A real-time analysis of secondary organic aerosol (SOA) particles formed from cyclohexene ozonolysis in a smog chamber was performed using a laser-ionization single-particle aerosol mass spectrometer (LISPA-MS). The instrument obtains both size and chemical compositions of individual aerosol particles with a high time-resolution (∼2 s at the maximum). Both positive and negative-ion mass spectra are obtained. Standard particles generated from dicarboxylic acid solutions using an atomizer were also analyzed. For both standard and SOA particles, the negative-ion mass spectra provided information about the molecular weights of the organic compounds in the particles, since the intense ions in the negative-ion mass spectra are mainly attributable to the molecular-related ions [M-H]^-. It was demonstrated that the real-time single-particle analysis of SOA particles by the LISPA-MS technique can reveal the formation and transformation processes of SOA particle in smog chambers.

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The double-bond conversion of UV-cured resins prepared from pentaerithritol triacylate (PETA) was determined by pyrolysis-gas chromatography in the presence of an organic alkali, tetramethylammonium hydoxide (TMAH). The pyrogram of the uncured prepolymer compound, consisting of PETA and a photoinitiator, 2,2-dimethoxy-2-phenylacetophenone, contained specific products reflecting the original acrylate structure, such as methyl acrylate (MA) and methyl ethers of pentaerithritol. Meanwhile, in pyrograms of the UV-cured PETA, the yields of MA considerably decreased. The double-bond conversions of the cured resins, irradiated with various UV dosages, were calculated based on the relative yields of MA among specific products in the pyrograms. The conversions determined by this approach were analyzed by comparing them with those estimated by Fourier-transform infrared spectroscopy.

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The changes induced by biologically active substances in the permeability to K⁺ and calcein of liposomes composed of egg phosphatidylcholine and cholesterol were measured simultaneously in order to rapidly screen the sizes of pores formed in a membrane, using different sized markers. The substances examined in the present study were classified into three types based on differences in the rates at which K⁺ and calcein were released. The first type released only K⁺, and included gramicidin A. The second type predominantly released K⁺, preceding the release of calcein, and included amphotericin B and nystatin. The third type, including antimicrobial peptides, such as gramicidin S, alamethicin, and melittin, and several membrane-active drugs, like celecoxib (non-steroidal anti-inflammatory drug), 1-dodecylazacycloheptan-2-one (named azone; skin permeation enhancer), and chlorpromazine (tranquilizer), caused the release of K⁺ and calcein simultaneously. Thus, the sizes of pores formed in a liposomal membrane increased in the following order: types one, two, and three. We determined the size more precisely by conducting an osmotic protection experiment, measuring the release of calcein in the presence of osmotic protectants of different sizes. The radii of pores formed by the second type, amphotericin B and nystatin, were 0.36 - 0.46 nm, while the radii of pores formed by the third type were much larger, 0.63 - 0.67 nm or more. The permeability changes induced by substances of the third type are discussed in connection with a transient pore formed in a lipid packing mismatch taking place during the phase transition of dipalmitoylphosphatidylcholine liposomes.

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A rapid and sensitive HPLC method for the simultaneous determination of paraquat and diquat in human serum has been developed. After deproteinization of the serum with 10% trichloroacetic acid, the samples were separated on a reversed-phase column, and subsequently reduced to their radicals with alkaline sodium hydrosulfite solution. These radicals were monitored with a UV detector at 391 nm. This method permitted the reliable quantification of paraquat over linear ranges of 50 ng - 10 µg/ml and 100 ng - 10 µg/ml for diquat in human serum. The within- and between-day variations are lower than 2.3 and 2.2%, respectively. This technique was also utilized to determine the paraquat and diquat serum levels in a patient who had ingested herbicide (Prigrox L^®) containing paraquat and diquat.

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A cloud-point extraction process using a mixed micelle of the cationic surfactant cetyl pyridinium chloride (CPC) and non-ionic surfactant Triton X-114 to extract beryllium from aqueous solutions was investigated. The method is based on the color reaction of beryllium with Chrome Azurol S (CAS) in acetate buffer and the mixed micelle-mediated extraction of the complex. This complex was concentrated in a surfactant-rich phase after separation. The optimal extraction and reaction conditions (e.g. pH, reagent and surfactant concentrations, temperature, incubation and centrifuge times) were evaluated and optimized. Under the optimized conditions, the analytical characteristics of the method (e.g. limit of detection, linear range and preconcentration factor) were obtained. Linearity was obeyed in the range of 0.30 - 18 ng mL^-1 of beryllium and the detection limit of the method was 0.05 ng mL^-1. The interference effect of some cations and anions was also studied. The proposed method was successfully applied to the determination of beryllium in real water samples.

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A novel method for the rapid and sensitive analysis of 1-hydroxypyrene (1-OHP) in human urine has been developed that uses a resonance light scattering (RLS) technique. The assay was based on the interaction of ethyl violet (EV) with 1-hydroxypyrene to form an ion-associate complex, which resulted in the enhancement of RLS intensity and the appearance of new RLS spectra. In the presence of anionic surfactant, the maximum RLS peak of the system was located at 396 nm at pH 8.0. Under the optimum conditions, it was found that the enhanced RLS intensity was directly proportional to the concentration of 1-hydroxypyrene in the range of 4.0 - 982 µg l^-1. The detection limit was 1.2 µg l^-1 and the recoveries of 1-hydroxypyrene were 92.8 - 102.3% (n = 6). The proposed method was successfully applied to the analysis of human urine samples. The results of 1-hydroxypyrene were in agreement with those obtained by the method of high-performance liquid chromatography.

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Due to specific adsorption to variable charge soils, low molecular weight organic acids (LMWOAs) have not been sufficiently extracted, even if common extractants, such as water and 0.1 M sodium hydroxide (NaOH), were employed. In this work, the method for extracting LMWOAs in soils with 0.1 M NaOH was improved for variable charge soils; e.g. 1.0 M potassium fluoride (KF) with pH 4.0 was applied as an extractant jointed with 0.1 M NaOH based on its stronger ability to change the electrochemical properties of variable charge soils by specific adsorption. With the proposed method, the recoveries of oxalic, tartaric, malic, citric and fumaric acids were increased from 83 ± 4, 93 ± 1, 22 ± 2, 63 ± 5 and 84 ± 3% to 98 ± 2, 100 ± 2, 85 ± 2, 90 ± 2 and 89 ± 2%, respectively, compared with NaOH alone. Simultaneously, the LMWOAs in Agri-Udic Ferrosol with field moisture were measured with a satisfactory result.

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A sensitive and multiplexed assay of allergen-specific human immunoglobulin E (IgE) is of great significance in the precise diagnosis of allergies. We report on the optimization of critical factors for chip-based analysis of IgE in human serum with a high reliability. Extracts of two mite species were used as model allergens, and were spotted onto a glass slide for the construction of an allergen chip. Respective allergen-specific IgE in human serum was analyzed by using biotinylated anti-human IgE and a streptavidin-Cy3 conjugate. Factors affecting the performance of the allergen chip were investigated and optimized. Especially, the effect of additives, the concentrations of biotinylated anti-human IgE and the streptavidin-Cy3 conjugate, the serum dilution factor, and the concentration of allergen extract as a capturing agent were examined in detail. Under the optimized conditions, a chip-based analysis for sera from 43 patients revealed a reliable and reproducible diagnosis of respective allergies, showing a good correlation with a conventional CAP assay.

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A porphyrin derivative (fluorophore) appended with bipyridine (ionophore) has been applied for preparation of a Cu²⁺-sensitive optical chemical sensor, which is based on fluorescence quenching of porphyrin derivative entrapped in a poly(vinyl chloride) membrane by the energy transfer process. The sensor exhibits a linear response toward Cu²⁺ in the concentration range 2.0 × 10^-8 - 1.0 × 10^-5 M, with a working pH range from 6.0 to 8.0 and a high selectivity. The detection limit is 5 × 10^-9 M. The response time for Cu²⁺ is less than 5 min with concentrations lower than 5 × 10^-6 M. The optode can be regenerated using 0.3 M EDTA (pH 9) and acetate buffer solution. The effect of the composition of the sensor membrane was studied, and the experimental conditions were optimized. The sensor has been used for direct determination of Cu²⁺ in water samples with satisfied results.

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A new spectrofluorometric method has been developed for the determination of trace amounts of coenzyme A (CoA). Using europium (Eu³⁺)-tetracycline (TC) complex as a fluorescent probe in the buffer solution of pH 6.80, CoA could remarkably enhance the fluorescence intensity of the Eu³⁺-TC complex at λ = 612 nm after adding H₅IO₆ and the enhanced fluorescence intensity is in proportion to the concentration of CoA. Optimum conditions for the determination of CoA were also investigated. The dynamic range for the determination of CoA is 6.08 × 10^-8 - 1.84 × 10^-5 mol L^-1 with detection limit of 4.62 × 10^-8 mol L^-1. This method is simple, practical and relatively free of interference from coexisting substances and can be successfully applied to determination of CoA in injection, human serum and pig liver samples. Moreover, the enhancement mechanisms of the fluorescence intensity in the Eu³⁺-TC system and the CoA-Eu³⁺-TC system have been also discussed.

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Electropolymerization of anthranilic acid/pyrrole (AA/PY) at solid substrate electrodes (platinum, gold, and glassy carbon) gave stable and water-insoluble films under a wide range of pH. Combining high conductivity of the polypyrrole (PPY) and pH independence of the electrochemical activity of the self-doped carboxylic acid-substituted polyaniline allows us to prepare an improved functionalized PPY-modified electrode to collect and measure Cu(I) species. The differential pulse stripping analysis of the copper ions using a polyanthranilic acid-co-polypyrrole (PAA/PPY)-modified electrode consisted of three steps: accumulation, electrochemical reduction to the elemental copper and stripping step. Factors affecting these steps, including electropolymerization conditions, accumulation and stripping medium, reduction potential, reduction time and accumulation time, were systematically investigated. A detection limit of 5.3 × 10^-9 M Cu(I) was achieved for a 7.0 min accumulation. For 12 determinations of Cu(I) at concentrations of 1.0 × 10^-8 M, an RSD of 3.5% was obtained. The log I_p was found to vary linearly with log[Cu^I] in the concentration range from 7.0 × 10^-9 to 1.0 × 10^-5 M.

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A highly sensitive electrochemical biosensor for the detection of trace amounts of promethazine has been designed. Double stranded (ds)DNA molecules are immobilized onto a pretreated glassy carbon electrode (GCE(ox)) surface. The voltammetric behaviors of promethazine on DNA-modified electrode were explored by means of cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The promethazine gave rise to a pair of well-defined peaks, which appeared at E_pc = 52 mV and E_pa = 96 mV (vs. Ag/AgCl) in 0.10 M acetate buffer (pH 5.0). The peak current was linearly enhanced with increasing the concentration of promethazine. The calibration was linear for promethazine over the range of 4.7 × 10^-10 to 9.3 × 10^-9 M with a correlation coefficient of 0.999. The limit of detection (LODs) was 3.0 × 10^-10 M (S/N = 3). The modified electrode was applied to determine promethazine in human blood samples with satisfactory results.

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A comparative study was made between developed chemically modified carbon paste electrodes and PVC membrane electrodes for the cationic surfactant cetyltrimethylammonium bromide (CTAB). The carbon paste electrode modified with cetyltrimethylammonium-tetrachloropalladate(II) (CTA-TClP) provides a more sensitive and stable device than that shown by electrodes with an inner reference solution. The best performance was obtained by an electrode based on the paste containing 3.6 wt% CTA-TCIP, 1.8 wt% ethylhexadecyldimethylammonium bromide, 37.6 wt% graphite and 57 wt% tricresyl phosphate. The sensor exhibited a Nernstian response for CTAB over a wide concentration range of 3.5 × 10^-7 to 1.0 × 10^-3 M with a detection limit of 2.0 × 10^-7 M between pH 2.7 and 8.2 with a fast response time of ≤15 s. The electrode showed excellent selectivity for CTAB over a large number of ions. Interferences caused by common cationic surfactants have been investigated in simulated mixtures containing high concentration levels of interfering surfactants, and the sensor was found to be tolerant against these compounds.

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In order to deal with the matrix effect in the simultaneous determination of multi-components in a complex system, we have developed a novel method named matrix coefficient multivariate calibration method (MCMCM) for simultaneously determining n analytes in complex systems. The calibration models of n analytes, which are based on the experimental data of known samples, are first transformed into n linear equations, and then the equations are solved to obtain matrix calibration coefficients of the analytes in congeneric samples. In this way, the concentrations of n analytes in the unknown sample could be obtained easily and simultaneously by solving another n-variate linear equations with the help of the matrix calibration coefficients obtained-above. The method proposed in this work has been tested by voltammetry and atomic absorption spectrometry (AAS) with satisfactory results. On determining the elements such as Cu, Pb, Cd, Ni, Zn, Fe, Mn, Co, Ca, Mg, etc. in synthetic samples, the relative standard deviations (RSDs) of the results were 0.91 - 4.5%, and the recoveries were 95.8 - 105%. For actual samples, the RSDs and the recoveries were 1.5 - 6.9 and 92.0 - 110%, respectively.

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The electron transfer (ET) reaction between bis(cyclopentadienyl)iron(II) ([Fe^II(C₅H₅)₂]) in 1,2-dichloroethane (1,2-DCE) and hexacyanoferrate redox couple ([Fe^II/III(CN)₆]^4-/3-) in water (W) at the interface has been studied by using cyclic voltammetry. The voltammetric results can be explained well by a theoretical equation for the so-called IT-mechanism, in which a homogeneous ET reaction between [Fe(C₅H₅)₂] (partially distributed from 1,2-DCE) and [Fe(CN)₆]^3- takes place in the W phase and the resultant [Fe(C₅H₅)₂]⁺ ion is responsible for current passage across the interface. The forward rate constant of the homogeneous ET reaction, [Fe(C₅H₅)₂] + [Fe(CN)₆]^3- = [Fe(C₅H₅)₂]⁺ + [Fe(CN)₆]^4- in W phase, k_f^IT, was determined to be (2.9 ± 2.2)× 10¹⁰ M^-1 s^-1, which was in good agreement with k_f^IT = (3.2 ± 2.0)× 10¹⁰ M^-1 s^-1, which had been determined by using normal-pulse voltammetry.

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This article reports on the development of a simple and cost-effective bioassay for the detection of biotin in urine and serum, based on the very selective binding of avidin and biotin. Avidin was allowed to react without isolating it from egg white. Egg white was treated with the dye HABA, which binds to avidin. Upon subsequent treatment with biotin, HABA is released due to the high affinity of biotin to avidin. The amount of HABA released is proportional to the amount of biotin used.

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Singlet oxygen generated in a reaction between N-bromosuccinimide and hydrogen peroxide was used for the chemiluminescence oxidation of imipramine. A strong chemiluminescence signal was observed when imipramine was mixed with N-bromosuccinimide and hydrogen peroxide under an alkaline condition. The chemiluminescence signal was linearly dependent on the concentration of imipramine in the range of 0.01 - 1.0 mg/L. The detection limit was 0.005 mg/L imipramine and the relative standard deviation was 1.5% for a 0.4 mg/L imipramine solution in 11 repeated measurements. The proposed method was successfully applied to the determination of imipramine in tablets, human plasma and urine samples.

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A simple and rapid spectrophotometric method for the determination of oxalate ion was established by the fading of a colored complex between N,N′-diethyl-N,N′-[[4,4′-dihydroxy-1,1′-binaphthalene]-3,3′-diyl]bisbenzamide and copper(II). Beer's law was obeyed in the concentration range of 0.1 - 2.0 µg cm^-3 for oxalate ion, with an effective molar absorptivity at 533 nm and the relative standard deviation being 8.0 × 10³ dm³ mol^-1 cm^-1 and 1.0% (n = 5), respectively. This proposed method has excellent reproducibility, and was applied to recovery tests of oxalate ion in tap water and human urine; the results were satisfactory. This is suggested that the method is based on the reaction of copper(II) to copper(I) with oxalate ion.

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Standard solutions (at 10^-5 M levels) of Cu(I)- and Fe(II)-cyanide complexes were stabilized for at least 5 h using 0.5 mM cyanide solution (around pH 9) as a medium. Complexes of Cu(I)- and Fe(III)-cyanide also could be stabilized without any dissociation by adding 1 mM cyanide to an acetonitrile-water (18:82, v/v) mobile phase (pH 7.0) containing 10 mM tetra-n-propylammonium salt (TPA). Under the optimal conditions, the six complexes of Cu(I)-, Ag(I)-, Ni(II)-, Fe(II)-, Fe(III)- and Au(I)-cyanides were resolved from their mixtures within about 45 min, with well-shaped chromatographic peaks.

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In order to obtain the precise Pu isotope composition of Irish Sea water reference material issued by the International Atomic Energy Agency (IAEA-381), we analyzed the activities of ²³⁹Pu, ²⁴⁰Pu and the atom ratio of ²⁴⁰Pu/²³⁹Pu by a highly sensitive isotope dilution SF-ICP-MS method combined with two-stage chromatographic separation and purification. With a mean chemical yield of 65% for ²⁴²Pu tracer, the experimentally established values for ²³⁹Pu, ²⁴⁰Pu and ^239+240Pu activities are in good agreement with the certified ones. For the ²⁴⁰Pu/²³⁹Pu atom ratio, we obtain a value of 0.2315 ± 0.0008 with a high precision (RSD, 0.35%), which is much more precise than the information value of 0.22 ± 0.03 (RSD, 13.6%) provided by the IAEA certification report. The precise determination of Pu isotopes in this seawater reference material will be useful for the validation of analytical methods for the study of radionuclides in the marine environment.

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