Liquid chromatography of the s-triazines

Summary A series of thirty s-triazine compounds have been separated using reversed-phase high-pressure liquid chromatography. A relationship between substituent activity and retention time was developed to predict molecular structure.Work partially completed at the CIBA-GEIGY Corp., McIntosh, Ala., USA.     

Mechanistic aspects of the Wolff-Kishner reaction. V. The cation effect on the reaction of benzophenone hydrazone in butyl carbitol and decyl alcohol

The rate of the Wolff-Kishner reaction of benzophenone hydrazone in butyl carbitol increases as the cation of the alkoxide base is varied in the order K>Na>Li>Mg. The replacement of butyl carbitol by 1-decanol also accelerates the reaction, and an additional increase is caused by the presence of crown ether. On the basis of changes in the activation parameters, it is concluded that the reactivity of the hydrazone anion increases as the contact ion pair becomes more fully solvated and dissociated.     

Zweikernige silylenverbrückte Cyclopentadienylrhodiumbis(ethen)-Komplexe,photochemische Reaktion mit Benzolderivaten und selektiver Einschluß von Methylcyclopentan in das Kristallgitter von [Me2Si{3-But-C5H3Rh(C2H4)2}2]

Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me₂Si{3-Bu^t-C₅H₃Rh(C₂H₄)₂}₂] By reaction of [{(C₂H₄)₂RhCl}₂] with Na₂[Me₂Si(C₅H₄)₂] or with Li₂[Me₂Si(3-Bu^t-C₅H₃)₂] in THF the dinuclear silylene bridged complexes [Me₂Si{C₅H₄Rh(C₂H₄)₂}₂] 1 and [Me₂Si{3-Bu^t-C₅H₃Rh(C₂H₄)₂}₂] 2 , respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si? C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η³:η³ benzene complex [Me₂Si(C₅H₄Rh₂)₂C₆H₆] which cannot be separated from unreacted 1 . However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3 .     

锆(Ⅳ)同7-碘-8-羟基喹啉-5-磺酸三元混配化合物的形成及其荧光光度研究

在 EDTA 存在下,Zr(Ⅵ)与 H_2QSI 在 pH6.0时形成三元荧光配合物。其组成为Zr:H_2QSI:EDTA=1:1:1。荧光强度与锆离子在0.1～1.0μg/10ml 范围内呈现线性关系。对EDTA 的作用机理作初步探讨。     

微波辐射下一步合成3-氨基-4-氰基-1-芳基-5,6,7,8-四氢异苯并吡喃

亚环己基马来腈与芳醛在哌啶催化下,经微波辐射一步合成3-氨基-4-氰基-1-芳基-5,6,7,8-四氢异苯并吡喃,反应7～11min,产率57%～94%.     

Y2O3薄膜处理对3Cr25Ni7N合金的抗高温氧化性能的影响

采用电沉积-热解法在3Cr25Ni7N合金表面制备了Y2O3薄膜,并研究了薄膜处理对合金在1000℃空气中的抗高温氧化性能的影响。氧化动力学曲线、SEM及XRD分析结果表明,Y2O3薄膜处理使合金表面氧化膜以尖晶石结构为主,氧化膜致密,有效地抑制了Cr2O3的挥发反应,且氧化膜与基体的附着性好,因此合金在高温下的抗氧化性能得到提高,这与氧化钇薄膜在较低温度下抗高温氧化性能提高的机制是不同的。在不同温度下,Y2O3薄膜处理均可以有效提高合金的抗高温氧化性能。     

室温熔盐二(三氟甲基磺酸酰)亚胺锂-尿素体系的分子动力学模拟

应用分子动力学模拟了25 ℃和50 ℃时新型室温熔盐二(三氟甲基磺酸酰)亚胺锂[LiN(SO2CF3)2, LiTFSI]与尿素(摩尔比为1:3.6)体系的结构与动力学性质. 在两个温度下体系的微观结构基本相同, Li+的配位数约为5, 且都是与溶剂和阴离子中的氧原子发生配位. 对TFSI-的研究表明, 每个TFSI-只提供四个氧中的一个与Li+配位; 而且在Li+的配位层中, TFSI-具有顺、反和gauche 等不同的构象, 并且不同构象出现的几率会随着温度的改变而改变.     

δ-（甲酰乙烯基）二氢卟吩衍生物的合成

以脱镁叶绿酸-a甲酯为原料,利用Vilsmeier反应合成δ-(甲酰乙烯基)二氢卟吩衍生物.镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用,生成了E环被打开的镍(II)δ-(甲酰乙烯基)红紫素-7-三甲酯和镍(II)δ-(甲酰乙烯基)二氢卟吩P6三甲酯.镍(II)N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用,生成了镍(II)δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺.当这些化合物脱去镍离子后,吸收波长明显红移,δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742nm.同时保留了对δ-位再进行化学修饰的可能性.合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实.     

Binding Ensembles of p53-MDM2 Peptide Inhibitors by Combining Bayesian Inference and Atomistic Simulations

Designing peptide inhibitors of the p53-MDM2 interaction against cancer is of wide interest. Computational modeling and virtual screening are a well established step in the rational design of small molecules. But they face challenges for binding flexible peptide molecules that fold upon binding. We look at the ability of five different peptides, three of which are intrinsically disordered, to bind to MDM2 with a new Bayesian inference approach (MELD × MD). The method is able to capture the folding upon binding mechanism and differentiate binding preferences between the five peptides. Processing the ensembles with statistical mechanics tools depicts the most likely bound conformations and hints at differences in the binding mechanism. Finally, the study shows the importance of capturing two driving forces to binding in this system: the ability of peptides to adopt bound conformations (ΔGconformation) and the interaction between interface residues (ΔGinteraction).