Ab initio and variational transition state approach to beta-C3N4 formation: kinetics for the reaction of CH3NH2 with H

The CH3NH2 molecule has been considered as either an important intermediate in methane and ammonia mixtures or a precursor in methylamine and hydrogen mixtures in the synthesis of carbon nitride thin films. The fast Hydrogen (H) abstraction from CH3NH2 is an important process involved in the formation of HCN or CNH in the chemical vapor deposition (CVD) of carbon nitride thin films. The energetic and kinetic characteristics of the H abstraction reaction from CH3NH2 by atomic H used in CVD of beta-C3N4 were studied using ab initio direct dynamics methods for the first time. Two primary processes were identified for this reaction: H abstraction from the CH3 group and H abstraction from the NH2 group. On the basis of ab initio data, the rate constants of each channel have been deduced by canonical variational transition state theory with small-curvature tunneling correction over a wide temperature range of 200 to approximately 3000 K. The theoretical results were compared with available experimental data.     

Enantiomers of sterically hindered n-aryl-4-pyridones: Chromatographic enrichment and thermal interconversion

N-Aryl-4-pyridones 1–6 were synthesized by condensation of the corresponding 4-pyrone with anilines. The enrichment of the enantiomers was achieved by liquid chromatography on triacctylcellulose, enantiomeric purities of(+)-1 and (+ )-2 being measured by ¹H-NMR in the presence of an optically active auxiliary. Barriers to partial rotation about the C-N bond in 1-4 were determined and compared with corresponding biphenyls.     

High-throughput cytochrome P450 inhibition screening via cassette probe-dosing strategy. IV. Validation of a direct injection on-line guard cartridge extraction/tandem mass spectrometry method for simultaneous CYP3A4, 2D6 and 2E1 inhibition assessment

A highly efficient direct injection on-line guard cartridge extraction/tandem mass spectrometry (DI-GCE/MS/MS) method has been validated for high-throughput evaluation of cytochrome P450 (CYP) 3A4, 2D6 and 2E1 inhibition potential via cassette dosing of midazolam, dextromethorphan and chlorzoxazone using human hepatic microsomes and 96-well microtiter plates. Microsomal incubations were terminated with formic acid, centrifuged, and the resulting supernatants were injected for analysis by DI-GCE/MS/MS. Due to the novel use of an extremely short C(18) guard cartridge (4 mm in length), this method exhibits several advantages such as no sample preparation, excellent on-line extraction, short run time (2.5 min), and minimized source contamination and performance deterioration. The DI-GCE/MS/MS method demonstrates acceptable accuracy and precision for the simultaneous quantification of 1'-hydroxymidazolam, dextrorphan and 6-hydroxychlorzoxazone in microsomal incubations. The inhibition potential of CYP3A4, 2D6 and 2E1 has been evaluated using their known selective inhibitors. The IC(50) values measured by the cassette dosing approach (high-throughput) are consistent with those observed by an individual dosing regimen (conventional) and are all in good agreement with the literature values. The results suggest that the cassette probe-dosing strategy may provide an in vitro approach to minimize cost while maximizing throughput of CYP inhibition evaluation of new chemical entities in support of drug discovery and development.     

High pressure Raman studies of 7,7,8,8-tetracyanoquinodimethane (TCNQ) and CuTCNQ

The high-pressure Raman studies of 7,7,8,8-tetracyanoquinodimethane (TCNQ) single crystals and polycrystalline CuTCNQ are presented in this paper. TCNQ shows a phase transition at 22 kbar, a pressure higher than reported earlier. CuTCNQ undergoes a first order phase transition at 30 kbar, which is characterized by the abrupt disappearance of all the Raman bands.     

Reactions of Tris(acetonitrile)tricarbonylchromium with Trimethylsilylarenes

The reactions of tris(acetonitrile)tricarbonylchromium 1 with trimethylsilyl derivatives 2–5 of phenalene, indene, 1,2-dihydronaphthalene and trans-β-methylstyrene gave products 10-13, respectively, containing no trimethylsilyl groups. The reactions of 1 with trimethylsilyl derivatives 6–8 of benzene, toluene and cycloheptatriene gave products 14–16, respectively, containing trimethylsilyl groups. The reaction of 1 with 1,2-bis(trimethylsily-1,2-dihydro)naphthalene 9 gave product 17 in which only trimethylsilyl at the allylic position was cleaved. Compound 10 crystallizes in the orthorhombic system, space group Pbca, with a = 12.228(4), b = 14.288(1), c = 15.128(3) Å, Z = 8, R_F= 0.046, and R_w = 0.047. X-ray crystallographic data confirm that the Cr(CO)₃ moiety is bonded to phenalene in a η⁶-mold.     

Gel permeation chromatographic characterization of sodium hyaluronate and its fractions prepared by ultrasonic degradation

Summary High-molecular-weight sodium hyaluronate isolated from rooster combs was degraded by ultrasonication. The molecular weight of hyaluronate and its polydispersity was determined by gel-permeation chromatography. During 75-min treatment the molecular weight value decreased from 1.39×10⁶ Da to 2.25×10⁵ Da while the polydispersity of the molecular weight increased from 1.29 to 2.36. The reciprocal value of the square of the hyaluronate's molecular weight was linearly proportional to the time of ultrasonication.     

Effect of replacing the primary quinone by different species on the ultrafast photosynthetic electron transfer in bacterial reaction centres

Using picosecond absorption spectroscopy it has been shown that in Rhodobacter sphaeroides reaction centres the substitution of the primary quinone acceptor (QA), ubiquinone-10, by other quinone species (with redox potentials higher or lower than that of ubiquinone-10) has essentially no modifying effect on the reaction centre protein. The molecular relaxation processes that accompany the localization and stabilization of a photo-excited electron on the intermediate acceptor, bacteriopheophytin (I), are not affected, although the subsequent transfer of the electron from I to QA is slowed down. Consequently, this leads to a lower quantum efficiency of high rate of direct I-----QA reaction is normally due to the specificity of the primary quinone species and its binding site in the reaction centre protein which provide optimum steric and chemical conditions for an effective interaction between I and QA.     

Single-sweep polarography of the copper(II)-3-hydroxy-1-p-sulphonatophenyl-3-phenyltriazene complex and its analytical applications

A polarographic investigation of the copper-3-hydroxy-1-p-sulphonatophenyl-3-phenyltriazene (HSPT) complex in 0.05 M sodium tetraborate medium is described and a simple and sensitive single-sweep polarographic method for the determination of trace amounts of copper in biological samples is proposed. The complex was shown to be Cu(HSPT)2 with log beta' = 11.38. The polarographic wave is caused by the reduction of copper(II) in the adsorbed complex to copper amalgam on the surface of a mercury electrode. The current peak is directly proportional to the concentration of copper in the range 8.0 x 10(-9)-4.0 x 10(-6) M and the detection limit is 5.0 x 10(-9) M.     

Reaction of Cα,O-dilithiooximes with functionalized carbonyl compounds. Part 2 . Reaction with α-chloroketones and α,β-unsaturated aldehydes and ketones

The reaction of Cα,O-Dilithiooximes 2 and α-chloroketones afforded 5-(hydroxymethyl)-Δ²-soxazolines 4 . α,β-Unsaturated aldehydes and ketones reacted with 2 to give the corresponding acyclic 1,2-addition products 5 . The latter were cyclized with phosphorus pentoxide to 5-vinyl-Δ²-isoxazolines 6 .     

Conducting polymers. I. Electrical conductivity of poly(bis-p-phenylenediaminosulphoxide)

Poly(bis-p-phenylenediaminosulphoxide) was prepared by Michael addition of p-bis-N-sulphinylphenylenediamine with p-phenylenediamine at 150°C. Thermal and electrical behaviors of the polymer have been studied. The polymer is found to have increased conductivity possibly due to the participation of lone pairs of electrons on nitrogen and sulphur atoms with σ bond of the macrochain. Thermogravimetric analysis indicates that the polymer is fairly stable than other conducting polymers up to 200°C. The activation energy of the polymer was measured and found to be 13 kcal mol^?1.