环糊精增强金属卟啉/蒽衍生物上转换及其应用  

Cyclodextrin Enhanced Low-power Upconversion Based on Metalloporphyrins/Anthracene Derivatives and Its Application

作　　者：傅燕 朱琳 于雪 叶常青 陈硕然 梁作芹 周宇扬 王筱梅 FU Yan;ZHU Lin;YU Xue;YE Chang-qing;CHEN Shuo-ran;LIANG Zuo-qin;ZHOU Yu-yang;WANG Xiao-mei(Jiangsu Key Laboratory for Environment Functional Materials, School of Chemstry, Biology and Materials Engineering, Suzhou University of Science and Technology, Suzhou 215009, Jiangsu, China)

机构地区：[1]苏州科技大学化学生物与材料工程学院江苏省环境功能材料重点实验室

出　　处：《精细化工》2018年第7期1136-1143,共8页Fine Chemicals

基　　金：国家自然科学基金(51673143);江苏省高校优秀科技创新团队;江苏高校优势学科建设工程资助项目;江苏省普通高校研究生科研创新计划(CXLX11-0970)~~

摘　　要：以2-氯-9,10-二甲苯基蒽（DTACl）为发光剂,分别与不同的光敏剂[四苯基卟啉钯（PdTPP）和四苯基卟啉铂（Pt TPP）]构成二元体系（PdTPP/DTACl和Pt TPP/DTACl）,并用不同的环糊精（a-CD、b-CD或g-CD）包络发光剂,构成光敏剂/发光剂/CD三元体系。利用紫外分光光度计、荧光光谱仪、二极管泵浦固态激光器、色度计对二元体系及三元体系进行了光谱性能测试,考察了光敏剂的三线态寿命和环糊精包络效应对上转换效率的影响。结果表明,在532 nm低功率（60 m W/cm2）半导体激光器激发下,PdTPP/DTACl和Pt TPP/DTACl体系的上转换效率分别达10.33%和7.15%;PdTPP的三线态寿命（9.63ms）长于Pt TPP的三线态寿命（6.41ms）。在PdTPP/DTACl体系中加入b-CD,上转换效率可提高至12.82%;将获得的蓝光上转换PdTPP/DTACl/b-CD辐照香豆素水溶液（Pt/WO3半导体为催化剂）,20 min后即出现7-羟基香豆素的荧光发射峰（469 nm）,表明蓝光上转换PdTPP/DTACl/b-CD可催化香豆素转化为7-羟基香豆素。2-Chloro-9,10-diptolylanthracene（DTACl） was used as emitter and 5,10,15,20-tetraphenylporphyrinpalladium（Ⅱ）（PdTPP） and 5,10,15,20-tetraphenylporphyrin-platinum（Ⅱ）（Pt TPP） used as sensitizer to prepare two binary systems PdTPP/DTACl and Pt TPP/DTACl. Then, alpha-cyclodextrin（α-CD）, beta-cyclodextrin（β-CD） and gamma-cyclodextrin（γ-CD） were introduced into the above two binary systems and gave ternary systems. The ultraviolet spectrophotometer, fluorescence spectrometer, diode pump solid state laser and colorimeter were used to investigate the spectral properties of the binary and ternary systems. Moreover, the effects of the triplet lifetime of sensitizers and the cyclodextrin envelope on the upconversion efficiency were studied. The results showed that under excitation of 532 nm at an ultralow power density at 60 m W/cm2, the upconversion efficiencies of PdTPP/DTACl and Pt TPP/DTACl were 10.33% and 7.15%, respectively. This was attributed to longer triplet lifetime（9.63 ms） of PdTPP than that of Pt TPP（6.41 ms）, which could improve triplet-triplet energy transfer and result in the enhancement of upconversion efficiency. The addition b-cyclodextrin could make the upconversion efficiency of PdTPP/DTACl system reach 12.82%. The suspension aqueous solution containing coumarin in the presence of Pt/WO3 as catalyst was irradiated by blue upconversion PdTPP/DTACl/b-CD, after 20 min the fluorescence emission peak of 7-hydroxycoumarin appeared at 469 nm, indicating that the blueupconversion could catalyze the conversion of coumarin to 7-hydroxycoumarin.

关 键 词：弱光上转换 四苯基卟啉钯 2-氯-9 10-二甲苯基蒽 环糊精包络 上转换光催化 功能材料 

分 类 号：TQ314[化学工程—高聚物工业]