Preparation of Clay Monolayr and its Application of Electrode Modifier for Asymmetric Syntheses

粘土单分子层的制备及其在不对称合成中电极改性剂的应用

• 批准号: 07404039
• 负责人: YAMAGISHI Akihiko
• 金额: $ 13.25万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07404039/
• 关键词: Clay Minerals; Monolayr Film; Modified Electrode; Asymmetric Syntheses; 不斉合成; 自己集積; 不斉電極; 修飾膜

In this project, the preparation of the ultra-thin film of a clay mineral has been achieved. The method is based on the layr-by-layr deposition of the monolayr of hydrophobic clay particles on an air-water interface (LB method). The structure of a film has been studied with FT-IR spectroscopy, X-ray diffraction measurements and atomic force microscopic observations. As a result, a homogenous film is obtained whose thickness is controlled on a nanometer scale. The clay layrs are oriented parallel with the film surface. Such a film has been used to modify an glassy carbon electrode. By immersing the modified electrode in an aqueous solution of a redox active metal complex, the film intercalates the metal complex and becomes electroactive. The measurements of cyclic voltammogram on the electrode have revealed that the diffusion constant of an electroactive species in a film depends on the thickness of a film critically. It increased exponentially with the layr number of a film. The dependence suggests that carrier transport takes place in a hopping mechanism. The modified electrode is now applied for the asymmetric syntheses of naphthol into optically active binaphthol.

本课题实现了一种粘土矿物超薄膜的制备。该方法是基于单层疏水粘土颗粒在空气-水界面上逐层沉积（LB法）。用傅里叶变换红外光谱、x射线衍射测量和原子力显微镜观察研究了薄膜的结构。结果，得到了厚度控制在纳米尺度上的均匀薄膜。所述粘土层取向与所述薄膜表面平行。这种薄膜已被用来修饰玻碳电极。通过将修饰电极浸入氧化还原活性金属配合物的水溶液中，膜嵌入金属配合物并具有电活性。电极上循环伏安图的测量表明，膜中电活性物质的扩散常数与膜的厚度密切相关。它随着薄膜层数的增加呈指数增长。这种依赖性表明，载流子输运是以跳跃机制进行的。该修饰电极现已应用于萘酚的不对称合成成旋光性双萘酚。

项目成果

Y.Inose & K.Naing: "Chiral Monolayr of Self-Assembled DELTA-[Os (bpy) _2L(Cl)] ^+ on a Platinum Electrode" Journal of Chemical Society. Chemical Communications.111. (1997)

伊诺什

Akihiko Yamagishi: "Stereochemical Effects on Monolayer Formation of 〔Ru (dpp)_3〕^<2+> (dpp=4,7-Diphenyl-1,10-phenanthroline) at an Air-Water Interface" The Journal of Physical Chemistry. 100・5. 1827-1832 (1996)

Akihiko Yamagishi：“空气-水界面上 [Ru (dpp)_3]^<2+> (dpp=4,7-二苯基-1,10-菲咯啉) 单层形成的立体化学效应”物理化学杂志。 100・5。1827-1832（1996）

A.Yamagishi, B.M.Sakamoto & K.Shimizu: "Stereochemical Effects on Monolayr Formation of a Chiral Amphiphilic Ruthenium (III) Complex." Langmuir. 13. 1689-1694 (1997)

A.山岸、B.M.坂本

A.Yamagishi: "Stereochemical Effects on Monolayr Formation of [Ru(dpp)_3] ^<2+> at an Air-Water Interface" Journal of Physical Chemistry. 100. 1827-1832 (1996)

A.Yamagishi：“空气-水界面上 [Ru(dpp)_3] ^<2 > 单层形成的立体化学效应”物理化学杂志。

Yuji Hotta: "A Clay Self-Assembled on a Gold Surface" Chemistry Letters. 83-84 (1997)

Yuji Hotta：“在金表面自组装的粘土”化学快报。