L-B膜

<正> L-B膜即 Langmuir-Blodgett单分子膜,它是人为地利用分子间相互作用而建立起来的特殊分子体系。在L-B膜中分子是有序的准晶体排列,其性质有别于固体和晶体,因而有人将其称为物质的第五相。用米制备L-B膜的技术称为L-B技术。     

卟啉类L—B膜分子间相互作用的光谱研究

以无取代的meso-四-(4-N)-吡啶基卟啉及其过渡族金属(主要Cu~(2+)、Zn~(2+))络合物制备L-B膜,以近紫外-可见吸收光谱和荧光光谱为手段,研究叶啉类分子在氯仿溶液中,L-B膜状态下以及固态状态下的相互作用。探讨分子聚集体的存在对光谱性质的影响。 为了研究叶咻类分子间的相互作用及其对光谱性质的影响,我们首先分析了叶啉在CHCl_3溶液中及固态状态下的近紫外-可见吸收光谱和荧光光谱。并将其与叶啉类分子的L-B膜作比较。结果表明,卟啉类的Soret吸收带带宽及峰位置在三种状态下均不相同,L-B膜的情况介于溶液中的和固体下的情况之间,说明了在L-B膜中,卟啉分子存在着某种形式的聚集体,且在这种聚集体中分子间的相互作用程度比固体弱,可以认为L-B膜上的分子呈准晶体状态。     

有机化合物的光物理研究 ⅩⅢ.β-萘甲酸十六碳酯在L-B膜中基态二聚体及激基缔合物形成的研究

制备了β-萘甲酸十六碳酯的L-B膜。分别用Y型、Z型,以及含有硬脂酸的β-萘甲酸十六碳酯与单纯硬脂酸间隔挂法,将分子膜转移至石英载片上,研究了β-萘甲酸十六碳酯分子膜吸收以及荧光光谱。并与溶液和固态中的荧光光谱作了比较。在氯仿溶液以及在固态,β-萘甲酸十六碳酯只呈现其单体的荧光。然而,在L-B膜中,除了观察到单体的荧光外,还观察到了激发态二聚体以及激基缔合物发射的荧光。通过对β-萘甲酸十六碳酯分子膜进行热和水处理后,发现L-B膜中亲水层的介质环境有所改变,从而造成亲水层中的亲水基团的某些物理和化学性质的改变。根据实验事实,提出了β-萘甲酸十六碳酯二聚体和激基缔合物在L-B膜中形成的机制。     

硬脂酸二茂铁酯L—B膜修饰SnO2电极的阻抗研究

测定了二茂铁衍生物——硬脂酸二茂铁酯L-B膜修饰SnO_2电极在Fe(CN)_6~(3-/4-)溶液中的阻抗性能,用单纯形法求出了等效电路中的元件参数值,计算了电极反应速度常数K_s。从分析SnO_2电极修饰不同层的硬脂酸二茂铁酯L-B膜的界面阻抗和电极反应的动力学性能,表明与在固相中研究的硬脂酸二茂铁酯L-B膜的阻抗性能明显不同,在Fe(CN)_6~(3-/4-)溶液中表现了电活性分子修饰电极的界面阻抗行为,进一步证实了修饰在SnO_2电极上的硬脂酸二茂铁酯L-B膜在Fe(CN)_6~(3-/4-)的氧化还原电极反应过程中,起电荷传递的中介作用。     

电活性分子L-B膜修饰CdSe薄膜电极的光电化学研究

用电活性分子——硬脂酸二茂铁酯L-B膜修饰了薄膜CdSe电极,在单色光650nm光照下用循环伏安法研究修饰的薄膜电极的光电化学性能。研究结果指出经多层L-B膜修饰后,薄膜CdSe电极的,I-V性能和光稳定性都有明显改善。用界面能级关系讨论了硬脂酸二茂铁酯L-B膜在光照的CdSe薄膜/Fe(CN)_6~(4-)溶液界面起传递电荷的中介作用,加速了界面的电荷转移。     

CuTsPc分子膜／P—si（11 1）界面的光致电荷转移及其机制研究

本文利用L-B技术,在p-Si(111)基底上铺展了单层厚度只有6的CuTSPc超薄分子膜(简称超分子膜)和具有C_(18)脂链间隙的CuTSPc L-B膜两种膜系,首次观察到了CuTSPc分子膜在这种特定界面中的表面光电压谱。并且发现,当CuTSPc仅为一个单分子层时,这两种膜系的表面光伏效应最强。我们的研究结果表明,只有紧邻半导体基底的一个单分子层厚度的染料分子对光致界面电荷转移起关键作用。最后在实验上证实这种电荷转移是电荷直接注入机制,而非间接注入机制。     

硬脂酸二茂铁酯L—B膜的电化学性能研究

本文研究二茂铁衍生物——硬脂酸二茂铁酯(FcOCOC_(17)H_(35))L-B膜技术修饰SnO_2电极的循环伏安性能.实验结果用电极表面吸附(修饰)分子的表面活度理论进行计算机拟合和此较,实验数据与理论符合较好.进一步求得修饰分子的标准电极电势和修饰量。结果表明硬脂酸二茂铁酯L-B膜电化学性能稳定,可逆性较好,可以作为快速电荷转移的修饰电极材料。     

甲醇-脂肪酸混合物临界参数及酯交换反应条件探讨

超临界甲醇法制备生物柴油反应涉及到拟二元混合物临界参数的计算。操作参数对系统热力学相态的影响直接关系到化学反应的机理,进而决定反应速度和产物转化率。为此,采用基团贡献法与L-B混合规则对甲醇和脂肪酸混合物的临界参数进行了计算。发现采用C-G基团贡献法与L-B混合规则可以较好地描述甲醇和大豆油混合物的临界参数,并且无需考虑相互作用参数。与文献值相比,平均误差为1.7%。据此,对反应器内混合物相态进行分析,讨论了低醇油摩尔比、反应温度和反应压力等条件对反应物相态和甲酯产率的影响。结果对于指导高压法制备生物柴油工艺设计有所帮助。     

酞菁锌衍生物L—B膜的光电性能研究

用L-B膜方法在SnO_2电极上修饰了不同链长烷氧基取代的酞菁锌化合物(ZnPc C_nH_(2n+1),n=3,9,12,16),分别研究了它们单分子膜成膜性能和转移性能,并测定了修饰在SnO_2电极上的单多层分子膜的光电性能和吸收光谱。研究结果指出链短的取代基即异丙氧基取代的酞菁锌(ZnPcC_3H_7(i))具有较高的转移比及较好的光电性能。     

修饰的薄膜CdSe电极／Fe（CN）6^4—溶液界面的电荷转移

本文研究了硬脂酸二茂铁酯L-B膜修饰的薄膜Cdse电极的光诱发界面多相电荷转移过程。通过测量异相电荷转移反应速度常数K_(et),进一步分析了修饰的薄膜CdSe电极光电化学过程的可能反应速度控制步。分析表明界面的电荷转移是反应的速度控制步。薄膜CdSe电极可以通过选择电活性修饰分子和溶液中氧化还原离子来进一步提高和改善其光电化学性能。     

水溶性菁染料与类脂物混合单分子膜中J-聚集体形成的研究

报道了具有相同发色团,并有不同电荷的二种菁染料单分子膜中J-聚集体的形成。测定了单分子膜的π/A,△V/A曲线,反射光谱及吸收光谱。从实验结果得出:带正电荷的染料与花生酸混合形成单分子膜后,膜中染料的二聚体与J-聚集体随着表面压力改变存在着一个平衡。而带负电荷的染料与二十烷基胺成膜后,即使在很低的表面压下也有J-聚集体形成。同时染料分子在水面上的取向是各向异性。     

Cyanine dyes of new heterocyclic ring systems: Synthesis and structure-spectra studies

New cyanine dyes including monomethine cyanine dyes (simple cyanine dyes) and trimethine cyanine dyes (carbocyanine dyes) incorporating benzo[2,3-b; 2′,3′-b′]bispyrazolo[4,5-b]-1,4-(oxa-, thia-, and pyra)-zine-6,12-dione were prepared. Structure-spectra studies were carried out via measuring the electronic visible absorption spectra of these dyes in 95% ethanol. Structural confirmations were determined through elemental analysis, IR, ¹H NMR spectroscopy and MS spectral data at the Micro Analytical Center, Cairo University.     

菁染料和份菁染料溶液的光降解机理的研究

利用UV－Vis吸收光谱仪和光化学反应器,研究了菁染料和份菁染料溶液的光降解动力学,认为染料在乙腈溶液中的光褪色反应服从假一级或零级动力学,利用GC／MS光谱仪检测了染料的光降解产物,与相应的份菁染料相比,携带正电荷的菁染料具有相对较好的光稳定性,研究结果表明,菁染料光降解反应的中间体可能是染料的半氧化态Dye^ ,并利用纳秒级闪光光解技术研究了Dye^ 的瞬态吸收光谱。     

Influence of Dye Aggregation on Photosensitized Hole Injection into Anthracene Crystals from Langmuir-Blodgett Monolayers Containing Cyanine Dyes

Monolayers containing cyanine dyes can be transferred to anthracene crystals and are able to inject holes into the crystal upon excitation. At low dye coverages only the dye monomer injects holes while at higher coverages energy transfer to aggregates is the most important decay process of an excited dye monomer. These aggregates are also able to inject holes but with a more than ten times smaller efficiency. The occurrence of dye aggregates is confirmed by the absorption spectra of the monolayers. In this system non-geminate recombination remains an unimportant pathway even at high dye coverages.     

菁染料和份菁染料的合成及其溶液的光稳定性研究

利用UV－Vis吸收光谱仪和光化学反应器,研究了菁染料和份菁染料的光降解动力学,研究结果表明,染料在乙腈溶液中的光褪色反应遵循假一级或零级动力学衰减,与相应的份菁染料相比,携带正电荷的菁染料具有相对较好的光稳定性。     

菁染料和份菁染料薄膜的光稳定性研究

利用UV－Vis吸收光谱仪和光化学反应器研究了菁染料和份菁染料薄膜的光降解动力学。与相应的份菁染料相比，携带正电荷的菁染料薄膜具有相对较好的光稳定性。运用量子化学中的SCF－MO－PM3方法，全优化计算了这些染料的分子几何构型和电子结构，并解释了染料的光稳定性与其分子结构的关系。     

Synthesis,absorption spectra studies,solvatochromism and halochromism of polymethine cyanine dyes

New polymethine cyanine dyes, including tetramethine and bis‐tetramethine cyanine dyes derived from benzo[2,3‐b;2′,3′‐b′]bis‐pyrazolo[4,5‐b]‐1,4‐(oxa‐, thia‐ and pyra‐)‐zine‐6,12‐dione, were synthesised. Absorption spectra for all the synthesised cyanine dyes were examined in 95% ethanol. The solvatochromism and halochromism for some selected dyes were investigated in pure solvents and in aqueous universal buffer solutions, respectively. Structural confirmations were carried out through elemental and spectroscopic analysis.     

MO-LCAO-Berechnungen an Polymethinen. XI Lokale spektrale Anregungen in polynuclearen Cyaninfarbstoffen

MO-LCAO Calculations on Polymethines. XI. Local Spectral Excitations in Polynuclear Cyanine Dyes Various branched-conjugated cyanine dyes display long-wavelength absorption bands similar in position to those of their straight-chain substructures. According to the analysis of results of PPP-type calculations this close similarity results from a partial localization of the electronic transitions, whereas the participating electronic states are highly delocalized. The long-wavelength absorptions of symmetrically-branched trinuclear cyanine dyes have an entire molecular chromophore origin resulting from twofold degenerate electronic transitions. Lowering of the symmetry brings about a splitting of the colour-band. In contrast to the branched-conjugated cyanine dyes various tetranuclear cyanine dyes can be considered as being composed of two subchromophores either directly linked or joined through a conjugative bridge. In accordance with PPP configuration analyses and LHM-type calculations the splitting of the colour band is best understood by composite-molecule approaches. In this context the applicability of the simple molecular exciton theory is discussed.     

Synthesis and antimicrobial activity of certain novel monomethine cyanine dyes

A series of novel monomethine cyanine dyes were synthesized by using 3-methyl-5-substituted-1-phenyl-pyrano[2,3-c]pyrazole derivatives 2a–c. Reaction of equimolar ratios of 2a–c with 2(4)-methyl heterocyclic quaternary salts afforded the corresponding monomethine cyanines 3a–c. Reaction of compound 5 with 2(4)-methyl heterocyclic quaternary salts gives monomethine 6a–c. Condensation reaction of equimolar ratios of compounds 7 and 9a,b with 2(4)-methyl heterocyclic quaternary salts afforded the corresponding monomethine cyanines 8a–c and 10a,b respectively. The new synthesized monomethine cyanine dyes were identified by elemental analyses, IR, ¹H-NMR and Ms spectral data. The electronic absorption spectra in ethanolic solution of novel monomethine cyanine dyes were measured and the antimicrobial activity of some selected monomethine cyanine dyes was discussed.     

Bright fluorescent dsDNA probes: novel polycationic asymmetric monomethine cyanine dyes based on thiazolopyridine‐quinolinium chromophore

Seven tri‐ and tetracationic monomeric and homodimeric monomethine cyanine dyes based on thiazolo[4,5‐b]pyridinium and quinolinium end groups were synthesised and characterised. The dyes were tested as fluorescent DNA intercalating probes to apply in DNA gel electrophoresis. The DNA samples stained with all dyes from the series demonstrated bright fluorescent signals. DNA fragments were successfully visualised under orange and green filters as well as under standard UV transillumination. Two of the studied dyes revealed higher sensitivity to DNA when compared with the commercial dimeric cyanine dye TOTO‐1. Their sensitivity reached that of the commercial dimeric cyanine dye YOYO‐1, but the emission was shifted to longer wavelengths. These qualities make the dyes suitable to apply in a wide range of medical and scientific analytical methods.