Theoretical Similarity of Macro- and Nano-Interfaces
Theoretical Similarity of Macro- and Nano-Interfaces
批准号:
12640588
负责人:
OSAKAI Toshiyuki
金额:
$2.37万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (C)
财政年份:
2000
资助国家:
日本
项目状态:
已结题
起止时间:
2000 至 2001
中文摘要
标题中的“宏观界面”是指普通电极|溶液或油|水界面,而“纳米界面”是指离子和溶剂分子之间的分子级界面。最近,我们提出了一种新的离子在油桶-水界面上的吉布斯转移能的非玻氏理论,其中离子-溶剂相互作用能由离子表面场强度的二次函数给出。这种依赖性非常类似于汞电极表面张力的电位依赖性(即,电毛细管曲线)。然后,我们建立了一个工作假设-如果宏观界面和纳米界面的界面能本质上相同,那么作为宏观界面的汞电极的表面能也将用电极表面场(E)的二次函数表示,并且二阶系数将与经验溶剂参数(如供体数(D_N),受体数(A_N)等)相关。为了验证这一工作假设,用交流阻抗法测定了汞电极在不同溶剂中的差分容量。利用容量数据,修正了扩散双层的贡献,确定了电极的界面能(γ_1)是E的函数。对于每种溶剂,γ_1都可以由E的二次函数给出,在正或负电位范围内。然后,在E < 0和E < 0时,求二阶系数a_+和a_-。在所有10种溶剂中,a_+和a_-的值与溶剂的任何性质都没有很好的相关性。然而,当排除甲酰胺和n -甲基甲酰胺两种溶剂时,a_+和a_-值与经验溶剂参数D_N (r = 0.821)和A_N (r = 0.910)具有良好的相关性,从而支持工作假设。
英文摘要
The "macro-interface" in the title means common electrode | solution or oil | water interfaces, whereas the "nano-interface" means molecular-level interfaces between an ion and solvent molecules. Recently, we proposed a new, non-Bornian theory of the Gibbs transfer energy of ions across the oil | water interface, in which the ion-solvent interaction energy was given by a quadratic function of the surface field strength of an ion. This dependence is very similar to the potential dependence of surface tension of a mercury electrode (I.e. , electrocapillary curves). We then established a working hypothesis―If interfacial energies of macro- and nano-interfaces are intrinsically the same, the surface energy of a mercury electrode as a macro-interface will also be expressed by a quadratic function of the surface field (E) of the electrode, and the second-order coefficient will correlate with empirical solvent parameters such as donor number (D_N), acceptor number (A_N) , etc.In order to verify this working hypothesis, the differential capacities of a mercury electrode in various solvents were measured by means of an a.c. impedance method. By using the capacity data, the interfacial energy (γ_1) of the electrode, being corrected for the contribution from the diffuse double layer, was determined as a function of E. For every solvent, γ_1 could be given by a quadratic function of E in either positive or negative potential range. The second-order coefficients, a_+ and a_-, were then evaluated for E > 0 and E < 0. Regarding all ten solvents examined, the values of a_+ and a_- did not show good correlation with any properties of the solvents. However, when excluding two solvents, formamide and N-methylformamide, the a_+ and a_- values showed good correlation with empirical solvent parameters such as D_N (r = 0.821) and A_N (r = 0.910), thus supporting the working hypothesis.
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J.Ding: "Ion Transfer of Reduced Keggin-type Heteropolymolybdate Anions at the Nitrobenzene/Water Interface and its Relevance to their Antitumoral Activities"Electroanalysis. (In press).
J.Ding:“硝基苯/水界面上还原的 Keggin 型杂多钼酸盐阴离子的离子转移及其与抗肿瘤活性的相关性”电分析。
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T. Osakai et al: "Mechanistic Aspects Associated with the Oxidation of L-Ascorbic Acid at the 1,2-Dichloroethane/Water Interface"J. Electroanal. Chem.. 510. 43-49 (2001)
T. Osakai 等人:“与 L-抗坏血酸在 1,2-二氯乙烷/水界面氧化相关的机理”J。
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A.G.Volkov: "Liquid Interfaces in Chemical, Biological, and Pharmaceutical Applications"Marcel Dekker, Inc.. 853 (2001)
A.G.Volkov:“化学、生物和制药应用中的液体界面”Marcel Dekker, Inc. 853 (2001)
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J.Ding: "Ion Transfer of Reduced Keggin-type Heteropolymolybdate Anions at the Nitrobenzene/Water Interface and its Relevance to their Antitumoral Activities"Electroanalysis. 13・5. 384-391 (2001)
J.Ding:“硝基苯/水界面上的还原Keggin型杂多钼酸盐阴离子的离子转移及其与抗肿瘤活性的相关性”13・5(2001)。
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大堺利行: "ベーシック電気化学"化学同人. 216 (2000)
Toshiyuki Osakai:“基础电化学”化学同人 216 (2000)。
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共 20 条
Can the oil/water interface be a model system of biomembrne? -Similarities and Differences as the reaction field of electron transfer-
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批准号:23550095
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$3.33万
-
财政年份:2011
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负责人:OSAKAI Toshiyuki
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依托单位:
Development of the Electrochemical Separation/Detection System for Proteins Using the Oil/Water Interface
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批准号:20550076
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$3.16万
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财政年份:2008
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负责人:OSAKAI Toshiyuki
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依托单位:
Development of a Sensor for Direct Detection of Proteins Based on Reverse Micelle Electro-extraction
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批准号:18550072
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$2.64万
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财政年份:2006
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负责人:OSAKAI Toshiyuki
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依托单位:
Scanning electrochemical microscopic study of electron transfer at the oil/water interface as a biomembrane model
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批准号:16550073
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$2.37万
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财政年份:2004
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负责人:OSAKAI Toshiyuki
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依托单位:
Does an electron transfer really occur at the oil/water interface?
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批准号:14540557
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$2.56万
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财政年份:2002
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负责人:OSAKAI Toshiyuki
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依托单位:
Water-Ion Interactions in Hydrophobic Environments
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批准号:10640593
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$2.37万
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财政年份:1998
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负责人:OSAKAI Toshiyuki
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依托单位:
海外基金