新型隔层材料LB交替多层膜的二次谐波研究

有机光学非线性材料在光计算和光通讯领域中有着非常广泛的应用前景［1，2］．非中心对称结构是二阶非线性光学器件的基本要求之一，对于有机两亲光学活性分子而言，使用能够在分子尺度上实现有序组装的Langmuir－Blodgett（LB）技术，可以制备具有稳定而非中心对称结构的多层膜．一般说来，Y型结构的多层膜比X型或Z型更稳定．然而，由单一材料组成的Y型LB多层膜只能形成中心对称结构，因而对宏观二阶非线性极化率X（2）没有贡献．为了解决稳定性与非中心对称性的矛盾，我们可以将光学非线性活性材料（如半花菁染料）与非活性隔层材料…     

一个对称萘酞菁的LB膜及其二阶非线性光学性质的研究

用水平提拉法制备了四叔丁基萘酞菁锌的LB膜。利用表面压-面积曲线、紫外-可见吸收光谱、小角X-射线衍射等表征了LB膜的结构,结果表明该化合物可以形成较高质量的具有很好层状结构的多层LB膜,在膜中分子大环平面垂直于基片平面并且以分子平面并不完全重合的H-聚集体存在。采用透射SHG方法测量了相应LB膜的二阶非线性光学性质,结果显示在实验条件下该化合物LB膜的宏观二阶非线性系数以及分子超极化率分别为X     

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．     

2-(1-萘基偶氮)-咪唑的合成及组装Langmuir-Blodgett膜

合成了一个非典型两亲性分子,2-(1-萘基偶氮)-咪唑(2-NDIM),对它在气/液界面上的组装和LB膜性质进行了研究。结果表明:2-NDIM不能在水相表面形成Langmuir膜,在Ag NO3水溶液亚相中能形成稳定、均匀的配位聚合物单分子膜,组装的LB膜为J-聚集体,最大吸收波长为403nm,归属于反式-N=N-双键的π-π*电子跃迁,光激发LB膜中偶氮基团的反-顺异构化作用不明显,具有较低的反-顺光异构化量子产率。     

CdS纳米微粒在LB膜层隙聚集形态的AFM观察

用LB技术制备纳米微粒与超薄有机膜的复合膜是近年来值得注意的研究进展＊．利用该方法所制备出的材料既具有纳米粒子所特有的量子尺度效应，又具有LB股的分子层次有序、股厚可控以及易于组装等特点．它可用来制备结构可控的有机无机交替膜．而且，通过改变LB膜成膜材料和制备条件还可改变纳米粒子的光电特性．因此它在微电子学、光电子学、非线性光学及传感器等研究领域有着十分广阔的应用前景问．纳米微粒的聚集形态及LB膜在生成纳米微粒后的结构变化对材料的特性有着很大的影响．但采用一般的电镜技术或光谱分析手段均不能在实空间和…     

2—（对—十二烷氧基苯基）吡嗪—5—羧酸的合成及其成膜性

在含有吡嗪环的对位双环羧酸化合物中,2-(对-十二烷氧基苯基)吡嗪-5-羧酸具有良好的成膜性。由于引入了推-拉电子的基因,因而分子长轴方向偶极矩较大,分子较舒展、刚直、形成的LB膜取向性较高。这类化合物可能在LB膜等有机功能材料上得到应用。本文报导化合物的合成及其成膜性的初步结果。     

新型偶氮苯自组装一LB组合有序膜的构造与表征

偶氮兹及其衍生物具有独特的光致异构化和电化学反应机制,其LB单分子膜作为一种高度有序的分子组装体系,以其诱人的应用前景引起了人们的极大兴趣．然而在这方面的研究中,LB膜通常是沉积在SnO。或镀金的基片上,其结构的相对木稳定性限制了实际应用的可能性．我们利用自组装技术,在金基底表面组装了具有特定末端基团的自组装单分子膜,然后利用LB技术构造偶氮苯衍生物的单分子膜,以期得到稳定而有序的偶氮苯LB膜,且不影响其光化学和电化学活性．本文报道了这种新型偶氮苯自组装一LB组合股的结构表征及其电化学行为．亚实验部分偶…     

多金属氧簇与倍半硅氧烷簇构筑的哑铃形杂化分子Langmuir膜和Langmuir-Blodgett膜

以两个形状杂化分子(Shape Hybrid Molecules)为目标分子, 研究了它们在气液界面上形成Langmuir膜的过程和Langmuir-Blodgett (LB)膜的聚集态结构. 杂化分子是由Wells-Dawson型磷钨氧簇(Polyoxometalates, POMs)和T₈型的倍半硅氧烷簇(Polyhedral Oligosilsesquioxane, POSS), 通过对苯二甲酸有机连接链(OL)用共价键构筑的具有杂化性质和哑铃形状的簇-簇杂化分子(POM-OL-POSS). 这两种杂化分子的差别在于POSS段中, 外围有机基团的尺寸不同. 在实验中, 采用Langmuir和LB膜技术, 了解POSS外围的七个取代基变化导致的分子尺寸变化对Langmuir膜形成过程和LB膜结构的影响. 采用Langmuir技术测定了表面压-平均分子面积(π-A)等温曲线和π-A循环等温曲线, 跟踪并研究了这两个杂化分子在水表面上形成Langmuir膜的过程. 实验结果表明, 两个杂化分子都表现出良好的两亲性, 从气相变化到固相的过程中, 杂化分子经历了从分散到集中的过程. 将这些膜转移到基片上, 得到单层的LB膜, 再利用原子力显微镜(AFM)和透射电子显微镜(TEM)研究了LB膜的表面形貌和聚集态结构. 由于POM段中含有钨和钒金属, 可以直接用TEM观察聚集态结构, 发现了在气-液和液-固相转变过程中, LB膜中杂化分子的聚集态结构都呈现涨落特征, 一种凝聚态物理中由相转变导致结构涨落的重要物理现象. 本研究获得的结果能够帮助我们以及这个领域的研究者们继续优化杂化分子的结构, 进一步构筑具有有序结构的膜和本体材料.     

四硫代富瓦烯及其CT复合物导电LB膜

通过Langmuir-Blodgett（LB）技术制备导电性有机超薄膜近年来受到了广泛的关注，导电LB膜的膜材料主要是含有电子受体77’，8，8’一四氨基二亚甲基本自（TCN则的电行转移（CT）复合物间以及给体分子特别是四流代宫瓦烯衍生物［‘刮.在以前的工作中，我们曾报导了四等基硫四硫     

一种含稀土半菁的二阶非线性光学材料的研究

LB膜技术作为一种重要手段，可以在分子水平上对材料进行组装．有机化合物作为非线性光学材料，由于具有很大的非线性系数、光学响应速度快及光损伤阈值大等优点而受到人们的重视[1]．对于二阶非线性光学材料而言，其发色团分子的非中。心对称结构是其非线性光学信号叠加的必要条件．LB膜技术以其不同的沉积方式，可有效地控制有机分子的排列和取向，形成非中，心对称结构，成为制备高性能二阶非线性光学材料的良好手段．我们首先将疏水性的稀土配阴离子引入非线性光学成膜材料中，由于其体积较大，可以避免对形成LB膜不利的H聚体的生成…     

半花菁LB多层膜的光学非线性各向异性研究

用偏振紫外-可见吸收及旋转样品二次谐波（SHG）测量法研究了半花菁／花生酸Y型交替多层膜中分子在基极平面内分布的各向异性．拉膜过程引发的半花菁分子在平面内沿提拉方向的规则取向具有镜面对称性，并随着拉膜速度或层数的增大而增强．     

半花菁分子在LB多层膜中的取向研究

Polarized UV-visible absorption spectroscopy was used to investigate the inplane orientation of the hemicyanine molecules in Y-type Langmuir-Blodgett(LB) multilayers. We demonstrated for the first time that the dipping-induced molecular alignment was enhanced significantly with increasing the layer number due to the interlayer interactions. Polarized UV nanosecond pulses were used to control the photoinduced reorientation of the hemicyanine molecules. Thermal-isotropic process was accompaniedd by dissocition of the H-aggregate in hemicyanine LB multilayers.     

花生酸-钌有机螯合物Ru(phen)_3~(2+)的单分子膜和LB膜中分子聚集行为的研究

以功能性的钌有机螯合物Ru(phen)_3~(2+)作为亚相离子,花生酸在亚相表面 上形成稳定的单分子膜。π-A等温线和动态弹性测量表明,此膜因花生酸与钌螯离 子发生了静电相互作用而有更大的可压缩性,并在固态区发生了分子聚集。用垂直 法成功地制备了嵌有Ru(phen)_3~(2+)离子的超薄有序Y-型LB膜。光谱实验表明, 所得LB膜是稳定、均匀的层状三明治结构,在层面内Ru(phen)_3~(2+)与花生酸结 合成相对稳定的分子基团形成了J-聚体。     

LB膜中聚集体的时间分辨荧光研究

利用吸收，稳态和时间分辨荧光方法研究了苯腙（ＰＤ）和半花菁（ＤＡＥＰ）分子在Ｚ型ＬＢ多层膜中的聚集性质，苯腙和半花菁吸收光谱的红移和兰移，说明它们分别以Ｊ和Ｈ型聚集体形式存在于ＬＢ膜中，苯腙和半花菁ＬＢ膜的荧光发射带分别在５６０ｎｍ和５８４ｎｍ处，亦分别对于它们溶液的荧光谱呈示出红移和兰移的特征，它们的荧光衰减曲线能很好地用双指数模拟拟合，在苯腙和半花菁ＬＢ多层膜中主要存在着荧光寿命分别在ｎｓ和１     

2-硝基-5-(N-甲基-N-十八烷基)氨基苯甲酸多层膜的制备和性质

用2-硝基-5-(N-甲基-N-十八烷基)氨基苯甲酸(NMOB)和花生酸制备了200层的交替多层膜, 测得其二次谐波信号强度与NMOB层数的平方成正比。论文着重讨论了NMOB的Y型膜和它与花生酸的交替膜中的取向, 并对两者之间的不同作了初步的解释。     

Relaxation of photo-excitations in films of oligo- and poly-(para-phenylene vinylene) derivatives

The photo-luminescence from solid films of poly(para-phenylene vinylene) polymers and an oligomeric model system, consisting of seven repeat units, are investigated at low temperature (8 K) using time-resolved spectroscopic techniques. Results are compared to those for the materials in solution. In the case of the oligomer, the shape of the visible absorption band observed for the film is quite different from the band shape for the polymer in frozen solution and is characteristic of H-type aggregates. Theoretical models are presented describing the dependence of the band shape of absorption and emission spectra on intermolecular excited state interactions, electron-vibration coupling and disorder represented by distributions of the molecular excitation and intermolecular interaction energies. Using these models, it is concluded that intermolecular interactions in the film of the oligomer are strong (1400 cm⁻¹), and the disorder low, implying delocalization of the excitation over several molecules. In accordance with these models the fluorescence lifetime for the film (2 ns) is considerably longer than for isolated molecules in solution (0.45 ns). The emission spectra of the film, taken early after excitation, are consistent with delocalization of the excitation over several molecules. A time-dependent red shift of the fluorescence band is observed and interpreted in terms of migration of localized excitations between disorder induced trap sites, which exist in the low energy tail of the density of excited states. For the polymers, differences between the shape of the absorption bands of solid film and frozen solution are smaller than for the oligomer indicating that interchain interactions that are, on average, weaker than for the oligomer. For the polymer films, a time-dependent red shift of the emission is observed and fluorescence depolarization measurements provide direct evidence for migration of the photo-excitations between trap sites. For one polymer, a time dependent change in the band shape of the fluorescence after pulsed excitation is observed with the band shape of the long-lived emission being compatible with that expected for an excitation delocalized over at least two, nearly parallel aligned, chains. For a second polymer, the emission band shape and its time evolution indicate that the major part of the fluorescence originates from disorder induced luminescent sites. These results indicate that the spectroscopic properties of films of π-conjugated polymer critically depend on parameters such as density of defects and excited state interchain interaction energy.     

Immobilization of a fluorescent dye in Langmuir-Blodgett films

We immobilized a hemicyanine dye, Di-8-ANEPPS, in ordered thin films of an organic matrix, dihexadecyl phosphate (DHP), and we transferred the mixed monolayers onto solid support by the Langmuir-Blodgett technique. We used gold and quartz slides and indium tin oxide (ITO) evaporated on glass slides as substrates. The multilayers formation was confirmed by ellipsometric and contact angle measurements. The optical response of the nanostructures was investigated collecting UV-Vis absorption and fluorescence emission intensity profiles.     

Synthesis of L-Lysine and L-Glutamic Acid Derivatives with Long Alkyl Chains and Polycondensation of Langmuir-Blodgett Films

Two esters of L-lysine and L-glutamic acid containing long alkyl groups were synthesized and their polycondensation in monolayers and multilayers was investigated. The pressure-area isotherms of the ester of L-lysine depend markedly on the time of residence at the air-water interface. The change of FT-IR spectra of the deposited film, which can be lifted as a Z-type film, indicates that polycondensation can occur in the monolayer at 10°C without any treatment. The spectrum of the film cast from chloroform hardly changed with time. These results lead to the conclusion that a regular arrangement of monomer molecules in the monolayer, where the amino and ester carbonyl groups are concentrated, is more suitable for the polycondensation. The ester of L-glutamic acid can also form stable monolayers which can be easily deposited on a hydrophobic plate as a Y-type film by the Blodgett technique. The polycondensation of multilayers under an atmosphere of triethylamine was investigated by IR spectroscopy. It indicates that the condensation in multilayers proceeds via intermolecular and intramolecular reactions, by which poly(L-glutamate) derivatives and 2-pyrrolidone derivatives are formed, respectively. The condensation in the bulk crystalline powder gives exclusively the 2-pyrrolidone derivative by intramolecular reaction. These results suggest that the monomer molecules in the multilayers are favorably aligned for the intermolecular reaction, in contrast to the situation in the bulk crystalline powder.     

Effects of high electrolyte concentration on DPPC-multilayers: an ESR and DSC investigation

The effects of salinity on the lateral headgroup interactions of dipalmitoylphosphatidylcholine (DPPC) molecules in fully hydrated multilayers have been investigated by spin label electron spin resonance (ESR) spectroscopy and differential scanning calorimetry (DSC).By increasing the NaCl concentration from 0 to 3 M in the multilayers' dispersion medium, the ESR measurements performed with the 5-stearic acid spin label and di-tert-butyl-nitroxide show an increase in the orientational degree of order of the lipid molecules, mainly in the gel phase, and a decrease of the membrane permeability. An upward shift from 31.5° to 36.5°C and from 40.5° to 41.9°C of the pre- and main DPPC phase transition temperatures, respectively, is observed with 5-SASL, while slightly higher values are detected with DTBN. Small effects are evident on the properties of the liquid crystalline phase of the DPPC multilayers.The DSC measurements also reveal an upward shift of the pre- and main transition temperatures. The shifts, however, are more marked if compared to the ones observed with the ESR technique.The findings suggest an increase in the packing density of the DPPC molecules in the multilayers in presence of high salt concentration. Dehydration of the DPPC interfacial region with a variation of the lateral electrostatic interactions between phospholipid polar heads trigger the phenomena observed.     

Fluorescence properties of trans-ethyl-p-(dimethylamino) cinnamate in presence of bile acid host

The knowledge of the formation of bile acid micellar aggregates is of great importance because of the biological significance of these compounds and their pharmacological applications. The intramolecular charge transfer (ICT) fluorescence property of trans-ethyl-p-(dimethylamino) cinnamate is used to study the micelles formed by aggregation of three most important bile acids, viz. cholic acid, deoxycholic acid and chenodeoxycholic acid by steady state and picosecond time-resolved fluorescence spectroscopy. The ICT fluorescence band intensity was found to increase with concomitant blue shift with the addition of bile acids. The blue shift in ICT fluorescence maxima as well as decrease in nonradiative decay constants in presence of bile acids indicate the passage of the probe towards the micro domains formed from the aggregated bile acids. Binding constant of the probe with micelles as well as critical micelle concentration and average polarity parameter of the micellar environments were obtained from the variation of fluorescence intensity on increasing concentration of bile acids in the medium.