Real Time Monitoring of Electron Transfer Dynamics at Solid/liquid Interfaces by Non-linear Spectroscopy

通过非线性光谱实时监测固/液界面的电子传递动力学

• 批准号: 16072202
• 负责人: UOSAKI Kohei
• 金额: $ 33.66万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16072202/
• 关键词: Non-linear Spectroscopy; electron transfer dynamics; semiconductor nanocluster; pump-probe measurement; solid; liquid interface

To understand the mechanism of electron transfer dynamics at solid/liquid interfaces, information of structures of molecules at electrode/electrolyte interface including short-lived intermediates and solvent at the interface is essential. The determination of the interfacial structures of the intermediate and solvent is, however, difficult by conventional surface vibrational techniques because of small number of molecules compared to bulk molecules. Temporal vibration of vibrational modes induced by electronic excitation is monitored by IR adsorption and surface-specific sum frequecy generation (SFG) techniques. We investigated the relations between interfacial structures and reaction dynamics by using these spectroscopic methods.1. Observation and dynamics of adsorbates at solid/liquid interfaces by SFG spectroscopyDynamics of adsorbed CO on Pt electrode was followed by visible pump SFG probe measurements. An SFG peak due to adsorbed CO at on-top site of Pt was observed at 2064cm-l. T … More he intensity of this peak decreased quickly upon excitation and recovered within few ten of os. A new broad peak was observed at 1980cm-l corresponding to adsorbed CO at multi-fold site, suggesting the site exchange upon excitation. The recovery rate was found to be dependent on potential.2. Carrier and charge transfer dynamics by visible pump-visible and IR techniqueTime-resolved visible-pump visible and infrared-probe techniques, in which very short UV or visible pulse excitation is combined with delayed ultrafast visible and mid-IR absorption, respectively, are powerful tools to monitor the changes in electronic and molecular structure, respectively, as after the photoexcitation. In the present study, (1) a system, which allows these two measurements, was constructed, (2) visible-pump infrared-probe technique was applied to study the effect of size and surface treatment on the carrier dynamics of CdS, and (3) visible-pump visible and infrared-probe techniques were applied to study the photo-induced intra-molecular charge transfer with a triruthenium complex [Ru_3(O)(CH_3CO2)_6(CO)L_2], where L=ligands, containing a strongly IR active ligand, CO, which act as a direct IR probe of the electron density at the metal center.3. Characterization of water structure at biomaterial surfacesMany biological systems such as proteins and enzymes are inactive without water. For a complete understanding of the function of such systems, information of the structure and dynamics of the water is essential. We incestigated the structure of water at several biomaterial surfaces. For example, we monitored the structure of interfacial water at hydro-polymer gel/solid interface by SFG spectroscopy under various pressures. The contribution of weakly hydorogen bonded water in SFG spectra increased with pressure, suggesting the inportant role of weakly hydorogen bonded water to the low friction properties at the hydro-polymer gel/solid interfaces. Less

为了了解固体/液体界面上电子传递动力学的机制，必不可少的电极/电解质界面上分子结构的信息是必不可少的。然而，由于与散装分子相比，由于分子数量少，在常规的表面振动技术中确定中间和偿付能力的内部结构很难。通过IR吸附和表面特异性的总和产生（SFG）技术来监测通过电子兴奋引起的振动模式的时间振动。我们通过使用这些光谱方法研究了界面结构与反应动力学之间的关系。1。 PT电极上吸附CO的SFG光谱动力学在固体/液体界面上对吸附物的观察和动力学，然后进行可见的泵SFG探针测量。在2064cm-L处观察到在PT的顶部位点吸附的CO引起的SFG峰。 t…兴奋后，他的强度更快迅速降低，并在OS几十个OS内恢复。在1980cm-l上观察到了一个新的宽峰，该峰在多折位点对应于吸附的CO，这表明兴奋时的现场交换。发现回收率取决于电势。2。通过可见的泵可见和IR技术排列的可见可见泵和感染的探针技术，载体和电荷传输动力学，其中非常短的紫外线或可见脉冲兴奋与延迟的超快可见和中等抽象相结合，是在电子和分子结构中的变化，又是Photosex的强大工具。在本研究中，（1）构建了允许这两个测量的系统，（2）应用可见的泵感染技术来研究尺寸和表面处理对CD的尺寸和表面处理对CD的载体动力学的影响，以及（3）可见的泵可见和可见的和红外的螺旋形技术，以研究与照片诱导的内部诱导的内部电荷转移，以研究形式诱导的环内电荷转移。 [ru_3（o）（ch_3co2）_6（co）l_2]，其中l =配体，包含强烈的IR活性配体Co，它充当金属中心的电子密度的直接IR探针3。在生物材料表面上的水结构（例如蛋白质和酶）在没有水的情况下表征。为了完整了解此类系统的功能，必不可少的水结构和动力学信息。我们激发了几个生物材料表面的水结构。例如，我们通过在各种压力下通过SFG光谱法监测了水聚合物凝胶/实心界面处的界面水的结构。 SFG光谱中虚弱的水力基因键合的贡献随压力增加，这表明弱氢键水对水力聚合物凝胶/固体界面的低摩擦特性的重要作用。较少的

项目成果

Interfacial Water Structure at As-Prepared and UV-Induced Hydrophilic TiO2 Surfaces Studied by Sum Frequency Generation Spectroscopy and Quartz Crystal Microbalance

• DOI: 10.1021/jp045173f
• 发表时间: 2004-11
• 期刊: Journal of Physical Chemistry B
• 影响因子: 3.3
• 作者: K. Uosaki;and Takanobu Yano;S. Nihonyanagi

分子素子及びその製造方法ならびに集積回路装置およびその製造方法

分子器件及其制造方法集成电路器件及其制造方法；

• 发表时间: 2005

Sum Frequency Generation Study at Solid/Liquid Interfaces(Invited)

固/液界面和频产生研究（特邀）

• 发表时间: 2006
• 作者: K. Uosaki;H. Noguchi;T. Okada;M. Ito;K. Uosaki
• 通讯作者: K. Uosaki

Oxidation States an CO Ligand Exchange Kinetics in a Self-Assembled Monolayer of a Triruthenium Cluster Studied by In Situ Infrared Spectroscopy

原位红外光谱研究三钌簇自组装单层中氧化态CO配体交换动力学

• 发表时间: 2005
• 期刊: Chemistry-A European Journal 11,No.17
• 作者: Makoto Sakai;Tsutomu Ohmori;Masaaki Fujii(章著);I. Yagi;H. Wano;Y. Sato;H. Noguchi;W. Zhou;M. Okamura;I. Yagi;I. Yagi;W. Zhou;H. Noguchi;Y. Sato;M. Okamura;H. Wano;I. Yagi;M. Abe;I. Yagi;Hiromi Wano;Yukari Sato;Hidenori Noguchi;Wei Zhou
• 通讯作者: Wei Zhou

Unfolding, aggregation, and amyloid formation by the tetramerization domain from mutant p53 associated with lung cancer

• DOI: 10.1021/bi051192j
• 发表时间: 2006-02-14
• 期刊: BIOCHEMISTRY
• 影响因子: 2.9
• 作者: Higashimoto, Y;Asanomi, Y;Sakaguchi, K
• 通讯作者: Sakaguchi, K