文献类型：期刊文献

中文题名：可活化卟啉光敏剂及其硫醇刺激响应性

英文题名：Activable Porphyrinic Photosensitizer and Its Response to Thiol-Stimulation

作者：陈剑波[1];刘峰[1]

机构：[1]华东理工大学材料科学与工程学院上海市先进聚合物材料重点实验室,上海200237

年份：2018

卷号：44

期号：1

起止页码：62

中文期刊名：华东理工大学学报（自然科学版）

外文期刊名：Journal of East China University of Science and Technology

收录：CSTPCD;;Scopus;北大核心:【北大核心2017】；CSCD:【CSCD_E2017_2018】；

基金：国家自然科学基金(21574039;51173044)

语种：中文

中文关键词：四苯基卟啉;2,4-二硝基苯;硫醇;猝灭;活化

外文关键词：tetraphenylporphyrin ; 2,4-dinitrobenzene ; thiol ; quenching ; activation

摘要：将2,4-二硝基苯磺酰氯(DNBS)与5-(4-氨基苯基)-10,15,20-三苯基卟啉(TPP-NH_2)通过对硫醇敏感的磺酰胺键键合,成功构建了一种失活型光敏剂5-[4-N-(2,4-二硝基苯)磺酰胺基苯基]-10,15,20-三苯基卟啉(TPP-DNB)。该光敏剂的荧光和单线态氧(1 O2)被2,4-二硝基苯(DNB)基元有效猝灭,而在二硫苏糖醇(DTT)或谷胱甘肽(GSH)的刺激下能重新激活。通过荧光光谱检测确认TPP-DNB的荧光被DNB基元明显猝灭并且在硫醇存在下逐渐恢复。单线态氧检测结果表明TPP-DNB的单线态氧量子产率为0.118;而在DTT刺激下能达到0.614,接近参比物四苯基卟啉(TPP)的量子产率(0.62);这说明光敏剂TPP-DNB的单线态氧显著失活并具有硫醇刺激激活性。
Deactivated photosensitizer 5- [4-N- （2, 4-dinitrobenzene） sulfonamidophenyl]-10, 15 , 20- triphenyl porphyrin （TPP-DNB） was successfully constructed through the reaction formed thiol-sensitive sulfonamide bond between 2,4-dinitrobenzenesulfonyl chloride （DNBS） and 5-（4-aminophenyl）-10,15,20- triphenylporphyrin （TPP-NH2）. The structure of TPP-DNB was characterized by iH-NMR, 13C-NMR in CDC13 and elemental analysis. In addition, the compound had a melting point of 205 ℃. It was a brand new activable photosensitizer, whose fluorescence and singlet oxygen C102 ） of the photosensitizer were significantly quenched by 2, 4-dinitrobenzene （DNB） motif and re-activated under the stimulation of dithiothreitol （DTT） or glutathione （GSH）. The UV-visible absorption spectrum showed that TPP-DNB had a strong absorption peak at 425 nm （S band） and a weak but broad absorption band at 500-600 nm （Q band） , which indicated that the compound had the similar absorption capacity as tetraphenylporphyrin （TPP） for UV light. The fluorescence intensity of TPP-DNB in PBS/DMF（99/1, volume ratio） at the wavelength of about 660 nm was very weak and significantly quenched by DNB primers compared to TPP？s. The fluorescence intensity of TPP-DNB in the presence of DTT or GSH was gradually recovered with the increase of time and showed a tendency of strengthening, indicating that the fluorescence of TPP-DNB had a rapid stimulus response to thiols. The singlet oxygen yield of TPP-DNB was measured using DPBF as a capture reagent for 1 02. The results of 1 0 2 test showed that the singlet oxygen yield of TPP- DNB was 0. 118 while elevated to 0. 614 in the presence of D T T , which was close to that of the reference substance tetraphenylporphyrin （TPP ） （0.62）. These results indicated that singlet oxygen of the photosensitizer TPP-DNB was significantly inactivated and had thiol stimulated activation, which provided a new method for the design and development of activable photosensitizer.