Simultaneous determination of serotonin and 5-hydroxyindole-3-acetic acid in human urine by automated precolumn derivatization and semi-microbore column liquid chromatography with fluorescence detection.

An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification.     

Improved detectability with a polymer-based trapping device in rapid HPLC analysis for ultra-low levels of bisphenol A (BPA) in environmental samples.

A new high-performance liquid chromatography (HPLC) method has been developed to detect ultra-low concentrations of bisphenol-A (BPA) (below 1 ng/L (ppt)) using column switching electrochemical detection (ECD). The results were superior to those obtained from manual pretreatment procedure with membrane stationary phase. BPA is inherently ubiquitous in the environment, including tools and solvents used for its analysis; to obtain meaningful results, therefore, the concentration of the overall BPA contamination must be below the detection limit for BPA using the analytical system. Therefore, purified water for preparing the standard BPA solution must be filtered with a hydrophobic membrane to suppress BPA background levels of contamination. In addition, we investigated methods for effectively preserving environmental water containing BPA. The addition of a small amount of ethylenediaminetetraacetic acid (EDTA) provided good recovery even after overnight storage. By employing these precautionary measures and procedures to reduce BPA contamination from the analytical procedure, we could accurately determine l(-10) ppt of BPA in environmental water samples using a column switching HPLC system.     

Bufadienolides and a new lignan from the bulbs of Urginea maritima

Thirty three compounds were obtained from the bulbs of Urginea maritima (Liliaceae). The compounds were identified by means of fast atom bombardment mass spectrometry (FAB-MS), nuclear magnetic resonance (1H-NMR), (13C-NMR), nuclear overhauser effects (NOE) and two dimensional (2D) NMR. Ten of them were new natural compounds. Nine were bufadienolides and only one was lignan in these compounds.     

Synthesis and ion selectivity of macrocyclic metacyclophanes analogous to spherand-type calixarenes

Novel macrocyclic compounds, hexahydroxy[1.0.1.0.1.0]- (2b) and octahydroxy[1.0.1.0.1.0.1.0]metacyclophane (2c) have been prepared in 50–70% yield by base-catalyzed condensation of 5,5-di-tert-butyl-2,2-dihydroxybiphenyl (1) with formaldehyde in refluxing xylene. An attempted alkylation of the flexible macrocycles2b and2c with ethyl bromoacetate in the presence of Cs₂CO₃ under acetonitrile reflux gave only one pure stereoisomer3 and4, respectively, while other possible isomers were not observed. The structural characterization of these products is also discussed. The two-phase solvent extraction data indicated that hexaethyl ester3 and octaethyl ester4 show strong metal affinity, comparable with that of the corresponding calix[n]arenes, and a high K⁺ selectivity was observed for octaethyl ester4.¹H-NMR titration of hexaethyl ester3 and octaethyl ester4 with KSCN clearly demonstrate that a 11 complex is formed which is stable on the NMR time scale.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Vibrational spectra and rotational isomerism of ethyl trichloroacetate

The IR and Raman spectra of ethyl trichloroacetate (E-TCA) and its deuterate (E-TCA-d₅) have been measured in the liquid, glassy and crystalline states. Vibrational assignment was made by referring to isotopic wavenumber-shift, characteristic group frequencies of related esters and with the aid of a normal coordinate calculation on E-TCA and E-TCA-d₅. It is suggested that in the liquid and glassy states there exist two molecular forms (trans—trans—trans and trans—trans—gauche) with regard to the internal rotations about the ClC---C---O---CH₂CH₃ axis, and that the former persists in the crystalline state. The band pairs of E-TCA and the other ethyl esters are discussed in relation to the nature and number of rotational axes, effect of the heavy trichloromethyl group, and enhancement of band intensity by vibrational coupling.     

Thermal latency of novel chelating borate catalysts as latent catalysts for epoxy–phenolic resins

Novel quaternary ammonium bis(2‐oxybenzoyloxy)borate salts ( 1a – 1c ) or quaternary ammonium bis(1,2‐benzenedioxy)borate salts ( 2a and 2b ) with tetra‐n‐butylammonium (TBA⁺), tetra‐n‐octylammonium (TOA⁺), or bis(triphenylphosphoranylidene)ammonium (PNP⁺) cations were synthesized as latent catalysts of epoxy/phenol–novolac resins by the complexation between boric acid and salicylic acid or catechol, followed by neutralization with quaternary ammonium hydroxide. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with 1a – 1c in diglyme at 150 °C for 6 h proceeded up to 85–96% conversions and gave polymers with number‐average molecular weights of 4180–10,500, whereas the polyaddition at 80 °C for 6 h gave less than 8% conversions. However, the polyaddition with 2a containing TBA⁺ cation proceeded to only a 32% conversion at 150 °C for 6 h in diglyme and to a 64% conversion even at 180 °C for 6 h in triglyme and only gave low molecular weight oligomers, and no reaction proceeded in the polyaddition at 80 °C. However, polyaddition with 2b containing PNP⁺ cation proceeded up to a 96% conversion at 150 °C for 6 h in diglyme and gave a higher molecular weight polymer with a number‐average molecular weight of 8050, whereas the polyaddition at 80 °C for 6 h gave only a 5% conversion. The catalytic activity of ammonium borates 1a – 1c and 2a and 2b depended on the borate anion structure: 1a and 1c with bis(2‐oxybenzoyloxy)borate anion revealed higher activity than 2a and 2b with bis(1,2‐benzenedioxy)borate anion, respectively. In comparison with tetra‐n‐butylammonium bromide (TBAB) as a conventional ammonium salt or tetra‐n‐butylammonium tetrakis(benzoyloxy)borate (TBA‐TBB), 1a – 1c and 2b revealed better thermal latency. The catalytic activity of ammonium borates also depended on the bulkiness of the ammonium cation, and the order of activity was 1c (PNP⁺) > 1b (TOA⁺) ≧ 1a (TBA⁺) and 2b (PNP⁺) > 2a (TBA⁺). The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts 1a – 1c and 2a and 2b in bulk at 40 °C was much better than that with TBAB and TBA‐TBB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2702–2716, 2002     

Ruthenium-catalyzed one-pot hydroformylation of alkenes using carbon dioxide as a reactant

A new hydroformylation of alkenes using carbon dioxide as a reactant is shown to take place in the presence of ruthenium cluster complexes and halide salts. Similar or even better yields of alcohols were formed as compared to the conventional hydroformylation with CO under the same reaction conditions. The reaction proceeded in three steps: CO₂ is first converted to CO; then it is used as a reagent for hydroformylation to give aldehyde; subsequently, it is hydrogenated to alcohol. ESI-mass spectrometric analyses of the reaction solutions indicated formation of four kinds of ruthenium anionic complexes including tetra-, tri-, and mononuclear species. On the basis of experimental findings, possible roles of these complexes are discussed.     

On the photochemical conversion of an alpha, beta-unsaturated gamma, delta-epoxy ketone: 3-oxo-6-alpha, 7-alpha-oxide-17-beta-acetoxy-Delta-androstane

The α,β-unsaturated γ,δ-epoxyketone 7 is isomerized almost exclusively to the δ-diketone 9 both upon irradiation in the n → π* absorption band with light of wavelengths above 310 nm (in anhydrous dioxane or benzene solutions) and upon triplet sensitization using acetophenone in benzene. The reaction may be formulated by the cleavage of the C_γ? O oxide bond and the shift of the δ-hydrogen to the γ-position, and thus bears a formal “double bond homology” to the photochemical α,β-epoxyketone rearrangement. Excitation in the π → π* absorption band of 7 with light of wavelength 253,7 nm (in anhydrous dioxane solution) leads to the formation of product 10 as well as to the triplet rearrangement to 9 . With this result a novel partial synthesis of O-acetyl-B-nortestosterone has been accomplished, which has the advantages of fewer steps and higher product yield ( 7 → 10 : ～30% yield) than previously published syntheses. On the basis of the presently available experiments, the mechanism of the transformation 7 → 10 , which constitutes one of the still few examples of enone photoreactions induced selectively from the π,π* excited singlet, remains unknown.     

Thermodynamic properties of the Cu-Au system using a face-centered-cubic lattice model with a renormalized potential

A Monte Carlo simulation is carried out to study thermodynamic properties of Cu-Au alloys using a face-centered-cubic (fcc) lattice-gas model. To obtain quantitatively accurate results, a Finnis-Sinclair-type potential, which has been widely used for molecular dynamics (MD) simulations, is employed. To overcome some shortcomings of lattice-gas models such as neglecting vibrational entropy, the potential is mapped onto the fcc lattice using the renormalization technique. The renormalized potential gives an improved Cu-Au phase diagram compared to the original MD potential applied directly on the lattice.     

Preparation and properties of aromatic polyamides from 5-t-butylisophthalic acid and various aromatic diamines

Aromatic polyamides (aramids) having pendant t-butyl group were synthesized by the direct polycondensation of 5-t-butylisophthalic acid with various aromatic diamines in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. The aramids having inherent viscosities of 0.6–2.4 dL/g were obtained in quantitative yields. These polymers were readily soluble in various solvents such as NMP,N,N-dimethylacetamide, dimethyl sulfoxide, and pyridine, and gave transparent, tough and flexible films by casting from the NMP solutions. The aramids had glass transition temperatures between 250 and 330°C, and started to lose weight around 350°C, with 10% weight loss being recorded at about 450°C in air.