Noncovalent Assembly of Picket‐Fence Porphyrin on Carbon Nanotubes as Effective Peroxidase‐Like Catalysts for Detection of Hydrogen Peroxide in Beverages

A newly developed electrochemical sensor for determination of hydrogen peroxide (H₂O₂) in beverages using a water‐insoluble picket‐fence porphyrin (FeTpivPP) functionalized multiwalled carbon nanotubes (MWNTs) is demonstrated. Introduction of FeTpivPP on MWNTs led to enhanced electron transfer. As a new platform in electrochemical analysis, the resultant sensor showed excellent electrocatalytic activity toward the reduction of H₂O₂ due to the synergic effect between MWNTs and FeTpivPP, thus leading to highly sensitive amperometric sensing of H₂O₂ with a detection limit of 0.05 µmol L^?1. The developed method is successfully used to detect H₂O₂ in beverages and shows great promise for routine sensing applications.     

Synthesis and investigation of photovoltaic properties for polymer semiconductors based on porphyrin compounds as light-harvesting units

We reported on two polymer semiconducting copolymers based on porphyrin compounds, poly[9,9-dioctylfluorene-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PFPor) and poly[9-(heptadecan-9-yl)carbazole-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PCPor), for use as organic photovoltaic materials. The thermal, optical, electrochemical, and photovoltaic properties of the two polymers were investigated. In addition, PC₆₁BM and PC₇₁BM were introduced as acceptor materials to confirm the acceptor effect in bulk heterojunction photovoltaic devices. Moreover, in order to establish acceptor effects, morphologies of polymer/PCBM blend films were analyzed through atomic force microscopy (AFM). PFPor and PCPor exhibited the best device performance with power conversion efficiencies (PCE) of 0.62% and 0.76%, respectively, upon the introduction of PC₇₁BM as the acceptor in the device where 86 wt.% of the PC₇₁BM was contained in the active layer (pol:PC₇₁BM = 1:6, w/w).     

MP-C60(M=Cu,Co)化合物的合成、表征及光电性能研究

卟啉和金属卟啉不仅是良好的电子给予体,而且在紫外可见光区有着非常广泛的吸收,这有利于太阳能的利用.富勒烯(C60)由于自身独特的结构而成为较好的电子受体.近年来,大量共价键连卟啉-富勒烯D-A化合物被合成与研究[1-4].通过柔性连接体形成的卟啉-富勒烯化合物有利于增加给-受体间电子的流动性,使化合物具有优良的光电转换性能[2].中间体和产物的合成见图1.1和2的合成、纯化参照文献[2].3的合成:在N2下把37.2mg对羟基苯甲醛、75.2mg2、过量灼烧的无水碳酸钾加入30mL DMF中,80°C反应8h后,甲苯和蒸馏水分液,粗产品用硅胶柱层析,甲苯淋洗,…     

O2 binding to cytochrome c oxidase-inspired nanomaterials

We investigate O₂ binding to cytochrome c oxidase (CcO)-inspired nanomaterials using ab initio density functional calculations. We consider iron-porphyrin (FeP) and copper-(imidazole)₃ [Cu(Im)₃] as a representative of the active binuclear center, and explore the effect of the Cu(Im)₃ on the FeP-O₂ adduct in relation to the geometric, vibrational, electronic and energetic properties. We find that the Cu(Im)₃ induces the weak O-O and Fe-O bonds mainly because of the electron transfer to the O₂ and the spin polarization of the Fe and O₂ by bridging the O₂ between the Fe and Cu, possibly resulting in the facile O₂ dissociation.     

5,10,15,20—四（4—甲氧基苯基）卟啉锌,钴配合物的合成与表征

合成了两种新配合物:Zn[T(4-MOP)P]及co[T(4-MOP)P],进行了元素分析,电子光谱,红外光谱和质子核磁共振波谱研究。     

5,10,15,20-四苯基卟啉锌与甲醇加合物谱学及结构研究

在氯仿溶液中利用紫外－可见光谱及核磁共振研究了5，10，15，20－四苯基卟啉锌（TPPZn)与甲醇（MeOH)的相互作用，发现MeOH可与TPPZn发生加合反应。单晶衍射分析表明加合物中MeOH通过氧原子与锌配位并形成五配位化合物。     

（TPPS4）2二聚体系吸光光度法测定铜的研究

研究了ｐＨ４．０－６．０，乙酸－乙酸钠体系中ｍｅｓｏ－四（４－磺酸苯基）卟啉发二聚反应的条件。ＴＰＰＳ４二聚物在４８９ｎｍ处有一个较强的吸收峰，利用Ｖｕ＾２＋－ＴＰＰＳ４络合物的形成使此峰线性降低，从而测定痕量铜，表观摩尔吸光系数为５．０＊１０＾５，与ＡＡＳ值相比较，结果令人满意。     

金(Ⅲ)-meso-四(4-乙酰氧基苯)卟啉-十二烷基硫酸钠-TritonX-100显色反应的研究

本文研究了在适量镉和混合表面活性剂存在下,meso-四(4-乙酰氧基苯)卟啉[T(4-AOP)P]与Au(Ⅲ)的显色反应。结果表明,在pH10.0～11.2介质中,Au(Ⅲ)与T(4-AOP)P形成了灵敏度很高的稳定络合物,其摩尔吸光系数ε_(420nm)=1.62×10~6L·mol~(-1)。cm~(-1),金(Ⅲ)浓度在0～1.2μg/10ml范围内服从比耳定律。络合物中的摩尔比为Au(Ⅲ):T(4-AOP)P=1:1。用泡沫塑料预分离富集金;将拟定的新方法应用于岩矿中金的测定,得到较为满意的结果。     

两种新型二氯代苯基卟啉-5-氟尿嘧啶衍生物的合成与表征

用5-[4-(5-溴戊氧基)苯基]-10,15,20-三(3,4-二氯苯基)卟啉或5-[4-(6-溴己氧基)苯基]-10,15,20-三(3,4-二氯苯基)卟啉与5-氟尿嘧啶反应,合成了1-[5-(4-戊氧苯基)-10,15,20-三(3,4-二氯苯基)卟啉]-5-氟尿嘧啶(A)和1-[5-(4-己氧苯基)-10,15,20-三(3,4-二氯苯基)卟啉]-5-氟尿嘧啶(B),产率分别为29.92%和30.01%。并通过红外光谱、紫外可见光谱、核磁共振谱和质谱表征了其结构。对目标化合物的合成条件进行了研究,结果表明:以DMF为溶剂,反应温度为115℃,反应时间2h,产率较高;采用硅胶G(200—300目)装柱,以氯仿和氯仿∶乙醚(V∶V=50∶1)为洗脱液,柱层析,再用氯仿:丙酮(V∶V=7∶1)洗脱产品色带,分离效果较好。     

系列甲基苯基卟啉-5-氟尿嘧啶化合物的合成与表征

设计合成了6种甲基苯基卟啉-5-氟尿嘧啶化合物。通过红外光谱、紫外-可见光谱、核磁共振谱和质谱对所合成的化合物结构进行了确认。探索出了合成反应的最佳条件和目标化合物的分离纯化方法。实验结果表明,选择DMF为溶剂,反应温度在115℃,反应时间2h,产率较高,A1、A2,B1、B2、C1和C2分别为25.66%、25.02%,24.89%、26.17%、28.43%和24.19%;采用硅胶G(粒径为48—75μm)柱层析,分离效果较好。