Adsorption Kinetics of Polyelectrolyte onto Monolayers

聚电解质在单分子层上的吸附动力学

• 批准号: 01470101
• 负责人: MIYANO Kenjiro
• 金额: $ 4.16万
• 依托单位: The University of Tokyo, Faculty of Engineering
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470101/
• 关键词: Polyion comprex; ATR method; Monolayer; Electrostatic absorption; LB film; ポリマ-吸着

The adsorption kinetics of an electrolyte polymer onto a monolayer spread on the solution has been studied by means of the attenuated total reflection (ATR) method. The polymer was PSSK (potassium poly-(Stylenesulfonate) : anion) and the monolayer DOAB (dioctadecyl-dimethyl-ammonium-bromide : cation). A glass prism (SFS-1 glass) whose hypotenuse surface was coated with a thin (-500 A) Ag film was pressed onto a monolayer of DOAB spread on pure water. The ATR signal caused by the SPP (surface plasmon polariton) at the Ag/monolayer interface was monitored. The subphase water was then slowly replaced with the polymer solution of varing concentration. The shift of the ATR dip indicates the thickness of the polymer adsorbed onto the monolayer and the width signals the inhomogeneity of the polyemer layer. We found that the adsorption occurred in two steps ; first the adsorbed layer was monomolecular (thickness - 5A), then it grew into a thick and inhomogeneous film. The initial layer thickness was independent of the molecular weight of the polymer. The final thickness, however, depended on the molecular weight weakly (d=16A for n=3500 and d=33A for n=42000, where n is the degree of polymerization) suggesting loops and tails in the film at this stage. We also found that the adsorption was completely absent onto a non-cationic monolayer (stearic acid) within the resolution of our method. CONCLUSION : The polymer adsorption onto a spread monolayer is completely governed by the charge nutrality (at least in the early stage of the adsorption) and a 1 : 1 polyion complex is indeed formed at the solution/monolayer interface as has long been speculated.

用衰减全反射（ATR）方法研究了电解质聚合物在溶液表面单层膜上的吸附动力学。聚合物是PSSK（聚苯乙烯磺酸钾：阴离子）和单层DOAB（双十八烷基二甲基溴化铵：阳离子）。将斜边表面涂有薄（-500A）银膜的玻璃棱镜（SFS-1玻璃）压在涂在纯水上的单层DOAB上。在Ag/单层界面处由SPP（表面等离子体激元）引起的ATR信号被监测。然后用不同浓度的聚合物溶液缓慢地替换亚相水。ATR倾角的偏移指示了吸附到单层上的聚合物的厚度，并且宽度指示了聚合物层的不均匀性。我们发现，吸附发生在两个步骤，首先吸附层是单分子（厚度-5A），然后它生长成一个厚的和不均匀的膜。初始层厚度与聚合物的分子量无关。然而，最终厚度弱地依赖于分子量（对于n=3500，d= 16 A;对于n=42000，d= 33 A，其中n是聚合度），表明在该阶段膜中存在环和尾。我们还发现，在我们的方法的分辨率内，吸附完全不存在于非阳离子单层（硬脂酸）上。结论：扩散单层上的聚合物吸附完全由电荷中性（至少在吸附的早期阶段）和1：1的聚离子复合物确实是在溶液/单层界面形成，长期以来一直推测。

项目成果

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M.Shimomura：“固定在双层膜带电表面上的紫罗碱聚合物的二维排序”Langmuir - 出版中（1991 年）。

M. Shimomura et al.: "Two-dimensional Ordering of Viologen Polymers Fixed on Charged Surface of Bilayer Membranes" Langmuir. (1991)

M. Shimomura 等人：“固定在双层膜带电表面上的紫罗碱聚合物的二维排序”Langmuir。

N. Oyama et al.: "In-situ Quartz Crystal Microbalance Responses and Electrochemistry Regarding LB Film of Viologen Polyion Comprexes on Electrode Surface" J. Electroanal. Chem.(1991)

N. Oyama 等人：“关于电极表面紫罗碱聚离子复合物 LB 膜的原位石英晶体微天平响应和电化学”J. Electroanal。

K.Miyano: "Adsorptin Kinetics of Waterーsoluble Polymers onto a Spread Monolayer" Langmuir ー in press. (1991)

K. Miyano：“水溶性聚合物在铺展单层上的吸附动力学”Langmuir - 出版中（1991 年）。

N. Oyama: "Inーsitu Quartz Crystal Microbalance Responses and Electrochemistry Regarding LB Film of Viologen Polyion Complexes on Electrode Surface" J. Electroanal. Chem.(1991)

N. Oyama：“关于电极表面紫罗碱聚离子络合物 LB 膜的原位石英晶体微天平响应和电化学”J. Electroanal Chem。（1991）