One-electron Reduction and Electron Transfer Reaction Controlled by Cyclodextrin Inclusion Complexation

环糊精包合络合控制的单电子还原和电子转移反应

基本信息

  • 批准号:
    05650826
  • 负责人:
  • 金额:
    $ 1.22万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
  • 财政年份:
    1993
  • 资助国家:
    日本
  • 起止时间:
    1993 至 1994
  • 项目状态:
    已结题

项目摘要

Cyclodextrins (CDs) form inclusion complexes with various organic molecules in aqueous solution depending on the sizes of their hydrophobic cavities and of the guest molecules. The preset pulse radiolysis study is concerned with the one-electron reduction of aromatic carboxylates and sulfonates controlled by the inclusion comlexation. The pulse radiolysis of aqueous solutions of the aromatic electrolytes results in the one-electron reduction of the aromatic moieties of the solutes by the hydrated electron. The reaction is effectively retarded when the hydrophobic aromatic moieties are included in the CD cavities. Thus, the rate constants for the one-electron reduction of biphenyl-4-carboxylate (BPC), biphenyl-4-asetate (BPA) and biphenyl-4-sulfonate (BPS) are appreciably reduced by the complexation with beta-CD,whose cavity best fits to the biphenylyl group. Similarly, the one-electron reduction of pyrene-1-carboxylate (PyC), 4-pyren-1-ylbutyrate (PyB) and pyrene-1-sulfonate (PyS) is r … More etarded by the best fitting gamma-CD.The control of the one-electron reduction and electron transfer reactions has been examined for the solutions of mixtures of the sulfonates. The selective reduction of a mixed BPS and PyS solution has been achieved by using beta-and gamma-CDs. The electron transfer from the reduced BPS to PyS is also retarded effectively by the complexation of PyS with gamma-CD.The pH dependence of the effect of the complexation has demonstrated that a 1 ; 2 complex is formed between BPC and alpha-CD but not between BPC and alpha-CD because of the steric effect of the methylene group of BPA.The apparent retarding effect of alpha-CD on the one-electron reduction of BPC is observed at much higer host concentrations compared with that of beta-CD.PyC,PyB and PyS form 2 ; 2 complexes with gamma-CD,and the complexes of PyC and PyS undergo a structural change upon the one-electron reduction of the guests. The association constants of the 1 ; 1 complexes of BPC,BPA and BPS have been determined from the pulse radiolysis data. Less
环糊精(CDS)在水溶液中与各种有机分子形成包合物,这取决于它们的疏水空腔和客体分子的大小。预置脉冲辐解研究由包合物配位控制芳香族羧酸盐和磺酸盐的单电子还原。芳香电解质水溶液的脉冲辐解导致溶质的芳香族部分被水合电子单电子还原。当CD腔中含有疏水的芳香族部分时,反应被有效地延缓。因此,联苯-4-羧酸酯(BPC)、联苯-4-辛酸酯(BPA)和联苯基-4-磺酸盐(BPS)的单电子还原反应的速率常数通过与β-CD的络合而显著降低,其空穴最适合联苯基团。类似地,1-吡喃-1-羧酸酯(PYC)、4-吡喃-1-丁酸(PYB)和1-磺酸(PYS)的单电子还原为r…考察了磺酸盐混合物溶液的单电子还原反应和电子转移反应的控制。用β-和伽马-镉实现了对BPS和Pys混合溶液的选择性还原。Pys与α-CD的络合作用也有效地抑制了还原的BPS向Pys的电子转移。络合效应的pH依赖性表明,由于BPA的亚甲基的空间位阻效应,BPC与α-CD之间形成了1:2的络合物,而BPC与α-CD之间没有形成1:2的络合物。2与γ-Cd的络合物,以及PYC和PYS的络合物随着客体的单电子还原而发生结构变化。由脉冲辐解数据确定了BPC、BPA和BPS的1:1络合物的缔合常数。较少

项目成果

期刊论文数量(16)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Y.Yamamoto,S.Shiraki,D.Gao: "Hydrophobic Acceleration of p-Styrenesulfonate Polymerization by γ-Cyclodextrin" J.Chem.Soc.,Perkin Trans.2. 1119-1122 (1993)
Y.Yamamoto、S.Shiraki、D.Gao:“γ-环糊精对苯乙烯磺酸盐聚合的疏水加速”J.Chem.Soc.,Perkin Trans.2 (1993)。
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    0
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Y.Yamamoto,S.Shiraki,Y.Kawamura: "Effects of Cyclodextrin Complexation on One-electron Reduction and Electron Transfer of Aromatic Sulfonates" J.Chem.Soc.,Perkin Trans.2. 2241-2245 (1992)
Y.Yamamoto,S.Shiraki,Y.Kawamura:“环糊精络合对芳香族磺酸盐的单电子还原和电子转移的影响”J.Chem.Soc.,Perkin Trans.2。
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    0
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Y.Yamamoto, Y.Naka, Y.Yoshida and S.Tagawa: "Inclusion Complexation of Biphenyl-4-carboxylate and Biphenyl-4-acetate with alpha- and beta-Cyclodextrins Studied by Pulse Radiolysis" J.Chem.Soc., Perkin Trans. 2. (1995)
Y.Yamamoto、Y.Naka、Y.Yoshida 和 S.Takawa:“通过脉冲放射分解研究联苯-4-羧酸酯和联苯-4-乙酸酯与 α-和 β-环糊精的包合络合”J.Chem.Soc.,
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    0
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Y.Yamamoto: "Pulse Radiolysis of Aromatic Carboxylates in Aqueous Solution and Effect of Cyclodextrin Complexation on One-electron Reduction by the Hydrated Electron" J.Chem.Soc.,Perkin Trans.2. 1555-1559 (1994)
Y.Yamamoto:“水溶液中芳香族羧酸盐的脉冲辐射分解和环糊精络合对水合电子单电子还原的影响”J.Chem.Soc.,Perkin Trans.2。
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    0
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Y.Yamamoto: "Pulse Radiolysis of Aromatic Carboxylates in Aqueous Solution and Effect of Cyclodextrin Complexation on One-electron Reduction by the Hydrated Electron" J.Chem.Soc., Perkin Trans. 2. 1555-1559 (1994)
Y.Yamamoto:“水溶液中芳香族羧酸盐的脉冲辐射分解以及环糊精络合对水合电子单电子还原的影响”J.Chem.Soc.,Perkin Trans。
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YAMAMOTO Yukio其他文献

YAMAMOTO Yukio的其他文献

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{{ truncateString('YAMAMOTO Yukio', 18)}}的其他基金

Activation balance of nuclear receptors ERα and CAR regulates hepatic lipid metabolism
核受体ERα和CAR的激活平衡调节肝脏脂质代谢
  • 批准号:
    20580318
  • 财政年份:
    2008
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Proteomic analysis of pain-regulated and amyloid components in cerebrospinal fluid of patients with rheumatoid arthritis
类风湿性关节炎患者脑脊液中疼痛调节成分和淀粉样蛋白成分的蛋白质组学分析
  • 批准号:
    19591828
  • 财政年份:
    2007
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Development of novel probes for single-molecule imaging of proteihs
蛋白质单分子成像新型探针的开发
  • 批准号:
    19350084
  • 财政年份:
    2007
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Studies in a new pain control of spinorphin, an endogenous peptide, in rheumatoid arthritis
旋诺啡(一种内源性肽)在类风湿性关节炎中的新疼痛控制研究
  • 批准号:
    16591577
  • 财政年份:
    2004
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Studies in~a new pain control by spinorphin, an endogenous factor : Changes in level of spinorphin and dipeptidyl peptidase III in cerebrospinal fluid from patients with pain
内源性因子旋诺啡新的疼痛控制研究:疼痛患者脑脊液中旋诺啡和二肽基肽酶 III 水平的变化
  • 批准号:
    14572172
  • 财政年份:
    2002
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Synchrotron radiation effect on CIS thin films prepared by laser ablation for solar cell application
同步辐射对太阳能电池用激光烧蚀制备的 CIS 薄膜的影响
  • 批准号:
    11680508
  • 财政年份:
    1999
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Studies in anti-inflammatory effect of spinorphin, an endogenous factor
内源性因子螺旋啡的抗炎作用研究
  • 批准号:
    10672168
  • 财政年份:
    1998
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
A Scholary Research on the Shakyosho Documents of Shosoin
正仓院释教书文献的学术研究
  • 批准号:
    10410085
  • 财政年份:
    1998
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B).
New Development of Enzyme Utilization in Organic Solvents
有机溶剂中酶利用的新进展
  • 批准号:
    04806019
  • 财政年份:
    1992
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
Metabolism in root nodules and function of leghemoglobin
根瘤的代谢和豆血红蛋白的功能
  • 批准号:
    62490009
  • 财政年份:
    1987
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)

相似海外基金

Clarification of the biological activity profiles inclusion complex of aroma compounds with cyclic dextrins.
芳香化合物与环糊精包合物的生物活性特征的澄清。
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    21780129
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Inhibitory mechanism of lenthionine against platelet aggregation and biological activity of its inclusion complex in α-cyclodextrin
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  • 批准号:
    20580145
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    2008
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Simulation of inclusion complex formation and molecular recognition of cyclodextrin
环糊精包合物形成模拟及分子识别
  • 批准号:
    19740261
  • 财政年份:
    2007
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Nutritional Function of Inclusion Complex of -Cyclodextrin with Octacosanol
β-环糊精与二十二烷醇包合物的营养作用
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    10660116
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    1998
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Development of color-change indicators using inclusion complex formation
利用包合物形成开发颜色变化指示剂
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    04453096
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    1992
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Formation of Inclusion Complex Powder of Liquid Flavor Substance by Twin Screw Extruder
双螺杆挤出机制备液体香料包合物粉末
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    02660148
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