Synthesis and Photochemical Properties of a New Substituted Phenol Covalently Linked to Ruthenium （Ⅱ） Tris-bipyridine Containing Four Ester Groups as Sensitizer

As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups had been synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures of the new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical and photochemical properties were also studied.     

红外光谱法研究含CeSt3的LDPE膜紫外光氧降解

报道了硬脂酸铈（ＣｅＳｔ_３）、及其在各种浓度、或不同温度、或延长贮放时间下含ＣｅＳｔ_３的低密度聚乙烯（ＬＤＰＥ）膜紫外光氧化降解过程的红外光谱。结果表明，只要在ＬＤＰＥ膜中加入０．１ｗｔ＋％～０．３ｗｔ＋％ＣｅＳｔ_３光敏剂，即可控光降解ＬＤＰＥ膜的寿命。     

几种新型卟啉的合成及其光敏性质

合成了４种新的卟啉配体及其锌的配合物，并用红外光谱、紫外可见光谱、元素分析等手段对它们进行了表征。初步实验表明所合成的卟啉配体和金属卟啉均具有光敏性。     

TiO_2/CuPc/NiFe-LDH photoanode for efficient photoelectrochemical water splitting

Photoelectrochemical(PEC) water splitting is a promising approach for renewable hydrogen production.However,the practical PEC solar-to-fuel conversion efficiency is still low owing to poor light absorption and rapid recombination of charge carriers in photoelectrode.In this work,we report a ternary photoanode with simultaneously enhancement of light absorption and water oxidation efficiency by introducing copper phthalocyanine(CuPc) and nickel iron-laye red double hydroxide(NiFe-LDH) on TiO_2(denoted as TiO_2/CuPc/NiFe-LDH).An experimental study reveals that CuPc loading on TiO_2 bring strong visible light absorption;NiFe-LDH as an oxygen evolution reaction catalyst efficiently accelerates the surface water oxidation reaction.This synergistic effect of CuPc and NiFe-LDH gives enhanced photocurrent density(2.10 mA/cm2 at 0.6 V vs.SCE) and excellent stability in the ternary TiO_2/CuPc/NiFeLDH photoanode.     

Recent progresses on the development of thioxo-naphthalimides

Thioxo/dithioxo-naphthalimide is a class of rarely visited fluorophore, first synthesized in 1999. Facile chemistry was devised to achieve mono or dual thionation of the two carbonyl groups of 1,8-naphthalimide. Thionation effectively shifts absorption maximum to longer spectral wavelength, significantly increase absorption coefficients, and dramatically enhances intersystem crossing efficiency with respect to their oxo-analogues. They were first explored as potent photocleavers to induce DNA strand break and novel photosensitizers for photodynamic therapies. In recent years, the unique chemistry of thioxo groups has been harnessed to achieve new applications, such as fluorescent sensors for heave metal ions. These unique photochemical and photophysical characteristics revitalize them intriguing functional molecules to investigate. In this short review, we wish to revisit their first discovery, facile synthesis, and the endeavors on the use of thioxo/dithioxo-naphthalimides for novel chemical and biomedical applications.     

A Combined Spectroscopic and Theoretical Study on a Ruthenium Complex Featuring a π-Extended dppz Ligand for Light-Driven Accumulation of Multiple Reducing Equivalents

The design of photoactive systems capable of storing and relaying multiple electrons is highly demanded in the field of artificial photosynthesis, where transformations of interest rely on multielectronic redox processes. The photophysical properties of the ruthenium photosensitizer [(bpy)₂Ru( oxim-dppqp )]²⁺ ( Ru ), storing two electrons coupled to two protons on the π-extended oxim-dppqp ligand under light-driven conditions, are investigated by means of excitation wavelength-dependent resonance Raman and transient absorption spectroscopies, in combination with time-dependent density functional theory; the results are discussed in comparison to the parent [(bpy)₂Ru(dppz)]²⁺ and [(bpy)₂Ru( oxo-dppqp )]²⁺ complexes. In addition, this study provides in-depth insights on the impact of protonation or of accumulation of multiple reducing equivalents on the reactive excited states.     

A Cyanine-based Liposomal Nanophotosensitizer for Enhanced Cancer Chemo-Photodynamic Therapy

Currently, chemotherapy is one of the most important treatment modalities for malignant tumors in the clinic, however, it exhibits some shortcomings, such as poor selectivity, limited efficacy and serious adverse effects. Therefore, synergistic therapy and accurate drug delivery at tumor sites become a promising strategy for achieving tumor eradication. Herein, a smart NIR fluorescence imaging-guided nanoliposome was fabricated by encapsulating a chemotherapeutic drug(doxorubicin, DOX), liposomes(L) and a near-infrared(NIR) photosensitizer(CY) to form L@CY@DOX, which could realize enhanced therapeutic efficacy of chemo-PDT in cancer therapy(PDT=photodynamic therapy). L@CY@DOX can induce mitochondrial apoptosis and produce severe toxicity at the cellular level, and L@CY@DOX can enrich in the tumor site, which significantly induces tumor death. In vitro and in vivo studies demonstrated that L@CY@DOX exhibited great antitumor efficacy compared with each one of these monotherapies, indicating that the combination of chemotherapy and PDT possessed potential development prospects and is anticipated in clinical application.     

Mitochondrion-anchoring AIEgen with Large Stokes Shift for Imaging-guided Photodynamic Therapy

Photosensitizers that can target and accumulate in mitochondria are expected to achieve good therapeutic effects in photodynamic therapy,as mitochondria are the energy generation factory in cells.Herein,we designed and synthesized a novel mitochondrion-targeting photosensitizer TPC-Py with aggregation-induced emission characteristics for image-guided photodynamic therapy.TPC-Py possessed an efficient production of 1O2,with a quantum yield of 11.65%,upon mild white light irradiation(6 mW/cm²).TPC-Py exhibited good biocompatibility under dark condition,but showed remarkable cytotoxicity towards human cervical carcinoma(HeLa)cells with a half maximal inhibitory concentration(IC50)of 3.2μmol/L when exposed to white light irradiation(14.4 J/cm²).In addition,the Stokes shift of TPC-Py was as high as 150 nm,so that it could prevent self-absorption and increase the signal-to-noise ratio of fluorescence imaging.The excellent performance of TPC-Py makes it a promising candidate in imaging-guided clinical PDT for cancer in the near future.     

酞菁配合物的结构与其光动力抗癌活性

光动力治疗是一种正在发展中的治疗癌症的新方法.主要是利用抗癌光敏剂可优先在 肿瘤组织中富集的特性和随后在适当波长的光照下所引发的光敏化反应来杀死癌肿瘤.自198 5年以来,酞菁配合物作为抗癌光敏剂的研究越来越引人注目. 此文在总结51篇参考文献的 基础上,提出了酞菁配合物的结构与其光动力抗癌活性的某些相关性,着重讨论了中心离子 、环取代基、轴向配体对光动力活性和相关物化性质的影响.得出的一个主要的结论是两亲 性酞菁是极具潜力的光敏剂.     

Synthesis and effect on SMMC-7721 cells of new benzo[c,d]indole rhodanine complex merocyanines as PDT photosensitizers

Photodynamic therapy (PDT) represents a modern and noninvasive therapeutic approach, however, it relies on the development of photosensitizers. Here five new benzo[c,d]indole rhodamine complex merocyanines (BIRCM) D1-D5, displaying low dark toxicity and significant photo toxicity, were synthesized as PDT photosensitizers, and characterized by ¹H NMR, IR, UV–Vis and HRMS. The investigation of their absorption spectra in different solvents showed that the absorption maxima and molar extinction coefficient were in the region 507–679 nm and 0.21 × 10⁴–1.27 × 10⁵ L · mol^?1cm^?1, respectively. The evaluation of PDT activity showed that only irradiation could not kill SMMC-7721 cells, and the cell survival rate and inhibition rate at the application dose and duration was 92%–87% and 78%–49%, respectively. Especially, using D2, absorbed in the red zone, as photosensitizer for PDT analyzed its effect on SMMC-7721 cells survival, it could be found that the cell survival rate was 92% without irradiating and the cell inhibited rate was 78% under irradiating at concentrations of 2.5 × 10^?6 mol/L, displaying low dark toxicity and high photo toxicity, which was valuable for PDT of some microvascular diseases or other superficial diseases.