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Showing papers in "Analytical Sciences in 2012"


Journal ArticleDOI
TL;DR: The principles and advantages of NIR spectroscopy are described first, and then its applications to various fields, including polymer science, on-line monitoring, inorganic material research, medical diagnosis, and NIR imaging are introduced.
Abstract: The purpose of this review article is to outline recent progress in near-infrared (NIR) spectroscopy. Some particular emphasis is put on the delineation of its versatility in analytical chemistry. NIR spectroscopy is versatile in many aspects. For example, it is electronic spectroscopy as well as vibrational spectroscopy. It is also all-round in applications from basic to practical applications. NIR spectroscopy can be applied to various kinds of materials, bulk materials, thin or thick polymers, tablets, human bodies, and so on. It is particularly powerful in non-invasive, non-destructive, and in situ analysis. In this review, the principles and advantages of NIR spectroscopy are described first, and then its applications to various fields, including polymer science, on-line monitoring, inorganic material research, medical diagnosis, and NIR imaging are introduced.

212 citations


Journal ArticleDOI
TL;DR: An efficient simplified isotope dilution method was developed to determine four carboxyl containing phytohormones simultaneously in 200 mg of fresh tomato tissues using ultra high performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-MS/MS) with negative electrospray ionization.
Abstract: An efficient simplified isotope dilution method was developed to determine four carboxyl containing phytohormones simultaneously in 200 mg of fresh tomato tissues using ultra high performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-MS/MS) with negative electrospray ionization. The four phytohormones are indole-3-acetic acid (IAA), abscisic acid (ABA), jasmonic acid (JA), and salicylic acid (SA). Only one purification step of Oasis MAX solid phase extraction (SPE) was employed to enrich target phytohormones after crude extraction. In addition, two endogenous isomers of JA, (-)-JA and (+)-7-iso-JA, were separated directly. The validated method has been applied to monitor changes of JA, SA, IAA, and ABA in both local and systemic leaves of wild-type and transgenic 35S::prosystemin (35S::PS) tomato lines. Meanwhile, the JA burst amplified by the overexpressed prosystemin in 35S::PS was verified. Furthermore, the spatial and temporal changes of JA, SA, ABA, and IAA were analyzed.

155 citations


Journal ArticleDOI
TL;DR: The original method for H-ORAC determination was improved, and the precision of the two improved methods were evaluated by interlaboratory studies using 5 antioxidant solutions and 5 food extracts as test samples.
Abstract: Hydrophilic oxygen radical absorbance capacity (H-ORAC) is a method for evaluating antioxidant capacities of solutions of hydrophilic compounds. In this study, we improved the original method for H-ORAC determination, and evaluated the precision of the two improved methods (methods A and B) by interlaboratory studies using 5 antioxidant solutions and 5 food extracts as test samples. An interlaboratory study of method A, in accordance with the harmonized protocol, demonstrated satisfactory performance (intermediate precision relative standard deviations (RSD(int)) ranging from 4.6 to 18.8%; the reproducibility relative standard deviations (RSD(R)) ranging from 7.0 to 21.1%, and the HorRat values ranging from 0.40 to 1.93). However, methodological problems remained, and a further improved method, method B, was thus developed. An interlaboratory study of method B by 5 participating laboratories showed better intermediate precision and reproducibility (RSD(int) and RSD(R) ranging from 1.8 to 9.4%, and from 4.4 to 13.8%, respectively), and all HorRat values for the test samples were less than 1.3, suggesting good performance for the H-ORAC measurement.

78 citations


Journal ArticleDOI
TL;DR: Serum samples from BC patients show decreased levels of isoleucine/leucine, tyrosine, lactate, glycine, citrate, as well as increased levels of lipids and glucose, which will offer valuable information for noninvasive diagnosis of the disease.
Abstract: Bladder cancer (BC) is one of the most common cancers and has a high mortality rate. However, both metabolite variations and metabolic pathways related to the pathogenic process of BC remain to be addressed, such results might contribute to early detection of the disease. (1)H nuclear magnetic resonance (NMR)-based metabolomics was applied to identify differences of serum metabolic profiles among BC, calculi patients and healthy subjects. Serum metabolic profiles of BC patients are distinctly different from those of calculi and healthy subjects. Compared with those from healthy subjects, serum samples from BC patients show decreased levels of isoleucine/leucine, tyrosine, lactate, glycine, citrate, as well as increased levels of lipids and glucose. The results reveal disturbed metabolic pathways of aromatic amino acids, glycolysis and citrate cycle, as well as lipogenesis metabolism in BC patients. Our work will be of potential benefit to understanding the pathogenic process of BC and will offer valuable information for noninvasive diagnosis of the disease.

71 citations


Journal ArticleDOI
TL;DR: LbL films composed of insulin and polymers are sensitive to environmental pH, and release insulin in response to pH changes, suggesting that insulin L bL films can be used in the development of orally administered insulin.
Abstract: We present an overview of the preparation and properties of layer-by-layer (LbL) deposited thin films and microcapsules in relation to their use in the development of biosensors and controlled release systems. Enzyme biosensors can be constructed by immobilizing enzymes on the surface of electrodes by LbL deposition without loss of their catalytic activity. In addition to synthetic polymers, binding proteins, such as avidin and lectin, are also used for constructing LbL films through avidin-biotin and lectin-sugar interactions. The performance characteristics of LbL film-based biosensors can be tuned by controlling the number of layers and by the choice of film components. The permeability of polyelectrolyte LbL films to ions and molecules is discussed in relation to the use of the films for eliminating interference in biosensors. The possible use of polysaccharide LbL film-coated electrodes for the construction of biosensors is highlighted, and examples of LbL film- and microcapsule-based optical sensors are described. We then focus on the use of LbL films and microcapsules as vehicles for controlled release, in particular on recent progress in the controlled release of insulin from LbL films and microcapsules. LbL films composed of insulin and polymers are sensitive to environmental pH, and release insulin in response to pH changes, suggesting that insulin LbL films can be used in the development of orally administered insulin. The construction of glucose-dependent insulin release systems using LbL insulin microcapsules functionalized with phenylboronic acid, lectin, and glucose oxidase is also examined.

65 citations


Journal ArticleDOI
TL;DR: The proposed sensor is a selective and fast tool for the determination of ciprofloxacin in tablet, plasma, and urine samples and the repeatability of the sensor was investigated by preparing nine similar electrodes.
Abstract: A new sensor containing MgFe2O4 nanoparticles in modified multiwall carbon nanotubes (MgFe2O4-MWCNTs) was prepared, and its electrochemical behavior was investigated. MgFe2O4-MWCNTs were used as a voltammetric sensor for the electrocatalytic determination of ciprofloxacin. The synthesized materials were characterized by different methods such as transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry, and electrochemical impedance spectroscopy. The MgFe2O4-MWCNTs electrode showed an oxidation peak potential at around 250 mV. The immobilized composite films facilitate interfacial electron transfer and electrocatalytic activity on the oxidation of ciprofloxacin. The oxidation peak current was dependent on the ciprofloxacin concentration, which was linear over the range of 0.10 - 1000 µmol L(-1) with a detection limit and quantification limit of 0.01 and 0.08 µmol L(-1), respectively. The relative standard deviation for the determination of 1.0 µmol L(-1) ciprofloxacin was 1.1%. The repeatability of the sensor was investigated by preparing nine similar electrodes. The proposed sensor is a selective and fast tool for the determination of ciprofloxacin in tablet, plasma, and urine samples.

60 citations


Journal ArticleDOI
TL;DR: A micro total bioassay system that mimics physiological processes that could correctly assay the overall digestive properties of ingested anticancer agents, as well as intestinal absorption, hepatic metabolism, and bioactivity toward target cells.
Abstract: A micro total bioassay system that mimics physiological processes was developed as a means of evaluating orally administered drugs. A new feature accounting for gastrointestinal digestion was added to the previous system, which consists of microintestine, microliver, and target components. The artificial micro-gastrointestinal tract employs synthetic digestive juices. The system could correctly assay the overall digestive properties of ingested anticancer agents, i.e., the stability during digestive processes, as well as intestinal absorption, hepatic metabolism, and bioactivity toward target cells.

59 citations


Journal ArticleDOI
TL;DR: 1-norm, 2- norm, and quantile normalization methods were applied to liquid chromatography-mass spectrometry (LC-MS)-based metabolomic data from human urine samples after oral administration of cyclosporine in healthy volunteers and compared the effectiveness of the three methods.
Abstract: In metabolomic research, it is important to reduce systematic error in experimental conditions. To ensure that metabolomic data from different studies are comparable, it is necessary to remove unwanted systematic factors by data normalization. Several normalization methods are used for metabolomic data, but the best method has not yet been identified. In this study, to reduce variation from non-biological systematic errors, we applied 1-norm, 2-norm, and quantile normalization methods to liquid chromatography-mass spectrometry (LC-MS)-based metabolomic data from human urine samples after oral administration of cyclosporine (high- and low-dose) in healthy volunteers and compared the effectiveness of the three methods. The principal component analysis (PCA) score plot showed more obvious groupings according to the cyclosporine dose after quantile normalization than after the other two methods and prior to normalization. Quantile normalization is a simple and effective method to reduce non-biological systematic variation from human LC-MS-based metabolomic data, revealing the biological variance.

46 citations


Journal ArticleDOI
TL;DR: The sensitivity of this method enables the determination of mercury species in water samples at sub-ppb levels and was applied to biological samples in combination with acid leaching and liquid-liquid extraction using emetine-CS(2) as an extraction reagent.
Abstract: A sensitive determination method for mercury speciation analysis was developed. Four mercury species, mercury ion, methylmercury, ethylmercury, and phenylmercury, were complexed with emetine-dithiocarbamate (emetine-CS(2)), and then injected onto a HPLC instrument coupled with a tris(2,2'-bipyridine)ruthenium(III) chemiluminescence detection system. The emetine-CS(2) complexing agent was effectively used to measure the concentration in addition to serving as a separation and detection reagent. The calibration curves for these mercury complexes were linear in the range of 0.050 - 10 μg L(-1) (as Hg). The limit of detection for (emetine-CS(2))(2)Hg, emetine-CS(2)-methylmercury, emetine-CS(2)-ethylmercury, and emetine-CS(2)-phenylmercury were 30, 17, 21, and 22 ng L(-1), respectively. The sensitivity of this method enables the determination of mercury species in water samples at sub-ppb levels. Furthermore, the method was applied to biological samples in combination with acid leaching and liquid-liquid extraction using emetine-CS(2) as an extraction reagent. The determination results were in good agreement with the values of the certified reference materials.

45 citations


Journal ArticleDOI
TL;DR: This device provides a convenient, disposable, and high-throughput platform that could function as a progressive motile sperm sorter for potential use in intracytoplasmic sperm injection.
Abstract: We present a novel method for the separation of progressive motile sperm from non-progressive motile and immotile sperm. This separation was accomplished by inducing chemotaxis along a longitudinal chemical gradient in a microchip composed of a biocompatible polydimethysiloxane layer and a glass substrate. In a preliminary experiment using fluorescent rhodamine B as a marker, we verified that a chemical gradient was generated by diffusion within the microchannel. We used acetylcholine as a chemoattractant to evaluate the chemotactic response of sperm. We tested the response to a 1/2 to 1/64 dilution series of acetylcholine. The results of a mouse sperm chemotaxis assay showed that progressive motile sperm swam predominantly toward the outlet at an optimal chemical gradient of 0.625 (mg/ml)/mm of acetylcholine. This device provides a convenient, disposable, and high-throughput platform that could function as a progressive motile sperm sorter for potential use in intracytoplasmic sperm injection.

41 citations


Journal ArticleDOI
TL;DR: RMNS produced by state-of-the-art techniques are currently available for global use to improve the comparability of nutrients data in the open ocean and, as discussed here, are reliable candidates to be used for certified reference materials.
Abstract: The development of Reference Materials for Nutrients in Seawater (RMNS) has been in progress since 1993. When RMNS were produced for nitrate, silicate, and phosphate, their initial homogeneities were as low as 0.1 to 0.2% in samples of high-nutrient seawater, such as deep water from the Pacific Ocean. The relative standard uncertainties associated with instability during long-term (4.8 years) storage were approximately 0.2, 0.2, and 0.4% for nitrate, silicate, and phosphate, respectively. No instability was observed for 1.9 to 6.4 years based on the ISO Guide 35:2006 criteria; however, the relative standard uncertainties associated with instability during long-term storage were larger than the initial homogeneities of RMNS. RMNS produced by state-of-the-art techniques are currently available for global use to improve the comparability of nutrients data in the open ocean and, as discussed here, are reliable candidates to be used for certified reference materials.

Journal ArticleDOI
TL;DR: The metabolism of anti-breast cancer drug, tamoxifen, in a single human hepatocellular carcinoma cell, HepG2, was directly monitored by a video-mass spectroscope, and Unchanged drug molecules were found in cy toplasm and a vacuole, but the metabolites were only found in the cytoplasm.
Abstract: The metabolism of anti-breast cancer drug, tamoxifen, in a single human hepatocellular carcinoma cell, HepG2, was directly monitored by a video-mass spectroscope. The cytoplasm, a vacuole or nucleus of the cell was directly sucked by a nano-spray tip under a video-microscope, and then was introduced into a mass spectrometer. Unchanged drug molecules were found in cytoplasm and a vacuole, but the metabolites were only found in the cytoplasm. This direct detection of drug metabolites in a live single cell is useful for speedy drug metabolism monitoring.

Journal ArticleDOI
TL;DR: The results suggest that the proposed flexible SWCNT film electrodes can be applied as simple, efficient, cost-effective, and/or disposable electrodes for simultaneous detection of heavy metal ions.
Abstract: A flexible, transparent, single-walled carbon nanotube (SWCNT) film electrode was prepared by vacuum filtering methods, followed by photolithographic patterning of a photoresist polymer on the SWCNT surface. The morphology of the SWCNT film electrode surface was characterized using a field-emission scanning electron microscope coupled to an energy-dispersive X-ray spectrophotometer. The electrodes were successfully used as a mercury-free electrochemical sensor for individual and simultaneous detection of cadmium (Cd(2+)) and lead (Pb(2+)) in 0.02 M HCl by square-wave stripping voltammetry. Some important operational parameters, including deposition time, deposition potential, square-wave amplitude, and square wave-frequency were optimized for the detection of Cd(2+) and Pb(2+). The newly developed sensor showed good linear behavior in the examined concentration. For individual Cd(2+) and Pb(2+) ion detection, the linear range was found from 0.033 to 0.228 ppm with detection limits of 0.7 ppb (R(2) = 0.985) for Cd(2+) and 0.8 ppb (R(2) = 0.999) for Pb(2+). For simultaneous detection, the linear range was found from 0.033 to 0.280 ppm with a limit of detection of 2.2 ppb (R(2) = 0.976) and 0.6 ppb (R(2) = 0.996) for Cd(2+) and Pb(2+), respectively. SWCNT film electrodes offered favorable reproducibility of ± 5.4% and 4.3% for Cd(2+) and Pb(2+), respectively. The experiments demonstrated the applicability of carbon nanotubes, specifically in the preparation of SWCNT films. The results suggest that the proposed flexible SWCNT film electrodes can be applied as simple, efficient, cost-effective, and/or disposable electrodes for simultaneous detection of heavy metal ions.

Journal ArticleDOI
TL;DR: Three potential methods for obtaining quantitative information regarding the chemical state of lead in fly ash are identified and it is concluded that multiple analyses should be compared multilaterally to improve the accuracy of the final analysis.
Abstract: Understanding the chemical state of lead in fly ash generated from a waste thermal treatment is important, since the toxicity and solubility of the element depends on its chemical state. This study identified three potential methods for obtaining quantitative information regarding the chemical state of lead in fly ash: X-ray absorption near edge structure (XANES) analysis, extended X-ray absorption fine structure (EXAFS) analysis, and the sequential extraction procedure. The result of this procedure was strongly affected by the pH and sample matrix, and did not necessarily accurately reflect the chemical state. It was difficult to quantitatively examine the chemical species using only EXAFS. However, an XANES fitting enabled direct quantification of the chemical species. An XANES analysis showed that PbSiO(3), PbCl(2), or Pb(2)O(OH)(2) was the predominant chemical species in fly ash. We concluded that multiple analyses should be compared multilaterally to improve the accuracy of the final analysis.

Journal ArticleDOI
TL;DR: The LFD accurately identified 7 species of bacteria, but had no cross-reactivity with human genomic DNA, and the limit of detection of the LFD assay was as low as 10(1) copies/µL of 16S rDNA for plasmid.
Abstract: In the present study, we aimed to develop a nucleic acid lateral-flow method for the rapid and sensitive detection of multiple bacteria that contaminate platelet concentrations (PCs). Polymerase chain reaction (PCR) amplicons were produced by a set of board-range primers that recognize the conserved region of bacteria 16S rDNA, followed by hybridization with both an FITC (fluorescein isothiocyanate)-labelled probe and biotin-labelled probe, and then a nucleic acid lateral-flow dipstick (LFD) assay. The LFD accurately identified 7 species of bacteria, but had no cross-reactivity with human genomic DNA. The limit of detection (LOD) of the LFD assay was as low as 10 1 copies/μL of 16S rDNA for plasmid. In the case of spiked PCs without enrichment, the detection limit of LFD for K. pneumonia was 5 CFU/mL, 6.5 × 10 4 CFU/mL for the S. epidermidis and 35 CFU/mL for P. aeruginosa.

Journal ArticleDOI
TL;DR: The results of recovery tests using model compounds showed that the developed method can quantitatively analyze most SVOC, except for very polar substances, and is a good tool for rapid screening of chemical pollution in sediments.
Abstract: A comprehensive analytical method for nearly 1000 semi-volatile organic compounds (SVOC) in sediments has been developed using an automated identification and quantification system with a GC-MS database. The results of recovery tests using model compounds, which comprise of 119 non-polar to polar compounds, showed that the method can quantitatively analyze most SVOC, except for very polar substances. Analytical results of a standard reference material were close to certified concentrations. The detection limits of the method were 4 μg/kg when measuring by TIM and 0.4 μg/kg by SIM. The method was applied to actual sediments in rivers in Ho Chi Minh City, Vietnam. A large number of substances, including persistent organic pollutants, which seem to be discharged from domestic sources, were found at relatively high concentrations. From these results, it is confirmed that the developed method is a useful way to obtain a holistic picture of pollution by SVOC, and is a good tool for rapid screening of chemical pollution in sediments.

Journal ArticleDOI
Yamin Li1, Shufang Wu1, Peili Luo1, Jie Liu1, Ge Song1, Kai Zhang1, Baoxian Ye1 
TL;DR: The results indicated that this ultrasensitive voltammetric sensor exhibited a special recognition capacity to determine theophylline as well as having high sensitivity due to the excellent characteristics of graphene and the adsorption action of Nafion for theophyLLine.
Abstract: An ultrasensitive voltammetric sensor, a simply coated graphene-Na?on suspension on a glass carbon electrode surface, was fabricated and used to investigate the electrochemical behavior of theophylline as described in the present paper. The results indicated that this voltammetric sensor exhibited a special recognition capacity to determine theophylline as well as having high sensitivity due to the excellent characteristics of graphene and the adsorption action of Nafion for theophylline. Under the selected condition using differential pulse voltammetry, the response peak currents had a linear relationship with the theophylline concentrations in two ranges from 1.0 × 10(-8) - 1.0 × 10(-6) and 2.0 × 10(-6) - 3.0 × 10(-5) mol L(-1) with a low detection limit of 6.0 × 10(-9) mol L(-1). Moreover, according to the results obtained in the analysis of theophylline in two standard samples, it demonstrated the applicability of present method into real sample determination.

Journal ArticleDOI
TL;DR: In this paper, an effort is made to critically present the achievements in silver ion chromatography during the last decade, including columns, mobile-phase compositions and detectors, and the tendencies in the application of the method in complementary ways with reversed-phase chromatography, chiral chromatography and especially, mass detection.
Abstract: An effort is made to critically present the achievements in silver ion chromatography during the last decade. Novelties in columns, mobile-phase compositions and detectors are described. Recent applications of silver ion chromatography in the analysis of fatty acids and triacylglycerols are presented while stressing novel analytical strategies or new objects. The tendencies in the application of the method in complementary ways with reversed-phase chromatography, chiral chromatography and, especially, mass detection are outlined.

Journal ArticleDOI
TL;DR: It is demonstrated that the C1-APB/3-PB-γ-CyD complex functioned as an efficient supramolecular sensor for selective glucose recognition in water.
Abstract: A boronic acid fluorophore (C1-APB)/boronic acid-modified γ-cyclodextrin (3-PB-γ-CyD) complex as a supramolecular sensor has been designed for selective glucose recognition in water. The fluorescent response behavior of the C1-APB/3-PB-γ-CyD complex under various pH conditions revealed that a C1-APB/3-PB-γ-CyD complex solution containing glucose showed a large increase in the fluorescence intensity under alkaline pH conditions. In contrast, only small increases in the fluorescence intensity were noted for fructose and without sugar solutions. The observed response selectivity for the C1-APB/3-PB-γ-CyD complex was on the order of glucose >> galactose, mannose > fructose. The evidence on a large value of the inclusion constant (K(L·CyD) = 6.5 × 10(3) M(-1)), a marked broadening of the (1)H NMR spectra, and an enhancement of induced circular dichloism (ICD) intensity for the C1-APB/3-PB-γ-CyD complex by glucose binding supported the multi-point interaction of the C1-APB/3-PB-γ-CyD complex with glucose. These results demonstrated that the C1-APB/3-PB-γ-CyD complex functioned as an efficient supramolecular sensor for selective glucose recognition in water.

Journal ArticleDOI
TL;DR: The combination of the PANI with the Au-NPs and the BDD electrode can create synergetic effects for the performance of the biosensor, such as a fast response time, a lower detection limit, a wider linear range, enhanced selectivity, and higher sensitivity for the determination of DA.
Abstract: A selective dopamine (DA) sensor was developed using gold nanoparticles (Au-NPs) dispersed overoxidized-polyaniline (PANI(ox)) based on a boron-doped diamond (BDD) thin-film electrode. The concentration of the DA was determined using voltammetry as a non-enzymatic sensor. BDD thin film has a high signal-to-noise ratio, a long-term stability, a high sensitivity, and a good reproducibility. PANI nanocomposites were directly synthesized on the BDD electrode and overoxidized using 0.5 M H(2)SO(4) solution. The overoxidized PANI film enhances selectivity and sensitivity toward DA. The Au-NPs were dispersed on the PANI nanocomposite by electrochemical deposition. The nanometer-sized Au-NPs favor the sensing of DA in the presence of ascorbic acid (AA). The combination of the PANI with the Au-NPs and the BDD electrode can create synergetic effects for the performance of the biosensor, such as a fast response time, a lower detection limit, a wider linear range, enhanced selectivity, and higher sensitivity for the determination of DA.

Journal ArticleDOI
TL;DR: A simple method to change the hydrophilic nature of the glass surface in a poly(dimethylsiloxane) (PDMS)-glass hybrid microfluidic device to hydrophobic by an extra-heating step during the fabrication process is presented.
Abstract: This paper presents a simple method to change the hydrophilic nature of the glass surface in a poly(dimethylsiloxane) (PDMS)-glass hybrid microfluidic device to hydrophobic by an extra-heating step during the fabrication process. Glass substrates bonded to a native or oxygen plasma-treated PDMS chip having microchambers (12.5 mm diameter, 110 μm height) were heated at 200°C for 3 h, and then the hydrophobicity of the glass surfaces on the substrate was evaluated by measuring the contact angle of water. By the extra-heating process, the glass surfaces became hydrophobic, and its contact angle was around 109°, which is nearly the same as native PDMS surfaces. To demonstrate the usefulness of this surface modification method, a PDMS-glass hybrid microfluidic device equipped with microcapillary vent structures for pneumatic manipulation of droplets was fabricated. The feasibility of the microcapillary vent structures on the device with the hydrophobic glass surfaces are confirmed in practical use through leakage tests of the vent structures and liquid handling for the electrophoretic separation of DNA molecules.

Journal ArticleDOI
TL;DR: The ultrasonic extraction with water, even without heating, was found to be an acceptable monitoring method for an evaluation of water-soluble inorganic As, since it could extract about 80% of total As.
Abstract: An aqueous extraction of inorganic As species, such as arsenite (As(III)) and arsenate (As(V)), was developed for monitoring inorganic As in the edible brown alga Hizikia fusiforme (hijiki). The ultrasonic extraction with water, even without heating, was found to be an acceptable monitoring method for an evaluation of water-soluble inorganic As, since it could extract about 80% of total As. Such an extraction efficiency was almost the same as those of enzyme assisted extraction methods. The developed extraction procedure was applied to 15 hijiki samples that had been collected at different coasts in Japan. All samples contained a substantial proportion of As as arsenosugars; the relative amounts of the different As species extracted were dependent on the sample. The percentages of extractable As species in the hijiki samples were in the range from 70 to 90%, and the sums of the concentrations of As(III) and As(V), which was defined as i-As, were in the range from 36 to 79% of the total As concentration in each sample. The proposed method is appropriate for environmental monitoring for inorganic As speciation in algae.

Journal ArticleDOI
TL;DR: It is demonstrated that HSA-Fe(3)O(4) NPs effectively captured small drugs from human urine and serum via the interactions between HSA and these drugs, and can open up new approaches to the analytical detection of small drugs in biological liquids by SALDI-MS.
Abstract: Here, we report on the use of human serum albumin (HSA)-modified Fe(3)O(4) nanoparticles (NPs) (HSA-Fe(3)O(4) NPs) for affinity-SALDI-MS of small drugs in human biological liquids. We demonstrated that HSA-Fe(3)O(4) NPs effectively captured small drugs from human urine and serum via the interactions between HSA and these drugs. The drugs adsorbed on HSA could then be identified by directly introducing the HSA-Fe(3)O(4) NPs into a mass spectrometer for SALDI-MS analysis. The ability of HSA to interact with multiple small drugs facilitated the simultaneous detection of a 4-drug-mixture in serum, viz., phenytoin, ibuprofen, camptothecin, and warfarin sodium, by affinity-SALDI-MS using HSA-Fe(3)O(4) NPs. In contrast, matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) with an organic matrix could detect only warfarin sodium. We also demonstrated the capacity of affinity-SALDI-MS to quantify warfarin sodium in urine samples across a range of 50 - 1000 μM (R(2) = 0.998) when using HSA-Fe(3)O(4) NPs. The detection sensitivity was further improved to a range of 5 - 100 μM (R(2) = 0.999) by using denatured HSA. The open structure of denatured HSA may enhance the effective extraction of small drugs from biological liquids, and increase the detection-sensitivity of affinity-SALDI-MS. Affinity-SALDI-MS using protein-modified Fe(3)O(4) NPs can open up new approaches to the analytical detection of small drugs in biological liquids by SALDI-MS.

Journal ArticleDOI
TL;DR: The auto-protolysis constant K(s) value for [(EtOH)(2)EtNH(+)][TFSA(-)] is smaller than that for TFS(-) based PIL, indicating that HTFSA behaves as a stronger acid than HTFS in the respective PIL.
Abstract: Physicochemical properties such as a thermal behavior, ionic conductivity, viscosity and density, and acid-base properties of a new class of 2-hydroxyethylammonium-based protic ionic liquids (PILs) have been investigated. Thirty-six potential PILs were surveyed to find 32 salts with a melting point below 373 K. Among them, [(EtOH)(n)Et((3-n))NH(+)][TFS(-)] (Et, C(2)H(5); n = 0 - 3) and [(EtOH)(2)EtNH(+)][X(-)] (X = TFS, trifluoromethanesulfonate; TFSA, bis(trifluoromethanesulfonyl)amide; NO(3)) were studied in terms of the Walden plots, molar volume and auto-protolysis reaction for effect of the number of 2-hydroxyethyl groups introduced in the cations and for dependence of the anion nature, respectively. With regard to [(EtOH)(n)Et((3-n))NH(+)][TFS(-)] (n = 0 - 3), the ion-ion interactions between cation-anion and cation-cation were enhanced with increasing the number of the 2-hydroxyethyl groups. In addition, the auto-protolysis constant K(s) value for [(EtOH)(2)EtNH(+)][TFSA(-)] is smaller than that for TFS(-) based PIL, indicating that HTFSA behaves as a stronger acid than HTFS in the respective PIL. On the other hand, in [(EtOH)(2)EtNH(+)][NO(3)(-)], the emf jump was rather small, which suggests that the proton of HNO(3) does not easily transfer to (EtOH)(2)EtN in the liquid state.

Journal ArticleDOI
TL;DR: This review highlights recent developments and applications of on-line sample preconcentration techniques to enhance the detection sensitivity in microchip electrophoresis (MCE); references are mainly from 2008 and later.
Abstract: This review highlights recent developments and applications of on-line sample preconcentration techniques to enhance the detection sensitivity in microchip electrophoresis (MCE); references are mainly from 2008 and later. Among various developed techniques, we focus on the sample preconcentration based on the changes in the migration velocity of analytes in two or three discontinuous solutions system, since they can provide the sensitivity enhancement with relatively easy experimental procedures and short analysis times. The characteristic features of the on-line sample preconcentration applied to microchip electrophoresis (MCE) are presented, categorized on the basis of "field strength-" or "chemically" induced changes in the migration velocity. The preconcentration techniques utilizing field strength-induced changes in the velocity include field-amplified sample stacking, isotachophoresis and transient-isotachophoresis, whereas those based on chemically induced changes in the velocity are sweeping, transient-trapping and dynamic pH junction.

Journal ArticleDOI
TL;DR: Using multi-walled carbon nanotubes (MWCNTs) as an adsorbent has been established for the on-line separation and preconcentration Cr(III) and chromium speciation and is further applied for the speciation of chromium in electroplating wastewater samples with satisfactory results.
Abstract: Using multi-walled carbon nanotubes (MWCNTs) as an adsorbent has been established for the on-line separation and preconcentration Cr(III) and chromium speciation. The surface functional groups and negative charges of MWCNTs are beneficial to the adsorption of Cr(III). At pH 3.0 - 6.0, a discrimination of Cr(III) and Cr(VI) is achieved on the MWCNTs surface. Cr(III) ions are adsorbed onto the oxidized MWCNTs surface, while Cr(VI) has no affinity for the MWCNTs. The adsorbed Cr(III) is quantitatively eluted by 10% (v/v) nitric acid with detection by flame atomic absorption spectrometry. By loading a 6.0-ml sample solution, an enrichment factor of 22, a detection limit (3σ) of 1.15 μg l(-1) and a precision of 1.7% RSD at the 30 μg l(-1) level (n = 7) are achieved for Cr(III) within a linear range of 5 - 200 μg l(-1) (r = 0.9994). After Cr(VI) has been reduced to Cr(III) with hydroxylamine hydrochloride, the total amount of chromium is obtained, and the content of Cr(VI) is given by subtraction. The procedure is validated by analyzing chromium in a certified reference material, and is further applied for the speciation of chromium in electroplating wastewater samples with satisfactory results.

Journal ArticleDOI
TL;DR: E evaluation by analyzing real samples shows that this method for the speciation of iron in aqueous samples by the simultaneous analysis of divalent and trivalent iron ions with ion chromatography equipped with chemiluminescence detection (IC-CLD) is rapid, accurate, sensitive, and selective.
Abstract: This study reports on a method for the speciation of iron in aqueous samples by the simultaneous analysis of divalent and trivalent iron ions with ion chromatography equipped with chemiluminescence detection (IC-CLD). Ferrous and ferric ions are first chelated by pyridine-2,6-dicarboxylic acid (PDCA) to form complexed anions, and separated by a mixed-bed ion-exchange column. The separated complexed ions are then detected with a CLD system containing luminol and hydrogen peroxide in a basic solution. This luminescence system has a linear dynamic range of ca. 3 orders of magnitude, with method detection limits as low as 7 µg L(-1) for Fe(II) and 3 µg L(-1) for Fe(III), measured in the simultaneous detection mode. This system resists interferences from common cations such as Cd, Ca, Cr, Cu, Mg, Ni, Pb, and Zn. Evaluation by analyzing real samples shows that this method is rapid, accurate, sensitive, and selective.

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TL;DR: The technical examination presented in this paper is considered to represent a seamless coupling of crystallization to X-ray analysis and several diffraction patterns were of sufficiently fine quality for the crystal structure factors to be generated.
Abstract: We describe the technical aspects of the in-situ X-ray diffraction of a protein crystal prepared by a nanodroplet-based crystallization method. We were able to obtain diffraction patterns from a crystal grown in a capillary without any manipulation. Especially in our experimental approach, the crystals that moved to the nanodroplet interface were fixed strongly enough to carry out X-ray diffraction measurements that could be attributed to the high surface tension of the nanodroplet. The crystal was damaged by an indirect action of the X-rays because our in-situ X-ray diffraction measurement was carried out in the liquid phase without freezing the crystal; however, the obtained several diffraction patterns were of sufficiently fine quality for the crystal structure factors to be generated. We consider the technical examination presented in this paper to represent a seamless coupling of crystallization to X-ray analysis.

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TL;DR: A novel technique for inserting viable bacilliform bacteria into polypyrrole films is successfully developed and it was found that the poly pyrrole layer was important to keep the cells alive.
Abstract: We have successfully developed a novel technique for inserting viable bacilliform bacteria into polypyrrole films. All of the five different bacterial cells (Pseudomonas aeruginosa, Acinetobacter calcoaceticus, Serratia marcescens, Bacillus subtilis and Escherichia coli) studied in this work were inserted normal to the film surface, and the viability of P. aeruginosa was unaffected by this immobilization procedure. It was also found that the polypyrrole layer was important to keep the cells alive.

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TL;DR: By exposure to appropriate UV intensities, rapid and quantitative oxidation/reduction of inorganic selenite, selenate and several organoselenium compounds representative of those of biochemical/metabolic interest, including selenomethionine,selenobetaine, L-selenocystine, SeCO, γ-glutamyl-seleno-methylselanocysteine and selenocystamine is achieved.
Abstract: By exposure to appropriate UV intensities, rapid and quantitative oxidation/reduction of inorganic selenite, selenate and several organoselenium compounds representative of those of biochemical/metabolic interest, including selenomethionine, selenobetaine, L-selenocystine, selenomethylselenocysteine, γ-glutamyl-seleno-methylselenocysteine and selenocystamine, is achieved. In the presence of acetic acid, quantitative conversion to volatile SeH(2) and SeCO occurs using a flow-through system comprising a highly efficient 40 W UV lamp for oxidation in tandem with a lower power 8 W UV photocatalytic reactor utilizing a thin-film coating of titania. The volatile reduced species are detected by atomic absorption spectrometry using a heated quartz tube atomizer. Direct photochemical conversion of selenite, selenomethionine, L-selenocystine, γ-glutamyl-Se-methylselenocysteine and selenocystamine occurs in the presence of 5% acetic acid, following exposure to an 8 W UV field, to yield volatile detectable species, whereas selenobetaine and selenate are unresponsive unless the latter is first subjected to oxidation by exposure to a highly efficient 40 W UV lamp and the selenate reduced in the presence of titania.