作者单位
摘要
1 吉林大学 口腔医学院,吉林 长春 130021
2 吉林大学 电子科学与工程学院,集成光电子学国家重点实验室,吉林 长春 130012
卟啉-金属有机框架(MOFs)材料是由金属节点和卟啉有机配体构成的一类新型多孔材料,MOFs骨架上的卟啉配体在光激发下,可以发挥光动力学治疗(PDT)作用。这类多孔结构的PDT材料在疾病治疗中,可以发挥载药、多功能修饰等功能,某些金属位点独特的MOFs还具有纳米酶功能。近年来,这类卟啉-MOFs已经成为PDT领域的重要研究方向。目前,在推向临床前,这类材料还需要解决氧气浓度、能量传递效率等问题,研究者也给出了诸多解决方案,根据实际应用过程中所面对的不同环境,采取不同手段来增强PDT的效果,包括提高氧气浓度、改进能量传递过程、消耗功能分子、产生信号分子以及协同策略等。本文综述了近年来的代表性工作,包括卟啉-MOFs材料以及PDT产生的机制,卟啉-MOFs材料PDT的应用和最新进展,并针对卟啉-MOFs材料的PDT在生物医学领域未来发展趋势进行了展望。
卟啉 金属有机框架 光动力疗法 porphyrins metal-organic frameworks photodynamic therapy 
发光学报
2023, 44(8): 1505
作者单位
摘要
咸阳师范学院化学与化工学院, 陕西 咸阳 712000
用于光动力疗法(PDT)中的光敏剂是一类吸收一定波长的光后达到激发三重态, 然后将三重态能量转移给生物体内的氧分子使得基态氧激发为单线态氧的一类物质。 目前, 临床应用的光敏剂大部分是以卟啉为主的平面型分子。 平面分子一般具有较大的共轭键, 被光激发后系间窜跃小, 三重态寿命较长, 因此可以获得高产率的单线态氧。 然而临床使用的这类光敏剂吸收波长位于紫外区域, 照射光会对人体组织造成光损伤, 因此改善临床光敏剂光毒性特征, 合成具有可见光区域吸收波段的光敏剂是光动力疗法研究的重要内容之一。 该研究依据密度泛函(DFT)及其含时理论(TD-DFT), 对三类平面型卟啉衍生物[耳坠型卟啉(a), 三磺酸基酞菁(b), 三磺酸基酞菁合Ni(Ⅱ)(c)]的基态和激发态性质进行了严格的密度泛函计算。 几何优化计算显示: 分子(a)的最稳定构型中, 所有原子都处于一个平面, 分子直径大约是7 Å, 分子空穴达到5 Å。 分子(b)所有的原子也处于同一平面, 分子直径达到8 Å, 但是分子空穴只有4 Å。 分子(c)的最稳定构型与平面结构发生了偏离, 这是由于金属Ni的四配位倾向形成变形四面体, 分子的空穴变得更小。 几何优化结果说明耳坠型卟啉分子大的空穴有助于其捕获更多的基态氧并进行能量传递。 前线轨道能量和轨道布局计算显示: 耳坠型分子(a)最高占据能量是最高的, 即电子更易被激发。 三类分子的最高占据轨道与最低空轨道的能级间隔分别为0.072, 0.076和0.075 a.u., 可以看出耳坠型分子(a)有最低的能级间隙。 从轨道布局来看, 三类分子中所有原子的p轨道参与了共轭大π键的形成, 其中分子(c)中金属d轨道也参与了大π键的形成。 对三类分子的吸收光谱进行了模拟, 三类分子都具有卟啉特有的Soret带和Q带。 (a)分子Q带位于450~900 nm, (b)分子和(c)分子的Q带位于400~800 nm, 其中(a)分子的最大吸收波段是939 nm。 该研究从分子结构, 轨道能量以及吸收光谱对三类卟啉类光敏剂的微观特性进行了理论计算和讨论, 研究结果将为发现和开发近红外吸收的卟啉类高效光敏剂提供理论依据。
光敏剂 卟啉 密度泛函 吸收光谱 Photosensitizer Porphyrins Density functional Absorption spectra 
光谱学与光谱分析
2022, 42(6): 1769
Author Affiliations
Abstract
1 H. Buniatyan Institute of Biochemistry, National Academy of Sciences of Armenia, 5/1 Paruir Sevak Street, Yerevan 0014, Armenia
2 INSERM U1204, Universite d'Evry val d'Essonne–Universite Paris-Saclay, 1 Rue du Pere Jarlan, Batiment Maupertuis, 91025 Evry-Courcouronnes, France
3 SPC "Armbiotechnology", National Academy of Sciences of Armenia, 14 Gyurjyan Street, Yerevan 0056, Armenia
4 B. I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, 68-2 Nezavisimosti Avenue, Minsk 220072, Belarus
5 Science Medical Center, Saratov State University, 83 Astrakhanskaya Street, Saratov 410012, Russia
6 Laboratory of Laser Molecular Imaging and Machine Learning (LMIML), National Research Tomsk State University, 36 Lenin Avenue, Tomsk 634050, Russia
7 Laboratory of Laser Diagnostics of Technical and Living Systems, Institute of Precision Mechanics and Control, Russian Academy of Sciences, Saratov 410028, Russia
Photodynamic inactivation of microorganisms known as antibacterial photodynamic therapy (APDT) is one of the most promising and innovative approaches for the destruction of pathogenic microorganisms. Among the photosensitizers (PSs), compounds based on cationic porphyrins/metalloporphyrins are most successfully used to inactivate microorganisms. Series of meso-substituted cationic pyridylporphyrins and metalloporphyrins with various peripheral groups in the third and fourth positions of the pyrrole ring have been synthesized in Armenia. The aim of this work was to determine and test the most effective cationic porphyrins and metalloporphyrins with high photoactivity against Gram negative and Gram positive microorganisms. It was shown that the synthesized cationic pyridylporphyrins/metalloporphyrins exhibit a high degree of phototoxicity towards both types of bacteria, including the methicillinresistant S. aureus strain. Zinc complexes of porphyrins are more phototoxic than metal-free porphyrin analogs. The effectiveness of these Zn–metalloporphyrins on bacteria is consistent with the level of singlet oxygen generation. It was found that the high antibacterial activity of the studied cationic porphyrins/metalloporphyrins depends on four factors: the presence in the porphyrin macrocycle of a positive charge (+4), a central metal atom (Zn2tT and hydrophobic peripheral functional groups as well as high values of quantum yields of singlet oxygen. The results indicate that meso-substituted cationic pyridylporphyrins/metalloporphyrins can find wider application in photoinactivation of bacteria than anionic or neutral PSs usually used in APDT.
Antibacterial photodynamic therapy cationic porphyrins/metalloporphyrins phototoxicity Zn–metalloporphyrins singlet oxygen quantum yield Gram negative and Gram positive bacteria S. aureus MRSA E. coli Salmonella typhimurium. 
Journal of Innovative Optical Health Sciences
2022, 15(1): 2142007
作者单位
摘要
南京航空航天大学材料科学与技术学院, 江苏 南京 211106
通过系统分析绿色植被在紫外可见波段光谱的产生机理, 得出绿峰和红边是由叶绿素产生的。 从叶绿素的结构上看, 它属于卟啉类化合物, 为了进一步探究红边产生的机理, 合成了四苯基卟啉、 四(4-甲氧基苯基)卟啉、 四(4-磺酸钠苯基)卟啉、 四吡啶基卟啉、 四甲基卟啉、 四(4-甲氧基苯基)卟啉合锌和四(4-甲氧基苯基)卟啉合铜, 并采用紫外可见光谱、 红外及核磁进行表征。 通过对其紫外可见光谱的系统分析, 提出“红边”不仅限于叶绿素, 而是卟啉类化合物特有的光谱特征, 红边是由卟啉环a2u(π)-eg(π*) 跃迁产生的Q带所致。 其位置不仅与卟啉的浓度相关, 与卟啉化合物外侧取代基类型也有关系, 金属卟啉对红边的位置影响较大。
红边 叶绿素 卟啉 金属卟啉 Red edge Chlorophyll Porphyrins Q band 
光谱学与光谱分析
2017, 37(12): 3940
Author Affiliations
Abstract
1 Institute of Electronics, Bulgarian Academy of Sciences 72, Tsarigradsko Chaussee Blvd., 1784 Sofia, Bulgaria
2 National Institute for Optoelectronics, Atomistilor 409 077125 Magurele, Romania
3 National Oncological Center, 6, Plovdivsko Pole Str. 1156 Sofia, Bulgaria
Many up-to-date optical techniques have been developed and applied recently in clinical practice for obtaining qualitatively and quantitatively new data from the investigated lesions. Due to their high sensitivity in detection of small changes, these techniques are widely used for detection of early changes in biological tissues. Light-induced fluorescence spectroscopy (LIFS) is one of the most promising techniques for early detection of cutaneous neoplasia. Increasing number of recent publications have suggested that optical coherence tomography (OCT) also has potential for non-invasive diagnosis of skin cancer. This recent work is a part of clinical trial procedure for introduction of LIFS technique into the common medical practice in National Oncological Medical Center in Bulgaria for diagnosis of non-melanoma skin cancer. We focus our attention here on basal cell carcinoma lesions and their specific features revealed by LIFS and OCT analysis. In this paper we prove the efficiency of using the combined LIFS-OCT method in skin lesions studies by integrating the complimentary qualities of each particular technique. For LIFS measurements several excitation sources, each emitting at 365, 385 and 405 nm maxima are applied. An associated microspectrometer detects in vivo the fluorescence signals from human skin. The main spectral features of the lesions and normal skin are discussed and their possible origins are indicated. OCT images are used to evaluate the lesion thickness, structure and severity stage, when possible. The obtained results could be used to develop a more complete picture of optical properties of these widely spread skin disorders. At the same time, our studies show that the combined LIFS-OCT method could be introduced in clinical algorithms for early tumor detection and differentiation between normal/benign/malignant skin lesions.
Cutaneous fluorescence OCT BCC images endogenous porphyrins skin cancer 
Journal of Innovative Optical Health Sciences
2009, 2(3): 261–268
作者单位
摘要
复旦大学物理系, 上海 200433
建立了单光子光化烧孔的三能级模型,求解了反映质子转位变构机制的速率方程组,推导了成孔过程的动力学特性,获得了可与实验进行比较的解析解.用时域和频域两种方法测量了THP/PMMA和TMP/PMMA薄膜样品光谱烧孔的动力学过程,得到与理论分析一致的规律,并测得了有效成孔速率和成孔时间等参数.这些参数对于评价频域光存贮材料性能有一定意义.
持久光谱烧孔 动力学 自由基卟啉分子 
光学学报
1994, 14(9): 924

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