A mass spectral study of some symmetric and unsymmetric sulfides,disulfanes, and trisulfanes

The low-resolution mass spectra of 13 trifluoromethyl and/or methyl sulfur-containing compounds (CF₃S_nCF₃, CF₃S_nCH₃, CH₃S_nCH₃, CF₃S_mCl, and CH₃S_mCl; n = 1, 2, 3; m = 1, 2) are reported and discussed. There is a considerable similarity between the fragmentation pattern of compounds with the same terminal groups. However, with a fluorinated and a non-fluorinated methyl group, the major fragmentation products produced are similar to those for the dimethyl compounds.     

Pyridine and pyrimidine ring syntheses from 4-(4-morpholino)-3-pentenone and from ethyl 3-(4-morpholino)-2-butenoate

3-Substituted 2(1H)-pyridones are produced from reaction of 4-(4-morpholino)-3-pentenone 1 with each of the following carbon acids: cyanoacetamide, malononitrile, cyanothioacetamide, acetylacetamide, benzoyl-acetonitrile. Reaction of ethyl 3-(4-morpholino)-2-butenoate 2 with cyanoacetamide gives the corresponding hydroxypyridone. Pyrimidines are formed by reaction of 1 and of 2 with benzamidine and with S-benzylthio-urea; in the last case, the eliminated morpholine displaces the benzylthio group to give the final product.     

The 1,2,4-triazolyl cation: thermolytic and photolytic studies

The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five pi electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.     

SPECTRA AND EXTINCTION COEFFICIENTS OF NEAR-INFRARED ABSORPTION BANDS IN MEMBRANES OF Rhodobacter sphaeroides MUTANTS LACKING LIGHT-HARVESTING AND REACTION CENTER COMPLEXES

Abstract— Membranes from Rhodobacter (formerly Rhodopseudomonas) sphaeroides mutant strains that lack one or more of the bacteriochlorophyll a (BChl)-protein complexes were used to obtain spectra and molar extinction coefficients of the near-IR absorption bands. The strains examined were NF57 which lacks the B875 light-harvesting and reaction center complexes, and M21 which lacks the B800–850light-harvesting complex. The extinction coefficients obtained for the B800, B850 and B875 bands were 226 ± 10, 170 ± 5, and 118 ± 5 m M ^-1cm^-1, respectively, in reasonable agreement with values reported for detergent-isolated complexes (Clayton, R. K. and B. J. Clayton, Proc. Natl. Acad. Sci. USA 78 ,5583–5587, 1981). The results also demonstrated that detergent solubilization altered the spectra, causing a band broadening on the blue side of the B875 and B800 peaks. The data obtained from the analysis of the mutant strains were used for deconvolution of the BChl species in membranes of the wild-type. A short BASIC computer program for performing this deconvolution is included.     

Triolsulphonate derivatives of amino acids

The synthesis and chemical properties of a series of amino acid derivatives containing the thiolsulphonate functionality are described.     

Investigation of electronic structure and associated nuclear quadrupole interaction of adsorbed fluorine atoms on silicon surface

The electronic energy levels and wave functions of fluorine and chlorine atoms adsorbed at the <111> surface of silicon are obtained by the Hartree-Fock procedure applied to clusters simulating the surface structure. Minimising the total energy with respect to the positions of the halogen atoms, the Si-Cl distance in the adsorbed system was found to be in good agreement with that from a recent SEXAFS measurement, there being no corresponding data presently available for fluorine on silicon surface. The calculated¹⁹ f ^* nuclear quadrupole coupling constants using the electronic wave functions for SiH₃F and the larger cluster Si₄H₉F, simulating the surface, differed substantially in contrast to the situation for the Si-F distance, indicating that the quadrupole coupling is a more sensitive indicator of the adequacy of the cluster chosen to represent the surface system. Experimental results for the coupling constants are awaited for comparison with theory.     

Diiodine complex of diferrocenyl(phenyl)phosphine sulfide: the structural and electrochemical behaviour of Fc2(Ph)PS · I2

The title compound, Fc₂(Ph)PS · I₂, has been prepared and characterised in both the solid state and solution. Single crystal X-ray crystallography reveals that the adduct adopts a molecular charge-transfer structure in the solid state. Mössbauer spectroscopy confirms the presence of low spin Fe²⁺ but also indicates the presence of ca. 24% of an Fe³⁺ species. The electrochemistry of Fc₂(Ph)PS · I₂, Fc₂(Ph)PS and Fc₂(Ph)P has been studied using a combination of cyclic voltammetry and differential pulse voltammetry. The data for Fc₂(Ph)PS · I₂ show two redox processes, consistent with the sequential oxidation of the ferrocenyl groups to ferrocenium species.     

The absolute stereochemistry of several cis-dihydrodiols microbially produced from substituted benzenes

The absolute stereochemistry of a series of 3-substituted cis-dihydrodiols obtained by microbial oxidation of toluene, ethylbenzene, chlorobenzene, and biphenyl has been assigned from chemical and spectrophotometric studies. ?-Halogenated toluenes also have been investigated as substrates in these oxidations, and the corresponding cis-dihydrodiols isolated. Implications from the observation that some of the cis-dihydrodiols are racemic are discussed. Oxidation of an olefin, (±)-3-methylcyclohexene, by these microorganisms leads only to cis-diols whose absolute stereochemistry about the hydroxyl-bearing carbons is the same as that found for the cis-dihydrodiols formed from the aromatic substrates.     

The determination of anionic detergents with the bis (ethylenediamine)copper(II) ion

A method is described for the determination of anionic detergents. The detergent anions are extracted into chloroform as an ion-association compound with the bis(ethylenediamine)copper(II) cation. Determinations are completed by colorimetry or atomic absorption spectrometry. With a 150-ml water sample, the limit or detection is 0.03 μg ml^-1 (as LAS) for colorimetry or 0.06 μg ml^-1 for a.a.s. The method requires only one phase separation step and is highly selective. It is directly applicable to brine and sea-water samples.     

Determination of lactate or oxalate using injected lactate oxidase and peroxidase by capillary electrophoresis with UV detection

Two reactions, catalyzed by lactate oxidase (LO) and peroxidase, are initiated by a single injection of the enzymes and the substrate 2,2'-azino-bis(3-ethylene-thiazoline-6-sulfonic acid) (ABTS) into the capillary previously filled with the sample (lactate or lactate-oxalate mixture) and the run buffer containing NADH. The oxidized ABTS product upon reaction with NADH is converted to NAD(+) which is separated and detected in less than 2 min at 266 nm with a sample throughput of 7 min (including wash steps between samples). Simplex trade mark software is used to optimize the enzyme concentrations and reaction temperature. Consumption of the more expensive LO enzyme is only 1.4 x 10(-3) U per assay assuming 27 nL per injection. Linearity is established within the range from 0.0025 to 1 mM with R(2) of 0.9982. Recoveries of lactate from five spiked serum samples averaged 101%. Application of this method for the determination of oxalate as an inhibitor of LO is demonstrated.