Synthesis of Tetra—Schiff Base Macrocyclic Compound Containing Benzo—12—crown—4

Tetra-Schiff base macrocyclic compound containing benzo-12-crown-4 was synthesized via condensation of 2,6-diformyl-4-methyl-phenol with 4′，5′-diaminobenzo-12-C-4 promoted by proton. The compound was characterized by MS,IR ^1HNMR spectroscopy and elemental analysis.     

An all-atom simulation study on intermolecular interaction of DMSO–water system

An all-atom dimethyl sulfoxide (DMSO) model and a TIP5P water model have been adopted for molecular dynamics simulation. Two new qualities η_rel^E and η_rel are introduced to describe the anomalous nonideal behaviors of DMSO–water mixtures. The simulation is compared with chemical shift and excess enthalpy of mixing, which shows good concentration dependences. In addition, our all-atom simulation also indicates that the C–H groups of DMSO may interact with the oxygen atoms of water and DMSO. The weak C–HO contacts and the strong O–HO hydrogen bonds represent the consistent concentration dependences, which exhibits the cooperation effect.     

苯并[b]萘并[2'''',3'''':5,6][1,4]二噻英并[2,3-i]噻蒽-5,7,9,14,16,18-六酮的合成及其三阶非线性光学性能

以1,4-萘醌为原料,合成了含硫的醌构稠杂环化合物苯并[b]萘并[2',3':5,6][1,4]二噻英并[2,3-i]噻蒽-5,7,9,14,16,18-六酮(4),其结构经1H NMR和IR确证.采用波长为800 nm,脉宽为80 fs的Ti:Sapphire飞秒激光,运用双光束简并四波混频法测定了4的三阶非线性光学性能,结果表明,4的三阶非线性光学极化率χ(3),非线性折射率n2,分子二阶超极化率γ和响应时间分别为2.89×10-13 esu, 5.31×10-12 esu, 3.14×10-31 esu和101 fs.并分析了4的分子结构对其三阶非线性光学性能的影响.     

电热蒸发进样—等离子体原子发射光谱中钒和钛的蒸发机理研究

自1974年Nixon报道钽丝电热蒸发作为ICP-AES进样技术以来,这一技术已引起了人们的极大兴趣,受到越来越广泛的重视。电热蒸发(ETV)-ICP-AES是一种将蒸发和激发分步进行的联用技术。石墨是目前普遍使用的蒸发器材料。然而,在高温下某些元素和石墨材料可以发生碳化反应,形成热稳定的碳化物,使分析物蒸发不完全或根本不蒸发,从而影响分析结果的灵敏度和准确性。为了解决这一问题,我们曾提出了以聚四氟乙烯(PTFE)悬浮体为氟化剂,氟化辅助ETV-ICP-AES直接测定粉煤标样中钒和钛的新方法,其检出限     

Amphiphilic miktoarm star copolymers can self-assemble into micelle-like aggregates in nonselective solvents: a case study of polyoxometalate based miktoarm stars

It is well-known that amphiphilic star-shaped copolymers can self-assemble in selective solvents to form complicated micellar constructs as a synergistic result of both the topological constraints and relative volume fractions of the arms. Although the association phenomena of amphiphilic stars have been observed in nonselective solvents, both the structural detail and formation mechanism of these associates are not clear yet. Moreover, these experimental observations are controversial with respect to molecularly dispersed starlike copolymers in nonselective solvents as is popularly believed. To clarify these issues, we have synthesized a series of polyoxometalate-based polystyrene-poly(ethylene glycol)(PS-PEG) miktoarm star supramolecular copolymers(SEW-1–5) by coupling a Keggin-type polyoxometalate of K_4[α-SiW_(12)O_(40)] with 1,2,3-triazolium bridged block copolymers of-PS_n-b~+-PEG_mI~-(n=17, 26, 39, 57, 81; m=45) through ionic exchange reactions, respectively. TEM imaging,contact angle and ~1H NMR studies reveal that SEW-2–5 self-assemble in chloroform, THF, and toluene to create micellelike aggregates ranging from cylinder to sphere with a PS corona and a PEG core, while for SEW-1, reverse bilayers are captured with a PEG corona and a PS core. Among these aggregates, the Keggin clusters of [α-SiW_(12)O_(40)]~(4-) localize at the core-corona interfaces between PS and PEG. In terms of solvent quality, chloroform, THF, and toluene are only slightly poorer for PEG than that for PS with a relative order of chloroformTHFtoluene. These unexpected aggregates originate from the topological constraints of the chemically different arms of PS and PEG in the miktoarm stars, where the weak incompatibility between the PS and PEG arms is intensified appropriately. The presence of the reverse bilayered structures of SEW-1 is due to the magnified steric hindrance of the PEG45 arm with decreasing the molecular weight of the PS17 arm. However, to the best of our knowledge,these are the first examples clearly indicating that miktoarm star copolymers can self-assemble in common good solvents or slightly selective solvents to generate micellelike aggregates. This scenario is not only in sharp contrast to the intuitively considered behavior of unimolecular miktoarm stars in nonselective solvents, but also rather different from the conventional selfassembly behavior of amphiphilic star copolymers in selective solvents.     

Structural Characterization of Anhydroicaritin Glycosides Using ESI—FT—ICR Mass Spectrometry

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was used to determine the structures of anhydroicaritin glycosides by the MS/MS experiments of anhydroicaritin glycosides and their methylated derivatives,With high accuracy FT-ICR-MS provides much information about the structures of compounds ,FT-ICR-MS shows the great potential application in the structural characterization of unknown compounds.     

银微电极微分电位溶出分析法研究

本文首次报道了银微电极微分电位溶出分析法。用化学刻蚀法方便地制作了银微电极，用于ＤＰＳＡ具有背景值低，分辨率好、精密度及灵敏度高，在不搅拌，仅需一定酸度而酸度而无其它介质的条件下就能测试等优点，对人工试样及自来水样分析，结果令人满意。     

毛细管电泳在拮抗药物对氨基苯甲酸、对羟基苯甲酸和磺胺分析测定中的应用

本文报道了一种用毛细管区带电泳法(CZE)分离与测定对氨基苯甲酸、对羟基苯甲酸及磺胺类药物的新方法.电泳条件为:用 20mmol/L硼砂-20mmol/L H_3PO_4-20 mmol/Lβ-环糊精-4％乙醇(pH 7.0)作电泳液,L-抗坏血酸为内标,280nm为检测波长,样品由电进样方式(10kV/10s)引入毛细管(51.2 cm×50μm i.d.,有效分离长度为 38.5 cm).在24.5°C下,6 min内三者可达基线分离(电泳电压 25kV),且在一定范围内可进行定量分析,保留时间(Tr)及A_(样品)/A_(内标)的RSD值分别小于1.0％和5.0％.本法的建立为研究这三者共存于高等动物及微生物体内时的生理作用提供了一种可共选择的新方法.     

双核金属酞菁类化合物催化脱硫机理研究Ⅳ──中心金属离子对MPc－PcM催化活性的影响

实验研究结果表明双核金属酞菁类化合物ＭＰｃ－ＰｃＭ（Ｍ＝Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ）是催化Ｈ＿２Ｓ液相氧化反应的良好催化剂，且其催化活性顺序为Ｃｏ＞Ｎｉ＞Ｖ＞Ｆｅ＞Ｃｕ＞Ｃｒ＞Ｍｎ．采用量子化学理论计算方法（ＩＮＤＯ／Ｓ）分析了其前线分子轨道的构成特征，结果表明这几种ＭＰｃ－ＰｃＭ的ＬＵＭＯ轨道皆为有金属离子参与形成的π轨道，但ＨＯＭＯ轨道间的差异却很大．Ｍ＝Ｃｏ、Ｎｉ、Ｃｕ、Ｃｒ时，其ＨＯＭＯ为π轨道；而Ｍ＝Ｆｅ、Ｍｎ时，其ＨＯＭＯ却为σ轨道．正是在前线分子轨道的轨道类型、共轭程度及金属轨道贡献三方面因素的协同作用下，才导致ＭＰｃ－ＰｃＭ的催化活性顺序并非按中心金属离子价电子层ｄ电子数的递变而呈现出规律性的变化．