A reusable extended-gate field-effect transistor (FET) sensor with an 11-ferrocenyl-1-undecanethiol (11-FUT) modified gold electrode was developed for applying to enzyme immunoassay. It was found that the 11-FUT modified FET sensor detected a thiol compound 50 times or more repeatedly after a treatment with a 5% hydrogen peroxide solution. The gate-voltage shift of the FET sensor showed a fairly good linearity (R² = 0.998) within a range from 10^-2 to 10^-6 M on the concentration of 6-hydroxyl-1-hexanethiol, which is a thiol compound, at a Nernstian response of 58.5 mV/decade. The FET-based immunoassay was constructed by combining the 11-FUT modified-FET sensor with the enzyme-linked immunosorbent assay (ELISA), in which the enzyme chemistry of acetylcholinesterase (AChE) was used to generate a thiol compound. The 11-FUT modified FET sensor with an AC voltage at 1 MHz superimposed onto the reference electrode detected the AChE-catalyzed product corresponding to a serum concentration of interleukin 1β from 10 to 5000 pg/mL. In addition, all measurements were successfully performed by using the same FET-sensor chip after a treatment with a 5% hydrogen peroxide solution.

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The use of a naphthalene urea derivative as a host molecule for selective fluoride binding allows us to develop a highly selective and sensitive electrochemical method for fluoride analysis without the interference of other halogen atoms. All the parameters affecting the differential pulse voltammetric response of the host molecule used as a fluoride receptor have been optimized and the mechanisms of the electrochemical behavior have been elucidated. The inhibition in the electrochemical signal of the anionic receptor due to the increase of the fluoride amounts allows the determination of F-with an LOD of 3.16 × 10^-6 M with an RSD (%) value lower than 4.8% and an Er (%) value lower than 3.8%.

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The interaction of clarithromycin (CAM) with bovine serum albumin (BSA) was investigated in pH 4.5 - 8.0 phosphate buffer solutions in which three irreversible reduction waves P₁, P₂ and P₃ of CAM appeared on linear-sweep voltammetry on a static dropping mercury working electrode. In the acidic media, with the addition of BSA into the CAM solution, a new electrochemically active complex was formed and there was interaction between the carbonyl group C=O in the C-9 position of CAM and BSA. It was found that electrostatic and hydrophobic forces played an important role in the binding reaction. However, new electrochemically non-active complexes were formed at physiological pH condition. The study showed that the formation constant and formation ratio of the interaction between CAM and BSA were 1.51 × 10¹² and 3:1 for P₂ wave, and 4.53 × 10⁵ and 1:1 for P₃ wave, respectively. The ion strength enhanced the hydrophobic interaction between CAM and BSA.

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The behavior of nicotinamide has been studied by differential pulse polarography and cyclic voltammetry in the presence of certain ionic and nonionic surfactants, viz. cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) and Triton X-100 (TX-100). The cathodic peak potential (E_pc) and peak current (I_pc) of nicotinamide were found to be remarkably dependent on the charge and concentration of the surfactant. The presence of SDS and that of TX-100 cause a shift in peak potential and a change in peak current of nicotinamide. In the presence of the cationic surfactant, CTAB, an enhancement in the sensitivity of nicotinamide was observed. A sharp peak with more than two-fold increase in current was used to determine the limit of detection and linear working range using the differential pulse polarographic technique. The present method was successfully used for the simultaneous determination of nicotinamide and pyridoxine hydrochloride, and for the determination of nicotinamide in multivitamin pharmaceutical preparations.

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A coulometric analysis method and an ion-exclusion chromatographic method were developed for the determination of antimony(V) in a large excess of antimony(III). Antimony(V) reacted with potassium iodide in a high concentration hydrochloric acid; the liberated iodine was determined by the standard-addition method using coulometrically generated iodine. Using a Dionex ICE-AS1 ion-exclusion column, antimony(V) was eluted with 40 mmol/L sulfuric acid; on the other hand, antimony(III) was strongly retained on the column. The content, expressed as the amount ratio of antimony(V) to antimony(III), was 0.035% in a 10 g/kg antimony(III) solution prepared from an antimony(III) oxide reagent by the coulometric analysis method and 0.036% in a 1 g/kg antimony(III) solution prepared from the same antimony(III) oxide by the ion-exclusion chromatographic method. The results of both methods were in good agreement with each other. The detection limit of antimony(V) in antimony(III) oxide by the former method was 0.004% of antimony(III), and that by the latter method was 0.002% of antimony(III).

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Layer by layer films of protein and redox polymer were constructed and used to simultaneously analyze ascorbic acid and hydrogen peroxide. The films were made using hemoglobin and poly[4-vinylpyridine Os(bipyridine)₂Cl]-co-ethylamine (Pos-Ea). The film growth was monitored using cyclic voltammetry, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). Reversible pairs of oxidation-reduction peaks were observed using cyclic voltammetry corresponding to the Os^II/Os^III from redox polymer and HbFe^III/HbFe^II redox couples at 0.35 and -0.25 V vs. Ag/AgCl, respectively. The two redox centers were independent of each other. This enabled the simultaneous and independent determination of ascorbic acid and hydrogen. Peak currents were linearly related to concentration for both analytes in a mixture. The linear range of ascorbic acid was 0 - 1 mM (R² = 0.9996, n = 5) at scan rate of 50 mV s^-1 (sensitivity 3.5 µA/mM) while hydrogen peroxide linear range was 1.0 - 10.0 µM (R² = 0.991, n = 6) with sensitivity of 1.85 µA/µM.

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Firefly bioluminescence (BL) was greatly affected by cationic surfactants coexisting with liposomes containing phosphatidylcholine and cholesterol. In this study, the effects of the type and concentration of cationic surfactants on BL were studied in the presence of the liposomes. Three types of cationic surfactant: benzalkonium chloride (BAC), n-dodecyltrimethylammonium bromide (DTAB), and benzethonium chloride (BZC), were used. As a common effect in these surfactants, BL intensity was increased and then drastically decreased with increasing surfactant concentration. This can be explained by the formation of cationic liposomes as BL enhancers at low concentration of the surfactant, and by the transformation into cationic (mixed) micelles as inhibitors at high concentration. The maximal BL intensity and the concentration for the maximal BL were dependent on the type of the surfactants. To explain the differences in these parameters in the enhanced BL, we determined the distribution coefficient, K, of the surfactants to the liposomal membrane. The result indicated that the surfactant with higher K value gives the maximal BL intensity at lower concentration.

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In order to elucidate Se metabolism in a living body, ⁸²Se-enriched selenite was injected intravenously into mice fed Se-adequate and -deficient diets. We studied the time-dependent changes in the distribution of the labeled Se in organs, red blood cells, and plasma. The total Se was determined by flow-injection ICPMS, and Se speciation analysis was conducted by micro-affinity chromatography coupled with low-flow ICPMS. Total Se in almost all organs, including liver, showed the maximum at 1 h after injection. From speciation analysis, exogenous ⁸²Se as Se-containing proteins other than selenoprotein P (Sel-P) (selenium containing albumin (SeAlb) and extra cellular glutathione peroxidase (eGPx)), peaked at 1 h and quickly decreased from 1 to 6 h after injection, whereas that as Sel-P, peaked at 6 h, and gradually decreased from 6 to 72 h after injection. We found that there were two pathways for the transfer of Se in mice; one was as SeAlb until 1 h after injection, and the other was as Sel-P from 6 to 72 h after injection.

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The influence of simple salts on the ion exchange and protonation equilibria of an amphoteric ion-exchange resin, which has strong base and weak acid moieties in a single functional group fixed onto the styrene-DVB matrix, has been investigated. Concentrations of ionic species in the amphoteric ion-exchange resin in equilibrium with various sodium salt solutions were estimated by ²³Na NMR spectroscopy. For the NaClO₄ system, the ratio of sodium ion concentration in the resin phase to that in the equilibrium solution was greater than 1 and increased with a decrease in the salt concentration. In contrast to an ordinary cation-exchange resin, the ion exchange behavior of Mg²⁺ and Ca²⁺ on the amphoteric ion-exchange resin showed a marked dependence on the kinds of salts: the distribution coefficients for the NaCl system were independent of the salt concentration, while the log D vs. log[Na⁺] plots for the NaClO₄ system showed linear relationships with slopes being neither -2 nor 0. Apparent protonation constants of the carboxylate in the functional group of the resin in equilibrium with NaClO₄ solutions were greater than those with NaCl solutions. The ion exchange and protonation properties of the amphoteric ion-exchange resin were elucidated on the basis of the information about the salt concentrations in the resin phase estimated by the NMR method.

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To improve the extraction of polycyclic aromatic hydrocarbons (PAHs) from sediment samples, we optimized the conditions of pressurized liquid extraction (PLE). The yields increased as the extraction temperature increased from 100 to 190°C, but the effect of increasing pressure (from 15 to 20 MPa) was small. Parameters of 190°C and 20 MPa, near the maximum of the equipment, gave the highest yield. Under these conditions, the yields of 17 PAHs were 1.5 - 34 times those obtained by the Japanese official method (shaking and ultrasonic extraction with acetone at room temperature).

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The present paper reports on the application of modified multiwalled carbon nanotubes (MMWCNTs) as a new, easily prepared and stable solid sorbent for the preconcentration of trace Co(II) in aqueous solution. Multiwalled carbon nanotubes (MWCNTs) were oxidized with concentrated HNO₃ and modified with 1-(2-pyridylazo)-2-naphtol (PAN), and were then used as a solid phase for the preconcentration of Co(II). Factors influencing the sorption and desorption of Co(II) were investigated. Elution was carried out with 0.5 mol L^-1 HNO₃. The amount of eluted Co(II) was measured using flame atomic absorption spectrometry. The effects of the experimental parameters, including the sample pH, sample flow rate, eluent flow rate and eluent concentration, were investigated. The effect of coexisting ions showed no interference from most ions tested. The proposed method permitted a large enrichment factor (about 300). The precision of the method was 1.63% (for eight replicate determination of 0.5 µg mL^-1 of Co(II)) and the limit of detection was 0.55 ng mL^-1. The method was applied to the determination of Co(II) in water, biological and standard samples.

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The preparation and applicability of solid phase microextraction (SPME) fibers coated with a sol-gel organically modified silica based on 3-aminopropyltrimethoxysilane and polydimethylsiloxane (APTMS/PDMS) are described here. Micrographs of the coated fibers revealed a rugous surface; the thickness of the coating was estimated to be less than 30 µm. The APTMS/PDMS fibers were tested with synthetic samples and compared to commercial fibers for headspace SPME analysis of beer. Extraction and desorption using the APTMS/PDMS fibers were faster, which is typical for sol-gel SPME fibers. For polar and semi-polar compounds on beer headspace, the extraction efficiencies of the APTMS/PDMS fiber were superior to those of conventional fibers. The APTMS/PDMS fiber was found to be capable of extracting a broad range of analytes, including highly polar acidic species such as organic acids.

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An artificial neural network (ANN) calibration model was developed to determine aluminum in the presence of iron in soil extracts, using xylenol orange as chromogenic reagent. The spectral data of synthetic mixtures of Al³⁺ and Fe³⁺ as well as of the soil extracts, were recorded in the range between 410 and 580 nm. Method validation was carried out using 18 soil extracts. The results gave good linear correlations between the ANN model and the ICP OES measurements for both species.

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Bulk optode membranes based on a recently reported thiaglutaric diamide ionophore were developed for measurements of silver(I) and copper(II) ions in aqueous solutions. The response properties of optical films containing ionophore and chromoionophores with different pK_a values were investigated at different sample pH. At certain pH the measuring range of the optode can be shifted when choosing different chromoionophores. Optode with ionophore and chromoionophore V exhibited good responses to silver ions from 10^-6 - 10^-1 M at pH 5.5. The proposed sensor showed high selectivity, good reproducibility and stability. With a different chromoionophore ETH 5418 the optode could response to copper(II) ions from 10^-6 - 10^-2 M.

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Six different calixarene-bonded phases were characterized by analyzing 36 and 26 solutes at pH 3 and 7, respectively. Dolan and Snyder's multiple term linear equation was used to correlate retention factors k′ to parameters of the solutes and columns. The column parameters have been related to molecular properties of the stationary phases and new suggestions were made for the interpretation of steric selectivity. Ionic and polar interactions have been found dependent on pH value, while steric interactions are less dependent and hydrophobic interactions remain unchanged. Distinct differences of the supported interactions were confirmed between the calixarene-bonded and the common alkyl-bonded silicas. By use of the parameters, values of k′ can be estimated with an average deviation of 2.50 and 7.92% at low and neutral pH-value, respectively.

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In order to discuss the atomization process of an analyte element occurring in a graphite furnace for atomic absorption spectrometry, we measured variations in the characteristic temperature with the progress of an atomization stage, by using a two-line method under the assumption of a Boltzmann distribution. For this purpose, iron was chosen as the analyte element. Also, the atomic absorption of two iron atomic lines, Fe I 372.0 nm and Fe I 373.7 nm, was simultaneously monitored as a probe for the temperature determination. This method enables variations in the gas temperature to be directly traced, yielding a temperature distribution closely related to the diffusion behavior of the probe element in the furnace. This temperature variation was very different from the furnace wall temperatures, which were monitored in conventional temperature control for atomic absorption spectrometry. Correlations between the gas temperature and the charring/atomizing temperatures in the heating program of the furnace were investigated. The atomization of cadmium and tellurium was also investigated by a comparison between the gas temperature with the wall temperature of the furnace. The atomic absorption of cadmium or tellurium appeared to be apart from the absorption of iron while the gas temperature was still low. Therefore, the analyte atoms could be atomized through direct contact with the wall of the graphite furnace, which has a much higher temperature compared to the gas atmosphere during atomization. Their atomization would be caused by conductive heating from the furnace wall rather than by radiant heating in the furnace.

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A new algorithm, an alternating normalization-weighted error (ANWE) method, and the parallel factor analysis (PARAFAC) have been used to directly determine psoralen (PSO) in human plasma. The two methods fully exploit the second-order advantage of the applied three-way fluorescence data. Interestingly, the calibration samples need only the components of interest, and the prediction samples allow containing not only the components of interest, but also unknown interferents. Consequently, the determination of PSO in plasma becomes no longer troublesome or time-consuming. The results are satisfying. Furthermore, compared with PARAFAC, the newly introduced ANWE method can obtain more satisfactory results.

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Many natural products contain flavonoids that display biological effects when ingested by humans and animals. Flavonoids have received a great deal of research interest, especially for possible cancer and heart disease-preventive properties. The content and the quality of each flavonoid may be a key to their biological effects. The recent development of electrospray ionization mass spectrometry (ESI-MS/MS) has made it possible to use it to study molecular interactions. In the present work, we investigated the derivatization procedures for three flavonoids (chrysin, genistein, and luteolin) by using ESI-MS/MS. Each flavonoid and the derivatization reagent, N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), are mixed using acetonitrile and the mixture is introduced through an electrospray needle. The signal intensities for the derivative ions significantly increased, almost two or three orders of magnitude increased as compared to those for the protonated molecular ions of the flavonoids. Mass spectra of trimethylsilyl derivatives are fragmented at a fixed pattern by collision induced dissociation to obtain the structural relevance of the derivative flavonoids. Further fragmentation studies have been performed and results are discussed in detail. The results in the positive mode detection show that better high intensity data and more simplification of peaks appeared than that for the underivatized cases.

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Nuclear magnetic resonance (NMR) experiments on carbon-13 in the solid state were done with cross polarization (CP) and magic angle spinning (MAS) in order to overcome the low NMR sensitivity of ¹³C and the chemical shift anisotropy, respectively. In the present research, CPMAS ¹³C-NMR spectra were collected by modulating the contact time needed for cross polarization (variable contact times experiments, VCT) on two different humic acids (a soil-HA and a coal-HA). VCT data were fitted by a model containing either a monotonic or a non-monotonic cross polarization term. The non-monotonic model, which fitted the experimental results better than the monotonic one, provided two cross-polarization rates, thereby suggesting that two different mechanisms for the energy transfer from protons to carbons arise in amorphous and heterogeneous humic substances. The first mechanism was a fast proton-to-carbon energy transfer due to protons directly bound to carbons. The second mechanism was related to a slow transfer mediated by local segmental motions. Different domains in the humic acids were identified. Soil-HA was made of rigid domains, containing mainly aromatic and carboxylic moieties, and fast moving domains, containing alkyl, C-O and C-O groups. Coal-HA showed a rigid aromatic domain that was differentiated from a very mobile domain made of alkyl and COOH groups.

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A lanthanum (La) coprecipitation method with low sample consumption was explored for the preconcentration of oxo-anion forming elements prior to a measurement by inductively coupled plasma mass spectrometry (ICP-MS). The preconcentration procedure was composed of two main steps: (1) the formation of a coprecipitate with the lowest possible La and (2) the redissolution of target analytes with minimal use of nitric acid, and the elimination of high concentration La from the analysis sample. Each step was performed in a 25 mL-volume syringe to reduce the sample consumption and to avoid contamination from the experimental environment. Various parameters, such as the concentration and volume of La added into the sample solution, the precipitation pH, the aging time, and the volume of HNO₃ were optimized to obtain good recoveries and high detection sensitivities for V, As, Sb, and W, which could be hardly recovered by solid-phase extraction using a chelating resin. The obtained method was evaluated through the analysis of seawater reference materials (CASS-4 and NASS-5). The recoveries exceeded 80%, and the observed values were in good agreement with the certified values.

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For the accurate quantification of polycyclic aromatic hydrocarbons (PAHs) in environmental samples by isotope-dilution mass spectrometry (IDMS) and gas chromatography-mass spectrometry (GC-MS), we used deuterium-labeled PAHs (D-PAHs) as internal standards for µg g^-1-level certified reference materials and corresponding calibration solutions. Although pressurized liquid extraction (PLE) causes significant biases in the analytical results for ng g^-1-level samples (2.4 - 15%), biases in the analytical results by PLE (190°C, 20 MPa, 2 cycles) were small (<2.3%) and negligible for µg g^-1-level samples when expanded uncertainty (coverage factor k = 2) was considered.

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The use of anabolic steroids in racehorses is strictly regulated. We have developed a method for the simultaneous analysis of 11 anabolic steroids: fluoxymesterone, 17α-methyltestosterone, mestanolone, methandienone, methandriol, oxymetholone, boldenone, furazabol, methenolone, nandrolone, and stanozolol, for possible application to a doping test in racehorses. We selected 15 kinds of target substances for a doping test from the main metabolites of these anabolic steroids, and established a method for simultaneous analysis. Urine was hydrolyzed and subjected to solid-phase extraction. Then, the residue from the extracts was derivatized by trimethylsilylation. The derivatized samples were subjected to ion-trap gas chromatography-tandem mass spectrometry, and their mass chromatograms and product ion spectra were obtained. The limit of detection of the target substances was 5 - 50 ng/mL, and the mean recovery and coefficient of variation were 71.3 - 104.8% and 1.1 - 9.5%, respectively.

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A fluorescent dye, 9-anthraldehyde-thiosemicarbazone (AnthT), used for the determination of Cu(II) or Hg(II) in aqueous solutions, is described. The fluorescence intensity of the probe decreased with increasing concentration of Cu(II) or Hg(II), and was proportional to a certain concentration of Cu(II) or Hg(II). The prepared sensing system presented satisfactory sensitivity and low detection limits. The developed method was successfully employed for preliminary application in natural water and domestic sewage.

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