(2-Vinyloxyethyl)hydrazines

Reaction of hydrazine hydrate with 2-chloroethyl vinyl ether afforded (2-vinyloxyethyl)hydrazine and 1,1-bis(2-vinyloxyethyl)hydrazine in 20-38% yield.     

Fluorescence from the second excited singlet state of [18] annulenes

The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S₂ → S₀ emission. In addition, fluorescence from the S₁ state can be observed in monofluoro [13] annulene by exciting into the S₂ or directly into the S₁ absorption.     

Nitration of pentaerythritol by HNO3-H2SO4-H2O system

Conclusions It was shown experimentally that the nitrating agent in the O-nitration of pentaerythritol by HNO₃-H₂SO₄-H₂O nitrating mixtures is not the nitronium cation but evidently the free unionized nitric acid molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 134–140, January, 1970.     

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.     

The mechanism of bacteriorhodopsin functioning. I. The light-induced proton throw-over by retinal

The path of proton motion in protein bacteriorhodopsin is constructed: Tyr 43 → Tyr 26 → Asp 212 → Tyr 83 → Tyr 57 → Tyr 79 → Glu 204 → Tyr 64 → Glu 74. From the position of quantum theory the light-induced isomerization of retinal, the process carrying out the proton and throw-over from the inlet H-bond chain (Tyr 43 → Tyr 26 → Lys 216) to the outlet one (Lys 216 → Asp 212 → … → Glu 74) are investigated. The kinetics of the transition of the excitation from the π-electron subsystem to the vibrational one is studied; the function of the nonequilibrial excitation distribution of the collective intramolecular retinal vibrations is found. The mechanism of deprotonation of Schiff base (transmission of proton to the outlet channel) is considered. The correspondence between the theoretically estimated states and spectroscopically identified forms of bacteriorhodosin (initial form bR, intermediates J, K) is proposed.     

Crystallization of filled nylon 6 III. Non-isothermal crystallization

Summary DSC data on crystallization kinetics from the melt at different cooling rates of nylon 6 containing various amonts of untreated and surface-treated fillers, were analyzed in terms of a modified Kolmogorov-Avrami equation. It was established that mechanism of crystallinity development in molten nylon 6 does not change appreciably in presence of aminosilane-treated glass beads and small amounts of untreated glass beads, whereas time exponentn was found to decrease with increasing filler content in samples containing untreated glass beads and Aerosil. On the other hand, dependence of temperature of the onset of crystal nucleation on cooling rate obeyedm = 2 law for pure nylon 6 and samples containing surface-treated filler, whilem = 4 law seemed to hold for samples containing large amounts of untreated fillers at low cooling rates (m is the exponent at degree of supercooling). It was concluded that although isothermal conditions of crystallization should be preferred for further quantitative investigations of polymer-filler interactions in highly filled polymer melts, the above results qualitatively are consistent with trends discovered in isothermal crystallization experiments.     

Synthesis of(E)7-[[2-[4-(m-trifluoromethylphenoxy)-3α and 3β-hydroxy-1-butenyl]-5-oxo-1 -pyrrolidinyl]]heptanoic acids

The synthesis of an 8-aza-PGE₁ analog, (E)-7-[[2-[4-(m-trifluoromethylphenoxy)-3α and 3β-hydroxy-1-butenyl]-5-oxo-pyrrolidinyl]]heptanoic acids is reported.     

Random peptide synthesis using immobilized enzymes in high concentrations of organic solvents

Trypsin, leucine aminopeptidase, and carboxypeptidase B were separately immobilized on controlled pore glass and reacted with a dipeptide substrate in high concentrations of either acetone or 1-propanol. Hydrolytic activity was demonstrated and evidence for the possible synthesis of peptide polymer is presented. Directed synthesis using amino acids and blocked amino acids as substrates was not successful.     

Mechanism of the oxidation of cycloheptanone by chloramine-T

The oxidation kinetics of cycloheptanone by chloramine-T in alkaline media has been investigated. A mechanism involving the formation of an intermediate by the interaction between the enolic anion of cycloheptanone and chloramine-T in a slow step followed by its interaction with another molecule of chloramine-T in a fast step leading to products has been proposed. The scheme satisfactorily accords with the observed stoichiometry, negligible influence of ionic strength and a positive dielectric effect. Various rate parameters have been computed and 1.2-cycloheptanedione identified as the end product.With 2 Figures