Solid state reactions of nitrogenous heterocyclic compounds(Ⅰ)——Solid state reactions of 3-methyl-l-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolone (MPP) with aromatic aldehydes and ke-tones benzil derivatives and imides,and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-1-phenyl-5-pyrnzolone 2 were investigated.Some new solid state reactions between the reactants were found,from which a series of new compounds were obtained The structures of the products were identified by IR,1H NMR,MS,elemental analyses and also by X-ray crystal analysis,and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed     

Structure and temperature controlled synthesis of novel thiazolidin-4-one derivatives bearing an azasugar

Novel thiazolidin-4-one linked pseudo-aza-disaccharides and thiazolidin-4-ones containing C-pseudo-aza-nucleosides were synthesized via a one-pot three component reaction. The former was synthesized stereoselectively by the tandem Staudinger/aza-Wittig/cyclization reaction of azasugar aldehyde 1, an azidosugar, and mercaptoacetic acid. The reaction was structure and temperature controlled, and could be performed stereospecifically under 40 °C. It was the first report of a stereospecific synthesis of thiazolidin-4-one linked derivatives. However, these derivatives were synthesized with low stereoselectivity by involving the condensation reaction of azasugar aldehyde 1, aniline, and mercaptoacetic acid.     

Synthesis and characterization of thermally crosslinked polyimide with second-order nonlinear optical chromophore

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Solid state reactions of nitrogenous heterocyclic compounds (II)

Solid state Michael addition reaction of indole with α, β-unsaturated carbonyl compounds was carried out, by which a series of compounds containing three different heterocyclic groups binding to one carbon atom were ob-tained. In the presence of Lewis acid, indole could undergo the solid state condensation reaction with aromatic ketones and aldehydes or quinones. The solid state reaction showed higher selectivity and yield than solution reaction. The structures of products were identified by IR,¹H NMR, MS. elemental analysis and X-ray crystal analysis. The reac-tion mechanism was also proposed. Project supported by the National Natural Science Foundation of China     

聚乙烯胺类修饰萘酰亚胺衍生物的合成、DNA键合行为和活性研究

合成了二乙烯三胺、三乙烯四胺和四乙烯五胺等低分子量聚乙烯胺类修饰的萘酰亚胺衍生物.通过UV-Vis谱、荧光光谱、圆二色谱和热变性试验研究了合成化合物与小牛胸腺DNA的键合行为,同时通过四甲基偶氮唑蓝(MTT)染色法研究了化合物对Bel-7402(人肝癌细胞)、HL-60(白血病细胞)、A549(人肺癌细胞)和Hela(人宫颈癌细胞)等细胞株的体外抗肿瘤活性,化合物NI1对A549细胞显示良好的抑制活性,优于阳性对照顺铂.     

An efficient synthesis of δ-glyconolactams by intramolecular Schmidt–Boyer reaction under microwave radiation

δ-Glyconolactams were first synthesized by the intramolecular Schmidt–Boyer reaction using corresponding δ-azidosugars as starting material. The reaction could be efficiently performed in good yields of 61–69% under microwave radiation in acid condition, providing an alternative protocol to iminosugar δ-lactam.     

Evolution of highly symmetric curves under the shrinking curvature flow

Under the shrinking curvature flow with inner normal velocity V = k^α(α > 1), it is shown that highly symmetric, locally convex initial curves evolve into a point asymptotically like an multi‐circles. The proof relies on a crucial use of Bonnensen inequality for highly symmetric, locally convex curves. Copyright © 2016 John Wiley & Sons, Ltd.     

In-vitro oxidation of bisphenol A: Is bisphenol A catechol a suitable biomarker for human exposure to bisphenol A?

The extensive use of bisphenol A (BPA) in the manufacture of consumer products results in widespread human exposure to the chemical. In the body, BPA undergoes first-pass metabolism to form BPA glucuronide, considered to be a major BPA byproduct. Concentrations of total (free plus conjugated) urinary species of BPA are used to assess human exposure to BPA. However, because BPA can be present in numerous consumer and household products, potential contamination with parent BPA during collection and handling may pose a challenge when measuring BPA in such biological samples as blood or urine. In this study we investigated the in-vitro phase I metabolism of BPA in rat and human liver microsomes by using on-line solid-phase extraction–high-performance liquid chromatography–tandem mass spectrometry to identify phase I metabolites (e.g., BPA oxidation products) that could be used as potential alternative biomarkers of BPA exposure. We unambiguously identified 5-hydroxy BPA (BPA catechol) as an in-vitro oxidative metabolite of BPA, but human microsomes oxidized only about 10% of BPA to BPA catechol. We evaluated the usefulness of BPA catechol as a potential biomarker of human exposure to BPA by measuring total concentrations of BPA catechol and BPA in 20 urine samples. We detected BPA catechol at much lower concentrations and frequency than those of BPA. Furthermore, we found that free BPA catechol was rather unstable in urine, which highlights the importance of sampling techniques to adequate interpretation of biomonitoring data. Together, these findings suggest that BPA catechol may not be a suitable biomarker of environmental exposure to BPA, but could be used to confirm BPA exposure in special populations or in situations when urine specimens were potentially contaminated with BPA.     

Solid state reactions of nitrogenous heterocyclic compounds (I) —Solid state reactions of 3-methyl-1-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolon(eM PP) with aromatic aldehydes and ketones, benzil derivatives and imides, and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-lphenyl-5-pyrazolone2 were investigated. Some new solid state reactions between the reactants were found, from which a series of new compounds were obtained. The structures of the products were identified by IR,¹H NMR, MS, elemental analyses and also by X-ray crystal analysis, and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed. Project supported by the National Natural Science Foundation of China.     

Localization of spin and charge in phenalenyl-based neutral radical conductors

We report the development of an experimentally based structural analysis to examine the degree of localization of the spin and charge in the phenalenyl-based neutral radical molecular conductors--the results motivate a reinterpretation of the electronic structure of a number of the radicals that we have reported over the past 10 years. The analysis is based on the well-known relationship between bond order and bond length and makes use of the experimental bond distance deviations between the molecular structure of the radical and its corresponding cation. We determined the single crystal X-ray structure of the ethyl radical (1) at 11 temperatures between 90 K and room temperature so that we could follow the evolution of the structure and the electron density distribution through the magnetic phase transition that occurs in the vicinity of 140 K. We show that the enhanced conductivity in the dimeric ethyl (1) and butyl (3) radicals at the magnetic phase transition results from the development of a complex, but highly delocalized electronic structure and not to the formation of a diamagnetic pi-dimer. We find that the monomeric radicals 4, 12, and 13 have an asymmetric electron density distribution in the crystal lattice whereas radical 11 is the only monomeric radical which remains fully delocalized. The pi-chain radicals (7, 8, 14, and 15) retain the strongly delocalized electronic structures expected for a resonating valence bond ground-state structure.