卟啉降冰片烯聚合物的合成、表征及性质研究

本文设计合成了卟啉的降冰片烯单体,采用Grubbs催化剂与长链烷基的降冰片烯单体开环易位聚合,直接得到了卟啉降冰片烯聚合物,通过紫外-可见吸收光谱、荧光光谱、电化学等手段研究了卟啉降冰片烯聚合物的性质,与小分子单体相比,所得卟啉高分子共聚物相当好地保持了卟啉应有的光物理、电化学等特性.     

新颖的5,15-二(4-(5-乙酰基硫戊氧基)苯基)卟啉化合物的结构和性质的密度泛函理论计算

通过密度泛函理论计算比较性地研究了5,15-二(4-(5-乙酰基硫戊氧基)苯基)自由卟啉及其锌配合物的分子结构、电荷性质、分子轨道、电子吸收光谱和红外光谱.这类化合物具有在卟啉相对的两个中位的苯环上连有5-乙酰基硫戊氧基的新颖结构.模拟得到的这两个化合物的分子结构和电子吸收光谱以及红外光谱都与实验测得的符合得很好.通过与未取代的自由卟啉和卟啉锌的结构和性质进行比较,研究了中位取代基、极性溶剂和中心金属取代对此类卟啉化合物结构和性质的影响规律.对化合物的电子吸收光谱中的电子跃迁本质进行了归属,并通过基于正则坐标分析产生的动画对红外光谱的振动模式进行了指认.目前的工作将对理解此类新颖卟啉化合物的结构和性质以及取代基和溶剂效应提供很大的帮助.     

卟啉纳米组装与生物传感

卟啉是一类重要的有机共轭分子,可以模拟许多酶的活性中心。一系列卟啉仿生酶已被合成,并用于模拟生物蛋白酶的催化活性,包括平面卟啉、栅栏卟啉、扩展环卟啉和三元环卟啉。在生物体内,许多金属蛋白酶经常自组装成纳米尺度的超分子结构来实现其基本的生物催化作用。卟啉可以通过共价或者非共价作用有序组装在纳米材料上,实现其模拟金属蛋白酶的功能。金属卟啉是良好的电子媒介体,对生命过程相关小分子的氧化还原具有较好的电催化活性。因此,金属卟啉纳米组装形成的纳米材料复合物可用于新型电化学生物传感器的构建。基于卟啉纳米材料复合物的光物理和光化学性质构建的新型光电化学生物传感平台已用于生物分子的检测。本文主要从卟啉仿生酶的合成、有序纳米组装和卟啉纳米复合物的生物传感进行评述,为构建新型电化学和光电化学传感器提供有用信息。     

卟啉类试剂在分析化学中的应用进展

根据卟啉类试剂的特性,从其在分析化学中的显色性、荧光性、超分子特性、电化学活性等方面,简要综述了近几年来卟啉类试剂在分析化学中的应用进展情况.     

不对称酰胺基二茂铁卟啉的合成及其性能研究

合成了两种不对称酰胺基二茂铁卟啉化合物,利用质谱、核磁共振氢谱、紫外光谱和红外光谱等方法表征了其结构,并讨论了酰胺基二茂铁卟啉的荧光,电化学,拉曼光谱的影响和变化规律。光谱和电化学的研究表明,取代基(CH_3O)使酰胺基二茂铁卟啉发射光谱红移,荧光量子产率增大,对于拉曼光谱的苯环振动有很大的影响;电化学结果显示使卟啉更易失电子被氧化。研究结果表明通过改变卟啉周边的取代基可以调控二茂铁卟啉的光谱和电化学性能.     

水溶性稀土卟啉络合物的合成及电化学行为

对水溶性稀土卟啉络合物的合成、结构、稳定性及其电化学特性进行了系统研究，测定了络合物的稳定常数，讨论了稀土卟啉络合物的电极反应机理；对于镧系卟啉络合物，从Ｔｂ到Ｙｂ随着原子序数的递增，重稀土卟啉络合物的稳定性及还原性不断增强，还原峰电位不断正移，并从理论上解释了该规律。     

氧在稀土酞菁上的电化学还原

过渡金属大环配合物(例如酞菁和卟啉)对氧的电化学还原具有很高的催化活性,因而是目前电化学最活跃的研究领域之一.关于氧在过渡金属大环配合物上电化学还原机理,一般认为与过渡金属的价态变化有关.近年来,由于稀土双酞菁具有电致变色(electrochromic)的特性,引起了人们极大的兴趣,并对它们的电化学行为进行了一系列的研究,但关于它们对氧的电化学还原作用却未见报道.我们利用循环伏安法研究了某些稀土单酞菁和双酞菁对氧的电化学还原的影响,并提出了氧的电化学还原的反应历程.     

卟啉四臂星型聚乳酸的制备与表征

利用本体聚合方法,采用辛酸亚锡为催化剂,四氨基苯基卟啉为引发剂,引发丙交酯开环聚合,制备四臂星型聚乳酸功能高分子材料.采用1 H-NMR,FTIR,GPC等对星型聚合物的分子结构、分子量及其分布等进行了研究.利用溶液浇铸成膜方法,制备了聚乳酸薄膜材料;并利用XRD方法,研究了聚乳酸薄膜的结构.研究表明,利用四氨基苯基卟啉为引发剂,合成了以卟啉为核的四臂星型聚合物,其溶液浇铸薄膜具有正交晶系α晶型结构,而线型聚乳酸呈非晶态结构.利用紫外可见吸收光谱研究了星型聚乳酸的光谱性质,结果表明合成聚合物具有锡卟啉的光学特性.     

四(5,6-二氯-1,4-二硫杂环已烯)四氮杂卟啉的金属配合物的电化学还原及光谱电化学表征

关于卟啉和酞菁的金属配合物已有广泛的研究，这二类化合物因其具有特殊的结构和功能，在不同领域里得到广泛应用。四氮杂卟啉的分子结构是这两类化合物分子结构的“混种”，兼有两者的基本特性，而含硫四氮杂卟啉的金属配合物具有比金属卟啉和金属酞菁更为优良的物理化学...     

光谱烧孔材料苯并卟啉锌配合物的电化学及现场光谱电化学特性

在CH₂Cl₂、THF及DMSO中研究了系列光谱烧孔材料苯并卟啉锌配合物的电化学及光谱电化学特性,给出不同结构的苯并卟啉锌配合物的氧化还原电位及相应氧化还原态的光谱,结合光谱数据和氢化还原电位数值估算了与光化学光谱烧孔过程密切相关的分子激发态氧化还原电位。     

Photoinduced Electron Transfer of Porphyrin Isomers: Impact of Molecular Structures on Electron‐Transfer Dynamics

Porphyrins have been investigated for a long time in various fields of chemistry owing to their excellent redox and optical properties. Structural isomers of porphyrins have been synthesized, namely, porphycene, hemiporphycene, and corrphycene. Although the number of studies on these structural isomers is limited, they exhibit interesting properties suitable for various applications such as photovoltaic devices, photocatalysts, and photodynamic therapy. In the present review, we summarized their photoinduced electron‐transfer processes, which are key steps of various photofunctions. Their electrochemical and photophysical properties are summarized as basic properties for the electron transfer. Furthermore, differences among these isomers in the electron‐transfer processes are clarified, and its origin has been discussed on the basis of their molecular structures.     

卟啉化合物的固载化及其应用的研究概况

卟啉是一类重要的大环化合物,广泛存在于自然界和生命体中,具有广泛的应用。 由于自由卟啉化合物的化学稳定性差,天然卟啉通常在特定的天然大分子(多肽)环境中发挥其特性,因此,人们研究开发了多种担体,固载化卟啉和金属卟啉,大大拓展了其应用范围。 本文综述了文献报道的卟啉及金属卟啉的常用固载载体、常用的固载方法、以及固载型卟啉化合物在催化和传感器等领域的最新应用进展,展望了卟啉的固载化和固载型卟啉的应用前景。     

STM studies on porphyrins

Porphyrins are promising components to be used in molecular electronics due to their rich electronic/photonic properties. Preparation of supramolecular architectures of porphyrins on solid surfaces would constitute a basis for further development toward molecular circuitry or other constructs for molecular electronics applications. Assemblies on surfaces can be probed with scanning tunneling microscopy (STM) at submolecular resolutions to reveal the arrangements and conformations of molecules on an individual molecule basis. The electronic characteristics within a single porphyrin molecule can also be probed by means of the same technique. This review summarizes the status quo of STM studies on porphyrins on surfaces with regard to their assemblies, structures, and electronic properties at the single molecule level.     

卟啉超分子的组装合成及其应用新进展

卟啉超分子已被广泛地用于光学、催化、仿生等方面的研究,部分研究成果已获得实际应用．本文综述了卟啉超分子在组装合成及应用方面的新进展,包括基于不同结构卟啉砌块的新型二维与三维超分子的构筑以及卟啉超分子在光学、催化和分子识别等方面的应用．     

高分子担载卟啉及其金属络合物研究进展

本文介绍了高分子担载卟啉及其金属络合物在模拟细胞色素Ｐ－４５０，光学灭菌材料，阴离子载体及光敏化学材料等领域的最新研究进展。     

Fluorinated porphyrinoids and their biomedical applications

Porphyrins, phthalocyanines, chlorins and corroles create a compact group of macrocyclic compounds of established utility in medicine and technology. Fluorine atom insertion to their structures belongs to one of many ongoing approaches for improving their potency. The presence of fluorine in the structure of a photosensitizer may enrich it with required pharmacokinetic features. Photostability, high level of singlet oxygen production, lipophilicity and selective accumulation in tumor cells have made the fluorinated porphyrinoids potential entities for photodynamic therapy. Moreover, photosensitizers possessing intrinsic fluorescence may be applied as agents in photodynamic diagnosis of cancer. Noteworthy, magnetic resonance of fluorinated compounds constitutes excellent probe for sensitive and minimally invasive imaging.Porphyrins constitute the largest group within fluorinated porphyrinoids of potential anticancer and antimicrobial properties. Skillful combination of fluorine substituents with other functional groups in their structures, including glycol or sugars led to novel molecules possessing outstanding phototoxicity in both in vitro and in vivo studies. Furthermore, fluorinated porphyrins were researched as biomimetic systems imitating the active sites of some enzymes. Fluorinated chlorins are considered as promising photosensitizers due to a strong absorption and the least harmful effects to human tissues. Fluorine containing groups introduced to the periphery of phthalocyanines improved their solubility in common solvents and thus enhanced applications in in vitro and in vivo researches. Lately investigated porphyrinoids belonging to corroles showed on one hand potential as photosensitizers, but on the other hand they were found as catalytic anti-oxidants for attenuation of diabetes mellitus.     

卟啉衍生物的合成与性能研究进展

卟啉化学是有机化学研究中不可或缺的一个方向。由于卟啉在结构上具有一个大的共轭体系,从而具有典型的芳香性。其具有优异的光电性能、独特的光动力治疗作用、高效的催化活性,并且广泛存在于血红素、叶绿素、维生素B_(12)、过氧化氢酶等有机生物分子中,所有这一切都吸引着科学家们进行深入研究。本文从取代卟啉、缩合卟啉以及扩环卟啉三个方面分别讨论了卟啉的研究进展,通过列举一系列经典的反应以及卟啉衍生物,总结了卟啉衍生物的合成方法及其发展方向。另外,文中还对于卟啉的一些特殊物理、化学和光电性质,做了重点介绍。本文旨在为卟啉的研究者们提供参考。     

Combinatorial synthesis and characterization of new asymmetric porphyrins as potential photosensitizers in photodynamic therapy

Porphyrins play a major role as active photosensitizers in noninvasive optical photodynamic therapy (PDT). In a modular approach, this paper presents a short review of the recent developments of porphyrin structures and materials with improved photosensitizing properties and then presents the synthesis and characterization of a series of new second generation asymmetrical meso-tetraphenylporphyrins varied by substituent in the meta positions of the phenyl rings with either -OH or -OCH3 groups, whereas in the para positions only with -OCH3 groups. The new series of differentially functionalized porphyrins were obtained by a combinatorial multicomponent synthesis (Adler-Longo method) by simultaneously using two different aldehydes: 3,4-dimethoxybenzaldehyde and 3-hydroxybenzaldehyde. The porphyrins were isolated, purified and characterized by HPLC, TLC, UV-vis, fluorescence, MS, 1H-NMR, and 13C-NMR analysis, accompanied by DEPT 135 experiments. Because of the fact that the medium in cancerous tissues is often more acidic than in normal tissues, the capacity of these porphyrins to exist simultaneously in aggregated and protonated forms was also investigated, in tetrahydrofuran (THF) and acid THF-water systems, underlying the changes in the photophysical behaviour. The relative fluorescence quantum yields (Phif) were calculated in comparison with meso-tetraphenylporphyrin (TPP), and the values between 0.14-0.26 were found to be promising for further trials. The series of asymmetrically substituted tetraphenylporphyrins, as the new class of supramolecular materials, are suitable for further functionalization in order to improve their photophysical properties, and they could represent interesting potential PDT photosensitizers.     

Outstanding Quadratic to Septic Optical Nonlinearity at Dipolar Alkynylmetal-Porphyrin Hybrids

Porphyrins are important macrocycles with applications in several areas including therapy, catalysis, and sensing. Strong nonlinear optical (NLO) responses are the key to fully exploiting the potential of these biocompatible molecules. We herein report that certain metal-alkynyl donor/nitro acceptor-functionalized porphyrins are attractive candidates for NLO applications. We show that specific examples exhibit record quadratic optical nonlinearity, exceptional two-photon absorption, and outstanding three-photon absorption, and we report the first porphyrins that exhibit four-photon absorption. The two-, three-, and four-photon absorption maxima are found at the corresponding multiples of linear absorption bands that time-dependent density functional theory assigns as admixtures of porphyrin-localized π*←π and donor-porphyrin to porphyrin-acceptor charge-transfer transitions.     

Functional porphyrinic metal-organic frameworks: crystal engineering and applications

Metal-organic frameworks (MOFs) are a kind of material which are able to integrate functional groups on their framework backbones. The tunable functionalities let MOFs be applied in various fields of luminescence, gas storage, sensing, magnetics, catalysis and biomedical imaging. Because of their interesting properties of structural robustness, catalysis, charge and energy transformations, using porphyrins and metalloporphyrins as synthons for the fabrication of functional MOFs has attracted considerable interest. Many efficient strategies have been established for the construction of functional porphyrinic MOFs, and some of them present interesting properties for potential applications. This perspective is aimed to summarize recent progress on porphyrinic MOFs, including new synthesis strategies and applications.