STUDIES ON LANGMUIR-BLODGETT FILM OF METAL COMPLEXES(Ⅰ)-PREPARATION AND CHARACTERIZATION OF THE LB FILM OF N-HEXADECYL PYRIDINIUM TETRAKIS(1-PHENYL-3-METHYL-4-BENZOYL-PYRAZOL-5-ONE)EUROPIUM,C_5H_5NC_(16)H_(33)Eu(PMBP)_4

The LB film of the title complex was prepared by dropping a benzene solution of the title complex on the surfaceof water subphase at 25±1℃.The film was deposited in Z type on various hydrophilic pretreated substrates ofquartz,CaF;and electronic conductive glass for different purposes.The π-A curve of the film shows that thecross section per molecule is 125;,which indicates that the alkyl chain of the molecule is basically perpendiculalto the surface of the substrate.UV,IR spectra and transmission electronic microscopy of the film were also obtained.

Luminescent Properties of Europium Complexes with Different Long Chains in Langmuir-Blodgett (LB) Films

A series of europium(III) complexes with different chain length, tris [2-m-pyridylmethanamido-5-phenyl- (1,3,4)-oxadiazole] mono [2-(4-n-alkylphenyl)-iminazole (4,5-f)-1,10-phenanthroline] Eu(III) [Eu(PMA)3Nn (n = 6, 10, 14,18)] were synthesized. All of these amphiphilic europium(III) complexes could form stable Langmuir film at air/water interface and could be transferred onto hydrophilic quartz and mica substrates by measurement of UV spectra in which the absorbance of the LB films at about 288 nm scales showed the linearity with the number of layers deposited. In order to investigate relation between fluorescence properties and the arrangement of molecular in LB films, surface topography of monolayer films were observed by atomic force microscopy (AFM). Results showed that the emission spectra have Eu(III) characteristic peaks and strong emission strength. It is interesting that the molecular with looser arrangement in LB films has better monochromacity, which illustrated that energy might transferred more easily from ligand to Eu(III) in loosen structure films.

Acidichromism in the LB film of bolaform Schiff base

A bolaform （BNC10） and single-headed （HNOA） amphiphilic Schiff bases containing naphthyl group were designed and their Langmuir-Blodgett films were investigated. It was found that both the LB films show acidichromism, i.e. a reversible color change upon alternatively exposing the films to HC1 and NH3 gases, respectively. It was further found that the bolaform Schiff bases film could trap NH3 gas during the acidichromic process.

Synthesis and Langmuir-Blodgett Film Analysis of Atropisomers of “Picket Fence” Porphyrin

Four ＂picket fence＂ porphyrin atropisomers were respectively synthesized from the four corresponding atropisomers of meso-tetra（o-aminophenyl）porphyrin that had been chromatographed on a column eluted with petroleum ether and ethyl acetate. Results show that each atropisomer could be successfully synthesized by controlling the acylation temperature at 0 ℃. They were characterized by 1H NMR, HRMS, IR, UV-Vis and Langmuir-Blodgett（LB） film analyses. Although the results of HRMS, IR, UV-Vis analyses indicate there is no remarkable difference among the atropisomers, the results of the 1H NMR and the mean molecular areas obtained by LB film technique imply that the atropisomers are significantly discrepant. The former shows that the chemical shifts of the methyl and amide protons of each atropisomer are distinct, while the later presents that the different atropisomer molecules can occupy the different surface areas at the air/water interface.

Langmuir-Blodgett膜技术的应用研究进展

综述了Langmuir-Blodgett(LB)膜及膜技术的产生及发展过程、表征方法和具有可控堆积密度的成膜特性。分别介绍了LB膜技术在检测传感器、界面纳米结构、化学催化等方面的应用进展,重点阐述了其气体传感器、仿生学传感器、电化学传感器等领域的应用和研究现状,并讨论了应用过程中存在的优缺点,总结了LB膜技术的缺陷,并对膜制备材料与功能性溶剂毒性的问题进行了展望。

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.

Interfacial Behaviors of Azocalixarene Derivatives at the Air/Water Interface and Photochromism in the Langmuir-Blodgett Films

The interfacial behaviors of the non-typical amphiphilic compound p-methylphenylazocalix[4]arene 1 and p-chlorophenylazocalix[4]arene 2 at the air/water interface and photochromism in the Langmuir-Blodgett films were studied by surface pressure-area isotherm and UV-Vis spectra. The results indicate that they can form stable monolayers at the air / water interface although they have no hydrophobic alkyl chains, and their LB film underwent reversible trans-cis photoisomerization on UV and daylight illumination.

The Aggregates in LB Films of Schiff base Aluminium (III) Complex

The surface pressure-area (pi -A) isotherm of Schiff base aluminium (III), tris (2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium (III) (denoted as Al(TAl2)(3)), on pure water subphase was investigated. The molecular area, 0.48 nm(2), is one-third of expected value that indicated the aggregation took place. The Langmuir-Blodgett (LB) films of Al(TAl2), was transferred and characterized. The AFM image confirmed the formation of aggregates.

The LB Films of Dansyl Chloride Labeled Octadecylamine and Its Fluorescence Lifetime

Octadecylamine was derivatized with dansyl chloride (5-dimethylaminonaphthalene-1-sulfonyl chloride) In order to simplify and understand the LB films of fluorescent probe labeling proteins. its monolayer and multilayers in the absence and presence of stearic acid were deposited by LB technique. Fluorescence spectra and lifetimes of the fluorescent products were studied to elucidate the microenvironment of molecules in the LB films.

PREPARATION OF PHOTOFUNCTIONAL POLYMER THIN FILMS BY LANGMUIR-BLODGETT TECHNIQUE

Polymer LB films containing photofuntional groups were prepared by the copolymerization of N-dodecylacrylamide (DDA), which has an excellent property to form a stable monolayer and LB multilayerswith photofunctional monomers. Tris(2, 2'-bipyridine) ruthenium complex, Ru(bpy)_3^(2+), one of the most well-known redox-active sensitizer, was incorporated into the DDA copolymer. The photogalvanic effect based onthe photoinduced electron transfer using the ruthenium complex in the polymer LB monolayer was discussed.

Nanoscale Hybrid Langmuir-Blodgett Films Based on Cerium-Substituted Heteropolymolybdate and Polyquinoline

Nanoscale hybrid organic/inorganic Langmuir-Blodgett films of cerium-substituted heteropolymolybdates(Ce-HPMo) and π-conjugated macromolecule poly(1,2-dihydro-2,2,4-trimethyl)quinoline(PQ) were obtained with auxiliary film-forming material stearic acid(SA) or octadecylamine(ODA). The surface pressure-area isotherms illuminate the formation of the hybrid LB films of PQ/ODA/Ce-HPMo and PQ/SA/Ce-HPMo. The different film-forming mechanism was discussed when the different auxiliary film-forming materials were used in the system. The absorption spectra indicate that the molecules of PQ and Ce-HPMo are incorporated into the LB films. Tapping-mode AFM image reveals a granular surface texture of nanosized Ce-substituted heteropolymolybdate. STM image shows that the conductivity is greatly improved after Ce-substituted heteropolymolybdates are incorporated in the films.

FLUORESCENCE AND ITS ENHANCEMENT OR QUENCHING OF Eu(TTA)_3 Phen LB FILMS

For the first time, LB films containing Eu(TTA)3Phen are obtained by using composite subphase. Eu(TTA)3Phen itself is dimcult to be transferred onto solid substrate.mixed or alternate LB films are prepared. Hydrogen bonds form between Eu(TTA)3Phen and AA or TPP(-COOH). TOPO and SB have a fluorcscence enhanGement effect on Eu(TTA)3Phen. TPP(-COOH) and Fc have a fluorescence quenching effect on it.

PHASE SEPARATION OF RETINAL SCHIFF BASE IN TWO-COMPONENT LB FILM WITH DIFFERENT LIPIDS

Phase sepertion of 9-cis-retinal schiff base in two-component LB film with different lipids has been observed under Brewster Angle Microscope

Monolayers Langmuir-Blodgett Films of Synthetic Artificial Mimic Molecules That Resemble the Following Tetraether Lipids on Silicon Wafers

This study investigated the behavior and molecular organization of synthetic artificial mimic molecules that resemble the following tetraether lipids: di-O-hexadecyl-glycero-3-phosphatidyl-glycerol (DHGPG) and bis-4-dodecylphenyl-12-phosphate. These molecules were analyzed using Langmuir film balance, ellipsometry and atomic force microscopy. The monolayer Langmuir-Blodgett films of DHGPG and bis-4-dodecylphenyl-12-phosphate were stable on the solid surface silicon wafers. The ellipsometry and AFM results showed that monolayers Langmuir-Blodgett films of DHGPG and bis-4-dodecylphenyl-12-phosphate were present, and the thickness of the observed films varied from 1.2 - 5.0 nm.

Gas Sensitivity of Poly (3, 4-ethylene dioxythiophene) Prepared by a Modified LB Film Method

An arachidic acid/poly （3, 4-ethylene dioxythiophene） （AA/PEDOT） multilayer Langmuir-Blodgett （LB） film was prepared by a modified LB film method. The theories were utilized to explain the effects between HCl molecule and LB film. The gas sensitivity mechanism of poly （3, 4-ethylene dioxythiophene） （PEDOT） multilayer film can be explained by the charge transfer between p system of PEDOT and oxidization HCl system. The gas sensitivity of PEDOT LB film deposited interdigital electrode to HCl was tested. The results showed that film thickness, treating temperature, deposition speed had different influence on film gas sensitivity. The AA/PEDOT film deposited device exhibited nonlinear behavior to HCl gas at lower concentration （20-60 ppm） and linear response behavior at higher gas concentration was observed. The time of the compound LB film of the AA/PEDOT responding to the 30 ppm HCl gas is about 20 seconds, which is far quicker than the time of the film to the PEDOTPRESS film（about 80 seconds）. It is not higher film press to better film. When the film press attains 45 mNs/m, the sensitivity of the AA/PEDOT film on the contrary descends.

Preparation and Characteristics of Stearic Acid/PEDOT(PSS) Langmuir-Blodgett Films

Mixed Stearic acid and poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) Langmuir- Blodgett(LB) films were successfully fabricated by the conventional vertical dipping method.Stearic acid and PEDOT/PSS was dissolved in chloroform and spread on subphase containing 0.04wt% FeCl_3.Conductive Y-type mixed LB films was successfully prepared under the condition of surface pressure with 30 mN/m,pH 3.8,and 19℃.UV-VIS spectrum showed that well ordered layer-by-layer fabrication of mixed films were obtained and thickness of single layer film with about 5 nm was evaluated.The morphology image of mixed LB film was observed by atomic force microscopy (AFM).The conductivity of mixed LB film was about 1.8×10^(-5)S/cm and the film showed sensitivity to NH_3 at the same time.

Novel Mixed LB Films of Porphyrin and Phthalocyanine Based on Molecular Recognition

The potassium salt of monocarboxylic substituted porphyrin acid mono crown ether substituted phthalocyanine can form heterodimer in solution and this kind of heterodimer can be fabricated into highly ordered LB films. The structures of the film were identified by absorption spectra polarized absorption spectra and low angle X-ray diffraction methods.

A New Method of Photopatterning with LB Films Based on a Chemically Amplified Mechanism

A new approach to introducing a photoacid generator（PAG） into Langmuir-Blodgett （LB） films to draw photopatterns as a lithographic process is described here. The chemically amplified positive-tone resist system used here consists of two components ： a copolymer, poly （ dodecrylacrylamide-co-4-t-butyloxylvinyl-phenylcarbonate ） [ P （ DDA-t- BVPC53 ） ] and a PAG, tri （2,3-dibromopropyl） isocyanurate （ TDBPIC ）. In the two-component system, the acid generated by the PAG catalyzes the deprotection reaction of P（ DDA-t-BVPC53）, to remove the tert-butoxycarbonyl group（t-BOC） in the exposed region during the postexposure baking process, thus rendering the exposed region soluble to alkaline aqueous solvents to form a positive tone. Photolithographic properties of the LB films have been evaluated. The patterns can be resolved with a resolution of 1 μm line width by UV irradiation, followed by development with an alkaline solution. The LB films can be used to generate etched gold relief images on a glass substrate via an aqueous iodide, like ammonium iodide, in alcohol/water as the etchant. The etch resistance of such LB films is sufficiently good, allowing patterning of a gold film suitable for photomask fabrication.

Structure and Orientation of 1-(Hydroxyl)-5-(dodecyloxy)-naphthalene LB Films by Polarized Fluorescence Spectroscopy

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Preparation and Luminescence Properties of LB Films Based on 4-Hexadecyloxybenzoic Terbium

LB films of 4 hexadecyloxybenzoic terbium by using the subphase containing Tb 3+ were prepared. The monolayer behavior of 4 hexadecyloxybenzoic acid (HOBA) on the subphase containing rare earth ions was studied. IR and UV spectra show that the rare earth ions were bound to carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The luminescence spectra show that the LB films have the fine luminescence properties, and the LB films emit strong luminescence under UV light irradiation.