Sulfur Compounds. 183. A Derivative of Perthiocarbonic Acid H2CS4: X-ray structural analysis of bis(triphenylmethyl) perthiocarbonate (Ph3C)2CS4

The molecular structure of Ph₃CSSC(S)SCPh₃ · CS₂ has been determined by X-ray structural analysis. The substance crystallizes in the triclinic crystal system [a = 884.9(2) pm, b = 1 039.5(2) pm, c = 2 064.6(3) pm, α = 75.86(1)°, β = 79.83(2)°, γ = 77.31(5)°, Z = 2, space group P1 ]. The CS₃ group is planar; the S? S-bond (201.4 pm) forms an angle of 5.7° with the CS₃ plane. The torsional angle CSSC equals 96.3°. (Ph₃C)₂CS₄ was obtained by reaction of TosNSCl₂ (Tos = p-MeC₆H₄SO₂) with Ph₃CSH in CS₂ in the presence of triethylamine. The reaction mechanism is discussed.     

Investigation of the pharmacokinetics of celecoxib by liquid chromatography-mass spectrometry

A new method for the quantification of celecoxib in human plasma based on reversed-phase high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) after liquid-liquid extraction is presented. The method is rapid, sensitive and highly selective. The retention time of celecoxib was 2.3 min. The limit of quantification was 5 microg/L. Rofecoxib was used as internal standard. After validation, the method was used to study the pharmacokinetic profile of celecoxib following administration of a single oral dose (200 mg) in 12 healthy volunteers. Since celecoxib should be metabolized primarily by cytochrome 2C9 (CYP2C9), a poor metabolizer (PM) for this cytochrome P450 enzyme was included in the study. Pharmacokinetic characteristics (mean +/- SD) of extensive metabolizers (EM) were t(max) 2.9+/-1.2h, c(max) 842+/-280 microg/L, AUC(infinity) 6246+/-2147 microg h/L and t(1/2) 7.8+/-2.7h. The area under the curve (AUC(infinity)) for the PM was 12561 microg h/L. However, we found no noticeable increase in half life in the PM (11.5 h) after a single dose of celecoxib.     

Sequentially photocleavable protecting groups in solid-phase synthesis

[reaction: see text] A sequential solid-phase peptide synthesis was developed using both photolabile linker and protecting groups. The chromatic sequential lability between a tert-butyl ketone-derived linker (sensitive to irradiation at 305 nm) and a nitroveratryloxycarbonyl (NVOC) group (sensitive at 360 nm) was exploited to prepare Leu-Enkephalin in a 55% overall yield. This new strategy allows the preparation of peptides in essentially neutral medium, by avoiding the use of common deprotection reagents such as trifluoroacetic acid or piperidine.     

Fermentation of a skim milk concentrate with Streptococcus thermophilus and chymosin: structure, viscoelasticity and syneresis of gels

Fermentation of a reconstituted skim milk concentrate (8% protein) was investigated to elucidate the effects of various fermentation parameters on the structural, rheological and visual (wheying-off) properties of the resulting gels (pH 4.60). Fermentation trials were performed with non-exocellular polysaccharide-producing strains of Streptococcus thermophilus at various fermentation temperatures and at various chymosin levels. Oscillatory vane rheometry carried out on the intact gels (at 4 °C) showed that the level of chymosin had a significant impact on the gel strength (storage modulus G′). This can be explained by the arrangement of casein micelles into more compact aggregates and the enhanced fusion of aggregated casein micelles as revealed by transmission electron microscopy for the gels fermented with chymosin. Wheying-off of the stirred gels as measured by a centrifugation test (at 4 °C) and pore size of the intact gel structures investigated by scanning electron microscopy both increased with increasing level of chymosin and increasing fermentation temperature (resulting in an increase in acidification rate). A higher level of syneresis (wheying-off) is explained by the larger pore size, since larger pores present a lower resistance to the outflow of whey from the gel.     

Determination of organophosphorus, triazine and 2,6-dinitroaniline pesticides in aqueous samples via solid-phase microextraction (SPME) and gas chromatography with nitrogen-phosphorus detection

Solid-phase microextraction (SPME) represents a very simple and rapid method for the extraction of organophosphorus, triazine and 2,6-dinitroaniline pesticides from aqueous samples without making use of any solvents. The same fiber can be used repeatedly. Moreover, a sample volume as small as 3 mL can be employed with no loss in sensitivity. 34 compounds have been extracted from aqueous samples by SPME using a 85 m polyacrylate fiber. For organophosphorus pesticides, a 100 m polydimethylsiloxane fiber has been used additionally for comparison. The fibers were directly introduced into the heated split/splitless injector of the gas chromatograph and determined using a nitrogen-phosphorus detector. The method was evaluated with respect to the limit of detection (LOD), linearity and precision. The limit of detection (LOD) depends on the compound and varies from 0.005–0.09 g/L. The method is linear over at least three orders of magnitude with coefficients of correlation usually >0.999. For triazines and 2,6-dinitroanilines the coefficient of variation (precision) is <8% while for organophosphorus compounds it may reach values up to 18% (however, if the latter compounds are extracted using the polydimethylsiloxane phase considerably higher precision is achieved). The partitioning of the analyte between the aqueous phase and the polymeric phase depends on the hydrophobicity of the compound as expressed by the octanol/water partitioning coefficient (P_ow). For triazines it was shown that there is a linear dependence of the logarithm of the analyte response on the log(P_ow) i.e. the higher the hydrophobicity, the higher the affinity of the analytes to the polymeric phase of the fiber and the higher the response. Salt addition has a strong effect on the extraction efficiency. This effect increases with decreasing hydrophobicity (increasing polarity) of the compound. The triazines ametryn, atrazine, propazine, simazine and simetryn have been identified in a ground water well sample by SPMEGC/NPD.     

Complete solutions of a family of quartic Thue and index form equations

Continuing the recent work of the second author, we prove that the diophantine equation

for has exactly 12 solutions except when , when it has 16 solutions. If denotes one of the zeros of , then for we also find all with .

     

Inhomogeneous quantum groups and their quantized universal enveloping algebras

The quantum group IGL _q (N), the inhomogenization of GL _q (N), is formulated with -matrices. Theq-deformed universal enveloping algebra is constructed as the algebra of regular functionals in this formulation and contains the partial derivatives of the covariant differential calculus on the quantum space.     

Franck-Condon matrix elements for bound-continuum vibrational transitions calculated by numerical integration and basis set expansion techniques

Franck-Condon factor distributions for bound-to-continuum transitions of one-dimensional vibrational states are calculated by a) using numerical integration, b) employing a finite number of square integrable harmonic oscillator functions. The methods are generally applicable to any kind of bound or repulsive potential involved. Results are presented and compared to model potential calculations previously reported by Krüger [1].     

First structural characterization of binary AsIII and SbIII azides

The highly explosive molecules As(N(3))(3) and Sb(N(3))(3) were obtained in pure form by the reactions of the corresponding fluorides with (CH(3))(3)SiN(3) in SO(2) and purification by sublimation. The crystal structures and (14)N NMR, infrared, and Raman spectra were determined, and the results compared to ab initio second-order perturbation theory calculations. Whereas Sb(N(3))(3) possesses a propeller-shaped, pyramidal structure with perfect C(3) symmetry, the As(N(3))(3) molecule is significantly distorted from C(3) symmetry due to crystal packing effects.     

Röntgenstrukturanalysen von Cyclododekaschwefel (S12) und Cyclododekaschwefel-1-Kohlendisulfid (S12 · CS2) [1]

X-Ray Structural Analyses of Cyclododecasulfur (S₁₂) and Cyclododecasulfur-1-Carbon-disulfide (S₁₂ · CS₂) S₁₂ · CS₂ crystallizes in space group R&3macr;m–D with hexagonal lattice constants a = 1066.8(3), c = 1155.1(4) pm, Z = 3, d_calc. = 2.04 g · cm^?3. The S₁₂ molecules occupy sites of D_3d symmetry with bond distance (d_ss) of 205.4(1) pm, bond angles (α) of 105.80(5) and 106.65(6)º and torsional angle (τ) of 87.20(7)º. The CS₂ molecule interacts only very weakly with the S₁₂ units. S₁₂ crystallizes in space group Pnnm–D with lattice constants a = 472.5(2), b = 910.4(3), c = 1453.2(3) pm, Z = 2, d_calc = 2.045 g · cm^?3. The molecules with mean parameters d = 205.2 pm, α 106.6º, τ 88.0º occupy sites of C_2h symmetry.