铱(Ⅲ)配合物乏氧肿瘤光动力治疗

光动力治疗因其无创、可控和不易产生耐药性等显著优点,成为一种新型的肿瘤靶向治疗模式。光敏化过程涉及光敏剂对氧分子的光激活反应,然而实体肿瘤的乏氧环境严重限制了传统有机光敏剂的疗效。金属铱配合物具有良好的光物理和光化学性质,是理想的新一代光敏剂,近些年,铱光敏剂被发现可以应用于乏氧肿瘤的光动力治疗。本文总结了近些年金属铱配合物应用于乏氧肿瘤光动力治疗的研究;同时介绍了基于铱配合物的乏氧纳米复合体系的构建和乏氧肿瘤的光动力治疗研究,为开发新型高效的乏氧肿瘤治疗光敏剂及其载体提供参考。     

光动力肿瘤精准治疗的研究进展

光动力治疗是一种局部、温和及相对安全的治疗模式,在癌症精准治疗方面展现了良好应用前景。光敏剂、光源以及氧气是光动力治疗的三个关键要素。首先,传统小分子光敏剂的吸收光谱大多在紫外或可见光区,且缺乏肿瘤靶向性和特异性,组织穿透深度不足且存在非特异性损伤。其次,光动力治疗效率依赖于外光源连续照射,易引发光毒性和组织损伤。另外,实体肿瘤组织处乏氧等微环境限制了光动力治疗效率。因此,提高光动力治疗效率的同时降低副作用,并实现深层组织的高效特异性治疗,是亟待解决的难题。近年来,新型光动力治疗体系不断涌现,以期解决上述限制光动力治疗进一步发展与应用的瓶颈问题。本文从光动力治疗所需三要素角度,综述了近年来发展的各类新型光动力治疗体系及其在肿瘤精准治疗中的应用进展。     

生命分析化学国家重点实验室在肿瘤治疗方面取得新进展

肿瘤的高效、高选择性治疗是癌症治疗研究的热点。与传统的癌症治疗(手术、放疗、化疗)技术不同,光动力治疗用光激发光敏剂,将能量传递给周围的分子氧(3O2),产生具有瞬时强氧化性的单线态氧(1O2),这种1O2可破坏肿瘤组织和癌细胞,实现癌症的高效治疗。在光动力治疗研究领域,光敏剂的设计与选择是其核心问题。目前临床使用的光敏剂,大多对肿瘤组织或细胞选择性不高,导致肿瘤组织周围的正常组织也受到损伤,而且病人在接受光动力治疗以后仍需长时间避光以减轻皮肤红肿、色素沉着等光毒性反应。因此,寻找新型光敏剂以实现1O2在肿瘤组织和细胞中的选择性释放是光动力治疗技术应用的关键问题。     

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.     

八烷氧基萘酞菁锌的激发三重态性质及光动力抗癌活性

采用激光闪光光解技术测定了系列八烷氧基萘酞菁锌配合物ZnNc(OR)8(R=C4H9,C8H17,C12H25)激发三重态的寿命,研究了该系列化合物光敏化产生单重态氧的能力和对HL60癌细胞的光动力活性,并探讨了它们作为光敏剂在肿瘤光动力治疗中的光敏反应机制。     

八烷氧基萘酞菁锌的激发三重态性质及光动力抗癌活性

采用激光闪光光解技术测定了系列八烷氧基萘酞菁锌配合物ZnNc(OR)8(R=C4H9,C8H17,C12H25)激发三重态的寿命,研究了该系列化合物光敏化产生单重态氧的能力和对HL60癌细胞的光动力活性,并探讨了它们作为光敏剂在肿瘤光动力治疗中的光敏反应机制。     

磷光环金属化铱(Ⅲ)配合物在癌症治疗方面的应用

配位饱和且取代惰性的环金属化铱（Ⅲ）配合物由于优秀的磷光特性,在生物成像和生物传感等方面有着广泛的应用。近年来,该类铱配合物由于有效的抗肿瘤效力和新颖的抗肿瘤机制,在抗肿瘤方面的应用也引起了广泛关注。本文主要对磷光环金属化铱（Ⅲ）配合物（结构通式为[Ir（C^N）₂（N^N）]⁺）在抗癌化疗和光动力治疗两方面的最新研究进展进行了综述;分类总结了靶向不同细胞器,作为蛋白-蛋白相互作用抑制剂,以及应用于单光子和双光子光动力治疗的环金属化铱（Ⅲ）配合物,为开发新型金属抗肿瘤药物提供参考。最后,对环金属化铱（Ⅲ）配合物在抗癌应用方面的前景进行了展望。     

肿瘤光动力治疗临床应用的光敏剂及其研究概况

光动力治疗是一种非侵蚀性并具有一定靶向性的肿瘤治疗新方法。 光动力治疗需要光敏剂、光和氧结合产生光动力反应。 光敏剂是光动力治疗的关键和物质基础。 本文概括介绍了已上市的和已被批准进入临床试验中的光敏剂,并根据其分子的骨架结构,将其分为分卟啉类、二氢卟吩（叶绿素）类和菌绿素/酞菁三类。 同时从理想光敏剂应具备特点出发,探讨了研究中的光敏剂和光动力治疗的发展前景。     

靶标性酞菁类光敏剂的光动力疗法研究进展

光动力治疗（Photodynamic therapy,PDT）作为一种有别于传统癌症治疗方式的新型疗法,近些年来受到了科学家们越来越多的关注.它凭借着自身创伤性小,毒性低微,适用性好,可协同手术治疗以及可重复治疗等独特优势,在许多肿瘤的治疗方面有着广泛的应用.本文简要概述了光动力疗法的原理以及光敏剂的发展历程,并对理想光敏剂的特点作了总结.目前,以酞菁类化合物为主的第三代光敏剂已经成为光动力疗法的研究热点,然而如何提高光敏剂分子的靶向性达到精准的光动力治疗仍然是亟待解决的问题.因此,主要综述了近年来靶向性酞菁类光敏剂的研究进展,并对未来光敏剂的重点研究方向做出了展望.从目前来看,如何克服癌症低氧微环境的限制,发展Type I型不依赖氧的体系以及光穿透力强的靶向光敏剂在光动力治疗方面存在着巨大的潜质,有望成为新一代十分优良的光动力疗法用光敏剂.     

光敏剂在癌症诊断和治疗中的研究新进展

光敏剂在特定波长的光照射下,产生荧光和单线态氧,已广泛应用于癌症的诊断和治疗.当前的研究热点是如何提高光敏剂的肿瘤选择性,尤其是光敏剂的靶向输送和特异性激活两方面.本文系统评述了提高光敏剂肿瘤选择性的方法及其在癌症诊断和治疗中的应用.引用文献56篇.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.