An europium-chelating [2Fe-2S] cluster was used to assemble an optical molecular chemosensor highly selective for phosphate-containing anions. Phosphate, pyrophosphate, AMP, ADP, ATP, DNA and RNA were well distinguished by UV/Vis absorption or fluorescence studies.

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A novel sample-pretreatment method for time-of-flight secondary ion mass spectrometry (TOF-SIMS) was developed using supercritical fluid extraction (SFE). In SFE, the extraction efficiency of a certain organic matter is controlled by the pressure and temperature of supercritical CO₂. Two-step SFE (1st step at 10 Mpa, 40°C; 2nd step at 30 MPa, 120°C) was applied to diesel exhaust particles containing many kinds of n-alkanes and aromatic species. n-Alkanes and polycyclic aromatic hydrocarbons (PAHs) were extracted in the 1st and 2nd steps, respectively. This selectivity was utilized for the sample preparation of TOF-SIMS analysis. Diesel exhaust particles after the 1st step of extraction were analyzed with TOF-SIMS, aiming at PAHs as analytical targets. The obtained spectrum was simplified, and mass peaks of individual PAHs were easily assigned, because unwanted compounds, like n-alkanes, were selectively removed by SFE. Furthermore, a simple calculation elucidated the outline of the spectrum.

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This study describes the determination of polycyclic aromatic hydrocarbons (PAHs) in water using high-performance liquid chromatography (HPLC) coupled with fluorescence detection (FLD). Because individual PAHs are generally present in water only at trace levels, a sensitive and accurate determination technique is essential. The separation and detection of five PAHs were run completely within 25 min by the HPLC/FLD system with an analytical C₁₈ column, a fluorescence detection, and acetonitrile-water gradient elution. Calibration graphs were linear with very good correlation coefficients (r > 0.9998), and the detection limits were in the range of 2 - 6 ng/l for five PAHs. Solid phase microextraction (SPME) was performed for sample pretreatment prior to HPLC-FLD determination, and the governing parameters were investigated. Compared to conventional methods, SPME has high recovery, saves considerable time, and reduces solvents waste. The extraction efficiencies of five PAHs were above 88% and the extraction times were 35 min in one pretreatment procedure. One particular discovery is that 1.5 M sodium monochloroactate (ClCH₂COONa) can improve the extraction yield of PAH compounds more than other inorganic salts. The SPME-HPLC-FLD technique provides a relatively simple, convenient, practical procedure, which was here successfully applied to determine five PAHs in water from authentic water samples.

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The binding properties of metal ions to a pectic polysaccharide, rhamnogalacturonan II (RG-II), from plant cell walls were analyzed by size-exclusion HPLC/ICP-MS. The dimeric RG-II borate complex (dRG-II-B) from sugar beet and red wine contained 0.8 - 1.1 mol/mol of B, 0.8 - 1.1 mol/mol of Ca, 0.1 - 0.3 mol/mol of Sr, and 0.03 - 0.07 mol/mol of Ba. The treatment of dRG-II-B with Sr²⁺, Ba²⁺, Pb²⁺ or La³⁺ exchanged the originally present Ca, Sr and Ba. In contrast, monomeric RG-II (mRG-II), which contained ∼0.1 mol/mol of Ca, formed complexes with La³⁺, Eu³⁺, and Lu³⁺ added to the solution, but did not do so with Ca²⁺, Sr²⁺, Ba²⁺ and Pb²⁺. The HPLC/ICP-MS and HPLC/RI (refractive index detector) analysis of the partially hydrolyzed mRG-II that was treated with La³⁺ indicated that the side chains and backbone of mRG-II together form a lanthanoid binding site.

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Peculiarly shaped chromatograms of some compounds that consist of two reversible isomers have been reported. Those of a compound that consists of three reversible isomers are described here. Because disulfide of captopril has two cis-trans convertible bonds, it exists in three forms of cis-cis, cis-trans and trans-trans isomers. The disulfide has produced various HPLC-UV profiles under various conditions, such as three split peaks, three peaks with bridging plateaus and one broad peak. The effect of the column temperature and the eluent flow rate on the profile was investigated and explained by interconversion among three isomers. A profile analysis could provide some kinetic constants of this reaction.

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A selective and simple method for the determination of iodate (IO₃^-) and bromate (BrO₃^-) by microcolumn ion chromatography (IC) is presented. In this study, IO₃^- and BrO₃^- were determined as IBr₂^- and tribromide (Br₃^-), respectively, via a postcolumn reaction with bromide (Br^-) under acidic conditions with the aid of α-cyclodextrin (α-CD) in microcolumn IC. IO₃^- and BrO₃^- were selectively detected by the present method at a wavelength of 253 or 265 nm. The present system achieved good selectivity for IO₃^- and BrO₃^- as well as good repeatability under suitable conditions. Precolumn enrichment improved the detection limit, and allowed the determination of BrO₃^- in bottled water as low as sub µg L^-1 level in microcolumn IC.

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The influence of the mobile-phase composition and temperature on the surface structure of the octadecylsilica (ODS) stationary-phase was investigated by applying a molecular-dynamics (MD) simulation. The molecular model to which the MD simulation was applied consisted of three parts: an amorphous silica base, dimethyloctadecylsilyl ligands and mobile-phase solvents. More detailed information on the effect of the mobile-phase composition was obtained by constructing larger molecular models than those used in our previous study. The thickness of the hydrocarbon layer of the stationary phase could be estimated based on the distance between the carbon atom located at the terminal end of the ODS ligand and the silica gel surface. The structural information obtained by the calculation showed good consistency with the experimentally observed values. The gauche fraction in the ODS ligand conformation could be also estimated to obtain a more detailed ligand conformation for each molecular model. It was found that as the temperature increased, the ligand conformation collapsed more. This trend was the same as the experimentally observed trends obtained by NMR, FT-IR, and Raman spectroscopic techniques.

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A reliable method is presented for the chiral separation of three basic drugs (mexiletine, chlorpheniramine and propranolol) with serum albumins (human and porcine, HSA and PSA) as chiral selectors by capillary electrophoresis in combination with the partial filling technique. Based on the systematic optimization of operation variables, the chiral separation of mexiletine, chlorpheniramine and propranolol was achieved in the pH 7.4 phosphate buffer by using HSA, PSA and PSA as selectors, respectively. The chiral recognition ability of HSA and PSA was compared. HSA and PSA show a different chiral recognition ability for each of the three drugs. In addition, the association constants between enantiomeric drugs and proteins were determined to be 2.00 and 3.80 × 10² M^-1 for mexiletine and HSA, 0.59 and 1.12 × 10³ M^-1 for chlorpheniramine and PSA, and 0.87 and 1.42 × 10³ M^-1 for propranolol and PSA. The method for the chiral separation and determination of association constants possesses the advantages of simple performance, effective avoiding of the interference of the UV detection from protein, and lowering of the reagent consumption.

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This paper describes a novel, simple and sensitive method for the determination of glyphosate in water samples by alternating-current oscillopolarographic titration. Under an acidic condition, glyphosate can be transferred into a nitroso-compound by reacting with NaNO₂. The titration end-point was obtained by the formation of a sharp cut in the oscillopolarographic with infinitesimal NaNO₂ on double platinum electrodes. The results showed that glyphosate had an excellent linear relationship over the range of 7.16 × 10^-6 - 4.14 × 10^-3 mol L^-1, the RSD of the proposed method was lower than 3%, and the spiked recoveries of three real water samples were in the range of 97.7 - 100.2%.

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Hydrogen-ion selective solid contact electrodes based on tribenzylamine, dibenzylnaphthalenemethylamine, and dibenzylpyrenemethylamine ionophores were prepared. With these electrodes, we showed that the response ranges were influenced by the number of phenyl rings in the ionophores. The lower limits for a linear pH response in acidic solutions were pH 2.50, 0.65, and 0.50, respectively. As the number of phenyl rings in the ionophores increased, the slopes of the EMF responses of these electrodes did not change significantly, but their response extended toward an acidic range (shifted to pH 0.50). Thus, their dynamic response range became wider. A solid contact electrode with dibenzylpyrenemethylamine ionophore, in particular, showed the best selectivity, from the interference of cations and anions, and the best reproducibility of the EMF. This electrode was stored in Tris buffer solutions, artificial serum, and hydrofluoric acid solutions for one month without any loss of performance. Their response time was 8 s. Satisfactory results were obtained when it was tested directly with artificial serum (in pH range 6.0 - 8.5) and hydrofluoric acid.

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A silver ion-selective electrode was prepared with a polymeric membrane incorporating 2,6-bis-methylsulfanyl-[1,3,5]thiadiazine-4-thione as an ionophore, tri-n-butylphosphate (TBP) as a plasticizer and sodium tetraphenylborate (NaTPB) as an additive. The electrode exhibited a near-Nernstian response of 52 mV/decade over a wide linear concentration range of 1.0 × 10^-5 - 1.0 × 10^-1 M with a lower detection limit of 9.77 × 10^-6 M. The electrode exhibited excellent selectivity for silver ion over many of the alkali, alkaline-earth and transition metal ions. The electrode worked well over a wide pH range of 1.77 - 7.13. The response time of the electrode was less than 20 s. The sensor can be applied as indicator electrode for the potentiometric titration of Ag⁺ ions with Cl^- ions.

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A highly selective poly(vinyl chloride)-based membrane sensor produced by using N,N-diethyl-N-(4-hydroxy-6-methylpyridin-2-yl)guanidine (GD) as active material is described. The electrode displays Nernstian behavior over the concentration range 7.0 × 10^-5 - 1.0 × 10^-1 M. The detection limit of the electrode is 5.0 × 10^-5 M. The best performance was obtained with the membrane containing 30% PVC, 55% benzyl acetate, 5% GD and 10% oleic acid. The response of the sensor is pH-independent in the range of 3.0 - 7.0. The sensor possesses satisfactory reproducibility, fast response time (< 20 s), and specially excellent discriminating ability for Eu(III) ion with respect to the alkali, alkaline earth, transition and heavy metal ions. The membrane sensor was used as an indicator electrode in potentiometric titration of Eu(III) ion with EDTA. It was also applied in determination of fluoride ions in mouth wash preparations.

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A new ammonia optical sensor was designed using bis(acetylacetoneethylendiamine)tributylphosphin cobalt(III) tetraphenylborate complex, coated on transparent triacetylcellulose film as membrane. The change in the absorbance of the optode at the maximum wavelength of 408 nm was related to ammonia concentration in aqueous samples. A buffer solution with a pH of 9 (sodium borate-HCl) was used. The optode was fully regenerated in pH 2. The linear dynamic range for determination of ammonia was 3.3 × 10^-4 to 6.9 × 10^-3 mol l^-1 with a detection limit of 5.0 × 10^-5 mol l^-1 and a response time range of 4 - 6 min. This membrane was successfully applied for determination of ammonia in drinking water.

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A very simple flow-through sensor is presented for the determination of the intense sweetener aspartame in low-calorie and dietary products. The sensor is implemented in a monochannel flow-injection system with UV spectrophotometric detection using a Sephadex CM-C25 cationic exchanger packed 20 mm high in a flow cell. This method is based on the transient retention of a cationic species of the sweetener on the solid phase when a pH 5.0 acetic acid sodium acetate buffer (0.01 M) is used as a carrier (2.6 mL^-1 min). The carrier itself elutes the analyte from the solid support, regenerating a sensing zone. Aspartame was determined by measuring its intrinsic absorbance at 219 nm at its residence time without any derivatization. Calibration graphs were linear over the range of 5.0 - 600.0 µg mL^-1 with an RSD of 0.55% (peak height). This sweetener was determined in several samples by measuring the height or peak area, obtaining recoveries ranging between 95 - 101% and 97.5 - 101%, respectively. The procedure was validated for its use in the determination of aspartame in low-calorie and dietary products, giving reproducible and accurate results.

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A new sensitive spectrophotometric method has recently been developed for the trace determination of cyanide with ninhydrin. Cyanide ion was supposed to act as a specific base catalyst. Nevertheless, this paper demonstrates that the reported assay is based on a novel reaction of cyanide with 2,2-dihydroxy-1,3-indanedione, which affords purple or blue colored salts of 2-cyano-1,2,3-trihydroxy-2H indene. Hydrindantin is merely an intermediary of the reaction. The formation of a stable and isolable ninhydrin-cyanide compound has been confirmed by its preparation in crystalline form. Also, it is thoroughly characterized by elemental as well as MS, IR, UV/VIS and ¹H NMR analyses. The Ruhemann’s sequence of reactions of cyanide with ninhydrin has been reconsidered and an adequate mechanism of the reaction is proposed. As a consequence, the interference of oxidizers as well as copper, silver and mercury ions with the cyanide determination has been elucidated.

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This paper describes a simple and highly selective method for separation, preconcentration and spectrophotometric determination of trace amounts of mercury. The method is based on the flotation of an ion-associate of HgI₄^2- and ferroin between aqueous and n-heptane interface at pH 5. The ion-associate was then separated and dissolved in acetonitrile to measure its absorbance. Quantitative flotation of the ion-associate was achieved when the volume of the water sample containing Hg(II) was varied over 50 - 800 ml. Beer’s law was obeyed over the concentration range of 3.2 × 10^-8 - 9.5 × 10^-7 mol l^-1 with an apparent molar absorptivity of 1 × 10⁶ l mol^-1 cm^-1 for a 500 ml aliquot of the water sample. The detection limit (n = 25) was 6.2 × 10^-9 mol l^-1, and the RSD (n = 5) for 3.19 × 10^-7 mol l^-1 of Hg(II) was 1.9%. A notable advantage of the method is that the determination of Hg(II) is free from the interference of the almost all cations and anions found in the environmental and waste water samples. The determination of Hg(II) in tap, synthetic waste, and seawater samples was carried out by the present method and a well-established method of extraction with dithizone. The results were satisfactorily comparable so that the applicability of the proposed method was confirmed in encountering with real samples.

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The structural features of humic acid (HA) at the sediment surface of the tideland at the Hayatsuegawa-river mouth at the Ariake Sea were investigated for the utilization of HA toward an environmental indicator of the features of the river basin and coastal region. ¹H NMR analysis revealed a high-content hydrocarbon residue with a similar type of terrigenous HA. Direct and methylation-pyrolysis-GC analysis suggested the incorporation of long-chain carboxylate in HA in the tidelands. The incorporation of branched-chain carboxylate residues in HA is the result of the microbial decomposition of detritus; these residues could be one of the characteristic structural features of HA in this area, which is rich in biodiversity and microbial activity. Because the structural features of coastal zone HA appear to reveal the characteristics and activities of the biological environment, these findings suggest the possibility of becoming an indicator of the detailed analysis of the structural features of coastal zone HA.

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A sensitive liquid chromatograph/tandem mass spectrometric technique (LC/MS/MS) was applied to determine aliphatic and aromatic carbonyl compounds in ambient air. Traces of the carbonyl compounds were sampled by passing through a Sep-Pak^® DNPH-silica cartridge. Their derivatives were thus eluted with acetonitrile, separated by reversed-phase liquid chromatography and determined by quadrupole tandem mass spectrometry in an atmospheric pressure chemical ionization (APCI) mode with multiple reaction monitoring (MRM). The detection limits (DL) of the carbonyl compounds were 0.8 - 15 ng/m³. A number of the carbonyl compounds were detected at n.d. - 14 µg/m³ levels. The precursor ion scanning analysis was applied to identify the unknown compounds.

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This investigation looked at the extraction ability of divalent transition metal ions onto an octadecyl silica gel (C18g) with a 4,4-trifluoro-1-(2-thienyl)-1,3-butadione (TTA) chelating agent. A method of retaining TTA onto C18g (TTA-C18g) was developed in order to adsorb the metal ions. The difference in the half-adsorption and half-extraction pH values between transition metals Ni²⁺-Co²⁺ was found to be 0.7 in this system. This is better than previously published results of 0.3 for the conventional extraction method using TTA in nitrobenzene. More than 96% of the metal ions in aqueous solution could be adsorbed onto TTA-C18g. Our system, which has no organic phase, can achieve a better removal or separation of transition metal ions than the conventional solvent-extraction methods using TTA in toluene or nitrobenzene.

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An electrochemical determination of the O₂^- concentration from KO₂ in DMSO solution using steady state microelectrode voltammetry shows that the KO₂/DMSO method with the combined use of a crown compound or sonication is a reliable and simple technique for introduction of O₂^- to the biomimitic reaction system.

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A difference diffusion-based NMR technique and cold-spray ionization mass spectrometry were employed as a solution-based approach for identifying a ligand binding with a protein receptor. The difference diffusion-based NMR technique, called difference NOE-pumping, can directly detect the ligand interacting with a protein receptor. This technique uses a simple pulse sequence and the diffusion filter can easily be optimized. The cold-spray ionization mass spectrometry (CSI-MS), a variant of electrospray ionization mass spectrometry (ESI-MS) operating at low temperature, has been applied to detect the ligand-receptor complex. The efficiency of these techniques for identifying binding ligands is demonstrated with the human serum albumin (HSA)-drug system.

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A structural characterization of bound water molecules in ribonuclease T₁ (RNase T₁) was carried out by nuclear magnetic resonance spectroscopy and molecular dynamics simulation. Amide protons of residues Trp59, Leu62, Tyr68 and Phe100 were found to cross-relax with protons of bound waters. Molecular dynamics simulations of the 120 water molecules observed in the free form of the crystal structure indicate that these amide protons donate hydrogen bonds to the less mobile water molecules. Hydrogen-bonded chains of the water molecules that are identified in the simulation study are located in the hairpin-like loop of RNase T₁, comprising residues 62 to 76. The temperature factors of the observed water molecules in the crystal structure are very low, indicating that these bound waters are intrinsic components of RNase T₁.

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¹⁹F NMR techniques were employed to characterize the binding property of the widely used general anesthetic halothane with human serum albumin (HSA). It was found that ¹⁹F{¹H} NOE and 2D ¹H-¹⁹F HOESY experiments detected intermolecular NOEs between halothane ¹⁹F and HSA protons. Measurements of the diffusion coefficients for halothane were also carried out by ¹H and ¹⁹F NMR, indicating the interaction of halothane with HSA. The present results indicate that these techniques are very suitable to identify a fluorine-containing ligand binding with a protein receptor in the drug-discovery process.

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