Inelastic electron tunneling spectroscopy (IETS) is a unique surface and interface analytical technique using electron tunneling through a metal/insulator/metal tunneling junction at cryogenic temperatures. It gives the vibrational spectrum of a very thin (nm) insulator film and the adsorbed species on it. The high sensitivity, good resolution, and wide spectral range inherent in IETS enable us to analyze the surface and interface of the insulator in detail. The tunneling junction is a good model system for oxide catalysts, electronic devises, and solid state sensors. Information about the surfaces of alumina and magnesia, the adsorption states and chemical reactions of adsorbed species occurring on these oxides can be obtained through an analysis of the tunneling spectra. The structures and properties of evaporated thin semiconductor films can also be studied. In this review, the surface characterization of alumina and magnesia, the adsorption and surface reactions of organic acids, esters, amides, and nitryls on these oxides, and the characterization of thin evaporated films of Si, Ge, and the oxides are summarized.

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A distributed-feedback dye laser with a quenching cavity was designed and constructed for generating a tunable picosecond pulse with a narrow spectral linewidth. This nearly transform-limited pulse was succeedingly amplified by a triple-pass off-axis amplifier. The pulse duration and the spectral linewidth were 60 ps and 9.4 pm, respectively. The amplified pulse was frequency-doubled by second-harmonic generation, producing a 0.5-mJ pulse with no background emission. The potential advantage of this laser in the analysis of dioxin based on supersonic jet/resonance-enhanced multiphoton ionization/mass spectrometry is discussed.

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A fully automated, continuous-flow-through type analyzer was developed to observe rapid changes in the concentration of total inorganic carbon (C_T) in coastal zones. Seawater and an H₃PO₄ solution were fed into the analyzer’s mixing coil by two high-precision valveless piston pumps. The CO₂ was stripped from the seawater and moved into a carrier gas, using a newly developed continuous-flow-through CO₂ extractor. A mass flow controller was used to assure a precise flow rate of the carrier gas. The CO₂ concentration was then determined with a nondispersive infrared gas analyzer. This analyzer achieved a time-resolution of as good as 1 min. In field experiments on a shallow reef flat of Shiraho (Ishigaki Island, Southwest Japan), the analyzer detected short-term, yet extreme, variations in C_T which manual sampling missed. Analytical values obtained by the analyzer on the boat were compared with those determined by potentiometric titration with a closed cell in a laboratory: C_T(flow-through) = 0.980·C_T(titration) + 38.8 with r² = 0.995 (n = 34; September 1998).

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For the determination of total mercury in hair, an amount (25.0 mg) of hair sample was digested with conc. HNO₃ (400 µl) at 90°C for 10 min in a 7-ml teflon microreaction vessel. After digestion, the pH of the acidic hair mixture was adjusted to 5.0 - 6.0 by NaOH and was then passed through a clean-up Sep-Pak C₁₈ cartridge. To the eluate, 2,3-dimercaptopropane-1-sulfonate (DMPS) and sodium acetate buffer (pH = 6.0) were added to form a mercury-DMPS complex. This complex was preconcentrated on two Sep-Pak C₁₈ cartridges in series, and each cartridge was eluted with methanol and adjusted to 2.00 ml. A portion (50 µl) was introduced into a graphite cuvette and then atomized according to a temperature program. The method detection limit (MDL, 3 σ) was 0.064 (µg g^-1); the calibration graph was linear up to 7.52 µg g^-1. Good accuracies were obtained when testing two human hair certified reference materials (GBW 09101 and BCR-397). Six real samples were analyzed, and the recoveries were 95.8 - 98.2% with a relative standard deviation (RSD, n = 3) < 2.1%. For the determination of methylmercury (CH₃Hg⁺), 25.0 mg of hair sample was extracted with 2.0 mol dm^-3 HCl (1.0 ml) by ultrasonicating for 1 h. The supernatant solution was used for CH₃Hg⁺ analysis and the hair residue was used for the analysis of inorganic mercury (Hg²⁺). The MDL of CH₃Hg⁺ was 0.068 µg g^-1; the calibration graph was linear up to 6.00 µg g^-1. Six real samples were analyzed, and the recoveries were 96.0 - 99.2% with RSD (n = 3) < 2.3%. The sum of the concentrations of CH₃Hg⁺ and Hg²⁺ was very close to that of the total mercury measured with a relative error within 3.6%. The proposed method can be accurately applied to the measurement of CH₃Hg⁺, Hg²⁺, and total mercury in hair samples.

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A surface plasmon resonance (SPR) sensor was applied to analyses of some amine compounds (n-butylamine, isobutylamine, aniline, and N,N-dimethylaniline) by using a polymer film and an acid-base reaction in it. Poly(acrylamide) (PAA) was adopted as the polymer film and was immobilized on an Au film to prepare a sensor chip. Pivalic acid was entered into the PAA film as an acid. The PAA film with a thickness of 50 nm gave the highest sensitivity to the SPR sensor. Although water was better concerning the sensitivity for the SPR sensor as the solvent, ethanol was adopted because it dissolves well all of the amine compounds used. The Au film coated with the PAA film gave higher sensitivity for analyses of n-butylamine and isobutylamine, and lower sensitivity for analyses of aniline and N,N-dimethylaniline than an Au film without the PAA film. The PAA film containing pivalic acid gave 4 - 5 orders of magnitude higher sensitivity to the SPR sensor for analyses of all the amine compounds due to the reaction between pivalic acid and these amine compounds.

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The characteristics of a surface plasmon resonance (SPR) sensor prepared by coating a metal film evaporated on a prism with a polymer film containing tetra-n-butyl thiuram disulfide (TBTDS) were studied. The differences in the sensitivity, selectivity, and detection limit for a Zn²⁺ ion of the SPR sensor were reported as a function of the thickness of the polymer film, the kind of a metal film, and the kind of a polymer film. The thinner was the polymer film, the higher was the sensitivity, and the lower was the detection limit. The Ag film gave to the SPR sensor higher sensitivity than the Au film. TBTDS contained in the poly(vinyl chloride) (PVC) film slightly improved the selectivity toward the Zn²⁺ ion. A non-conditioned poly(methyl methacrylate) (PMMA) film containing TBTDS gave a lower detection limit of 1.0 × 10^-6 mol/l, which is similar to that obtained by using an ion selective electrode (ISE) method, than the PVC film. The PVC film, however, gave higher concentration resolution than the PMMA film.

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The uptake of Cu²⁺ was investigated using various types of liposomes composed of phosphatidylcholine (PC), cholesterol (Chol) and dicethylphosphate (DCP). DCP played a role as a ligand for Cu²⁺. Multilamellar vesicles (MLVs) were more effective for the uptake of Cu²⁺ compared to unilamellar vesicles prepared by the extrusion technique. The uptake efficiency of MLVs for Cu²⁺ was dependent on the molar ratio of DCP in MLVs. The uptake percent of Cu²⁺ was 92% using MLVs having a PC:DCP:Chol molar ratio of 4:3:3; 95% of the total vesicle Cu²⁺ was bound to DCP of the outer membrane surface of the MLVs, and the remaining 5% of the total Cu²⁺ was distributed into the interior side of the MLVs. MLVs having a PC:DCP:Chol molar ratio of 4:3:3 were also effective as separation media for Mn²⁺, Co²⁺, Ni²⁺ and Zn²⁺. The uptake efficiency of the MLVs for the transition-metal ions increased in the order Co²⁺< Zn²⁺ < Ni²⁺ < Mn²⁺ < Cu²⁺.

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Polypropyleneglycol acrylate (PGA), one of the typical acrylic oligomers manufactured industrially, was comprehensively characterized by gas chromatography (GC), supercritical fluid chromatography (SFC) and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The homologous series of polypropyleneglycol diacrylate (DA), polypropyleneglycol monoacrylate (MA), and unreacted polypropyleneglycol (PG) were observed as Na adducts in the MALDI-MS spectra of the PGA samples. The relative intensities of these peaks reflect the distributions of the homologues, although their accurate quantification was generally difficult because of change in the ionization efficiency depending on the chemical structure and the molecular weight of the species. On the other hand, the DA and the MA homologues were observed in the chromatograms obtained by SFC in a temperature-programming mode, while the PG homologues were not detected under the given SFC conditions using UV detection. Here, the determination of the degree of polymerization of each component in the chromatograms was accomplished through SFC fractionation for the corresponding peaks, followed again by MALDI-TOF-MS measurement. Furthermore, most of the components in the PGA samples were almost completely separated in the resulting gas chromatograms, and their unequivocal assignments were made also using the retention data on the gas chromatograms of the SFC fractions. As for the quantitative analysis, the relative abundances among DA, MA and PG for lower degrees of polymerization can be easily calculated based on the observed gas chromatograms, whereas the distribution of DA and MA can be estimated from the observed SFC data even for the relatively higher molecular weight fractions, which are generally difficult to determine accurately by GC because of their lower volatility. These results demonstrated that even the complex PGA samples were able to be characterized in detail by using GC, SFC and MALDI-TOF-MS complementarily.

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A new method for the qualitative and quantitative analysis of citrinin in Monascus by gas-chromatography-selected ion monitoring (SIM) mass spectrometry has been developed. GC separation of citrinin in Monascus extract was achieved without the need for chemical derivatization, and could be detected as a single peak when the SIM mode selected 5 prominent fragmentations (m/z of 220, 205, 177, 105 and 91). The quantitative detection limit for citrinin was ∼1 ppb. Finally, the GC-separated analyte from Monascus extract, at a retention time of 10.89 min, was examined by the method of pattern recognition by comparison with a citrinin standard. The results show that the 2 compounds had a 94% similarity when the SIM mode was used.

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A highly selective PVC membrane electrode based on a cerium-salen complex was prepared. The sensor displays an anti-Hofmeister selectivity sequence with a preference for iodide ion over many common organic and inorganic anions. The proposed electrode exhibits a near-Nernstian behavior over a wide concentration range (5.0 × 10^-2 - 8.0 × 10^-6 M) with a slope of 57.5 mV per decade, and a detection limit of 6.0 × 10^-6 M. The electrode has a very fast response time and can be used in the pH range of 3.0 - 11.0. It was applied, as an indicator electrode, in potentiometric titration of Ag⁺ ions.

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Dopamine (3,4-dihydroxyphenylethylamine, DA) is applied as an electroactive chelant for indirect determination of aluminum (Al) in biological fluids. It is observed that the decrease of the differential pulse voltammetric (DPV) anodic peak current of DA is linear with the increase of Al concentration. Under optimum experimental conditions (pH 8.6, 2.0 × 10^-4 M DA, and 0.03 M NH₄Ac-NH₃·H₂O buffer solution), two linear ranges, 5.0 × 10^-8 - 4.0 × 10^-7 M and 4.0 × 10^-7 - 7.2 × 10^-6 M Al^III, are obtained. The detection limit of Al is 1.9 × 10^-8 M and the relative standard deviation for 4 × 10^-6 M Al^III is 3.1% (N = 8). Many biologically active foreign species have been selected for interference. Excellent recoveries and accuracy have been obtained in the measurements of Al in biological samples such as synthetic renal dialysate, Ringer’s solution, human whole blood, cerebrospinal fluid of demented patient, and urine of diabetic patient. The methodological principle that Al complexes with DA on the electroactive position result in the depression of electrochemical activities of DA has been verified by comparing both the electrochemical behaviors and the spectroscopic responses like UV-vis and Raman of DA in the presence and in the absence of Al.

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The testing of various types of carbon paste electrodes (CPEs) for their use in stripping potentiometry was carried out by means of specially proposed procedures and by using various model analyte systems. CPEs containing three different pasting liquids (paraffin oil, silicone oil, tricresyl phosphate) were tested as supports for mercury- and gold films, and as substrates for electrolytic, adsorptive, ion-pair forming, and extractive accumulation. Test measurements in organic solvent-containing media and studies of some irreversible electrochemical reactions were performed as well. Individual examples to be studied allowed one to formulate and outline some perspectives of CPEs in potentiometric stripping analysis and related constant current stripping analysis.

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A simple and rapid liquid-liquid extraction of palladium has been studied involving ion-pairing of bromocomplexes of palladium(II) with hexadecylpyridinium bromide (HDPB) dissolved in chloroform. The stoichiometry and distribution of (HDP)₂PdBr₄ between the aqueous and organic phase was investigated by spectrophotometric mole ratio method. The extraction efficiency of palladium(II) by HDPB was studied as a function of several variables: acid, salt, surfactant concentration and equilibrium time. The results showed that PdBr₄^2- extraction could be explained by assuming the formation of (HDP)₂PdBr₄ complexes in the aqueous solution and transfer to organic phase. The extraction was fast and the shaking time was only a few min. The average recovery of palladium(II) from an aqueous solution containing 10 µg/ml of analyte was 99% with an RSD% of 0.95. The percentage recovery of 0.2 µg/ml palladium(II) was 96%.

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A focused-microwave-assisted procedure was adopted for the extraction of Al, Ca, Mg, and Mn in tea leaves. The efficiency of extraction was evaluated using diluted acids and a water-soluble alkaline tertiary-amines solution. The extraction procedure was implemented in 5 min. A conventional hot-plate digestion procedure was employed for a comparison. A colorless digest was obtained for all tea samples and the total contents determined for each analyte were employed for estimating the efficiency of extraction. Tea infusions were also prepared. Subsequent determinations of Al, Ca, Mg, and Mn were carried out using flame atomic absorption spectrophotometry (FAAS) and inductively coupled plasma optical emission spectrometry (ICP-OES). In most cases, quantitative, or at least semi-quantitative, extractions were attained for Ca, Mg, and Mn. Lower recoveries were attained to Al, which seems to be related to compounds that bind this element in the sample matrix. Large variations in the trace-element composition of teas were observed; these results are discussed with reference to both extraction media and type of tea.

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The synergic extraction of lanthanoids has been investigated using mixtures of high molecular weight β-diketone, LIX 54 (HA; major component, 1-phenyl-3-isoheptyl-1,3-propanedion) and bidentate neutral ligands (S) in toluene. The distribution behavior of bidentate amines (2,2′-bipyridine (bpy), 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp)) was investigated and their related equilibrium constants were evaluated. The synergic effect is produced by the formation of such adduct complexes as MA₃·S. The extraction constants with LIX 54 alone and those in the presence of bidentate ligands were determined for lanthanoid-series elements.

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A simple and sensitive method is described for the determination of trace lead in Chinese herbs by derivative atom trapping flame atomic absorption spectrometry (D-AT-FAAS) with a modified water-cooled quartz atom-trapping tube. The effects that influence the sensitivity of the derivative method, such as the trap position, the flame conditions and the collection time, were studied. The characteristics of the derivative atom trapping-atomic absorption signal and the linear nature of the working curve were investigated. The sensitivity of the derivative method is 2 or 3 orders of magnitude higher than that of FAAS, and the detection limit improved by 1 or 2 orders of magnitude. Satisfactory recoveries of 93.0 - 108.0% for lead were obtained by determining several Chinese herbs with a relative standard derivation range of 2.9 to 4.2%.

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A method for sensitive and selective determination of silver based on the catalytic effect of silver(I) ion on the oxidation of Janus Green by peroxodisulfate is described. o-Phenanthroline is used as an activator. The rate of the decrease in absorbance of Janus Green (at 615 nm) is proportional to the concentration of silver in the range of 0.3 - 4.0 ng mL^-1 and 4.0 - 500.0 ng mL^-1. The theoretical limit of detection was 0.25 ng mL^-1. The method is free from most interferences. The method was applied to the determination of silver in plants (the uptake of silver by plants), in photographic solutions, lake water and several synthetic samples.

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A modified parallel factors analysis (PARAFAC) algorithm with a penalty diagonalization error (PDE), newly proposed by the present authors, was utilized to simultaneously resolve drug mixtures of propranolol (PRO), dipyridamole (DIP) and amiloride (AMI) without any loss of sensitivity. The analyses were performed in aqueous solution. The experimental results demonstrated that the profiles of the spectra and the concentrations could be accurately resolved using the PDE algorithm with a high sensitivity and stable repeatability. That is to say, the closely overlapping problem of the spectra could be easily solved. Furthermore, simultaneous determinations of three kinds of tablets, which contain PRO, AMI and DIP, respectively, were successfully performed with satisfactory results.

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Several kinds of poly(vinyl alcohols) (PVAs) having different degrees of polymerization and hydrolysis were tested as a material of a solid substrate for room-temperature phosphorimetry (RTP). Effects of these differences on the efficiency of the solid substrate were investigated. Completely hydrolyzed PVAs acquired a luminescence property in the grinding process of substrate preparation, but partially hydrolyzed PVAs did not acquire this property. When the completely hydrolyzed PVA substrates were prepared by drying their aqueous solutions, their luminescence property almost disappeared. However, very weak background emission remained on the surface of a completely dried substrate which had been treated with an analyte aqueous solution. This residual background affected the spectrum of the analyte, especially at low concentrations. Stability of the phosphorescence intensity with the passage of time was superior on the partially hydrolyzed PVAs than on the completely hydrolyzed PVAs. On the other hand, the RTP intensity and reproducibility were superior on the completely hydrolyzed PVAs. Practically, partially hydrolyzed PVAs were more suitable as a material of the substrate because of the stability of its RTP intensity and the weakness of its background emission. The linear dynamic range of the analytical curve for p-aminobenzoic acid on the substrate of partially hydrolyzed PVA having a degree of polymerization of 3500 was 5 - 2000 pmol/spot (20 µL) and its correlation coefficient was 0.963 for 30 data points.

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