CuCl_2对聚乙二醇(PEG)构象和结晶行为的影响

用傅里叶变换红外光谱法(FT-IR)、差示扫描量热法(DSC)、广角X射线衍射法(WAXD)研究了少量过渡金属盐氯化铜(CuCl_2)对聚乙二醇(PEG)构象和结晶行为的影响.Cu~(2+)与PEG分子链中的氧原子有配位键生成,通过溶液电导率的测定,发现一个Cu~(2+)大约与3个PEG链节单元形成配位结构,从而使PEG的构象和结晶行为发生变化,随着体系中CuCl_2含量的增加,PEG分子链中OC-CO旁式构象相对反式构象含量逐渐增加,在CuCl_2含量(w)为7%左右时达到极大值,在CuCl_2含量(w)为9%时,反而是反式构象相对旁式构象含量多些.混合物中PEG的结晶度随着体系中CuCl_2含量的增加逐渐降低,含量(w)为9%时,又有所提高.     

变温红外法研究聚对苯二甲酸乙二酯分子链的松弛运动及其构象转变

在30～170 ℃范围内逐渐升温过程中,用红外光谱仪原位检测无定形聚对苯二甲酸乙二酯（PET）薄膜红外光谱图的变化情况。通过特征谱带吸光度与温度的变化特点,研究了PET分子链在热变化过程中的松弛运动及冷结晶过程中分子链的构象变化。实验结果表明在冷结晶过程中,随PET结晶的不断完善,对应左右式(gauche)构象的吸收峰减弱,对应反式(trans)构象的吸收峰增强,并计算出CH2面外摇摆振动结晶前和结晶后反式构象和左右式构象的相对百分含量随温度的变化关系,以及玻璃化转变和冷结晶的温区范围。     

月桂胺盐酸晶体相变的红外光谱研究

在290-365K的温度区间内考察了月桂胺盐酸盐晶体红外光谱随温度的变化规律。结果表明:月桂胺盐酸盐在339K发生了固-固结构相变, 该相变的预相变起始点为327K。在327K以下的低温相中, 晶体中分子的碳氢链以高度有序的全反式构象存在, 极性头部的三个N-H-Cl氢键是不等价的。在327-339K的中间过渡相, 碳氢链中出现了旁式构象, 分子链间相互作用减弱。不等价的N-H-Cl氢键的差异减小。在339K以上的高温相中, 分子旁式链构象的增多导致了分子链横向堆积无序性的明显增加, 三个N-H-Cl氢键已变得等价。     

月桂胺盐酸晶体相变的红外光谱研究

在290-365K的温度区间内考察了月桂胺盐酸盐晶体红外光谱随温度的变化规律。结果表明:月桂胺盐酸盐在339K发生了固-固结构相变, 该相变的预相变起始点为327K。在327K以下的低温相中, 晶体中分子的碳氢链以高度有序的全反式构象存在, 极性头部的三个N-H-Cl氢键是不等价的。在327-339K的中间过渡相, 碳氢链中出现了旁式构象, 分子链间相互作用减弱。不等价的N-H-Cl氢键的差异减小。在339K以上的高温相中, 分子旁式链构象的增多导致了分子链横向堆积无序性的明显增加, 三个N-H-Cl氢键已变得等价。     

气相白炭黑/低分子量聚乙二醇悬浮体系的分子弛豫与流变行为

采用亲水气相二氧化硅(FS)、非缠结聚乙二醇(PEG,重均分子量400)制备悬浮体系,考察FS体积分数(φ)对PEG本体相α-松弛、结晶行为及悬浮体系流变行为的影响.结果表明,FS可延缓PEG本体相α-松弛,提高玻璃化转变温度,并显著增加浮体系黏度,降低本体PEG相结晶与熔融焓.低填充时,FS起成核作用;高填充时,FS延迟PEG分子扩散,并降低结晶温度.FS对PEG结晶的不同作用发生在悬浮体系溶胶-凝胶转变附近,此时悬浮液非线性动态流变行为呈现显著的硬化软化特性,线性动态流变行为呈现最为显著的频率依赖性.通过建立线性动态流变行为叠加曲线,揭示了FS对PEG分子链扩散行为的显著推迟作用.     

硬弹性聚丙烯晶相和非晶相分子链取向的研究

本文用力学-振动光谱研究了硬弹性聚丙烯(HEPP)晶区和非晶区分子链在拉伸时取向的变化.我们发现在红外光谱中,1130—1190cm~(-1)波数范围内存在着三个峰,其中1167cm~(-1)处的峰是与结晶相长螺旋分子链相关的构象谱带,其谱带的强弱变化是与998cm~(-1)结晶谱带在拉伸时的变化趋势一致的.1159cm~(-1)谱带能够被归属于无定形谱带.而1152cm~(-1)处的峰也许是与短螺旋分子链构象谱带相关的.我们用计算机的二次微分、解卷积以及分峰程序测定了拉伸时HEPP晶区和非晶区分子链的取向函数,结果发现HEPP无定形分子链取向随拉伸比增加而增加,而晶区分子链的取向随拉伸比的增加先下降,直至拉伸比为1.5(第二次屈服点)后才逐渐增加.     

共聚酯PEIT-PEG结晶性能的研究

通过偏光显微镜、广角X衍射与FTIR三种测试手段对共聚酯PEIT-PEG的结晶性能进行了系统的研究，重点分析了间苯二甲酸(IPA)、聚乙二醇(PEG)分子量和含量对共聚酯结晶性的影响。研究表明，PEIT与PEG之间发生了共聚反应，IPA的引入使PET结晶性能下降，晶粒尺寸减少，结晶度降低。引入PEG后，当PEG分子量和含量较低时，共聚酯结晶性能提高；当PEG含量较高时，在PEG分子量不变的情况下，随着PEG含量的增加，结晶性能下降；若PEG重量含量相同，PEG分子量越高，结晶性能越好。     

聚对苯二甲酸乙二酯非晶区反式构象结构的探讨

<正> 聚对苯二甲酸乙二酯(PET)的重复单元中有乙撑基。它的碳碳键内旋转产生反式构象(T)和左右式构象(G)。用其不同的构象来表征PET的聚集态结构,对研究结构与性能的关系是十分重要的。许多工作都已指出,乙撑基反式构象的谱带热处理时随结晶度的增加而增加。X-射线衍射的结果证实     

用傅里叶变换红外光谱法研究聚对苯二甲酸乙二酯的结构

用傅里叶变换红外光谱法,将一系列不同温度下退火的PET光谱与熔融淬火的PET光谱进行数字吸光度相减,得到不同结晶状态的“反式构象光谱”。进一步将不同温度退火的“反式构象光谱”(240℃和120℃)彼此相减,可得到“纯晶区的光谱”和“非晶区的反式构象光谱”。通过差示光谱的比较,发现一些新的谱带和谱带的变化。可用PET 的晶区和非晶区中其分子链的内旋转构象的变化解释。     

变温傅里叶红外光谱技术研究硬脂酸C-H伸缩振动

采用傅里叶红外光谱技术研究了温度对于硬脂酸C-H伸缩振动、分子脂肪链构象改变和分子间作用力的影响。运用变温红外技术在293~393K范围内,分别测定了硬脂酸C-H的一维红外光谱、二阶导数红外光谱、四阶导数红外光谱和去卷积红外光谱。结果表明:1在293~333K范围内,一维红外光谱中2 965,2 870cm-1附近的弱吸收谱带分别归属于甲基的不对称伸缩振动模式νas(-CH3)和对称伸缩振动模式νs(-CH3),相应的导数光谱及去卷积红外光谱能提高一维红外谱的分辨率;2在293~333K范围内,硬脂酸脂肪链处于全反式构象,在348~353K范围内,硬脂酸分子脂肪链构象由全反式构象向无序构象转变;3随着测量温度的升高,硬脂酸分子间的作用力不断降低。     

浓度及冷冻鄄解冻处理对CuCl2水溶液中Cu2+区域结构的影响

应用扩展X射线吸收精细结构(EXAFS)光谱研究了CuCl2水溶液中Cu2+的区域环境结构, 通过测定CuCl2水溶液在不同浓度条件下及冷冻-解冻(FT)处理前后Cu K边EXAFS 吸收谱, 研究了浓度及冷冻-解冻处理对Cu2+第一配位层结构的影响. EXAFS实验结果表明, CuCl2水溶液中Cu2+第一配位层距离中心原子Cu最近邻原子为O原子, 配位数介于3.0-4.3之间, Cu—O键长在0.192-0.198 nm 之间, 这种结构与Cu2+的Jahn-Teller效应有关. 不同浓度的CuCl2水溶液中Cu2+的区域环境结构有很大不同, 随着CuCl2水溶液浓度的升高, Cu2+第一配位层配位数减小, Cu—O键伸长. 结构参数拟合结果证实冷冻-解冻处理对Cu2+的区域环境结构有影响, CuCl2溶液经冷冻-解冻处理后, Cu2+第一配位层配位数变大, 热无序度增加.     

Controllable growth of straight nanorods and nanowires in the Langmuir films of a bolaamphiphilic par derivative.

A novel bolaamphiphilic compound, 1, 10-bis[3'-hydroxy-4'-(2'-pyridylazo)phenoloxy] decane [(PAR)2C10], was synthesized and its spreading film and in situ coordination with metal ions in the Langmuir monolayer at the air/water interface were investigated. It was found that (PAR)2C10 could be spread on the water surface, and the Langmuir film showed a phase transition from a flat conformation to a U-shaped conformation upon compression. Interfacial coordination between (PAR)2C10 and metal ions could occur in situ in the Langmuir monolayer. Depending on the concentration of the subphase, different coordination modes were observed. A 2:1 (ligand-PAR-to-metal-ion) complex was formed at a lower concentration of the subphase, while a 1:1 complex was obtained on the subphase with a higher concentration of the salt. Interestingly, very straight nanowires, extending to several micrometers, were observed in the AFM images of the films transferred from the subphase containing CuCl2 in higher concentrations. However, tortuous nanowires were observed under the subphase containing Cu(CH3COO)2. The formation of such kind of wire-like structures was only observed for the combination of the bolaamphiphilic PAR derivative with the Cu(II) ions. Other metal ions or the single-chain PAR derivative did not show this behavior. A possible growth mechanism of the nanowires was proposed based on the coordination of the bolaamphiphilic (PAR)2C10 with the Cu(II) ions as well as with the counteranions.     

Electrodeposition of copper on a Pt(111) electrode in sulfuric acid containing poly(ethylene glycol) and chloride ions as probed by in situ STM

This study employed real-time in situ STM imaging to examine the adsorption of PEG molecules on Pt(111) modified by a monolayer of copper adatoms and the subsequent bulk Cu deposition in 1 M H(2)SO(4) + 1 mM CuSO(4)+ 1 mM KCl + 88 μM PEG. At the end of Cu underpotential deposition (~0.35 V vs Ag/AgCl), a highly ordered Pt(111)-(√3 × √7)-Cu + HSO(4)(-) structure was observed in 1 M H(2)SO(4) + 1 mM CuSO(4). This adlattice restructured upon the introduction of poly(ethylene glycol) (PEG, molecular weight 200) and chloride anions. At the onset potential for bulk Cu deposition (~0 V), a Pt(111)-(√3 × √3)R30°-Cu + Cl(-) structure was imaged with a tunneling current of 0.5 nA and a bias voltage of 100 mV. Lowering the tunneling current to 0.2 nA yielded a (4 × 4) structure, presumably because of adsorbed PEG200 molecules. The subsequent nucleation and deposition processes of Cu in solution containing PEG and Cl(-) were examined, revealing the nucleation of 2- to 3-nm-wide CuCl clusters on an atomically smooth Pt(111) surface at overpotentials of less than 50 mV. With larger overpotential (η > 150 mV), Cu deposition seemed to bypass the production of CuCl species, leading to layered Cu deposition, starting preferentially at step defects, followed by lateral growth to cover the entire Pt electrode surface. These processes were observed with both PEG200 and 4000, although the former tended to produce more CuCl nanoclusters. Raising [H(2)SO(4)] to 1 M substantiates the suppressing effect of PEG on Cu deposition. This STM study provided atomic- or molecular-level insight into the effect of PEG additives on the deposition of Cu.     

褐藻酸铜配合物膜催化VAc自由基聚合

以褐藻酸钠膜浸渍在15%CuCl2*2H2O水溶液中48 h的方法,于室温制备了疏水性的褐藻酸铜(Ⅱ)配位聚合物膜,并通过ESR、 UV-Vis、 IR、 XPS和电导率等手段,研究此配位催化剂褐藻酸铜(Ⅱ)配位聚合物膜表面的组成、配位结构和性质,得知1个Cu2+ 是以dsp2杂化空轨道与褐藻酸2个链节单元的2个羧羟基氧及其2个脱质子带负电荷氧的孤对电子发生配位作用,形成低自旋构型的褐藻酸铜(Ⅱ)配位聚合物,中心Cu2+ 的配位数为4,这对于低分子配合物而言,其空间构型一般是正方形,但在褐藻酸铜(Ⅱ)配位聚合物中,由于褐藻酸分子链的缠绕和卷曲,使上述的空间构型被扭曲,甚至有些配位体没有到位,导致该配位聚合物的中心Cu2+ 存在一些空位中心而具有配位催化活性,因此,HSO3-能按配位催化机理产生初级自由基氢,使醋酸乙烯酯(VAc)按自由基加聚反应历程进行聚合,这有别于CuCl2-Na2SO3-H2O氧化还原引发聚合体系。测定VAc在本体系和室温、pH=7条件下聚合的诱导期为90 s,反应时间24 h。聚醋酸乙烯酯(PVAc)得率82%, mw=1.02×106, mn=2.27×105, mw/mn=4.49。     

Influence of solvent and counter ion on copper complexes with N-alkyl-pyridine-2-carboxamides as studied by electrospray ionization mass spectrometry

The interactions of copper(II) with N-alkyl-pyridine-2-carboxamides (M) were studied by electrospray ionization mass spectrometry. The influence of solvent and counter ion (Cl-, ClO4-) on the type of ions (complexes) observed was discussed. By cone voltage increase, the fragmentation "in source" of the ions discussed was achieved. In methanol solution containing N-alkyl-pyridine-2-carboxamide (M) and CuCl2 the singly- and doubly charged-ions [M+CuCl]+ and [M2+Cu]+2 were detected. In acetonitrile solution containing N-alkyl-pyridine-2-carboxamide and CuCl2, the copper(I)-containing ions [M+CH3CN+Cu]+ were formed. The use of Cu(ClO4)2 instead of CuCl2 resulted in more abundant doubly-charged ions in both methanol and acetonitrlile solutions and, for the former solution, the ions containing methoxyl anion, namely [M+CuOCH3]+, were observed. When water was used as a solvent, the abundant ions corresponding to the protonated ligands were formed, while the ions corresponding to copper complexes were characterised by low abundances.     

用膜片钳研究CuCl2对萝卜液泡膜SV通道的影响

用膜片钳全液泡记录方式研究了CuCl2对萝卜SV通道的影响.研究表明,SV通道为阳离子选择性通道,细胞质钙可激活此通道,且其表现出钙依赖性.细胞质钙达2mmol/L时,SV通道电流基本上达到饱和.当在外液中加入不同浓度的CuCl2时,SV通道电流有明显的变化.高浓度的铜离子对通道电流有抑制作用,而低浓度(<0.1mmol/L)则增强通道电流.电极内液中的CuCl2对SV通道电流也有抑制作用.这为进一步研究铜离子对植物生理活动的影响以及铜肥对农作物的作用在通道水平上提供重要的依据.     

电化学聚合漆酚铜配合物的结构及其催化性能

 将电化学聚合法得到的聚合漆酚（EPU）与氯化铜的异丙醇溶液作用制成了电化学聚合漆酚铜配合物（EPU－Cu2＋）,并用顺磁共振波谱、红外光谱、X射线光电子能谱、动态机械热分析和原子发射光谱等手段进行了表征．结果表明,该配合物中每个铜离子与EPU分子中二个链节单元的羟基发生配位,铜含量达8．63％．实验结果还表明,该配合物在Na2SO3的水体系（pH＝7）中能催化引发MMA按自由基反应历程进行聚合．     

Asymmetric dinuclear copper(I) complexes of bis-(2-(2-pyridyl)ethyl)-2-(N-toluenesulfonylamino)ethylamine with short copper-copper distances

Addition of two equivalents of CuCl to deprotonated bis-(2-(2-pyridyl)ethyl)-2-(N-toluenesulfonylamino)ethylamine (PETAEA) and its derivatives yielded new types of dinuclear Cu(I) complexes, Cu(mu-PETAEA)CuCl, Cu(mu-PEMAEA)CuCl, and Cu(mu-PENAEA)CuCl (PEMAEA is the 4-methoxyphenyl derivative of PETAEA and PENAEA is the 4-nitrophenyl derivative), exhibiting a four coordinate N(4)Cu center, a two coordinate NCuCl center, and a metal-metal distance within the range of 2.6572(8) to 2.6903(3) A. Analysis of the covalent radii for four coordinate and two coordinate copper(I), the acute copper-nitrogen-copper angles, and density functional theory (DFT) calculations suggest a weak attraction between the two copper atoms. The complexes apparently formed in a two-step process with the formation of the tetracoordinate mononuclear complex preceding the coordination of a second equivalent of CuCl to the lone pair of the sulfonamidate ligand.     

Nucleation and crystallization of H-shaped (PS)2PEG(PS)2 block copolymers

<正>A series of H-shaped(PS)_2PEG(PS)_2 block copolymers with different PS chain lengths were prepared.The influence of different confinements active on the crystallization and self-nucleation(SN) behavior of the PEG blocks was investigated by differential scanning calorimetry(DSC).When the content of the crystalline block was high,a classical SN behavior was obtained.The block copolymer with PEG content of 49%(by weight) showed a classical SN behavior with a narrow self-nucleation domain and had bimodal crystallization exotherms.When the PEG dispersed as separated microdomains in the block copolymer,the self-nucleation domain disappeared and only annealing was observed.