Novel zinc porphyrin with phenylenevinylene meso-substituents: Synthesis and application in dye-sensitized solar cells

A novel zinc porphyrin, P, with phenylenevinylene segments at two opposite meso-positions and carboxyphenyl at the other two meso-positions of the porphyrin ring, was synthesized and characterized. The phenylenevinylene substituents were terminated with electron-accepting 4-nitro-α-cyanostilbene units. Elongation of the π-conjugation enhanced the solubility of P as well as broadened and strengthened the absorption spectrum. We have investigated the application of P in quasi solid state dye-sensitized solar cells (DSSCs). Under illumination intensity of 100 mW cm⁻², a power conversion efficiency of 2.90% was obtained for the DSSC based on P as sensitizer, which was significantly improved to 4.22% upon addition of deoxycholic acid (DCA) into the P solution for TiO₂ sensitization. Coadsorption of DCA decreased the dye adsorption, but significantly improved both short circuit current (J_sc) and open circuit voltage (V_oc). The breakup of π stacked aggregates might improve the electron injection yield and thus J_sc. The electrochemical impedance data indicate that the electron lifetime was improved by the coadsorption of DCA, which was attributed to the improvement in both V_oc and J_sc. The increase in J_sc has also been attributed to the reduction of the back reaction i.e., the recombination of electrons with tri-iodide ions.     

Temperature- and pH-responsive photosensitization activity of polymeric sensitizers based on poly-N-isopropylacrylamide

We previously reported that a copolymer consisting of N-isopropylacrylamide (NIPAM) and benzophenone (BP) units, behaves as a photosensitizer showing temperature-controlled oxygenation activity in water (J. Am. Chem. Soc.2006, 128, 8751). This polymer shows a heat-induced oxygenation enhancement at low temperature region (5-20 °C), while showing a heat-induced oxygenation suppression at high temperature region (20-60 °C), resulting in an off-on-off activity profile against the temperature window. This is driven by a heat-induced phase transition of the polymer from coil to micelle and then to globule states. In the present work, effects of adding an amine component (N-[3-(dimethylamino)propyl]acrylamide: DMAPAM) to the polymer on the sensitization activity were studied, where the relationship between the phase transition behavior and the activity was clarified by several spectroscopic analyses. The polymers, poly(NIPAM_x-co-BP_y-co-DMAPAM_z), show activity controlled by temperature and pH. The off-on-off activity profile shifts to higher temperature with a pH decrease. This is because protonation of the DMAPAM units leads to an increase in the polymer polarity and, hence, the polymer aggregates at higher temperature. In addition, increase in the DMAPAM content of the polymer leads to further shift of the activity profile. In contrast, at pH < 8, no activity enhancement is observed because complete protonation of the DMAPAM units suppresses polymer aggregation.     

可见光条件下光敏剂引发的Aza-Henry反应

合成了3-甲氧基噻吨酮,并通过核磁共振、红外光谱、高分辨质谱对其结构进行表征。3-甲氧基噻吨酮紫外-可见光谱表明,其在可见光范围内的紫色光(380 nm)附近有吸收,是一种可见光光敏剂。将该光敏剂应用于2-苯基-1,2,3,4-四氢异喹啉和硝基甲烷的Aza-Henry反应中,在紫色LED光照射的条件下,摩尔分数为5%的光敏剂使反应在6 h内产物的分离产率为84%。根据实验结果,提出了光催化的Aza-Henry反应机理,光敏剂在光照条件下进行能量转移产生单线态氧,单线态氧促进Aza-Henry反应的进行。     

光敏剂（PSD—OO7）—γ射线辐射对小鼠白血病细胞DNA的影响

小鼠白血病L7712细胞经与不同浓度PSD-007保温后,该药能抑制细胞DNA的合成,在10 µg/ml以下,随药物浓度增加抑制成比例增强,再增加药量,则抑制程度增加缓慢。可能与该药被细胞吸收结合部位渐趋饱和有关。经PSD-007处理过的细胞在避光条件下,用γ射线照射10 GY与未处理受10 GY照射细胞的DNA链断裂程度无差別,表明PSD-007不能增加电离辐射对DNA的损伤效应;但是处理过的细胞在不避光条件下照射10 GY,则DNA链断裂明显增加,与相应避光下照射细胞DNA损伤有显著差别;但经药物处理细胞只曝露在高压汞灯光照下却未检测出DNA的损伤,结果表明PSD-007只有在不避光下辐照才可增加γ射线对细胞DNA链断裂损伤。这种新现象的发现,提示在某些情况下利用光敏剂进行肿瘤放疗,以及在评价疗效上也许会有所裨益。作者对上述结果及检测中的影响因素进行了讨论。     

肿瘤导向光敏药物研究现状及发展构想

单克隆抗体偶联光敏药物介导的光动力靶向治疗肿瘤是继手术、放疗和化疗而来的肿瘤治疗方法。本文综述了抗体导向光敏药物的研究进展，并提出构建靶向光敏药物的新设想。