Theoretical prediction of fluorescent characteristics and development of fluorogenic derivatization reagents

荧光特性的理论预测及荧光衍生化试剂的开发

• 批准号: 11672137
• 负责人: SANTA Tomofumi
• 金额: $ 2.18万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11672137/
• 关键词: benzofurazan; fluorescence; semi-empirical molecular orbital calculation; HPLC; derivatization reagent; 誘導体化

We have already established the relationship between the fluorescence characteristics of 4,7-disubstituted benzofurazan compounds and Hammett substituent constants of the substituent groups. In this research, we studied the relationship between the fluorescence characteristics and energies of molecular orbitals of benzofurazan compounds by using the semi-empirical molecular orbital calculation method.At first, the compounds having the large difference of the energy between the lowest singlet excited state and the higher triplet excited state showed the strong fluorescent intensity, giving the prediction method of the fluorescent characteristics of the benzofurazan compounds by the theoretical molecular orbital calculation.Next, we developed the fluorogenic derivatization reagents, PSBD-NCO for alcohols, AABD-SH for carboxylic acids, ES-ABD-F, water-soluble reagents, for peptides, and MTBD-NCS for peptides sequencing analysis.As a result, we made clear the relationship between the fluorescence characteristics and the structure of benzofurazan compounds and we developed the fluorogenic reagents based on the relationship.

我们已经建立了4，7-二取代苯并呋咱化合物的荧光特性与取代基的Hammett取代常数之间的关系。本研究采用半经验分子轨道计算方法研究了苯并呋咱类化合物的荧光特性与分子轨道能量的关系，首先，最低单重激发态与较高三重激发态能量相差较大的化合物表现出较强的荧光强度，通过理论分子轨道计算，给出了苯并呋咱类化合物荧光性质的预测方法，并开发了相应的衍生试剂，如PSBD-NCO衍生醇类，AABD-SH衍生羧酸类，ES-ABD-F衍生水溶性，MTBD-NCS用于肽段序列分析，从而明确了苯并呋咱类化合物的荧光特性与结构之间的关系，并以此为基础开发了荧光试剂。

项目成果

Akira Toriba: "Development of an amino acid sequence and D/L-configuration determination method of peptide with a new fluorescence Edman reagent."Analytical Chemistry. 72. 732-739 (2000)

Akira Toriba：“使用新型荧光 Edman 试剂开发氨基酸序列和肽的 D/L 构型测定方法。”分析化学。

Seiichi Uchiyama: "Semi-empirical PM3 calculation predict the fluorescence quantum yields of 4-monosubstituted benzofurazan compounds."J.Chem.Soc.Perkin Trans 2. 1199-1207 (2000)

Seiichi Uchiyama：“半经验 PM3 计算预测 4-单取代苯并呋喃化合物的荧光量子产率。”J.Chem.Soc.Perkin Trans 2. 1199-1207 (2000)

Akira Toriba: "Develoment of an amino acid sequence and D/L-configuration determination method of peptide with a new fluorescence Edman reagent."Analytical Chemistry. 72. 732-739 (2000)

Akira Toriba：“使用新型荧光埃德曼试剂开发氨基酸序列和肽的 D/L 构型测定方法。”分析化学。

Seiichi Uchiyama: "A fluorogenic reagent, 7-phenylsulfonyl-4-(2,1,3-benzoxadiazolyl) isocyanate for alcohols, with development based on the empirical method for prediction."Analytical Chemistry. 71. 5367-5371 (1999)

Seiichi Uchiyama：“一种用于醇的荧光试剂，7-苯磺酰基-4-(2,1,3-苯并恶二唑基)异氰酸酯，其开发基于经验预测方法。”分析化学。

Seiichi Uchiyama: "Fluorescence characteristies of six 4,7-disubstituted benzofurazan copounds : an empirical and semi-empirical MO study"J. Chem. Soc. Perkin Trans 2. 2525-2532 (1999)

Seiichi Uchiyama：“六种 4,7-二取代苯并呋喃化合物的荧光特性：经验和半经验 MO 研究”J。