Structure and light switching of organic films with an amphiphilic polymer

两亲性聚合物有机薄膜的结构和光开关

• 批准号: 11695033
• 负责人: OZAKI Yukihiro
• 金额: $ 2.82万
• 依托单位: Kwansei Gakuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11695033/
• 关键词: Organic Thin Films; Light Switching; Langmuri-Blodgett-Film; Infrared Spectroscopy; Raman Spectroscopy; ラングミュアープロジェット膜

Molecular orientation, structure and phase transition in Langmuir-Blodgett (LB) films of an amphiphilic polymer consisting of a flexible hydrophilic epichlorohydrin-ethylenediamine slightly cross-linking microgels and a number of hydrophobic stearic chains (ES-3) have been studied by infrared (IR) transmission and reflection-absorption (RA) spectroscopy. The infrared study indicates that the LB films of ES-3 possess crystalline, tightly packed methylene chains and extended interchain hydrogen bonds between the amide groups which connect the alkyl chains with the microgels. A comparison of the band intensities between the transmission and RA spectra suggests that the hydrocarbon chains are highly oriented with a small tilt angle and that N-H and CO bonds of the amide groups and the interchain hydrogen bonds between the N-H and OO bonds are nearly parallel to the surface. The phase transitions have been observed in the narrow temperature ranges near 65, 105, and 140 ーC for multi-layer LB … More films of ES-3. The three temperatures are very close to those for the phase transitions of bulk materials of ES-3, but the transitions occur more sharply for the LB films. Of note is that the transition temperatures of the LB films are markedly different from those of the self-assembling (SA) films previously reported. This may be due to structural differences in the alkyl chains between the two kinds offilms ; the SA films have partial interdigitation of the alkyl tails while the LB films do not have it.A kind of amphiphilic polymer, ES- 1, was transferred onto solid substrates as so-called "reversed duckweed" polymeric LB films. The molecular orientation, structure and phase transition behavior of the films were studied by infrared (IR) transmission and reflection-absorption (RA) spectroscopy. The IR studies have revealed that the alkyl chains are nearly perpendicular to the film surface and assume highly ordered conformation. The first monolayer has different orientation and arrangement from other layers in the ES-1 LB films deposited on Au-evaporated glass slides because of the interaction between the hydrophobic gold surface and hydrophilic head group of ES-1. Temperature-dependent IR measurements of an ES-1 LB film on an Au-evaporated glass slide have shown that the order-disorder phase transition of the film takes place at about 60-C after pretransitional structural modifications. The packing density of alkyl chains decreases gradually with temperature after the order-disorder transition in the LB film. The alkyl chains in an ES-1 casting film on a CaF2 plate are nearly perpendicular to the film surface. However, the alkyl chains of an ES-1 casting film on an Au-evaporated glass slide are tilted considerably. The IR study on the phase transition behavior has revealed that the two casting films on the different substrates give rise to the order-disorder transition at about 75 ーC after undergoing pretransitional structural changes. The alkyl chains in the casting film of ES-1 on the Au-evaporated glass slide show a phenomenon of reorientation ; they change from a more tilted orientation to a more perpendicular orientation before the order-disorder transition takes place, and become tilted again above the transition temperature. Less

用红外透射光谱和反射吸收光谱研究了由亲水性环氧氯丙烷-乙二胺微凝胶和疏水性硬脂酸链组成的两亲聚合物（ES-3）的分子取向、结构和LB膜中的相变。红外光谱研究表明，ES-3的LB膜具有结晶的、紧密堆积的亚甲基链和连接烷基链与微凝胶的酰胺基团之间的延伸的链间氢键。透射光谱和拉曼光谱的谱带强度的比较表明，烃链是高度取向的，具有小的倾斜角，酰胺基团的N-H和CO键以及N-H和OO键之间的链间氢键几乎平行于表面。多层LB膜在65、105和140 ℃附近的窄温度范围内观察到相变 ...更多信息 电影ES-3这三个温度与ES-3体材料的相变温度非常接近，但LB膜的相变发生得更剧烈。值得注意的是，LB膜的转变温度是显着不同的自组装（SA）膜以前报道的。将两亲性聚合物ES- 1转移到固体基底上，制备了“反浮萍”聚合物LB膜.用红外透射和反射吸收光谱研究了薄膜的分子取向、结构和相变行为。红外光谱研究表明，烷基链几乎垂直于膜表面，并呈现高度有序的构象。由于ES-1的疏水性金表面和亲水性头基之间的相互作用，第一单分子层具有与沉积在Au蒸发载玻片上的ES-1 LB膜中的其他层不同的取向和排列。在蒸Au载玻片上的ES-1 LB膜的变温红外光谱测量表明，在预转变结构修饰后，膜的有序-无序相变发生在约60 ℃。LB膜中烷基链的堆积密度在有序-无序转变后随温度的升高而逐渐降低。在CaF 2板上的ES-1流延膜中的烷基链几乎垂直于膜表面。然而，在Au蒸发的载玻片上的ES-1流延膜的烷基链显著倾斜。红外光谱研究表明，在不同基底上的两种铸膜在经历了相变前的结构变化后，在75 ℃左右发生了有序-无序转变。ES-1在Au蒸发的玻璃载玻片上的流延膜中的烷基链显示出重新取向的现象;它们在有序-无序转变发生之前从更倾斜的取向改变为更垂直的取向，并且在转变温度以上再次倾斜。少

项目成果

S.Morita, K.Iriyama, Y.Ozaki: "Aging Effects on Molecular Orientation, Structure, and Morphology in Langmuir-Blodgett Films of 2-Dodecyl+D2-, 2-Pentadecyl-, and 2-ctadecyl-7, 7, 8, 8-tetracyanoquinodimethane Studied by Infrared and Ultraviolet-Visible Spe

S.Morita、K.Iriyama、Y.Ozaki：“老化对 2-十二烷基 D2-、2-十五烷基-和 2-十八烷基-7、7、8 的 Langmuir-Blodgett 薄膜中分子取向、结构和形态的影响

H-S.Wang, Y.Ozaki: "Preparation and Structural Characterization on Mixed-Stack Charge-Transfer Langmuir-Blodgett Films of 2-Octadecyl-7,7,8,8-tetracyanoquinodimethane and N, N, N', N'-Tetramethylbenzid"Langmuir. 16・7. 7070-7074 (2000)

H-S.Wang、Y.Ozaki：“2-十八烷基-7,7,8,8-四氰基醌二甲烷和 N, N, N, N-四甲基联苯胺的混合堆电荷转移 Langmuir-Blodgett 薄膜的制备和结构表征“朗缪尔.16・7.7070-7074 (2000)

A.Miura, N.Tamai: "Picosecond fluorescene dynamics of dioctadecylthodamine βat air/water interface ; Micropolarity and cluster Formation"Chem. Phys. Latt. 328. 23-31 (2000)

A.Miura，N.Tamai：“空气/水界面上的双十八烷基托丹明 β 的皮秒荧光动力学；微极性和簇形成”Chem. 328. 23-31 (2000)

H.S.Wang and Y.Ozaki: "An Infraared Spectroscopy Study on Molecular Orientation and Structure in Mixed Langmuir-Blodgett Films of 2-Octadecyl-7, 7, 8, 8- Tetracyanoquinodimethane and Deuterated Stearic Acid : Phase Separation and Freezing-in Effects of th

H.S.Wang 和 Y.Ozaki：“2-十八烷基-7,7,8,8-四氰基醌二甲烷和氘代硬脂酸混合 Langmuir-Blodgett 薄膜中分子取向和结构的红外光谱研究：相分离和冻结效应

A.Miura, N.Tamai: "Picosecond fluorescene dyamiss of dioctadecylrhodamme B at air/water inferface : micropolarity and cluster formation"J.Phys.Chem.B. (印刷中).

A.Miura，N.Tamai：“双十八烷基罗丹 B 在空气/水界面的皮秒荧光染料：微极性和簇形成”J.Phys.Chem.B（出版中）。