected to high‐performance liquid chromatographic analysis. The limit of quantification for the developed method was 5 ng/L formaldehyde in gas with a sampling volume of 600 ml. Proof‐of‐concept for formaldehyde determination in an aqueous sample was demonstrated using the developed cartridge in a purge‐and‐trap extraction setup. [ABSTRACT FROM AUTHOR]

Gaseous hydrogen selenide (H2Se) generated by the addition of sodium tetrahydroborate (NaBH4) into an acidic aqueous sample was collected using an aqueous ammonia solution. The selenium (Se) concentration was determined using graphite furnace atomic absorption spectrometry (AAS). Several experimental conditions, such as the type of the collection solution, volume of NaBH4 and hydrochloric acid, and collection time, were optimized. In addition, the effect of coexisting ions was quantitatively evaluated and eliminated. The limit of detection for Se in a standard water sample was 1.3 ng/mL. The additional recovery of spiked Se in tap water and river water samples ranged from 98 ± 2.4 to 100 ± 2.2%. The proposed method facilitates simple and sensitive analysis for Se in water samples without H2Se gas generator for AAS. [ABSTRACT FROM AUTHOR]

A novel partitioning collection device comprising a glass cartridge packed with poly(dimethylsiloxane)-coated macroporous silica particles was developed for the precise quantification of polycyclic aromatic hydrocarbons in air. The analyte collection and elution performances achieved using different amounts of poly(dimethylsiloxane) coating were quantitatively evaluated. The sample retention power increased with increasing the coating, and more than 250 L of air could be collected without analyte breakthrough at a sampling temperature of 35°C. During the air collection, the moisture in the air was not retained on the particles due to the hydrophobic surface of the sorbent. A complete and rapid elution of the collected analytes from the device was accomplished by the passage of only 10 mL of acetone with ultrasonication for 1 min. The proposed method was successfully applied for the determination of airborne polycyclic aromatic hydrocarbons in tunnel air. [ABSTRACT FROM AUTHOR]

• A new analytical method for soil VOCs using a needle extraction device was developed. • The analytes including low molecular weight VOCs like dichloromethane. • Greater recovery and sensitivity were obtained than the standard method. A rapid and quantitative analytical method for volatile chlorinated hydrocarbons and benzene, such as chloroethylene, dichloromethane, and carbon tetrachloride, in soil samples was developed using a needle-type extraction device packed with activated carbon-based adsorbents. The soil sample of 10 g was placed in a glass cartridge and fixed with quartz wool to make sure not to move during the extraction process. After the internal standard solution was spiked into the soil sample, the cartridge was sealed with a polytetrafluoroethylene adapter, and the needle extraction device was used to collect the headspace gas. Analytes were purged from the soil sample and collected on the adsorbent, while pure nitrogen gas was introduced to the soil sample during the sample collection. The sampling time was approximately 10 min for 100 mL of gas sampling. After the sampling process, the extraction needle was directly inserted into a heated injection port of gas chromatography equipped with flame ionization detector (GC-FID) or that hyphenated to mass spectrometry (GC–MS). The extracted VOCs were thermally desorbed and simultaneously introduced to a GC capillary column for subsequent separation and determination. The limit of detection and limit of quantification of all the examined analytes was less than 20 and 60 ng/10 g soil in GC-FID and less than 2.5 and 7.5 ng/10 g soil in the case of GC–MS. Linear calibration curves were obtained up to 10 μg/10 g soil for all the analytes. The relative standard deviations of the ratio of analyte peak area and internal standard peak area were less than 10%. The recovery and sensitivity of analytes confirmed in the proposed method were compared with that obtained with a standard method conventionally employed. [ABSTRACT FROM AUTHOR]

A novel sampling device based on the partition of target analytes to the extraction medium was developed for the determination of sesquiterpenes in air samples. The extraction medium was prepared by the chemical derivatization of a specially prepared macroporous silica, with a specific surface area of 2.0 m2/g. Taking advantage of the sample extraction, which was mainly based on the partition of sesquiterpenes between air and a C18-bonded phase, the extracted analytes were rapidly and quantitatively desorbed just by passing a small amount of desorption solvent for subsequent analysis by gas chromatography with mass spectrometry. Several experimental conditions, such as the sampling volume and temperature, were systematically evaluated. Under optimized conditions, desorption of the extracted analytes was completed within 1 min with a desorption efficiency of more than 99.9%, achieved using 5 mL of acetone for all the evaluated sesquiterpenes. The applicability of the developed device was confirmed by the determination of several sesquiterpenes from coniferous trees. Although further improvements of the device are required for collecting large volumes or high-temperature air samples, the potential of the developed sampling device was confirmed by determining traces of semivolatile organic compounds in air samples. [ABSTRACT FROM AUTHOR]

Very volatile organic compounds (VVOCs), such as methanol, acetaldehyde, ethanol, acetone, acetonitrile, and dichloromethane, were extracted from water samples using a needle-type extraction device based on purge and trap analysis. The extracted analytes could then be determined by gas chromatography–mass spectrometry. By introducing carbon molecular sieves as the extraction medium, aqueous VVOCs could be successfully extracted using the extraction needle. The limit of quantification for methanol, acetaldehyde, ethanol, acetone, acetonitrile, and dichloromethane were 75, 75, 7.5, 0.5, 10 and 0.5 μg/L, respectively. This newly developed method was also successfully applied to the determination of VVOCs in commercial samples, such as fruit juice. [ABSTRACT FROM AUTHOR]

A novel miniaturized sample extraction capillary was developed to provide a simple and sensitive method for analyzing gaseous formaldehyde (FA) using conventional high-performance liquid chromatography (HPLC). The extraction capillary was prepared by packing silica gel particles in a stainless steel capillary with a 1.6-mm o.d. Before the gaseous samples were collected, the silica gel particles were impregnated with a derivatizing reagent 2,4-dinitrophenylhydrazine (DNPH) by passing a solution of DNPH through the extraction capillary. FA was derivatized to form the corresponding hydrazone during the active sampling of a gaseous sample, and the derivative was sorbed by the silica gel. The capillary was then directly connected to a six-port valve, and desorption from the capillary and injection into the HPLC were achieved simultaneously by passing a solvent through the capillary. The run-to-run and device-to-device variabilities, as relative standard deviations, were both less than 6.9 %. The limit of detection for FA was 2.5 ng/L using a sampling volume of 100 mL, and a sample collection time of 2 min. Acetaldehyde and acetone in a gaseous sample could also be simultaneously extracted and determined using this method. The applicability of the developed method for determining FA in real indoor air samples was confirmed by comparing the results obtained using the proposed method and a conventional sample preparation method. The developed method enables the rapid and simple sample preparation of gaseous FA and gives a good level of sensitivity. [ABSTRACT FROM AUTHOR]

Abstract: Background: Isoprene in human breath is said to be related to cholesterol metabolism, and the possibility of the correlations with some clinical parameters has been studied. However, at this stage, no clear benefit of breath isoprene has been reported for clinical diagnosis. In this work, isoprene and acetone concentrations were measured in the breath of healthy and obese subjects using a needle-type extraction device for subsequent analysis in gas chromatography–mass spectrometry (GC-MS) to investigate the possibility of these compounds as an indicator of possible diseases. Methods: After measuring intraday and interday variations of isoprene and acetone concentrations in breath samples of healthy subjects, their concentrations were also determined in 80 healthy and 17 obese subjects. In addition, correlation between these breath concentrations and the blood tests result was studied for these healthy and obese subjects. Results: The results indicated successful determination of breath isoprene and acetone in this work, however, no clear correlation was observed between these measured values and the blood test results. Conclusions: Breath isoprene concentration may not be a useful indicator for obesity or hypercholesterolemia. [Copyright &y& Elsevier]

Highlights: [•] Very volatile organic compounds were extracted by a novel extraction needle. [•] Extracted VVOCs were stored in the extraction needle at room temperature for 3 days. [•] The effects of sample moisture on the determination of VVOCs were investigated. [•] The developed extraction needle was applied to the determination of breath VVOCs. [ABSTRACT FROM AUTHOR]

Highlights: [•] A purge-and-trap method was developed using a novel extraction needle. [•] The needle has multi-bed-type sorbent for extraction of VOCs in water sample. [•] The sampling time of the method was approximately 9min. [•] The method was successfully applied for the analysis of real tap water samples. [ABSTRACT FROM AUTHOR]

Abstract: A novel needle-type sample preparation device was developed for the effective preconcentration of volatile organic compounds (VOCs) in indoor air before gas chromatography–mass spectrometry (GC–MS) analysis. To develop a device for extracting a wide range of VOCs typically found in indoor air, several types of particulate sorbents were tested as the extraction medium in the needle-type extraction device. To determine the content of these VOCs, air samples were collected for 30min with the packed sorbent(s) in the extraction needle, and the extracted VOCs were thermally desorbed in a GC injection port by the direct insertion of the needle. A double-bed sorbent consisting of a needle packed with divinylbenzene and activated carbon particles exhibited excellent extraction and desorption performance and adequate extraction capacity for all the investigated VOCs. The results also clearly demonstrated that the proposed sample preparation method is a more rapid, simpler extraction/desorption technique than traditional sample preparation methods. [Copyright &y& Elsevier]

Abstract: A new approach to the determination of human breath acetone with particle-packed sample preparation needle was developed. The extraction needle was packed with a copolymer of methacrylic acid and ethylene glycol dimethacrylate as the extraction medium. For the analysis of breath sample, exhaled breath was collected in a sampling bag, and 50mL of the breath sample was extracted with the needle-type sample preparation device followed by analysis using gas chromatography–mass spectrometry (GC–MS). After the optimization of several basic extraction conditions for standard acetone samples, breath acetone concentration taken from controlled type-2 diabetic patients was determined. Furthermore, time variations of breath and urine acetone of four healthy individuals under fasting conditions were measured. Urine sample was collected in glass vial, and urine acetone concentration was also determined with the extraction needle by analyzing the corresponding headspace gas. The results demonstrated that the particle-packed extraction needle showed an excellent extraction performance for acetone in both breath and urine headspace samples, and that there is a clear correlation between the concentration of breath acetone and HbA1c level of controlled type-2 diabetic patients. The breath acetone level in controlled diabetic patients was in the range between 0.19 and 0.66ppmv, where its concentration in medically untreated type-2 patient was 0.92 and 1.20ppmv. The breath acetone concentration in healthy male was increased to 5.66ppmv under the 24h of fasting test, and a high correlation between the breath and urine acetone concentration was also observed. On the basis of the above results, the potential applications of the proposed method to the diagnosis of diabetes and/or ketoacidosis were suggested. [Copyright &y& Elsevier]

Abstract: Fiber-packed sample preparation device was applied to the simultaneous derivatization/preconcentration of ethylene oxide (EO) in air samples. The polymer-coated filaments were packed longitudinally into the needle, and hydrogen bromide (HBr) was loaded onto the filaments in the preconditioning process. Simultaneous derivatization with HBr in the needle was made during the sampling process of the gaseous EO, and the corresponding derivatized analyte, 2-bromoethanol, was desorbed by passing a small amount of methanol through the extraction needle in the heated gas chromatograph (GC) injector. The basic extraction/desorption parameters for EO have been evaluated. The limit of detection (LOD), limit of quantification (LOQ) and the relative standard deviation (RSD) of run-to-run repeatability were 1.8ng/L, 5.4ng/L and less than 4%, respectively, with an extraction time of about 10min. Satisfactory storage performance for three days at room temperature was also confirmed. [Copyright &y& Elsevier]

A miniaturized sample preparation technique that uses a fine-fiber-packed needle as the extraction medium is reviewed, especially in relation to its application to the analysis of volatile organic compounds by gas chromatography. When the needle was packed longitudinally with a bundle of fine filaments (12 µm o.d.) which were also surface-coated with polymeric materials, successful sample preconcentration was obtained. Improved sensitivity was also established by introducing simultaneous derivatization reactions into the extraction process in the fiber-packed needle. The storage performance of the needle clearly demonstrated the potential of the technique for typical on-site sampling during environmental analysis. In this short review, the fiber-packed extraction needle developed by the authors is summarized along with applications that use the fiber-packed needle as a miniaturized extraction device. [ABSTRACT FROM AUTHOR]

Abstract: Miniaturized needle extraction device has been developed as a versatile sample preparation device designed for the rapid and simple analysis of smoking-related compounds in smokers’ hair samples and environmental tobacco smoke. Packed with polymeric particle, the resulting particle-packed needle was employed as a miniaturized sample preparation device for the analysis of typical volatile organic compounds in tobacco smoke. Introducing a bundle of polymer-coated filaments as the extraction medium, the needle was further applied as a novel sample preparation device containing simultaneous derivatization/extraction process of volatile aldehydes. Formaldehyde (FA) and acetaldehyde (AA) in smoker''s breath during the smoking were successfully derivatized with two derivatization reagents in the polymer-coated fiber-packed needle device followed by the separation and determination in gas chromatography (GC). Smokers’ hair samples were also packed into the needle, allowing the direct extraction of nicotine from the hair sample in a conventional GC injector. Optimizing the main experimental parameters for each technique, successful determination of several smoking-related compounds with these needle extraction methods has been demonstrated. [Copyright &y& Elsevier]

A novel in-needle sample preparation device has been developed for the determination of volatile aldehydes in gaseous samples. The needle device is designed for the gas chromatographic (GC) analysis of aldehydes and ketones commonly found in typical in-house environments. In order to prepare the extraction device, a bundle of polymer-coated filaments was longitudinally packed into a specially designed needle. Derivatization reactions were prompted by 2,4-dinitrophenylhydrazine (NDPH) included in the needle, and so the aldehydes and ketones were derivatized to the corresponding hydrazones and extracted with the extraction needle. A reproducible extraction needle preparation process was established, along with a repeatable derivatization/extraction process that ensures the successful determination of aldehydes. The storage performance of the extraction needle was also evaluated at room temperature for three days. The results demonstrate the successful application of the fiber-packed extraction device to the preparation of a gaseous sample of aldehydes, and the future possibility of applying the extraction device to the analysis of in-house environments. [ABSTRACT FROM AUTHOR]

Abstract: A novel in-needle extraction device has been developed for the preconcentration of gaseous organic compounds prior to the determination in gas chromatography (GC). As the extraction medium, a copolymer of methacrylic acid and ethylene glycol dimethacrylate was synthesized. Based on the results in the preliminary experiments, the desorption conditions such as desorption temperature and time have been optimized along with the evaluation of the extraction efficiency. The storage performance of the needle extraction device was also studied. The results clearly demonstrated the excellent extraction performance for typical organic solvents and also suggested the future possibility such as in the applications for the analysis of working environments. [Copyright &y& Elsevier]

Resistivities of single-crystalline as well as poly-crystalline samples of CeOBiS 2 without fluorine doping were measured at temperatures down to 0.13 K, and were compared with those of poly-crystalline LaOBiS 2 and PrOBiS 2 . Both poly-crystalline and single-crystalline CeOBiS 2 exhibited zero resistivity below 1.2 K while poly-crystalline LaOBiS 2 and PrOBiS 2 did not show zero resistivity down to 0.13 K. Superconducting transition temperature of CeOBiS 2 was reduced by increasing the applied current density. The superconductivity of CeOBiS 2 without chemical doping is likely triggered by the carriers induced by the valence fluctuation between Ce 3+ and Ce 4+ . [ABSTRACT FROM AUTHOR]

Abstract: For two-dimensional reversed-phase liquid chromatography–gas chromatography (2D RPLC–GC), a specially-designed needle packed with a polymer-coated fibrous stationary phase was introduced as a novel interface. The bundle of synthetic fibers coated with polydimethylsiloxane (PDMS) was packed into the head section of the needle, and served as the extraction medium. Using the post-column dilution of the LC eluent by water and subsequent extraction with the needle interface, the analyte was successfully concentrated to the PDMS phase on the fibrous support in the needle. The concentrated analytes were directly injected to GC system by inserting the needle to a heated GC injector. 2D separations of aliphatic and aromatic hydrocarbons, and also kerosene-extract were performed with the off-line RPLC–GC system interfaced by the needle extractor. The results suggested that the fiber-packed needle interface could be one of the simple and effective approaches to develop an on-line coupled LC–GC system. [Copyright &y& Elsevier]

Abstract: Retention prediction models using multiple linear regression (MLR) and artificial neural networks (ANN) were developed for adrenoreceptor agonists and antagonists chromatographed on a diol column under hydrophilic interaction chromatographic (HILIC) mode at three pH conditions (3.0, 4.0 and 5.0). Using stepwise MLR, the retention behavior of the analytes was satisfactorily described by a five-predictor model; the predictors being the percentage of acetonitrile in the mobile phase (% ACN), the logarithm of partition coefficient (log D), the number of hydrogen bond donor (HBD), the number of hydrogen bond acceptor (HBA), and the total absolute atomic charge of the molecule (TAAC). Among the five descriptors, % ACN had the strongest effect on the retention as indicated by its relatively higher standardized coefficient compared to the other four predictors. The inclusion of the four predictors which are related to the properties of the compounds (log D, HBD, HBA and TAAC), suggested hydrophilic interaction, hydrogen bonding and ionic interaction as possible mechanisms of retention of the analytes on the studied system. The models derived from MLR also showed adequate fit as proven by the high correlation (R 2 as high as 0.9667) between observed and predicted log k values for the training set and good predictive power on the test set (R 2 greater than 0.97). ANN analyses of the data were also conducted using the five predictors derived from MLR as inputs and log k as output. The trained ANNs showed better predictive abilities as compared to MLR models as indicated by relative higher R 2 and lower root mean square error of predictions (RMSEP) for both training and test sets. The derived models can be used as references for method development and optimization of chromatographic conditions for the separation of adrenoreceptor agonists and antagonists. [Copyright &y& Elsevier]

A fiber-packed needle was developed as a novel extraction device for gas-chromatographic analysis of trace organic compounds in aqueous samples. In the extraction device, a bundle of the polymer-coated filaments as the sorbent material was longitudinally packed into a specially designed needle. The extraction was made by pumping the aqueous sample solution into the needle extraction device, and the subsequent desorption process was carried out with a flow of desorption solvent through the needle in a heated gas chromatograph injector. The needle device showed an excellent thermal stability for repeated use without any deterioration of extraction performance, and no carryover effect was observed after the optimization of the desorption conditions. Additionally, the extraction efficiency of the fiber-packed needle could be enhanced by optimizing the number of packed filaments. The selectivity for various compounds could be also tuned using an appropriate combination of the fibrous medium and the coating polymer. The relative standard deviation for run to run was from 3.88 to 4.55% ( n = 5), and that for needle to needle was 7.21% ( n = 3), clearly suggesting a good repeatability of the needle extraction technique developed. Upon successful optimization of the extraction conditions, a rapid extraction of trace organic compounds from an aqueous sample matrix was successfully demonstrated, where each extraction process was completed within 10 min. [ABSTRACT FROM AUTHOR]

Abstract: We review the approach to miniaturization of sample preparation using a fiber-packed capillary as the medium, especially for on-line coupling of the processes of sample preparation and chromatographic separation. We summarize our novel use of polymeric fiber filaments as the extraction medium for microscale liquid-phase and gas-phase separations that we have developed. [Copyright &y& Elsevier]

“F-free” CeOBiS 2 single crystals have successfully grown, thoroughly eliminating a concern about F-contamination by using a high-purity CsCl flux. The obtained crystals have a plate-like shape with a size of 1.0–3.0 mm in the well-developed plane. Single crystal X-ray structural analysis clearly revealed that the CeOBiS 2 crystallizes with a space group P 4/ nmm (with lattice parameters of a = 4.0189 (6) Å, c = 13.573 (2) Å). The bond valence sum estimation and X-ray photoelectron spectroscopy analysis showed that the chemical state of Ce was in the mixed valence of Ce 3+ and Ce 4+ . The single crystals show superconductivity with zero resistivity at ∼1.3 K. This is the first conclusive evidence of superconductivity driven by Ce valence fluctuation in surely non-doped CeOBiS 2 . The superconducting transition temperature was enhanced up to ∼3.8 K by applying hydrostatic pressure. [ABSTRACT FROM AUTHOR]

The effects of counter-anions on the reversed-phase HPLC retention of zwitterionic quinolones were studied. Four counter-anions, perchlorate, tetrafluoroborate, trifluoroacetate, and dihydrogenphosphate, were used as mobile phase additives. HPLC analysis was performed at a mobile phase pH 3, to ensure the complete protonation of the piperizine ring and to suppress the ionization of the carboxylic acid groups of the analytes. Results showed that retention factors of all analytes increased to varying degrees with increasing counter-anion concentration. The increase in retention of the analytes is attributed to the chaotropic effect exhibited by the counter-anions. Complete separation of all the studied compounds was achieved by varying the type and amount of counter-anions present in the mobile phase. The changes in selectivity offered by these counter-anions would be beneficial, especially for developing chromatographic methods for the analysis of quinolones in different sample matrices. [ABSTRACT FROM AUTHOR]

• Miniaturized sample preparation with braid-type extraction medium was developed. • The extraction capillary was prepared using the braid with a metal wire inside. • Applying low voltages to the metal wire, a heat-assisted desorption was made. A novel miniaturized sample preparation device with braid-type extraction medium was successfully developed. Introducing a set of bundles of fine synthetic filaments as the materials of the braid-type extraction medium and also the application of an appropriate tension during the braiding process, the outer diameter of the resulting braid has been controlled. Optimization of the tension enables an easy preparation of a group of braids that can be well-compatible to various internal diameters of capillaries to be packed. The extraction conditions were systematically optimized, and the efficient extraction was confirmed under the optimized conditions. All the parameters affects the desorption efficiency were also optimized, where typical extraction efficiency was more than 90% for the extraction of phenanthrene (1.0 μg/mL) in water. The extracted analyte was desorbed sufficiently by employing a sequential pumping process of two organic solvents. During the preparation of the braid, a different type of fibrous materials could be inserted to the opening at the center of the braid. Taking advantage of this feature of the braid, a stainless steel wire was inserted into the center of the braid. By applying low voltages to the stainless steel wire, a heat-assisted desorption of the extracted analyte was also studied. Experimentally complete desorption (higher than 99.0%) was obtained with the voltage application of 2 V. The lowest limit of quantification (LOQ) and the lowest limit of detection (LOD) for phenanthrene were 0.048 and 0.014 μg/mL, respectively. [ABSTRACT FROM AUTHOR]