二价钌有机螯合物Ru（dpphen）3^2＋与花生酸混合LB膜的结构及光谱特性

对不同组分的Ru(dpphen)3^2 [简称Ru(Ⅱ）]与花生酸（AA）在纯水来相上的混合单分子膜的相容性、分子间相互作用以及凝聚单分子膜的结构进行了研究,成功地将这种功能单体分子膜转移到固体载片上,制备成混合LB膜、紫外－可见光谱、发现光谱及小角X光笛射表明这种混合LB膜是一种稳定、均一、具有良好的层状结构,并且可在可见江范围内具有很强的吸收及发射峰的功能膜。     

二价钌有机螯合物Ru(dpphen)2+3与花生酸混合LB膜的结构及光谱特性

对不同组分的Ru(dpphen)2+3［简称Ru(Ⅱ)］与花生酸(AA)在纯水亚相上的混合单分子膜的相容性、分子间相互作用以及凝聚单分子膜的结构进行了研究. 成功地将这种功能单体分子膜转移到固体载片上,制备成混合LB膜. 紫外-可见光谱、发射光谱及小角X光衍射表明这种混合LB膜是一种稳定、均一、具有良好的层状结构, 并且在可见光范围内具有很强的吸收及发射峰的功能膜.     

组份可控的钌螯合物功能单分子膜

用作“表面离子”的钌螯合物Ru(dpphen)32+与脂肪酸类成膜分子以1:2混合时能够得到稳定的混合单分子膜.以十八烷基三氯硅烷（octadecayl trichloro silane, OTS）分子部分取代Ru(dpphen)32+,得到功能分子组份可控的混合单分子膜.研究表明,OTS分子在纯水表面上可以形成交联网状单分子膜结构,混入硬脂酸（SA）分子后,网状结构逐渐被破坏.SA含量增加,破坏的程度就增大,直至SA/OTS为3:1时,完全没有网状交联结构,形成可以用来沉积LB膜的均匀致密的单分子膜.表面离子Ru(dpphen)32+与OTS和SA一起构成三组份混合单分子膜,OTS和Ru(dpphen)32+为表面离子.单分子膜中混有Ru(dpphen)32+分子,可以有效地阻止OTS的交联发生,同时Ru(dpphen)32+/SA基团与OTS/SA基团是均匀共混的.改变Ru(dpphen)32+/SA基团与OTS/SA基团的混合比,即可以做到Ru(dpphen)32+的组份精确可控,得到可用来沉积LB膜的均一、稳定的单分子膜.     

由组分可控的LB膜前驱物法制备Y2O3稳定立方相ZrO2的超薄陶瓷膜

由有机LB膜技术发展了一种制备组分、厚度可控的无机超薄陶瓷膜的方法.以Zr、 Y的β-二酮络合物的作为"表面离子"代替传统的亚相离子,沉积它们与花生酸的混合LB膜.并将它作为前驱物,经臭氧处理和热处理,成功制得了Y2O3稳定的立方相ZrO2超薄膜(YSZ).用X射线衍射(XRD)、 X射线光电子能谱(XPS)等手段研究了YSZ薄膜的相结构和其组成.结果表明,超薄陶瓷膜中Zr与Y的含量比率控制得很好,且形成Y2O3稳定的立方相ZrO2.说明这种方法可以成功地用来制备组分和膜厚均可控的纳米陶瓷膜.     

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。     

酞菁铜化合物LB膜的制备及结构形态研究

利用LB技术研究了带有4个长碳氢链的酞菁铜化合物(CuC12Pc)的单分子膜及它与十八胺(ODA)、二十酸(AA)的混合LB膜的聚集结构形态. 结果表明这种酞菁铜化合物在气液界面上可以形成比较稳定有序的双层Langmuir膜, 且可以转移质量较好的多层LB膜. 利用原子力显微镜(AFM)研究了酞菁铜分子的聚集体结构, 发现CuC12Pc/AA混合膜表现为网状的聚集结构, 而CuC12Pc/ODA混合膜形成长岛颗粒状聚集, 并结合UV-Vis吸收光谱讨论了酞菁铜分子形成不同聚集结构的原因.     

稀土(III)三硬脂酸盐LB膜的制备及结构研究

用直接在5×10^-^5mol.dm^-^3稀土(III)氯化物水溶液的液面上铺展稀土(III)三硬脂酸盐(简称LnSt~3)的方法,在疏水光学玻璃片上连续沉积了44层以上的含稀土(III)(La、Nd、Sm、Eu、Tb)硬脂酸盐LB膜,转移比为0.7-0.8。低角度X射线衍射(2θ=0.3-14ⅲ)结果表明,膜的结构为高度有序的层状结构,相邻稀土离子面的间距为4.7-4.8nm。X射线光电子能谱(XPS)证实了五种膜中分别含有La、Nd、Sm、Eu和Tb元素。此外,还对LnSt~3LB膜进行了红外光谱考察,表明在亚相中加入一定浓度的稀土离子能有效地抑止界面上LnSt~3的水解作用,为制备含稀土(III)离子的优质LB膜提供了依据。     

稀土(III)三硬脂酸盐LB膜的制备及结构研究

用直接在5×10^-^5mol.dm^-^3稀土(III)氯化物水溶液的液面上铺展稀土(III)三硬脂酸盐(简称LnSt~3)的方法,在疏水光学玻璃片上连续沉积了44层以上的含稀土(III)(La、Nd、Sm、Eu、Tb)硬脂酸盐LB膜,转移比为0.7-0.8。低角度X射线衍射(2θ=0.3-14ⅲ)结果表明,膜的结构为高度有序的层状结构,相邻稀土离子面的间距为4.7-4.8nm。X射线光电子能谱(XPS)证实了五种膜中分别含有La、Nd、Sm、Eu和Tb元素。此外,还对LnSt~3LB膜进行了红外光谱考察,表明在亚相中加入一定浓度的稀土离子能有效地抑止界面上LnSt~3的水解作用,为制备含稀土(III)离子的优质LB膜提供了依据。     

用“表面离子”法制备组分可控的LB膜超分子体系

综述了LB膜超分子体系中“表面离子”法的概念及其与传统的“亚相离子”法的区别. 分别以钌螯合物(Ru(ph2phen)32＋)和金属β-二酮螯合物为例,详细描述这两类不同的“表面离子”在水面上的成膜作用机理,并举例说明“表面离子”法在铺展膜和LB膜中,功能分子二维密度和凝聚态结构精确可调,并对“表面离子”法在多功能分子体系中的应用作了详细描述.     

聚苯胺基LB膜的制备及气敏特性的研究

以聚苯胺 (PAN)为原料 ,利用LB(Langmuir Blodgett)超薄分子膜技术 ,制备了不同层数的纯聚苯胺LB膜及聚苯胺与乙酸 (AA)混合 (PAN AA)LB膜 ,对其进行了紫外 可见光光谱分析研究 ,并对不同层数的聚苯胺基LB膜的二氧化氮 (NO2 )气敏特性进行了研究 ,发现PANLB膜较PAN AALB膜具有更好的敏感性、响应性和可逆性 ,3层和 15层PANLB膜对相对百分比为 2 0× 10 -6NO2 的响应时间分别为 10s和 30s,15层PANLB膜的恢复时间约为 4min     

Study of molecular interaction in the mixed film of arachidic acid and metal beta-diketonate complexes by the "surface ions" method

Molecular interaction is very important for the mechanical properties and application of Langmuir films. In general, fatty acid film is stabilized by certain "subphase ions." In this work, two metal beta-diketonate complexes (M(tmhd)n, tmhd=2,2,6,6-tetramethyl-3,5-heptanedionate) were used as "surface ions" to form stable condensed films with different ratios at the air/water interface. The pi-A isotherms of the mixed films had been measured. The smaller molecular area of the metal beta-diketonate complexes indicated that the metal beta-diketonate complexes form multilayer condensed structures at high pressure at the air/water interface. However, arachidic acid (AA) retained a monolayer structure at high pressure in the mixed system. No considerable phase separations appeared during the compression of the mixed films, which indicated that the mixed films of metal beta-diketonate complexes and AA were miscible and stable. The molecular interaction of the two components in the mixed films was investigated in detail. Mixed systems with the mixing ratio of M(tmhd)n:AA=1:2 were chosen to study the effects of the interaction on the mechanical properties of the mixed films. The molecular interaction between AA and Ce(tmhd)4 is proved to be more significant than that between AA and Sr(tmhd)2, and the pi-A isotherms of the mixed films differ a lot from that of pure AA monolayer. Due to the strong intermolecular interaction, the liquid region disappears in the Ce(tmhd)4/AA mixed films, and dynamic elasticity is improved especially at high surface pressure. On the other hand, the interaction between the AA and the Sr(tmhd)2 is much weaker and the effects of the interaction on the properties (pi-A isotherm and dynamic elasticity) of the mixed films are not so significant, especially at low surface pressure. These results are in accordant with that of the UV spectra analyses.     

稀土螯合物发光体LB膜的研究(I)

稀土有机配合物的发光研究近年来取得了可喜的近展.铕(Ⅲ)、铽(Ⅲ)、钐(Ⅲ)与β-二酮(β-dik),三正辛基氧化膦(TOPO)所形成的螯合物,以及它们的硝酸盐与邻菲咯啉(Phen)所形成的螯合物都是高光效的发光体,有广阔的应用前景,在某些方面已获得应用.如能把这些具有发光功能的稀土螯合物组装成有序的分子组合体,则很可能在分子光学技术,光电子技术等领域发挥重要作用.如何组装?本文用LB 膜技术,通过交替成膜或混     

胆红素及其两亲衍生物的Langmuir-Blodgett膜研究

研究了亚相酸度和金属离子对胆红素(1)及其两个两亲衍生物胆红素二(十八烷基)酯(2)和胆红素二(十八烷基)酰胺(3)的单分子膜和LB膜性能的影响.通过π-A等温线、X射线光电子能谱、紫外-可见光谱等方法,研究了它们在有序分子膜中的分子伸展及与金属离子的配位方式.胆红素及其两亲衍生物与金属离子在有序分子膜中的配位(生成1:1型配合物)明显不同于其在本体溶液中的配位(1:1,1:2或2:1型配合物).小角X射线衍射表明1,2和3形成双层膜间距分别为2.15,5.55和5.65nm的Y型LB膜.     

Langmuir-Blodgett Films from Schiff Base Aluminium (Ⅲ) Complex

The characteristics of the LB films of Schiff base aluminium(Ⅲ), tris(2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium(Ⅲ)[Al(TA12)_3], were studied. The surface pressure-area(π-A) isotherm of Al(TA12)_3 in the pure water subphase was investigated. The molecular area, 0.48 nm~2, is one-third of the expected value that indicates the formation of an aggregate. The Langmuir-Blodgett(LB) films of Al(TA12)_3 were transferred and characterized. The UV-Vis spectra and the AFM image both confirmed that the J-aggregates formed. The polarized UV-Vis spectra indicated that the complex plane had to be oriented with an angle of about 30° to the substrate surface. The IR spectra suggested that the complexation took place between aluminium ions and the oxygen atoms of the ligand rather than the nitrogen atom.     

非典型双亲性β-二酮稀土配合物LB膜荧光稳定性 的研究

研究了一系列非典型双亲性β-二酮稀土配合物LB膜在紫外光激发下两种不同条件时的荧光稳定性：(1)每40s检测一次;(2)每周检测一次。第一种条件下,稀土配合物LB膜的荧光强度以直线关系缓慢衰减,30次后变化约4%。第二种条件下荧光强度呈单指数关系衰减。荧光强度衰减至原始值的1/e时间τ约为10周{如n[Eu·(TTA~3)Phen]:n(AA)=1:1LB的τ为11.4周}。相同激发次数(大于1次)时,第二种条件比第一种条件下LB膜荧光强度小。紫外可见吸收光谱结果表明,受紫外光激发后,LB膜中稀土配合物的吸光度降低且随时间延长吸光度进一步降低,导致荧光发射强度减小。放置半年后LB膜的光强度仍可被检测到。低角度X衍射结果表明,LB膜具有良好的周期性层状结构且层状结构可长时间稳定存在,有利于提高稀土配合物LB膜的荧光稳定性。     

Time-dependent complexation of glucose-reduced gold nanoparticles with octadecylamine Langmuir monolayers

We report on the reduction of aqueous chloroaurate ions by glucose to form gold nanoparticles of uniform size. We further demonstrate the complexation of these particles with octadecylamine (ODA) monolayers at the air-water interface. Pressure-area (pi-A) isotherms as a function of time of complexation revealed a significant expansion of the monolayer. Surface pressure variation with time for constant areas after spreading of the monolayer was carried out to observe the kinetics of complexation of the colloidal particles at the interface. The kinetics of complexation of the particles at the interface was also monitored by Brewster angle microscopy (BAM) measurements. Langmuir-Blodgett films of the particles complexed with ODA were formed at a subphase pH of 9 onto different substrates. Quartz crystal microgravimetry (QCM) was used to quantify the amount of particles deposited per immersion cycle of the quartz crystal. The LB films were further characterized by UV-vis and transmission electron microscopy (TEM) measurements. TEM measurements indicate a close packed and equidistant arrangement of colloidal particles in the LB film, probably due to hydrogen-bonding interactions.     

胆红素有序分子膜的行为研究

研究了不同亚相表面胆红素(BR)单分子膜和LB膜的性质,讨论了胆红素分子在有序分子膜中的堆积密度、分子伸展和金属离子配位。在气-水界面,BR与金属离子的配位导致BR单分子截面积、崩溃压和可见紫外光谱的变化。原子力显微镜表明BR-Cu单分子膜的厚渡为1.23 nm。     

Polymer-surfactant layered heterostructures by electropolymerization of phenosafranine in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films of the water-soluble dye phenosafranine (PS) have been prepared by its adsorption from aqueous dye solution to an arachidic acid (AA) monolayer at the air-water interface. Atomic force microscopy (AFM) images of the LB films revealed the effect of change in pH of deposition on the degree of complexation of AA with the PS dye. Well-defined circular islands and holes were observed which disappeared with the increase in pH. Polarized absorption studies indicated that the dye molecules are oriented uniaxially with their long axis titled at a constant angle to the surface normal of the LB film. Within the restricted geometry of the LB film, the PS dye was electropolymerized to form a two-dimensional film of poly(phenosafranine) sandwiched between arachidic acid layers. The film was characterized by IR spectroscopy, cyclic voltammetry, and AFM. X-ray diffraction studies reveal the presence of a layer structure in the AA-PS LB film before and after polymerization. The polymer film showed highly anisotropic electrical conductivity of ca. 10 orders of magnitude. This indicates the formation of two-dimensional polyPS layers between arachidic acid layers resulting in a layered heterostructure film having alternate conducting and insulating regions. Also, the conductivity of the polyPS prepared from LB film was found to be approximately 2.5 times higher than the conductivity of polyPS prepared by solution polymerization method.