新型金属卟啉光敏剂的合成及其抗肿瘤活性

合成了新型β-取代卟啉光敏剂2-氢醌-5，10，15，20-四（4-羟基苯基）卟啉铜（Ⅱ）（Cu（Ⅱ）P）和2-氢醌-5，10，15，20-四（4羟基苯基）卟啉锌（Ⅱ）（Zn（Ⅱ）P），并初步研究其抗肿瘤活性．实验结果表明：2-氢醌5，10，15，20-四（4-羟基苯基）卟啉锌（Ⅱ）对慢性骨髓性白血病肿瘤细胞（K562）具有很好的光敏毒性，Zn（Ⅱ）P的浓度为320nmol／L时，就能抑制90％以上的白血病肿瘤细胞的生长．     

光敏剂在光动力治疗中的应用研究进展

光动力疗法（PDT）以其超高时空分辨率、非侵入性及低毒副作用的优点,被认为是治疗癌症和各种非恶性疾病的有效疗法之一。本文主要综述了几类光敏剂发展历史、主要结构、特点及研究进展,分析了高性能光敏剂的开发动态,包括化学修饰;与具有特定细胞受体的其他配体缀合成复合光敏剂;采取纳米技术,如纳米颗粒输送,基于富勒烯的光敏剂等。基于此,指出具有临床应用前景的高性能光敏剂的基本特征、设计原则及发展趋势。     

鎓盐类阳离子光引发剂的研究进展

介绍了几种有代表性的鎓盐类阳离子光引发剂--芳基重氮盐、芳基翰盐和二烷基苯甲酰硫盐的研究进展情况,探讨了各引发剂的光解机理和优缺点,并提出了增强鎓盐光敏性的方法和相关机理,介绍了有代表性的3类光敏剂以及近年来研制的一些新型光敏剂,概述了大分子鎓盐引发剂的研究情况,最后简要说明了鎓盐阳离子引发刺的发展趋势及应用.     

三种卟啉类光敏剂的荧光量子产率

实验研究了喜泊分(Hiporfin),血啉甲醚(HMME)和癌光啉(PsD-007)等3种国产卟啉类光敏剂在水溶液中的吸收和荧光光谱特性,并利用对照法首次测定了它们在水溶液中的荧光量子产率.Hiporfin,HMME和PsD-007具有相似的吸收光谱和荧光发射特性,它们的荧光量子产率分别为0.013,0.026和0.020.实验表明光敏剂的荧光量子产率还与溶液中的氧含量有关.实验结果为光动力学诊断中光敏剂的选择,以及相应最佳荧光激发和检测波长的选取提供了理论依据.     

Regulated Necrosis in HeLa Cells Induced by ZnPc Photodynamic Treatment: A New Nuclear Morphology

Photodynamic therapy (PDT) is a cancer treatment modality based on the administration of a photosensitizer (PS), which accumulates preferentially in tumor cells. Subsequent irradiation of the neoplastic area triggers a cascade of photochemical reactions that leads to the formation of highly reactive oxygen species responsible for cell inactivation. Photodynamic treatments in vitro are performed with the PS, zinc-phthalocyanine (ZnPc). The PS is near the plasma membrane during uptake and internalization. Inactivation clearly occurs by a necrotic process, manifested by nuclear pyknosis, negative TUNEL and Annexin V assays and non-relocation of cytochrome c. In contrast, by increasing the incubation time, ZnPc is accumulated in the Golgi apparatus and produces cell inactivation with characteristics of apoptosis and necrosis: TUNEL positive, relocated cytochrome c and negative Annexin V assay. This type of death produces a still undescribed granulated nuclear morphology, which is different from that of necrosis or apoptosis. This morphology is inhibited by necrostatin-1, a specific inhibitor of regulated necrosis.     

Pheomelanin Effect on UVB Radiation-Induced Oxidation/Nitration of l-Tyrosine

Pheomelanin is a natural yellow-reddish sulfur-containing pigment derived from tyrosinase-catalyzed oxidation of tyrosine in presence of cysteine. Generally, the formation of melanin pigments is a protective response against the damaging effects of UV radiation in skin. However, pheomelanin, like other photosensitizing substances, can trigger, following exposure to UV radiation, photochemical reactions capable of modifying and damaging cellular components. The photoproperties of this natural pigment have been studied by analyzing pheomelanin effect on oxidation/nitration of tyrosine induced by UVB radiation at different pH values and in presence of iron ions. Photoproperties of pheomelanin can be modulated by various experimental conditions, ranging from the photoprotection to the triggering of potentially damaging photochemical reactions. The study of the photomodification of l-Tyrosine in the presence of the natural pigment pheomelanin has a special relevance, since this tyrosine oxidation/nitration pathway can potentially occur in vivo in tissues exposed to sunlight and play a role in the mechanisms of tissue damage induced by UV radiation.     

邻苯二甲酰亚氨基酞菁锌(ZnPcS2P2)的光谱特性

测定和研究光敏剂的光谱特性,可为确定最佳治疗的光源波长提供直接依据,同时也是荧光诊断中选定检测荧光波长的理论依据．本文研究新型光敏剂邻苯二甲酰亚氨基酞菁锌（ZnPcS2P2）的光谱特性,测出ZnPcS2P2在含10%人血清生理盐水的吸收光谱和荧光发射光谱,并与血卟啉衍生物（HpD）进行比较。实验结果表明：在吸收光谱中ZnPcS2P2的最大吸收峰位于670nm,而HpD的最大的吸收峰在405nm处,所以在光动力学治疗中ZnPcS2P2比HpD效果更好。当用波长为632nm的光源激发时,从荧光发射光谱可知,HpD比ZnPcS2P2获得的荧光激发效率高。因此,HpD在光动力学诊断中有更突出的优点。     

有机激发三重态参与的光化学反应研究进展

光化学反应包括直接光解和间接氧化反应,其中间接氧化反应主要通过活性氧化性物种（reactive oxygen species, ROS）包括单线态氧（¹O₂）、过氧自由基（{\mathrm{O}}_{\mathrm{2}}^{-}）和羟基自由基（·OH）等进行。近年来,有机激发三重态（³C^*）作为一种特殊的氧化剂参与光化学反应引起了广泛关注。本文主要综述了有机三重态光敏剂的形成和光化学反应机制、³C^*参与的环境光化学反应、³C^*自由基寿命、反应速率及稳态浓度测定和激发三重态的应用5个方面,并对未来有机分子激发三重态的研究方向进行了展望,指出³C^*是很多挥发性有机化合物（VOCs）或半/中等挥发性有机化合物（S/IVOCs）在大气中重要的汇,自然水体中溶解性有机质（dissolved organic matter,DOM）的激发三重态（³DOM^*）是污染物降解的主要氧化剂。今后应扩大³C^*与有机物反应的研究范畴,测定不同体系中³C^*的稳态浓度、产生速率（量子产率）等,为污染物治理提供理论依据。     

9,10-二氰蒽合成方法的改进

以蒽为原料,经溴化和氰化两步合成了光敏剂9,10-二氰蒽(DCA)。从反应溶剂的选择及提纯方法等方面改进了DCA的合成方法,提高了溴化和氰化反应的收率。结果表明,溴化反应时,控制溴的滴加温度为30℃,收率可达95%;合成DCA时,采用连续抽提法提纯,以DMSO为溶剂,反应中生成的无机盐完全溶解,粗产物不经抽提DCA收率可达74%～75%;而选用N-甲基吡咯烷酮为溶剂,DCA可与溴化铜形成配合物CuBr_2·DCA·CuBr_2,此配合物加热易分解,DCA收率达到93%。     

Potential Applications of Cucurbit[n]urils Inclusion Complexes in Photodynamic Therapy

Cucurbit[n]urils (CB[n]s) have emerged as potential candidates for drug delivery in several areas due to their strong binding interactions and low toxicity. More recently, their benefits for a type of cancer treatment termed Photodynamic Therapy (PDT) have been recognized. The outcomes of this therapy rely on better drug delivery strategies and improving overall photoactivity of the drugs, which is where CB[n]s could have a strong impact. The effects of these molecular containers on photoactivity are discussed and new interesting work is highlighted.