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Theoretical Similarity of Macro- and Nano-Interfaces

Theoretical Similarity of Macro- and Nano-Interfaces
宏观和纳米界面的理论相似性
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

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中文摘要
翻译
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”是指离子与溶剂分子之间的分子级界面。最近,我们提出了一种新的关于离子在油/水界面上的Gibbs转移能的非玻尔理论,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。这种依赖关系非常类似于汞电极表面张力的电势依赖关系(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,汞电极作为宏观界面的表面能也将由电极表面场(E)的二次函数表示,二阶系数将与经验溶剂参数相关,如施主数目(D_N)、受主数目(A_N)等。为了验证这一工作假设,用交流电流法测量了汞电极在不同溶剂中的微分电容。阻抗法。根据电容数据,经扩散双电层贡献修正后的电极界面能(γ_1)为E的函数。对于每种溶剂,γ_1均可由E在正负电势范围内的二次函数给出。然后评估了E>0和E<0的二阶系数a_和a_-。在所考察的10种溶剂中,a_和a_-值与溶剂的任何性质都没有显示出很好的相关性。在排除甲酰胺和N-甲基甲酰胺两种溶剂时,a_n和a_-值与D_N(r=0.821)和A_N(r=0.910)等经验溶剂参数有很好的相关性,从而支持了工作假说。
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.
期刊论文(21)
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会议论文
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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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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20
    Can the oil/water interface be a model system of biomembrne? -Similarities and Differences as the reaction field of electron transfer-
    • 批准号:
      23550095
    • 项目类别:
      Grant-in-Aid for Scientific Research (C)
    • 资助金额:
      $3.33万
    • 财政年份:
      2011
    • 负责人:
      OSAKAI Toshiyuki
    • 依托单位:
    Development of the Electrochemical Separation/Detection System for Proteins Using the Oil/Water Interface
    • 批准号:
      20550076
    • 项目类别:
      Grant-in-Aid for Scientific Research (C)
    • 资助金额:
      $3.16万
    • 财政年份:
      2008
    • 负责人:
      OSAKAI Toshiyuki
    • 依托单位:
    Development of a Sensor for Direct Detection of Proteins Based on Reverse Micelle Electro-extraction
    • 批准号:
      18550072
    • 项目类别:
      Grant-in-Aid for Scientific Research (C)
    • 资助金额:
      $2.64万
    • 财政年份:
      2006
    • 负责人:
      OSAKAI Toshiyuki
    • 依托单位:
    Scanning electrochemical microscopic study of electron transfer at the oil/water interface as a biomembrane model
    • 批准号:
      16550073
    • 项目类别:
      Grant-in-Aid for Scientific Research (C)
    • 资助金额:
      $2.37万
    • 财政年份:
      2004
    • 负责人:
      OSAKAI Toshiyuki
    • 依托单位:
    海外基金