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.     

8-羟基喹啉镧两亲性配合物LB膜的双层电致发光器件

以具有不同层数的两亲配合物二[2-(N-十六烷基氨基甲酰基)-8-羟基喹啉]合镧[La(HQ)₂Cl]的LB膜为发光层,PBD为电子传输层,制备了双层结构的电致发光(EL)器件:ITO/LB膜/PBD/Al.器件产生黄绿色注入式发光.LB膜的层数和沉积压对器件的性能具有重要影响.在16V激发电压下,5,11和21层LB膜双层EL器件的电流密度分别为48,29和16.4mA/cm²,启亮电压阀值为7.5,8.5和9.5V.器件的亮度随电流密度和驱动电压的增加而增加.在相同偏压下,21层LB膜EL器件的亮度大于5和11层LB膜的器件.在25mN/m沉积的LB膜制备的EL器件具有较高的亮度(1219cd/m₂)和击穿电压.     

Photoreactions and lateral patterning in Langmuir and Langmuir-Blodgett films

Reversible morphological changes occur with photoisomerization of azobenzene in Langmuir-Blodgett (LB) films complexed with polycations, which contradicts an implicit assumption of the concept of free volume that two-dimensional film structures are preserved during the photoisomerization. J-aggregates of chromophores are formed by two processes. The first process is "light-induced J-aggregation" in which photoisomerized molecules form J-aggregates. The other process is "triggered J-aggregation," in which photoisomerization of one of the components triggers J-aggregation of another chemical species in the mixed films. Both processes of J-aggregation are in many cases accompanied by large morphological changes of the films. However, LB films fabricated using processes under isobaric conditions do not change their morphology during light-induced J-aggregation and are patterned with J-aggregates using ultraviolet illumination through a photomask. Phase separation in mixed LB films gives rise to two-dimensional patterns, which are used to fabricate templates by using an amphiphilic silane-coupling agent as one of the components in the mixed LB films. Nanopatterns are also fabricated.     

半花菁染料LB膜的铁电性与厚度关系

报道了半花菁染料LB膜铁电性与膜厚度的依赖性.根据所测得的电滞回线发现,矫顽电场(Ec)随薄膜厚度(以薄膜的层数N表示)的增加而减少,在薄膜厚度为30～200 nm的范围内,它们之间的关系可用幂指数公式表示为Ec∝N－4/3,这种关系与其它传统的无机铁电材料完全相同.通过样品介电和铁电性能的测量,以存贮元件的物理参量－优值(Ps/εrEc)作为参比标准,可得铁电半花菁染料LB膜的最佳厚度为60 nm,且其优值的数值与偏氟乙烯-三氟乙烯共聚物P(VdF-TrFE) (n :n=70:30)的优值数值处在同一数量级上.     

2-苯乙烯基喹啉染料的无溶剂微波合成

在微波促进无溶剂条件下,由2-甲基喹啉与取代芳香醛在醋酐作用下合成了一系列2-苯乙烯基喹啉染料,该法操作简便、收率高.经元素分析, 1H NMR, MS, IR和UV确证了产物的结构.     

Fabrication and Efficient Acidichromism of Langmuir‐Blodgett Films of Azo Group‐Modified Phthalocyanines

Langmuir‐Blodgett thin films of the azo group‐modified phthalocyanines were successfully prepared, and the aggregated and acidichromic properties of their Langmuir‐Blodgett films were investigated.     

无长链席夫碱衍生物单分子膜和LB膜

在银离子的诱导下,两种含有苯并咪唑、没有长链取代基的席夫碱衍生物可以形成稳定的单分子膜,此单子分子膜可以用水平拉膜法转移到固体表面形成ＬＢ膜、ＬＢ膜的紫外吸收光谱和光电子能谱研究表明,Ａｇ（Ⅰ）离子被络合进行了单分子膜中。     

Encapsulation-Controlled Photoisomerization of a Styryl Derivative: Stereoselective Formation of the Anti Z-Isomer in the Cucurbit[7]uril Cavity

The photochemical isomerization of a styrylpyridinium dye ( SP ) bearing an unsymmetrically attached benzo-15-crown-5 ether has been studied in aqueous solution in the absence and presence of cucurbit[7]uril (CB[7]). The detailed analysis of the UV/Vis and NMR spectra showes that the isomeric composition of the photostationary mixtures of SP can be modulated by the host-guest complexation with CB[7]. It was found that steric hindrance caused by encapsulation of SP in the host cavity induces the exclusive formation of the anti conformer of Z- SP in contrast with the mixture of both anti and syn conformers obtained during photoisomerization of the dye without CB[7]. Remarkably, the displacement of anti Z- SP from CB[7] does not lead to the transformation of the anti Z-isomer into the syn Z-isomer pointing out the conformational memory of the system. The results provide an interesting example of the supramolecular stereorecognition by the achiral CB[7] host.     

Dicyanopyrazine-linked porphyrin Langmuir-Blodgett films

We investigated the influence of arachidic acid/cadmium dication (AA/Cd(2+)) as a transfer promoter for the deposition of dicyanopyrazine-linked porphyrin (2-DCPP) Langmuir-Blodgett (LB) films on both hydrophobic and hydrophilic substrates. In the case of LB deposition on a hydrophilic substrate, the presence of AA/Cd(2+) does not improve 2-DCPP LB deposition. The poor transfer in the case of the hydrophilic surface is believed to be due to 2-DCPP not wetting the surface during the down-stroke deposition, and this is not improved by the transfer agent. However, on a hydrophobic substrate, deposition of 2-DCPP is significantly improved by the presence of AA/Cd(2+). Comparison of the UV-visible spectrum of a 2-DCPP LB film with that of 2-DCCP dissolved in chloroform reveals that the Soret and Q bands for the 2-DCPP LB film are broadened and red-shifted due to aggregation of porphyrin rings in the LB film. UV-visible spectral changes and ellipsometry as a function of the number of deposition layers suggest continuous transfer of 2-DCPP/AA onto the hydrophobic substrate and reproducibility in the deposition process. The Soret and Q bands of the 2-DCPP LB film upon acid vapor exposure have also been investigated, and these measurements may have chemical sensor applications.     

Interfacial Langmuir-Blodgett assembly of straight and parallel aligned nanoribbons.

The fabrication of one-dimensional nanomaterials is currently an important issue in nanoscience and nanotechnology. Herein, we report the construction of long, straight, and parallel aligned nanoribbons, by the in situ assembly of a novel, triangular amphiphilic molecule at an air-water interface. The 1,3,5-trimesyl-tri-L-glutamic acid hexaester, which has an aromatic core with three hydrophilic arms bearing three amide units and ending with six ester groups, was spread on a water surface, forming a stable, ultrathin film with a plateau region in its isotherm. When the film was compressed to a surface pressures, which exceeded the plateau region, nanoribbons were formed. Atomic force microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, transmission electron microscopy, electron diffraction, and circular dichroism were used to characterize the film and the nanoribbons. The nanoribbons were formed due to the in situ transformation of a two-dimensional monolayer into a three-dimensional nanoarchitecture at the air-water interface. When the compound was spread onto the water surface, it first formed a monolayer. Compressing the film led to the overlap of the second layer on the monomolecular sublayer. This second layer formed nanoribbons in which the triangular molecules stood vertically (using two corners) on the sublayer. The nanoribbons were stabilized by the ordered packing of the triangular molecules, which were held together by intermolecular hydrogen bonding. The results present a facile procedure for constructing three-dimensional, regular nanoarchitectures in a two-dimensional environment.     

一种新型的铕络合物/TiO2发光薄膜

研究了Eu(DBM)3(DiBut-bpy)/TiO2/AA 单分子膜的表面压－分子面积(π－A)曲线和稳定性,单层膜中的TiO2纳米粒子是经TBT（tetrabutyloxyltitanium ,钛酸四丁酯）二维溶胶-凝胶法得到的.TiO2纳米粒子和铕络合物都被成功地转移到固体基片上，得到了具有良好的机械和热稳定性的新型发光薄膜.小角度X射线衍射结果证明这种复合膜具有层状有序的周期性结构.讨论了TiO2基质对复合膜发光机理的影响.     

两亲8-氨基喹啉化合物的LB膜及其电致发光器件

以8-氨基喹啉为亲水头基合成了两亲配体2-十二烷基丙二酸二(8-氨基喹啉)酰胺(H2A)的钢配合物(CuA)。研究了H2A、CuA在纯水亚相和H2A在CuCl2亚相表面的成膜性能。H2A与亚相中的Cu^2 发生配位形成了配合物(Cu-H2A)。X射线光电子能谱表明，H2A通过氮原子与Cu^2 配位，配位比为1：1。CuA的成膜性能最好，其次是Cu/|H2A。以H2A、Cu-H2A和CuA的LB膜制备了三层电致发光器件：ITO／TPD／LB膜/Alq3／Al，其起亮电压分别为7．5、6．7和6．5V，最大亮度分别为630、352和376cd/m^2，电致发光光谱的发射峰分别为503、510和514nm。配合物较弱的电致发光性能归因于Cu^2 的荧光淬灭作用．     

用自组装法制备聚合物纳米复合膜

文章比较了自组装法（ｓｅｌｆ－ａｓｓｅｍｂｌｙ,ＳＡ）与Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ技术（ＬＢ）及其它方法在制备聚合物纳米复合膜时的优劣。ＳＡ法由于操作简单、膜的结构稳定性较高,因此较ＬＢ技术等具有更大的实用价值。利用ＳＡ法,可以制备各种有机聚电解质与其带相反电荷的有机聚电解质、粘土化合物及无机纳米颗粒等组成的聚合纳米复合膜。     

Vesicle Formation from an Amphiphilic Porphyrin Derivative at the Air–Water Interface

A tetraphenyl porphyrin derivative with two C₁₆ alkyl chains covalently bound to each of the four peripheral phenyl rings through ether linkages formed multilayer clusters or vesicles at the air–water surface. More interestingly, spherical vesicles were also formed when deposited on appropriate solid surfaces, and these vesicles were stable even in dry conditions. Various microscopic images of the cast film deposited on a mica surface confirmed closed‐ended nanotube/nanorod‐type formation with necking and bulging. These narrow tubes are proposed to be intermediates for the formation of vesicles by fission at either side of the bulge. Such vesicular formation is not common when either cast or Langmuir–Blodgett films were deposited on a solid surface.     

A Uric Acid Biosensor Based on Langmuir-Blodgett Film as an Enzyme-Immobilizing Matrix

A uric acid biosensor was fabricated by the Langmuir–Blodgett (LB) technique to immobilize the uricase on chitosan/Prussian blue (CS/PB) prefunctionalized indium-tin oxide (ITO) electrode. The effects of ionic strengths, acidity of subphase, and uricase amount on the film were studied. The electrochemical properties of the uricase/n-nonadecanoic acid (UOx/NA) LB film proved that CS/PB was a good electro-catalyst for the reduction of hydrogen peroxide produced by enzymatic reaction of UOx, and protein molecules retained their natural electro-catalytic activity. The linear range of uric acid detection was from 5 × 10^?6 mol/L to 1.15 × 10^?3 mol/L with a detection limit of 1.8 × 10^?7 mol/L.     

Langmuir and Langmuir-Blodgett films of proline-rich N-terminal domain peptide of gamma-zein

The proline-rich N-Terminal domain peptides of γ-zein (VHLPPP)_n with n = 1 and 3 (peptides I and II) are shown to form stable Langmuir films at air/water interface and the films have been characterized using surface pressure–molecular area (π–A), surface potential–molecular area (ΔV–A) isotherms, respectively. The longer peptide sequence does not show dramatic increase in surface or interfacial properties suggesting that the minimum length of n = 1 is sufficient to achieve the necessary surface properties. Brewster angle micrographs also agreed with these results. The high surface-active nature of the peptide suggests a fairly non-polar character at air/water interface and at solid/air interface when coated expresses a high surface energy.

Additives such as isopropyl alcohol (IPA) and polyvinyl alcohol (PVA) with the peptides showed more homogenous films at the air/water interface and also improved mechanical and tensile properties. The organized assembly of peptide I at the air/water and solid/air interface suggests that even thin layer of the peptide could play an important role in coating the inner surface of protein body membrane in storage proteins. Composite films of such short peptides with biocompatible polymers may find applications as surface coatings and in biomaterials.     

Structuring of tricarbocyanine dye molecules in Langmuir-Blodgett films

The problems of formation of stable Langmuir monolayers containingN-sulfopropyl substituted thiatricarbocyanine dyes are considered: the effects of the composition of the mixture applied on the surface of an aqueous subphase and of the extent of compression of the monolayer on processes of ordering of molecular structure. Dyes are introduced into complex monolayers at the water-air interface and then are transferred on solid substrates as multilayered Langmuir-Blodgett (LB) films. For the first time the formation of J-aggregates has been observed for two tricarbocyanine dyes. The structure of J-aggregates depends on the composition of the mixture and the value of the constant pressure at which the transfer occurs. LB films of J-aggregated dyes are optically anisotropic, which is related to the fact that they are formed in the monolayer on the surface and there is no interlayer aggregation during the transfer to substrates. Heterodimers are formed in complex monolayers containing oppositely charged ions of dyes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1278–1283, July, 1995.The work was partially financially supported by the Foundation for Basic Research of the State Committee on Science and Technologies of the Ukraine (Project No. 2.2/48 Normal').     

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.     

Synthesis of side chain liquid crystalline copolymers and characterization of their polar structure

A series of side chain liquid crystalline copolymers having different spacer lengths, copolymer compositions, and chromophore types were synthesized and characterized both in the bulk and at the gas‐water interface. Liquid crystalline properties were identified by differential scanning calorimetry (DSC), optical microscopy, and X‐ray diffraction (XRD). Copolymer with spacer lengths 4, 5, 10, and 11 showed smectic A (S_A) phases with a bâtonnet texture. The liquid crystalline (LC) phase stabilized as the spacer increased. Copolymers with different compositions were investigated both as monolayers and transferred films. The isotherms suggest nanodomain formation at the gas‐water interface in copolymers with high nitrobiphenyl (NBP) content. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1057–1070, 1999