Design of Supramolecular Cyclodextrin Complex Sensors and Construction of Functional Interfaces

超分子环糊精复合传感器的设计及功能接口的构建

• 批准号: 16550066
• 负责人: HAYASHITA Takashi
• 金额: $ 2.3万
• 依托单位: Sophia University (2005)Tohoku University (2004)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550066/
• 关键词: Supramolecules; Molecular complexes; Cyclodextrins; Chemical sensor; Fluorescent probes; Azoprobes; Sugar recognition; Alkali metal ion recognition; 超分子形成; クラウンエーテル; アゾ色素; アルカリ金属イオン; 誘起円二色性

In this study, benzo-15-crown-5 (B15C5) azoprobes possessing different alkyl chain lengths of n=1 (C1-Az), n=2 (C2-Az), and n=4 (C4-Az) have been designed for construction of novel photosignal transduction systems in water based on supramolecular azoprobe/γ-CyD complexes. For all Cn-Az probes, the UV-Vis spectra exhibited a K^+-selective blue shift with reduction of molar absorptivity in the longer wavelength, indicating a selective 2:1 complex formation of Cn-Az with K^+. While in the ICD spectra, different spectral responses were observed. Thus for C1-Az and C2-Az, the K^+-selective ICD response was clearly intensified by increasing the alkyl chain length from methyl to ethyl. However for C4-Az possessing longer butyl chains, an abnormally strong ICD response was noted for TMA^+ instead of K^+. These different spectral responses between UV-Vis and ICD were ascribed to the formation of different mode of CyD inclusion complex. In addition, C4-Az was found to have a unique response function for K^+ in the absence of γ-CyD. These results were discussed in relation to their supramolecular complex structures. For chiral recognition of sugars in water, biphenylboronic acid fluorophore (BPB)/CyD complex sensors have been developed. BPB showed fluorescence emission response upon sugar binding at high pH regions (above pH 9.3). By using this pH regions, effect of CyD upon the D/L recognition ability of BPB for fructose have been examined. The results indicated that no D/L selectivity was noted in the absence of CyD or the presence of β-CyD possessing smaller inclusion cavity. Whereas in the presence of γ-CyD having larger inclusion cavity, twice higher selectivity for D(-)-isomer was found to appear for BPB/γ-CyD complex. This is a novel recognition function of supramolecular CyD complex sensors based on multi point interaction of OH groups in CyD.

本研究设计了具有不同烷基链长（n=1（C1-Az）、n=2（C2-Az）和n=4（C4-Az））的苯并-15-冠-5（B15 C5）偶氮探针，并基于偶氮探针/γ-CyD超分子复合物构建了新型的光信号转导体系。对于所有的Cn-Az探针，紫外-可见光谱显示出K^+选择性蓝移，在较长波长处摩尔吸光系数降低，表明Cn-Az与K^+选择性形成2：1复合物。而在ICD光谱中，观察到不同的光谱响应。因此，对于C1-Az和C2-Az，通过将烷基链长度从甲基增加到乙基，K^+-选择性ICD响应明显增强。然而，对于具有较长丁基链的C4-Az，发现对TMA^+而不是K^+的ICD反应异常强烈。这些不同的光谱响应之间的UV-Vis和ICD归因于不同模式的CyD包合物的形成。此外，在不存在γ-CyD的情况下，C4-Az对K^+具有独特的响应函数。这些结果进行了讨论有关的超分子复合物结构。为了对水中的糖进行手性识别，人们开发了联苯硼酸荧光团（BPB）/CyD复合物传感器。BPB在高pH区域（pH 9.3以上）糖结合时显示荧光发射响应。在此pH范围内，考察了CyD对BPB对果糖的D/L识别能力的影响。结果表明，在不含CyD或含有具有较小包合腔的β-CyD的情况下，没有D/L选择性。而当γ-CyD具有较大的包合腔时，BPB/γ-CyD复合物对D（-）-异构体的选择性提高了一倍。这是基于CyD中OH基团多点相互作用的超分子CyD复合传感器的一种新的识别功能。

项目成果

Lead Ion Selective Signal Amplification by a Supramolecular Podand Fluoroionophore/Surfactant Complex Sensor in Water

• DOI: 10.1080/10610270412331328899
• 发表时间: 2005-01
• 期刊: Supramolecular Chemistry
• 影响因子: 3.3
• 作者: T. Hayashita;Dai Qing;R. Bartsch;S. Elshani;R. Hanes;N. Teramae

Formation of structurally different solvated and non-solvated [Ni(PTSC)(PPh_3)] (PTSC=salicylaldehyde-N-phenylthiosemicarbazide anion) crystals from single pot

单锅形成结构不同的溶剂化和非溶剂化[Ni(PTSC)(PPh_3)]（PTSC=水杨醛-N-氨基苯硫脲阴离子）晶体

• 发表时间: 2005
• 期刊: Inorganica Chimica Acta 358
• 作者: Takeshi HASHIMOTO;Rathinam PRABHAKARAN
• 通讯作者: Rathinam PRABHAKARAN

Pottasium Ion Selective Signaling Based on Intramolecular Dimer Formation of Biscrown Ether Azochromophore-Chemosensor Exhibiting Forceps Function-

基于双冠醚固氮发色团分子内二聚体形成的钾离子选择性信号传导-具有镊子功能的化学传感器-

• 发表时间: 2004
• 期刊: Chem.Lett. 33(5)
• 作者: T.Hayashita;A.Murakami;N.Teramae
• 通讯作者: N.Teramae

ベーシック分析化学(第3章-第5章)

基础分析化学（第3章-第5章）

• 发表时间: 2006
• 作者: T.Hayashita;A.Murakami;N.Teramae;早下隆士(分担執筆)
• 通讯作者: 早下隆士(分担執筆)

ニューラルネットワーク解析を利用した化学センサー設計の新展開

使用神经网络分析化学传感器设计的新进展

• 发表时间: 2004
• 期刊: 化学 59(1)
• 作者: T.Hayashita;A.Murakami;N.Teramae;H.Imura;Dusan Miklos;T.Kojima et al.;早下隆士
• 通讯作者: 早下隆士