Synthesis of anticonvulsant activity of some 2-phenylcarbamoyl-1,2-diazabicyclo[2.2.2]octanes

A number of aryl isocyanates were adducted to 1,2-diazabicyclo[2.2.2]octane and afforded 2-phenyl-carbamoyl-1,2-diazabicyclo[2.2.2]octanes. Some of the products displayed anticonvulsant activity.     

等离子体聚合及其聚合物的应用

本文着重综述了烃,含氮、氧的有机化合物,碳氟化合物以及有机硅化合物的等离子体聚合。同时还系统地介绍了等离子体聚合物在制备反渗透膜、分离膜、材料表面的涂层等方面的国内外的最新研究成果。     

The chemistry of thujone. IX. Thujone as a chiral synthon for the synthesis of optically active steroid analogues. The vinylpicoline route

The thujone-derived enone 1 , upon base-catalyzed reaction with 2-methyl-6-vinylpyridine is converted to the pyridine analogue 5 (Scheme 1). Catalytic reduction of the latter to 6 generates two new centers of chirality which eventually become C(8) and C(14) in the ultimate synthetic steroid analogue 12 . An X-ray analysis of 6 establishes the structure and absolute configuration so as to determine its suitability in subsequent synthetic studies. The acetal derivative 7 , via Birch reduction, hydrolysis, and internal aldol cyclization, is converted into the cyclohexenone analogue 10 (Scheme 2). This ‘one-pot’ process affords an efficient conversion of the pyridine ring into a cyclohexenone system required for A-ring construction of the steroid skeleton. Finally, conversion of 10 , via the unsaturated diketone 11 , provides the chiral steroid analogue 12 .     

Multilayer vesicles and vesicle clusters formed by the fullerene-based surfactant C60(CH3)5K

The self-assembly behavior of a fullerene-based surfactant, C60(CH3)5K, in water was studied using a combination of static and dynamic light scattering, as well as transmission electron microscopy, and compared to that of the compound C60(C6H5)5K. Both fullerene surfactant systems spontaneously assemble into large vesicles consisting of closed spherical shells formed by bilayers, with critical aggregation concentrations (CAC) lower than 10(-6) g ml(-1). At low concentrations, the aggregate sizes of C60(CH3)5K (radius R approximately 26.8 nm) and C60(C6H5)5K (R approximately 17.0 nm) were found to be substantially different from each other, showing that the change of the substituents surrounding the polar cyclopentadienide head group makes it possible to control the size of the resulting aggregates. Furthermore, the C60(CH3)5K vesicles were found to exist in two qualitatively different types of aggregation with a critical reaggregation concentration (CRC) located at 3.30 x 10(-6) g ml(-1). Above the CRC, larger aggregates were observed (R approximately 37.6 nm), showing a more complex form of supramolecular aggregation, e.g., in terms of multi-bilayer vesicles and/or of clusters of bilayer vesicles.     

Laser-induced fluorescence of cyclohexadienyl (c-C6H7) radical in the gas phase

A laser-induced fluorescence spectrum was observed in the 500-560 nm region when a mixture of 1,4-cyclohexadiene and oxalyl chloride was photolyzed at 193 nm. The observed excitation spectrum was assigned to the A (2)A(2)<--X (2)B(1) transition of the cyclohexadienyl radical c-C6H7, produced by abstraction of a hydrogen atom from 1,4-cyclohexadiene by Cl atoms. The origin of the A<--X transition of c-C(6)H(7) was at 18 207 cm(-1). From measurements of the dispersed fluorescence spectra and ab initio calculations, the frequencies of several vibrational modes in both the ground and excited states of c-C(6)H(7) were determined: nu(5)(C-H in-plane bend)=1571, nu(8)(C-H in-plane bend)=1174, nu(10)(C-C-C in-plane bend)=981, nu(12)(C-C-C in-plane bend)=559, nu(16)(C-C-C out-of-plane bend)=375, and nu(33)(C-C-C in-plane bend)=600 cm(-1) for the ground state and nu(8)=1118, nu(10)=967, nu(12)=502, nu(16)=172, and nu(33)=536 cm(-1) for the excited states.     

A fully automated nanoelectrospray tandem mass spectrometric method for analysis of Caco-2 samples

Caco-2 cells offer a means to rapidly screen permeability of drug candidates, allowing pharmaceutical companies to eliminate candidates unable to cross the intestinal barrier early in the discovery process. This screening process is typically performed by conventional liquid chromatography/tandem mass spectrometry (LC/MS/MS), which can require time-consuming method development. An alternative to LC/MS/MS, automated nanoelectrospray tandem mass spectrometry (nanoESI-MS/MS), is introduced. This novel approach requires an off-line ZipTip desalting step followed by automated nanoESI-MS/MS, using the NanoMate 100 and ESI Chip. In addition to reduced method development time, automated nanoESI-MS/MS also offers no carry-over between samples, low sample consumption, and ease-of-use as compared with conventional pulled-capillary nanoelectrospray. Furthermore, the infusion system described has the potential to be high-throughput. A comparison of Caco-2 samples analyzed both by LC/MS/MS and by automated nanoESI-MS/MS is presented. The permeability and recovery data of the two compounds analyzed in this study obtained from conventional LC/MS/MS and by automated nanoESI-MS/MS were in excellent agreement.     

STRUCTURE CHARACTERIZATION AND CATALYTICACTIVITY TEST OF Ni(II) COMPLEXES CONTAINING2-(DIPHENYLPHOSPHINOAMINO) PYRIDINE(PAP)

IntroductionIn1962,N.V.Kutepow'SgroupfirstusedcomplexesofFe,CoandNiascatalyststocatalyzecarboXylationofethanoltopreparepropanoicacidanditsderivants.Thereactionpressurewashighandtheyieldwaslow.LateronPaulalsandhiscolleagueusedabC13andiodineascatalyst,which…     

模拟混凝土孔溶液中钢筋钝化膜生长动力学及孔蚀过程的研究

用恒电位电流衰减法及激光扫描光电化学显微技术研究了在于ＰＨ＝１２．５及１３．８的模拟混凝土孔溶液中钢筋钝化化膜的生长动力学及相应的破坏过程，实验结果表明，钢筋钝化膜的生长过程存在两个主要阶段，各阶段膜厚均与生长时间存在正比对数关系，但当ｔ＜３０秒和ｔ＞３０秒时，膜的生长表出出不同的动力学特征，在钝化发生点蚀前，钝化膜的微区光电流一定的预兆，腐蚀抑制剂ＮａＮＯ２影响膜的生长过程及膜厚，能提高钢筋的抗     

Oxidation of methionine residues in aqueous solutions: free methionine and methionine in granulocyte colony-stimulating factor

The free energy barriers and a mechanism of the oxidation of the amino acid methionine in water and in granulocyte colony-stimulating factor (G-CSF) are analyzed via combined quantum mechanical and molecular mechanical (QM/MM) methods, constrained molecular dynamics, and committor probability calculations. The computed free energy barrier of free methionine amino acid is very close to the measured value (14.7 +/- 1.2 versus 15.5 +/- 0.02 kcal/mol). The reaction coordinate was found to be the difference between the O-O bond of H2O2 and the S-O bond, where the S is the sulfur atom of the methionine residue. It was confirmed by computing the committor probability distribution and the distribution of constrained forces that this coordinate is not coupled to the activation of other degrees of freedom. The computed free energies of the oxidation of methionine residues in G-CSF indicate that the protein environment has insignificant effects on the reaction barriers of oxidation. This result further validates our proposal that the access of solvent to methionine sites, as measured by the two-shell water coordination number, governs the kinetics of the oxidation reaction of methionine groups in a protein molecule. We also found that the number of hydrogen bonds between the distal oxygen of H2O2 and the water molecules near the methionine increases along the reaction coordinate as oxidation progresses, indicating that the charge separation developed during the oxidation by H2O2 is stabilized by specific interactions with water molecules, such as hydrogen bonding.