Synthesis,characterization, DNA binding,cytotoxicity and molecular docking properties of three novel butterfly-like complexes with nitrogen-containing heterocyclic ligands

Three novel complexes, namely [Nd·L₁·HCOO·(H₂O)₄] ( 1 ), [Pr·L₁·HCOO·(H₂O)₄] ( 2 ) and [In·L₂·Cl·(H₂O)₂] ( 3 ) (L₁ = 1,1-bis(5-(pyrazin-2-yl)-1,2,4-triazol-3-yl)methane, L₂ = 1,1-bis(5-(pyrazin-2-yl)-1,2,4-triazol-3-yl)ketone), were synthesized and characterized. The molecular structures of 1 – 3 were confirmed using single-crystal X-ray diffraction. All three obtained complexes are zero-dimensional and connected to each other by hydrogen bonds. In 1 and 2 the metal is surrounded by nine donors and 3 has seven coordination sites. The interaction of 1 – 3 with calf thymus DNA (CT-DNA) was explored using UV absorption spectra and fluorescence spectra. The intrinsic binding constants of 1 – 3 with CT-DNA are about 1.9 × 10⁴, 1.4 × 10⁴ and 1.1 × 10⁴, respectively. Stern–Volmer quenching plots of 1 – 3 have slopes of 0.1508, 0.134 and 0.1205, respectively. The ability of these complexes to cleave pBR322 plasmid DNA was demonstrated using gel electrophoresis assay. Apoptosis studies of the three novel complexes showed a significant inhibitory effect on HeLa cells. Furthermore, MTT assays were used to evaluate the anticancer activity of the three complexes. The cytotoxicity study indicated that complex 1 possesses a higher inhibitory rate of HeLa cells than the other complexes. Especially, the efficacy of 1 was shown to be the highest for cisplatin at 24 h. A further molecular docking technique was introduced to understand the binding of the complexes toward the target DNA.     

臭氧氧化法合成全羟基葫芦[6]脲

葫芦脲(CB[n])的直接衍生化一直是一项难题。本文用臭氧氧化法将CB[6]衍生化,合成全羟基葫芦[6]脲((OH)12CB[6])。CB[6]与O3在20℃下反应 22h,生成(OH)12CB[6]的产率为44%,并探究了丙酮扩散法、柱层析法和DMSO提纯法三种去除无机盐的方法的可行性。臭氧由电解水制得,成本低,没有二次污染,且臭氧氧化能力强,在室温下即可氧化葫芦脲。本文为合成全羟基葫芦脲提供了新的方法。     

Development of a Chromatographic Fingerprint of Tobacco Flavor by Use of GC and GC-MS

A new chromatographic fingerprinting method has been established for quality control of tobacco flavor. Three different extraction techniques, simultaneous distillation extraction (SDE), liquid–liquid extraction, and solid-phase microextraction were evaluated for isolation of the components of interest. After comparison of their performance, a combination of SDE and GC-MS was used for simple, reliable, and reproducible development of a chromatographic fingerprint of tobacco flavor. Twelve samples of the flavor from different batches were used to establish the fingerprint. Thirty-nine volatile components of the tobacco flavor samples, accounting for 86.54% of the total content, were identified and quantified. The 12 samples had 28 peaks in common. The method of fingerprint analysis was then validated on the basis of the relative retention times and relative peak areas of the common peaks, sample stability, and similarity analysis. The similarities of the 12 samples of tobacco flavor were >0.80, showing that samples from different batches were, to some extent, consistent. The chromatographic fingerprint developed was successfully used to differentiate tobacco flavor samples from tobacco extract prepared from tobacco leaf, both by similarity comparison and by principal-components projection analysis. The method can be used for quality control of tobacco flavor.     

乙炔氢氯化反应中的负载金-离子液体催化剂:离子态金物种的稳定机制

聚氯乙烯(PVC)作为世界通用工程塑料之一,具有优异的物理、化学和机械性能,在工业、农业、建筑、包装、电力等行业中应用广泛.氯乙烯是生产聚氯乙烯的重要单体.氯乙烯的生产主要有电石法和乙烯法两种工艺路线,由于我国“贫油、富煤、少气”的资源现状,电石法产能占全部产能的83%以上.电石法生产氯乙烯的原理是在氯化汞催化剂存在下,将电石水解精制后的乙炔气与氯化氢加成直接合成氯乙烯.随着节能减排及环保要求的逐渐提高和国际涉汞公约的实施,开发新一代绿色无汞催化剂具有重要的战略意义.近年来,金基催化剂是无汞催化剂基础研究和技术开发中最重要的方向.在之前的工作中,我们课题组首先报道了负载离子液体-金催化剂体系(Au-SILP)在电石法生产氯乙烯工艺中的应用,并发现离子液体的存在可以显著提高金活性物种在载体表面的分散度和稳定其化学价态.在后续研究中,我们在负载离子液体-金催化体系中引入金属铜离子(Cu^2+),利用反应过程中Au-Cu之间的氧化还原循环,设计并制备了金属铜基配位离子液体,构建了负载离子液体-金-铜催化剂体系.铜离子的引入形成了一个催化剂自身维持氧化态的微环境,实现了被还原金物种的原位氧化再生.本文在上述研究基础上,利用配位离子液体[Bmim][N(CN)2]中[N(CN)2^–]阴离子和阳离子金之间的强配位作用,构建出比Au-Cl键更稳定的Au–N键,并通过X射线光电子能谱(XPS)、球差校正-扫描透射电镜(AC-STEM)和扩展X射线吸收精细结构(EXAFS)表征证明了Au以单原子状态存在于载体表面.制备的Au-N(CN)2/AC催化剂在乙炔氢氯化反应中表现出比Au-Cl/AC和Au/AC催化剂更高的稳定性和催化活性以及更短的诱导期.进一步表征分析发现,[N(CN)2^–]配体促进了阳离子金和配体之间的电子转移,提高了阳离子金的电子云密度,削弱了乙炔在阳离子金上的吸附强度,抑制了其还原,提高了催化剂的稳定性.更重要的是,与阳离子金配位的[N(CN)2^–]配体使得反应过程中的氯化氢在氮位点发生化学解离,促进了氯化氢活化,同时降低了反应能垒.对负载配位离子液体-金催化体系反应诱导期的分析结果表明,反应诱导期与反应物(乙炔、氯化氢)分子在离子液体层中的溶解度无关,而主要取决于催化剂中Au(Ⅲ)物种的含量和反应物分子在离子液体中的扩散速率.上述研究结果进一步深化了离子液体和活性金物种之间电子的作用机理,建立了负载离子液体-金催化剂体系对反应物的活化机制和反应机理,为进一步开发具有工业应用价值的乙炔氢氯化反应无汞催化剂提供了科学基础和参考.     

Indole-Based Tubulin Inhibitors: Binding Modes and SARs Investigations

Tubulin inhibitors can interfere with normal cell mitosis and inhibit cell proliferation through interfering with the normal structure and function of microtubules, forming spindle filaments. Indole, as a privileged pharmacological skeleton, has been widely used in anti-cancer inhibitors. A variety of alkaloids containing an indole core obtained from natural sources have been proven to inhibit tubulin polymerization, and an ever-increasing number of synthetic indole-based tubulin inhibitors have been reported. Among these, several kinds of indole-based derivatives, such as TMP analogues, aroylindoles, arylthioindoles, fused indole, carbazoles, azacarbolines, alkaloid nortopsentin analogues and bis-indole derivatives, have shown good inhibition activities towards tubulin polymerization. The binding modes and SARs investigations of synthetic indole derivatives, along with a brief mechanism on their anti-tubulin activity, are presented in this review.     

Nickel-thiolate complex catalyst assembled in one step in water for solar H2 production

We report the use of a simple complex assembled from Ni(II) salt and 2-mecaptoethanol in one step in water as the efficient catalyst in a molecular hydrogen system which can be sensitized by a low-cost xanthene dye, Erythrosin B. An excellent quantum efficiency of 24.5% is attained at 460 nm. This simple system is expected to contribute toward the development of economical and environmentally benign solar hydrogen production systems.     

Selective diethylzinc reduction of imines in the presence of ketones catalyzed by Ni(acac)2

A selective reduction method of an electronically deficient imine in the presence of ketone was developed by employing Et(2)Zn and 5 mol % of Ni(acac)(2). The method was applied in the reduction of S(S)-tert-butanesulfinyl ketimines 1 to afford amines 2 in 23-92% yields and 73:27 to 98:2 diastereoselectivities. A plausible mechanism was proposed on the basis of an NMR study.     

Syntheses of novel chiral sulfinamido ligands and their applications in diethylzinc additions to aldehydes

A novel class of sulfinamido alcohol ligands 1-6 was synthesized from (S)-tert-butanesulfinamide. These ligands showed excellent catalytic activities and enantiomeric selectivities in asymmetric additions of diethylzinc to aromatic aldehydes.     

丁二烯与丙烯腈共低聚反应中共聚物组成的控制

在二元共聚反应中,为了制备具有均匀组成的共聚物,对于分批聚合,在反应过程中须补加消耗较快的单体以保持单体的浓度比为常数。本工作提出了为控制共聚物组成在反应过程中补加单体的计算方法,它不仅适用于丁二烯与丙烯腈的共低聚反应,也适合于其它二元共聚反应。用这种方法制备了具有均匀组成的丁二烯与丙烯腈共低聚物。     

Diffusion bound and reducibility for discrete Schr?dinger equations with tangent potential

In this paper, we consider the lattice Schr?dinger equations $$i\dot q_n (t) = \tan \pi (n\alpha + x)q_n (t) + \varepsilon \left( {q_{n + 1} (t) + q_{n - 1} (t)} \right) + \delta v_n (t)\left| {q_n (t)} \right|^{2\tau - 2} q_n (t),$$ with ?? satisfying a certain Diophantine condition, x ?? ?/?, and ?? = 1 or 2, where v _n (t) is a spatial localized real bounded potential satisfying |v _n (t)| ? Ce^???|n|. We prove that the growth of H ¹ norm of the solution {q _n (t)}_n??? is at most logarithmic if the initial data {q _n (0)} _n??? ?? H ¹ for ? sufficiently small and a.e. x fixed. Furthermore, suppose that the linear equation has a time quasi-periodic potential, i.e., $$i\dot q_n (t) = \tan \pi (n\alpha + x)q_n (t) + \varepsilon \left( {q_{n + 1} (t) + q_{n - 1} (t)} \right) + \delta v_n \left( {\theta ^0 + t\omega } \right)q_n \left( t \right).$$ Then the linear equation can be reduced to an autonomous equation for a.e. x and most values of the frequency vectors ?? if ? and ?? are sufficiently small.