不同激发波长下ZnPcSP的光敏化能力和抗癌活性

研究了激发光的波长对金属酞菁配合物ＺｎＰｃＳＰ光敏化产生Ｏ２的能力和光动力癌作用的影响，结果表明，激发波长对ＺｎＰｃＳＰ配合物光敏化产生Ｏ２的能力和光动力抗癌作用的影响显示了同样的规律性，波长为６７０ｎｍ的光具有较佳的激发效率，研究结果同时说明ＺｎＰｃＳＰ在光动力治癌中的主要光敏反应机制可能是产生Ｏ２的Ⅱ型反应机制。     

喹啉氧基酞菁金属配合物光敏化氧化色氨酸能力的研究

酞菁金属配合物是光动力治疗的新一代光敏剂,其治疗作用的机理以及引起的生物效应一直是人们研究的热点.本文选用色氨酸作为与喹啉氧基酞菁金属配合物作用的靶分子,讨论了配合物的组成结构与其光敏化氧化色氨酸能力的相关性.结果表明,酞菁环内中心金属离子和环周边取代基的组成结构以及取代位置与数目都影响其光敏化氧化色氨酸能力,中心金属离子为闭壳层电子结构、取代基位于α位以及提高取代基数目均有利于提高光敏化氧化活性,同时显示,取代基的组成结构对靶分子有一定选择性,研究结果可为研发该类光敏剂提供依据.     

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.     

温敏性金属酞菁聚合物的制备及光活性

对氨基锌酞菁进行改性,并将其以共价键接枝到聚N-异丙基丙烯酰胺分子链上,制得一种新型的既有温敏性又有光活性的锌酞菁聚合物．与小分子氨基锌酞菁相比,所合成的锌酞菁聚合物能溶解于大多数有机溶剂和水,而且,在水溶液中表现出良好的温敏性,其低临界溶解温度为34．1℃．通过锌酞菁聚合物对单线态氧捕捉剂1,3-二苯基苯并呋喃的光催化降解测试,结果表明在可见光照射下,锌酞菁聚合物无论在溶解状态还是沉淀状态都具有较高的光活性．基于这些特殊性能,这种锌酞菁温敏聚合物作为一种新型光敏剂,有望在光动力学治疗领域得到广泛的应用．     

用于光动力治疗的金属酞菁配合物-- 两亲性酞菁锌配合物ZnPcS2P2的制备、表征及抗癌活性

用直接取代法合成得到含磺基和邻苯二甲酰亚胺甲基的一系列双取代的酞菁锌化合物, 产物经反相高效液相色谱法分离得5种不同组分, 经膜分离法进一步纯化和浓缩后, 用元素分析、红外光谱等进行表征. 测定各组分在光照下产生单线态氧的能力,并通过离体试验比较它们杀伤癌细胞的能力. 对其中具有较高光动力抗癌活性的物种二磺基二邻苯二甲酰亚胺甲基酞菁锌(ZnPcS2P2)进一步用紫外可见光谱、核磁、热分析、质谱等方法进行结构表征. 研究了ZnPcS2P2的在体抗肿瘤活性, 结果表明, 在670 nm激光的激发下(光照剂量为72 J/cm2), ZnPcS2P2(药剂量为2 mg/kg)对小鼠的U14和S180移植瘤的抑瘤率分别达到89.8%和90.8%. 探讨了构效关系, 初步分析了ZnPcS2P2具有较高活性的结构原因.     

单重态氧化学VIII.类卟啉稀土配合物光敏化产生单重态氧的ESR研究

用电子自旋共振(ESR)方法研究类卟啉稀土配合物([CO2H-APPC)Gd]Cl2)光敏产生单重态氧的II型机制。利用2,2, 6, 6-四甲基哌啶(TEMP)对单重态氧的捕捉, 测定所生成的氮氧自由基的ESR信号, 经加NaN3和CD3OD的实验, 证实了([CO2H-APPC)Gd]Cl2)光敏作用可有效地产生单重态氧, 并观察到在实验所用的浓度范围内, 随着光敏剂浓度加大, 生成的单重态氧也增加, 同时比较了几种不同稀土离子配合物产生单重态氧的差别。结合氧的消耗和氮氧自由基的ESR线宽变化对氧浓度的依赖性, 证明了类卟啉稀土配合物光敏化生成单态氧的II型反应在光动力光疗中起关键作用。     

单重态氧化学VIII.类卟啉稀土配合物光敏化产生单重态氧的ESR研究

用电子自旋共振(ESR)方法研究类卟啉稀土配合物([CO2H-APPC)Gd]Cl2)光敏产生单重态氧的II型机制。利用2,2, 6, 6-四甲基哌啶(TEMP)对单重态氧的捕捉, 测定所生成的氮氧自由基的ESR信号, 经加NaN3和CD3OD的实验, 证实了([CO2H-APPC)Gd]Cl2)光敏作用可有效地产生单重态氧, 并观察到在实验所用的浓度范围内, 随着光敏剂浓度加大, 生成的单重态氧也增加, 同时比较了几种不同稀土离子配合物产生单重态氧的差别。结合氧的消耗和氮氧自由基的ESR线宽变化对氧浓度的依赖性, 证明了类卟啉稀土配合物光敏化生成单态氧的II型反应在光动力光疗中起关键作用。     

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。     

联合化疗与光动力治疗于一体的水溶性铜(Ⅱ)、镍(Ⅱ)酞菁的合成及体外抗癌活性

以邻苯二腈法合成了全水溶性铜酞菁(Cu Pc)6与镍酞菁(Ni Pc)7。对该类酞菁进行了光物理化学特性测试及体外细胞生物试验。结果表明:合成的铜酞菁6与镍酞菁7不仅水溶性好,而且对光热都十分稳定,并能有效产生单线态氧。体外细胞测试证实,铜酞菁6与镍酞菁7表现出了对癌细胞的避光下的抑制效应以及光照下的光动力治疗效应,显示了金属配合物化疗效应与光动力治疗的协同抗癌活性。     

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。     

Towards near-infrared photosensitisation: a photosensitising hydrophilic non-peripherally octasulfanyl-substituted Zn phthalocyanine

A Zn(II) phthalocyanine substituted with eight hydroxylated sulfanyl moieties in non-peripheral positions was designed to exhibit properties desired for photodynamic therapy: hydrophilicity, isomeric purity and near-infrared absorption in addition to high singlet oxygen generation. Photophysical and photochemical studies proved to be promising.     

Solvent effects on the photochemical and fluorescence properties of zinc phthalocyanine derivatives

The effects of solvents on the singlet oxygen, photobleaching and fluorescence quantum yields for zinc phthalocyanine (ZnPc) and its derivatives; (pyridino)zinc phthalocyanine ((py)ZnPc), zinc octaphenoxyphthalocyanine (ZnOPPc) and zinc octaestronephthalocyanine (ZnOEPc), is presented. The effects of the solvents on the ground state spectra are also discussed. The largest red shift of the Q band was observed in aromatic solvents, the highest shift being observed for 1-chloronaphthalene. Higher singlet fluorescence quantum yields were observed in THF for ZnPc and ZnOPPC. Also in the same solvent phototransformation rather than photobleaching was observed for ZnOPPc. Split Q band in the emission and excitation spectra of ZnOPPc was observed in some solvents and this is explained in terms of the lowering of symmetry following excitation.     

The synthesis and photophysicochemical properties of low-symmetry zinc phthalocyanine analogues

The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (Ф_T) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest Ф_T values and triplet lifetimes (τ_T) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.     

Meso-substituted porphyrin photosensitizers with enhanced near-infrared absorption: Synthesis,characterization and biological evaluation for photodynamic therapy

Porphyrin derivatives are widely explored and used in photodynamic therapy, for their marvelous therapeutic properties. In order to fill in the gaps of insufficient photosensitizers with near-infrared absorption, three porphyrin molecules, 5,10,15,20-tetrakis(3,4-bis(2-(-2-(2-hydroxyethoxy)ethoxy)ethoxy)benzyl)zinc porphyrin(P1), 5,15-bis(3,4-bis(2-(-2-(2-hydroxyethoxy)ethoxy)ethoxy)benzyl)-10,20-bis(2-(2-(2-(4-ethynylphenoxy)ethoxy)ethoxy)ethanol)zincporphyrin(P2),5,15-bis(3,4-bis(2-(-2-(2-hydroxyethoxy)ethoxy)ethoxy)benzyl)-10,20-N,N-dibutyl-4-ethynylaniline zinc porphyrin(P3), were designed and synthesized targeting for more efficient cancer treatment. Excellent photophysical properties were illustrated by UV–vis absorption and emission spectra with enhanced absorbance between 650 and 750?nm and fluorescence emission within 600–800?nm. Besides, with high ¹O₂ quantum yield, especially P2 (0.89), all porphyrins were further evaluated in vitro by 3-(4, 5-dimethyl-2-thiazolyl)-2, 5-diphenyl-2-H-tetrazolium bromide (MTT) assay against Hela cells and exhibited negligible dark toxicity and robust phototoxicity. Fluorescence confocal laser microscopy confirmed cellular uptake and diffusion of these porphyrins, therefore demonstrated their potential and promising applications in photodynamic therapy.     

New soluble methylendioxy-phenoxy-substituted zinc phthalocyanine derivatives: Synthesis, photophysical and photochemical studies

The syntheses of new three phthalonitriles (1, 2 and 3), together with photophysical and photochemical properties of the resulting peripherally and non-peripherally tetrakis- and octakis 3,4-(methylendioxy)-phenoxy-substituted zinc phthalocyanines (4, 5 and 6) are described for the first time. Complexes 4, 5 and 6 have been synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, electronic spectroscopy and mass spectra. Complexes 4, 5 and 6 have good solubility in organic solvents such as CHCl₃, DCM, DMSO, DMF, THF and toluene and are mainly not aggregated (except for complex 6 in DMSO) within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO and toluene. Complex 4 has higher singlet oxygen quantum yields, fluorescence quantum yields, triplet quantum yields and triplet life times than complexes 5 and 6. The effect of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (4, 5 and 6) are also reported.     

Singlet oxygen generation ability of squarylium cyanine dyes

The quantum yields for singlet oxygen generation of several squarylium cyanine dyes derived from benzothiazole, benzoselenazole and quinoline, displaying absorption within the so-called “phototherapeutic window” (600–1000 nm), were determined, envisioning their potential usefulness for photodynamic therapy (PDT). The determination was performed by a direct method measuring the luminescence decay of the dyes in the near infrared. Considering the absorption and the quantum yields displayed by some of the dyes, these seemed to be potential candidates as sensitizers for PDT.     

Synthesis and photophysical characterization of a library of photostable halogenated bacteriochlorins: an access to near infrared chemistry

Near infrared (NIR) photons are ideally suited for photomedicine because they are relatively harmless and penetrate deeply in biological tissues. However, their use is impaired by lack of straightforward methods to synthesize large quantities of stable infrared-absorbing molecules with long-lived excited states. Here we present a one-step synthesis of amphiphilic meso-phenyl halogenated bacteriochlorins, via hydrazide reduction, possessing strong absorption about 750 nm. The reaction proceeds efficiently, in large quantities, with a solid-solid solvent-free methodology, that is characterized by its simplicity, efficiency and minimum environmental impact. The new bacteriochlorins have unprecedented chemical and photophysical properties, namely strong electronic absorption above 720 nm, adequate photostability, low fluorescence quantum yield and n-octanol/water partition coefficients (log P_OW) ranging from −1.7 to >4, meaning that the library of compounds synthesized in this work is versatile enough to be applied in photodynamic therapy for a range of biological targets.     

Synthesis of Sn nanocluster@carbon dots for photodynamic therapy application

Recently, photodynamic therapy (PDT) has been extensively applied in clinical and coadjuvant treatment of various kinds of tumors. However, the photosensitizer (PS) of PDT still lack of high production of singlet oxygen (¹O₂), low cytotoxicity and high biocompatibility. Herein, we propose a facile method for establishing a new core-shell structured Sn nanocluster@carbon dots (CDs) PS. Firstly, Sn⁴⁺@S-CDs complex is synthesized using the sulfur-doped CDs (S-CDs) and SnCl₄ as raw materials, and subsequently the new PS (Sn nanocluster@CDs) is obtained after vaporization of Sn⁴⁺@S-CDs solution. Remarkably, the obtained Sn nanocluster@CDs show an enhanced fluorescence as well as a higher ¹O₂ quantum yield (QY) than S-CDs. The high ¹O₂ QY (58.3%) irradiated by the LED light (400–700 nm, 40 mW/cm²), induce the reduction of 4T1 cancer cells viability by 25%. More intriguingly, no visible damage happens to healthy cells, with little impact on liver tissue due to renal excretion, both in vitro and in vivo experiments demonstrate that Sn nanocluster@CDs may become a promising PS, owning a high potential for application in PDT.