非对称八烷氧基取代酞菁聚硅氧烷的合成及其单分子膜

非对称八烷氧基取代酞菁聚硅氧烷的合成及其单分子膜穆劲，夏强，华玉晶，周伟东，肖童（山东大学胶体与界面化学研究所，济南，２５０１００）关键词酞菁聚硅氧烷，ＬＢ膜，π－Ａ曲线酞菁化合物是具有高稳定性的大π键共轭体系。目前，酞菁ＬＢ膜研究大多采用单体小分子...     

一种新的共轭桥联双二茂铁衍生物的单层LB膜及其电催化效应

合成并表征了一种新的非两亲性共轭桥联双二茂铁衍生物，该化合物在空气／水界面上易形成较稳定的单分子膜，与花生酸形成的混合膜易组装成ＬＢ膜，紫外－可见吸收光谱表明：ＬＢ上膜分子中发生了聚集，扫描电镜观察了混合单层ＬＢ膜的表面形貌及膜的相分离。循环伏安研究表明：混合单层ＬＢ膜修饰电极对Ｆｅ（ＣＮ）／Ｆｅ（ＣＮ）离子对的电化学反应具有良好的电催化效应，对抗坏血酸电化学氧化具有明显的促进作用。     

单臂液晶冠醚LB膜的研究

首次研究了４种单液晶冠醚（１～４）的ＬＢ膜成膜特性，实验发现它们在气－液界面均可形成单分子膜，但４的稳定性较差，３易转移到玻璃基片上形成Ｙ型膜。４种化合物与硬脂酸以１：１混合形成稳定的Ｙ型ＬＢ膜。小角Ｘ射线衍射证实了膜的有序结构。用ＣＰＫ原子模型对成膜分子构型和面积进行了估算，其结果与实验一致。并讨论了分子结构对成膜性能的影响。     

含磺酸盐基两性分子／聚乙烯亚胺LB膜的聚集结构

气液界面聚离子复合结构的形成能减弱两性分手亲水基间静电排斥作用，增加单分子膜的稳定性和累积性能．Ｘ－射线衍射结果表明，纯水和聚乙烯亚胺水溶液表面上的ＺＣ１４ＳＮａ单分子膜在聚苯乙烯基片上累积成Ｙ型膜，两种ＬＢ膜的等同周期差约为０．３０ｕｍ．     

有机HTDIOO分子LB膜结构的AFM研究

利用原子力显微镜（ＡＦＭ）对有机分子ＨＴＤＩＯＯ单层和多层ＬＢ膜结构进行了观察。实验结果表明，针尖与ＬＢ膜表面分子间的相互作用力会对成像的膜结构有影响。当悬臂针尖与ＬＢ膜表面分子的相互作用力较大时，针尖会扰动ＨＴＤＩＯＯ分子在单层ＬＢ膜中的有序排列。ＨＴＤＩＯＯ单层ＬＢ膜具有有序结构；而在多层ＬＢ膜中，ＨＴＤＩＯＯ分子则聚集在一起形成了一定的畴结构。     

C60的LB膜和自组装膜

制作Ｃ６０分子在固体基片上的有序薄膜是研究它们优异物性和付诸于实际应用的必要环节和关键问题之一。ＬＢ技术能够把分子形状呈球形的疏水分子Ｃ６０在空气－水的界面铺展成稳定的漂浮膜，并能沉积成ＬＢ膜。至于用“分子绳索”把Ｃ６０固定在基片上而形成的自组装膜更具有优良的特性。本文综述和评价了纯Ｃ６０、Ｃ６０混合物和Ｃ６０衍生物ＬＢ以及Ｃ６０自组装膜的制备及其结构特征和性质；并对这方面的工作做了一定的展望。     

十八胺单分子膜的研究

通过测定在纯水和CdCl2溶液亚相上十八胺单分子膜的平衡、循环π～A等温线及其动态弹性,发现在亚相中加入Cd2+可以使膜的液态相凝聚性增强,固态相凝聚性减弱.液态的单分子膜在两种亚相上有较好的可回复性,而在固态膜中则不然.这可归因于在水面上十八胺分子间可形成氢键,而在CdCl2水溶液亚相上的十八胺则与Cd2+发生配位,形成了多配位络合物,两种情况下十八胺分子在高膜压区都会发生稳定的聚集.静、动态弹性的比较表明,膜障的振动不利于十八胺分子与Cd2+间的配位作用.     

掺杂态聚苯胺LB膜的制备与性质

掺杂樟脑磺酸的聚苯胺在纯水表面可以形成稳定的单分子层,采用Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ技术可以将其较好地转移到氟化 基片上制成薄膜,对其ＬＢ膜的红外和紫外－可见－近红外光谱研究表明,在膜的压缩或转移过程中有少量的樟脑磺酸分子发生脱掺杂的现象,并且该ＬＢ膜在室温下对乙醇有较好的气敏性。     

硬脂酸单分子膜上电沉积Ag膜的研究

通过电沉积方法,以气/液界面上形成的硬脂酸单分子膜为模板诱导沉积金属银膜.考察了镀液pH值、单分子膜表面压及沉积电位对银膜形貌及结构的影响.实验发现,酸性镀液的气/液界面上形成的单分子膜不能诱导沉积银,而在中性和碱性镀液的气/液界面上可以诱导银膜的生长.当单分子膜处于液态或固态时,气/液界面有银膜形成;液态单分子膜上的银膜生长速度较快,且银膜的结构一致.随着电极电位的升高,银膜沉积的速度加快,呈环状向外生长的圆形银膜逐渐变得不规则.将不同实验条件下的银膜转移出来,采用扫描电镜(SEM)、透射电镜(TEM)对银膜的结构与形貌进行了表征.研究表明,银首先在单分子膜上异相成核,由八面体构型逐渐发展成星型,最终在气/液界面形成具有松枝状微观结构的光亮银膜.     

液晶冠醚LB膜的制备及其性质研究

本文首次研究了五种新合成的液晶冠醚ＬＢ膜的成膜特性。实验发现，其中的单臂胆甾型液晶冠醚在气－液界面易形成稳定的单分子膜，但不易累积形成ＬＢ膜；芳香酯类的单臂液晶冠醚膜的稳定性与链的长短有关；而双臂芳香酯型二氮杂１８－冠－６易形成稳定的膜，且具有特殊的相变性质。膜的特性与物质的化学结构有关，借助ＣＰＫ分子模型，对成膜后分子构型进行了估算，理论计算与实验一致。对纯组分以及单臂液晶冠醚与硬脂酸的混合膜结构，用表面压－面积曲线以及小角Ｘ衍射等进行了表征，并对其中的双臂液晶冠醚作了离子识别功能研究。     

Molecular structures and stability constants of gossypol and its aza-derivative complexes with silver(I) cations studied by potentiometric, ESI MS, NMR, and AM1d semiempirical methods

Stability constants of complexes formed by gossypol and by ten of its Schiff bases with Ag (+) cations were determined by the potentiometric method. The potentiometric and ESI MS experiments indicate the formation of AgL (+) and Ag 2L (2+) complexes between the Schiff bases G1-G7 and Ag (+) cations as well as the formation of AgL (+), Ag 2L (2+), AgL 2 (+) and Ag 3L 2 (3+) complexes between the Schiff bases G8-G10 and Ag (+) cations. The highest stability constant was found for the AgL (+) complex of G8 Schiff base and the lowest one for the AgL (+) complex of G molecule. The (13)C NMR spectra of mixtures between G and AgClO 4 as well as G1-G10 and AgClO 4 indicate that the complexation of the Ag (+) cations is exclusively realized by the aldehyde-aldehyde tautomer of gossypol and by the enamine-enamine form of gossypol Schiff bases, respectively. We show that the main coordination sites for the Ag (+) metal cations are either the oxygen or the nitrogen atoms of the amine parts of the Schiff bases of gossypol. The energetically most favorable structures of the Ag (+) complexes with gossypol (G) or with the gossypol Schiff bases (G1-G10) were calculated and visualized by the AM1d method at an semiempirical level of theory.     

Complexation studies of N,N′-ethylene-bis(salicylideneimine)-cation complexation behavior in dioxane-water mixtures by conductometric studies

The tetradentate-ligand Schiff base derived from salicylaldehyde and 1,2-diaminoethane has been synthesized. The stability constants and thermodynamic values for the complexation between ZnCl₂, Cu(NO₃)₂, and AgNO₃ salts and the ligand in 80% dioxane-water were determined by conductance measurements. The order of the formation constant for complexes of the ligand with Cu(II), Zn(II), and Ag(I) ions was found to be: Ag(I) < Cu(II) < Zn(II). The magnitudes of these ion association constants are related to the nature of the solvation of the cation and the complexed cation. The text was submitted by the authors in English.     

Acceleration Effect of Fe(II), Co(II), Ni(II) and Cu(II) on the Hydrolysis Rate of Ortho- or Para-Hydroxy Schiff Bases

The kinetics of hydrolysis of ortho- or para-hydroxybenzylidene-4-benzidine Schiff bases have been examined in the pH range 1.70–11.90, in aqueous media containing 20wt% dioxane, at 20 °C. In basic media, pH > 8.47, a slight increase in the hydrolysis reaction rate of the Schiff bases is observed. In such basic media, the rate-controlling step is the attack of hydroxide ion on the ionized Schiff base. Below pH 6.82, the rate-determining step is ascribed to be the attack of water molecules on the protonated substrate. The effects of Fe(II), Co(II), Ni(II) and Cu(II) ions on the hydrolysis reaction rate of the Schiff bases have been studied and discussed on the basis of formation of a monocyclic chelate rings. The various thermodynamic parameters have also been evaluated and discussed.     

Potentiometric Studies of Copper(II) Complexes of Some Substituted Benzylidene-2-Hydroxyanilines in Dioxane–Water Media

The formation and protonation constants of 17 Schiff bases-derived 2-hydroxyaniline with some substituted benzaldehydes, and the stability constants of Cu(II) complexes of these Schiff bases, have been determined potentiometrically in 20, 40, and 60% dioxane–water media. The data from the potentiometric titrations were evaluated with the BEST computer program. For all Schiff bases studied, it was observed that the log K_OH values related to the protonation equilibria of the phenolic oxygen are increased, and the log K_NH values related to the protonation equilibria of the azomethine nitrogen are decreased, as the dioxane content is increased. The variation of these constants is discussed on the basis of specific solute–solvent interactions and structural changes of Schiff bases from water to the dioxane–water media. Also, titrimetric-pH investigation of substituted benzilidene-2-hydroxyaniline systems has revealed the formation of stable mono-Schiff base complexes with the metal ion Cu(II).     

新荧光试剂双(2-苯并噻唑重氮氨基)-3,3′,5,5′-四甲基联苯的合成及其分析应用

将3,3′,5,5′-四甲基联苯胺和苯并噻唑类试剂结合, 并引入杂环三氮烯结构, 合成了新荧光试剂双(2-苯并噻唑重氮氨基) 3,3′,5,5′-四甲基联苯(BBTDTMB), 其结构经红外光谱、 核磁共振谱和元素分析证实. 研究结果表明, 在碱性介质中, 该试剂在λex/λem=342 nm/420 nm处产生强荧光, 并且Ag(Ⅰ)对其荧光有很好的猝灭作用, 因而建立了BBTDTMB测定Ag(Ⅰ) 的新荧光分析方法. 该方法的线性范围为1.0～240 μg/L, 检测限为 0.5 μg/L, 应用于人发、 茶叶中的Ag(Ⅰ) 的测定, 结果令人满意.     

Synthesis, potentiometric and antimicrobial activity studies on DL-amino acids-Schiff bases and their complexes

A relationship between antimicrobial activities and the formation constants of amino acid-Schiff bases and their Cu(II) and Ni(II) complexes was studied. For this purpose, a series of Schiff bases were prepared from DL-amino acids (DL-glycine, DL-alanine) and halo aldehydes (5-chloro-2-hydroxybenzaldehyde, 5-bromo-2-hydroxybenzaldehyde). Schiff bases and their Cu(II) and Ni(II) complexes were characterized by the elemental analysis, spectral analysis, magnetic moment (at ca. 25°C), molar conductivity, and thermal analysis data. The complexes were found to have general compositions [ML(H₂O)]. The protonation constants of the Schiff bases and stability constants of the complexes were determined potentiometrically in a dioxane-water (1: 1) solution at 25°C and 0.1 M KCl ionic strength. Antimicrobial activities of the Schiff bases and their complexes were estimated for six bacteria, such as Bacillus cereus RSKK 863, Staphylococcus aureus ATCC 259231, Micrococcus luteus NRLL B-4375, Escherichia coli ATCC 11230, Aeromonas hydrophila 106, Pseudomonas aeroginosa ATCC 29212, and the yeast Candida albicans ATCC 10239. The role of halogen substitution on the ligands, effect of the metal ion, and stabilities of the complexes are discussed on antimicrobial activities. The text was submitted by the authors in English.     

Fabrication of chiral Langmuir-Schaefer films of achiral amphiphilic Schiff base derivatives through an interfacial organization

Supramolecular chirality in the Langmuir-Schaefer (LS) films of two achiral amphiphilic Schiff bases, 2-(2'-benzimidazolyliminomethyl)-4-octadecyloxyphenol (BSC18) and 2-(2'-benzthiazolyliminomethyl)-4-octadecyloxyphenol (TSC18), was investigated. Both of these amphiphiles could form LS films from the water surface or coordinate with Ag(I) in the subphase to form Ag(I)-coordinated LS films. Although both of these amphiphiles were achiral, TSC18 formed a chiral LS film from the water surface, while BSC18 formed a chiral Ag(I)-coordinated LS film from the aqueous AgNO3 subphase. The supramolecular chirality in these LS films was suggested to be due to a cooperative stereoregular pi-pi stacking of the functional groups together with the long alkyl chains in a helical sense. The relationship between the chirality of the LS films and the molecular structures of TSC18 and BSC18 as well as their H-bond or coordination behaviors was discussed. The Schiff base films showed a reversible color change upon exposure to HCl and NH3 gas alternatively; however, the supramolecular chirality was irreversible during these processes.     

Reactions of 2-thiazolin-2-ylthiophene with some metal ions

The condensation of $\text{o}$-aminobenzenthiol with 2-thiophenecarboxaldehyde yields 2-thiazolin-2-ylthiophene rather than the expected Schiff base. However, upon reaction with metal ions, the thiazoline rearranges to the expected thiolate Schiff base. Complexes of the Schiff base with Ni(II), Cu(II), Zn, Cd, Pb(II), Ag(I) and Pd(II) have been isolated and characterized.     

Structural investigation on phenyl‐ and pyridin‐2‐ylamino(methylene)naphthalen‐2(3H)‐one. Substituent effects on the NMR chemical shifts

Schiff bases bearing phenyl and pyridyl groups were synthesized by condensation of appropriate amines with 2‐hydroxynaphthaldehyde. These Schiff bases were obtained as colored crystalline solids. The proton NMR spectra of these compounds showed a doublet for the NH protons indicating a keto tautomer for these Schiff bases. The pyridyl‐substituted Schiff bases containing hydroxyl moiety were found to show the most downfield shift for the NH protons in DMSO solvent, and this was rationalized due to the formation of a six‐ and five‐membered ring using hydrogen bonds for these two compounds. Correspondingly, the olefinic proton of the Schiff bases is also found to be a doublet due to coupling to the amine proton. These Schiff bases exhibited thermochromic properties. Detailed NMR spectral analysis for both the phenyl‐ and pyridyl‐substituted Schiff bases is presented. Copyright © 2010 John Wiley & Sons, Ltd.     

SYNTHESIS, CHARACTERIZATION AND SELECTIVITY STUDIES OF POLY(ACRYLAMIDE) INCORPORATING SCHIFF BASES

Three novel polymers incorporating Schiff bases,derived from condensation reactions of poly(acrylamide) with 5- chloro-2-hydroxybenzaldehyde,5-bromo-2-hydroxybenzaldehyde and 5-methyl-2-hydroxybenzaldehyde,have been synthesized,and their Cu(Ⅱ) and Ni(Ⅱ) complexes have been prepared.The ~1H-NMR signals of the—CH=N—and—NH_2 groups have been utilized to determine the relative abundances of Schiff base and acrylamide groups in the polymers containing Schiff bases.Poly(acrylamide) incorporating Schiff bases a...