Design of Membrane Surfaces for Molecular Recognition and Signal Transduction, and Their Application for Chemical Sensing

用于分子识别和信号转导的膜表面设计及其在化学传感中的应用

• 批准号: 05403016
• 负责人: UMEZAWA Yoshio
• 金额: $ 21.7万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05403016/
• 关键词: Charge separation; Ion channel; Multitopic molecular recognition; Active transport; Condensed monolayer; Second harmonic generation (SHG); Bilayer lipid membrane; Infrared attenuated total reflection (ATR-IR); 電荷分離; イオンチャンネル; 非化学量論的溶出; 原子間力顕微鏡(

1. Chemical Sensing Based on Charge Separation1) New liquid membrane potentiometric sensors for the discrimination of organic analytes based on host-guest recognition of charged groups, hydrogen bonding groups, or steric shapes of nonpolar moieties were developed. A membrane sensor using a cytosine-pendant triamine host showed potentiometric discrimination between guanosine and adenosine nucleotides by ditopic recognition, i.e., complementary base pairing and phosphate-ammonium charge-charge binding interactions at the membrane surface. A calix [6] arene derivative having a well-defined inclusion cavity for organic guests was synthesized and used as a sensory element for the potentiometric discrimination of the steric shapes of nonpolar moieties of dopamine.2) Permselective ion transport for metal cations at the interface (^-mum depth) of ionophore-based liquid membranes was successfully observed by infrared attenuated total reflection spectrometry (ATR-IR). Furthermore, optical second … More harmonic generation (SHG) was shown to be the first optical technique available for the selective observation of charge separation processes at the surface of liquid membranes. By observing the SHG signals from ionophore-based liquid membranes, the existence of SHG-active, oriented cation complexes at the membrane surface was shown.2. Chemical Sensing Based on Changes in Membrane PermeabilityThe control of membrane permeability through intermolecular channels by host-guest complexation was exploited by horizontal tough cyclic voltammetry with condensed monolayrs of long alkyl derivatives of beta-cyclodextrin formed at the air-water interface. Comparing the permeabilities of three kinds of electroactive markers, rigid evidence was obtained that this cyclodextrin derivative functions as an intramolecular channel. The selectivity of permeability inhibition by several organic guest was found to reflect the ability of the quests to block the channel entrance by host-guest complexation.3. Chemical Sensing Based on Active TransportBased on highly selective recognition and following efficient transport of D-glucose by Na^+/D-glucose contransporter, a bilayer lipid membrane sensing system for D-glucose was constructed. This active transport sensor enables detection of D-glucose concentrations as low as 10^<-9>M. Less

1.基于电荷分离的化学传感1）基于荷电基团、氢键基团或非极性基团的空间形状的主客体识别，开发了用于识别有机分析物的新型液膜电位传感器。使用胞嘧啶侧基三胺主体的膜传感器通过双位识别显示出鸟苷和腺苷核苷酸之间的电位辨别，即，互补碱基配对和磷酸-铵电荷-电荷结合相互作用在膜表面。合成了一种杯[6]芳烃衍生物，该衍生物具有良好的有机客体包合空腔，并将其用作电位分辨多巴胺非极性部分空间形状的传感元件。2）利用红外衰减全反射光谱（ATR-IR）成功地观察到了金属阳离子在离子载体液膜界面（μ m深度）的选择透过性离子传输。此外，光学秒 ...更多信息 谐波发生（SHG）被证明是第一个可用于选择性观察液膜表面电荷分离过程的光学技术。通过观察离子载体液膜的SHG信号，发现在膜表面存在SHG活性的、定向的阳离子络合物.基于膜渗透性变化的化学传感通过在空气-水界面处形成的β-环糊精的长烷基衍生物的凝聚单分子层，通过水平坚韧循环伏安法利用主客体络合通过分子间通道对膜渗透性的控制。比较三种电活性标记物的渗透性，得到了该环糊精衍生物作为分子内通道的有力证据。发现几种有机客体对渗透抑制的选择性反映了客体通过主客体络合作用阻断通道入口的能力.基于主动转运的化学传感基于Na^+/D-葡萄糖共转运蛋白对D-葡萄糖的高选择性识别和有效转运，构建了一种双层脂膜传感系统。这种主动转运传感器能够检测低至10 μ M的D-葡萄糖浓度<-9>。少

项目成果

S.Yoshiyagawa: "Optical Ion Sensor Based on Second-Harmonic Generation at the Surface of an Ionophore-Incorporated Poly (vinyl chloride) Liquid Membrane." Anal.Sci.9. 715-718 (1993)

S.Yoshiyakawa：“基于离子载体聚氯乙烯液膜表面二次谐波产生的光学离子传感器”。

M.Sugawara: "Studies on the Factors Affecting Background Permeabilities of Ordered Mono-,Bi-,and Multilayers as Channel Mimetic Sensing Membranes" Anal.Sci.10. 343-347 (1994)

M.Sukawara：“影响作为通道模拟传感膜的有序单层、双层和多层背景渗透率的因素的研究”Anal.Sci.10。

K.Odashima: "Potentiometric Discrimination of Organic Amines by a Liquid Membrane Electrode Based on a Long Alkyl Derivative of β-Cyclodextrin" Mikrochim.Acta. 113. 223-238 (1994)

K.Odashima：“基于 β-环糊精的长烷基衍生物的液膜电极对有机胺的电位辨别”Mikrochim.Acta。113. 223-238 (1994)

K.Tohda: "Cation Permeselectivity an the Phase Boundary of Ionophore-Incorporated Solvent Polymeric Membranes as Studied by Optical Second Harmonic Generation." Anal.Chem.67. 570-577 (1995)

K.Tohda：“通过光学二次谐波产生研究阳离子渗透选择性和掺入离子载体的溶剂聚合物膜的相边界。”

K.Yagi: "Channel Mimetic Sensing Membranes for Alkali Metal Cations Based on Oriented Monolayers of Calixarene Esters." J.Electroanal.Chem.and Interfacial Electrochem.(in press).

K.Yagi：“基于杯芳烃酯定向单层的碱金属阳离子通道模拟传感膜。”