Design and Synthesis of Multi-Information Dyes for the Application of Optical Chemical Sensings

用于光学化学传感应用的多信息染料的设计与合成

• 批准号: 08455390
• 负责人: SUZUKI Koji
• 金额: $ 4.54万
• 依托单位: Keio University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455390/
• 关键词: optical sensing; sensing dye; anion sensing; water-content; betain-type dye; solvato chromism; chemical sensing; chemical sensor; センシング用色素; 膜センサー; 化学センシング; スペクトル情報; センサーデバイス

Recently, the development of optical chemical sensors (optodes) have increased progressively, in an optode, dyes play an important role as a signal transducer component. Most of the dyes employed in the optodes were pH-indicator type dyes which can only tranduce one information which related to the proton dissociation-association. In this research, we developed multi-functional dyes that have capabilities to transduce many kind of informations (Multi- Information Dyes : MIDs) based on different color-changing mechanisms.The approach for designing the dye are as follows. 1) Introduction both positive and negative charges in the both ends of the large p-conjugated system of the dye molecule. This functional element is sensitive to the cange of the environment of the dye such as solvent polarity, the presence of ionic species, solvent viscousity, etc. 2) Introduction of electron donatings and/or electron withdrawing groups in the p-conjugated system, so that we can obatain dyes with difer … More ent pKa values. 3) Introduction of an immobilization site or a lipophilic terminal that is useful in the preparation of a sensing probe. Based on this concept, 12 dyes have been synthesized and their characteristics have been studied and discussed in relation to their chemical structures. The prospect of application of these MIDs into several kinds of chemical sensing system was investigated.The fundamental characteristic of the synthesized dyes based on the merosyanine-type (KDMl-KDM12) was studied spectrophotometrically. pH response profiles were determined in a methanol-water 1 : 1 (v/v) media and solvent-response profiles were studied using water (0.01 M NaOH)-contained methanol or THF.As a result, besides these dyes responded in the same characteristics as usual pH-indicator dyes, their lmax were shifted with the change of the polarity of the solvent. Accordingly, two dimensional informations could be gained from one spectrum.KD-M7 which has a small lmax shift was used in the application to an anion sensor using a proton-anion coextraction process in a chloroform-water system. The change of the absorbance of the dyes in the chloroform phase was measured and plotted against the concentration of the anion in phosphate-buffered aqueous phase. Moreover, PVC-based anion sensing membranes were constructed by dissolving the dyes in a membrane plasticizer (BEHS) and applied to measure perchlorate on in the aqueous solution. The experimental results showed that the absorbance of the dyes were varied with the concentration of the anions and the anionic selectivity was obeyed the Hoffmeister series. The PVC-based anion sensor was also exhibited absorbance changes with the anion concentration, and enabled to measure the concentration of an anion using this sensing system.KD-M5 which has large lmax shift and low pKa value was used in preparation of alcohol sensor. Experiment was conducted by extraction of the alcohol from the water phase with chloroform and measured the spectra of the dye in the chloroform phase. In addition, PVC-based alcohol sensing membranes were constructed by dissolving the dyes in a membrane plasticizer (BEHS) and applied to measure alcohol concentration in the aqueous solution. It was proved that lmax of the dye was shifted significantly with the change of the alcohol concentration in the water phase both in the extraction experiment and in PVC-based membrane sensor.From this result it would be possible to develop a novel cation optode based on different color changing mechanism using MID-type dyes. Less

近年来，光化学传感器的发展日益迅速，在光化学传感器中，染料作为信号转导元件起着重要的作用。大多数的染料是pH指示型染料，它们只能传递一种与质子解离-缔合有关的信息。在本研究中，我们根据不同的变色机理，开发了具有多种信息显示能力的多功能染料（Multi-Information Dyes：MID）。1)在染料分子的大p共轭体系的两端引入正电荷和负电荷。2）在p-共轭体系中引入给电子基团和吸电子基团，可以得到不同结构的染料，从而使染料分子中的电子结构发生变化 ...更多信息 输入pKa值。3)引入可用于制备传感探针的固定位点或亲脂末端。基于这一概念，合成了12种染料，并从化学结构上对它们的特性进行了研究和讨论。考察了这类染料在多种化学传感体系中的应用前景，并对所合成的基于merosyanine型的染料（KDM 1-KDM 12）的基本特性进行了电化学研究。在甲醇-水1：1（v/v）介质中测定了pH响应曲线，在含有0.01M NaOH的甲醇或THF中测定了溶剂响应曲线，结果表明，这些染料除了具有与常用pH指示染料相同的响应特性外，其最大吸收波长随溶剂极性的改变而移动。在氯仿-水体系中，采用质子-阴离子共萃取法，将具有小lmax位移的KD-M7应用于阴离子传感器。测量氯仿相中染料吸光度的变化，并将其与磷酸盐缓冲水相中阴离子的浓度作图。此外，通过将染料溶解在膜增塑剂（BEHS）中构建了PVC基阴离子传感膜，并应用于测量水溶液中的高氯酸盐。实验结果表明，染料的吸光度随阴离子浓度的变化而变化，阴离子选择性服从Hoffmeister级数。PVC基阴离子传感器的吸光度也随阴离子浓度的变化而变化，使该传感系统能够测量阴离子的浓度。用氯仿萃取水相中的乙醇，测定氯仿相中染料的光谱。此外，基于PVC的酒精传感膜的构建通过溶解的染料在膜增塑剂（BEHS）和应用于测量水溶液中的酒精浓度。在萃取实验和PVC膜传感器实验中均证明了染料的lmax随水相中乙醇浓度的变化而发生显著的偏移，这为利用MID型染料开发基于不同变色机理的新型阳离子光传感器提供了可能。少

项目成果

久本秀明: "感度・選択性の高いイオン検出デバイスの開発〜“イオン選択性オプトード"" 化学. 53. 76-77 (1998)

Hideaki Hisamoto：“开发具有高灵敏度和选择性的离子检测装置 - 离子选择性光极” 化学 53. 76-77 (1998)。

Dwi Siswanta: "Magnesium Ion-Selective Optodes Based on a Neutral Ionophore and a Lipophilic Cationic Dye" Analytical Sciences. 13. 429-435 (1997)

Dwi Siswanta：“基于中性离子载体和亲脂性阳离子染料的镁离子选择性光极”分析科学。

久本秀明: "Molecular Design, Characterization, and Application of Multiinformation Dyes for Multi-Dimensional Optical Chemical Sensing. 3. Application of MIDs for lmax-Tunable Ion-Selective Optodes" Analytical Chemistry. 71. 259-264 (1999)

Hideaki Hisamoto：“多维光学化学传感的多信息染料的分子设计、表征和应用。3. MID 在 lmax 可调离子选择性光极中的应用”分析化学 71. 259-264 (1999)。

Hideaki Hisamoto: "・Molecular Design, Characterization, and Application of the Multi-informaton Dyes for Multi-Dimensional Optical Chemical Sensing. Molecular Design Concepts of the Dyes and Their Fundamental Spectral Characteristics" Analytica Chimica Ac

Hideaki Hisamoto：“·用于多维光学化学传感的多信息染料的分子设计、表征和应用。染料的分子设计概念及其基本光谱特性”Analytica Chimica Ac

Hideaki Hisamoto: "Molecular Design, Characterization, and Application of Multiinformation Dyes for Multi-Dimensional Optical Chemical Sensings.1. Molecular Design Concepts of the Dyes and Their Fundamental Spectral Characteristics" Analytical Chimica Act

Hideaki Hisamoto：“用于多维光学化学传感的多信息染料的分子设计、表征和应用。1.染料的分子设计概念及其基本光谱特征”分析化学法案