不同金属卟啉光催化降解亚甲基蓝性能研究

以四苯基卟啉(TPP)为原料,通过金属插入反应,获得FeTPP、ZnTPP、CoTPP、MnTPP,并用UV-Vis对其进行了表征.将合成的金属卟啉用于光催化体系,进行亚甲基蓝溶液的光催化降解及催化剂回收实验.结果发现,以CoTPP为催化剂,在高压汞灯光照3 h后,亚甲基蓝溶液的脱色率可迭100%;不同光源的催化效果为...     

Substituent effects of iron porphyrins: Structural, kinetic, and theoretical studies

Substituent effects of iron porphyrin complexes on the structures and kinetic processes have been examined for the first time. Basing on the premise that iron porphyrin is functional analogous to heme, a series of iron porphyrin derivatives bearing different substituents at the meso positions of the corrole ring are investigated as to their electrochemistry, the relationships among the electron transfer (ET) processes, their structures, and orbital energies. The good coherence between the experiment and theory indicates that the ET rate can be accelerated when electron-donating substituents are introduced to the iron porphyrin ring. Finally, the implications of the results are discussed in the influence of stability of iron porphyrin complexes on the ability to carry molecular oxygen, which may suggest it possible to dominate the biological activity of heme by selecting the appropriate substituents to iron porphyrin ring.     

金属卟啉仿生催化制备环氧丙烷

制备了四苯基卟啉、四-4-甲氧基苯基卟啉、四-4-氟苯基卟啉及3种卟啉相对应的钴、锰、铁金属卟啉,并利用Cary紫外可见分光光度计(UV-vis)和傅里叶变换红外光谱仪(FTIR)对金属卟啉进行了表征;以制备的不同金属卟啉为催化剂,丙烯为原料,氧气为氧化剂,仿生催化丙烯氧化合成环氧丙烷。考察了金属卟啉催化剂类型、金属卟啉催化剂浓度、反应压力、反应温度、反应时间对反应的影响,结果发现上述因素对反应收率、转化率、选择性均有显著影响,且都有一个最佳值,获得的最优化反应条件为:选取四-4-氟苯基铁卟啉为催化剂,催化剂浓度为1.35×10^-5mol/L,反应压力1.75MPa,反应温度100℃,反应时间为2h。在最优化的反应条件下,环氧丙烷的收率达到了40.38%,丙烯转化率达到了47.09%,环氧丙烷选择性达到了85.75%。     

卟啉化合物在抗肿瘤方面的应用现状及进展

卟啉化合物的出现,在抗肿瘤方面起到了重要的作用,它可以在肿瘤前期对患者进行有效的治疗。天然的卟啉化合物,在实际的使用中,没有合成的卟啉化合物方便,加上现在的天然卟啉化合物已经不满足于现在的试验研究,所以现在也在大量的出现人工卟啉化合物。人工卟啉化合物在特性上和化学性质上和天然卟啉化合物相同,在药用方面也比天然卟啉化合物更好。     

卟啉化学的产生发展及应用

简要介绍了卟啉化学的产生、发展及应用,卟啉化合物的结构特征及特性。详细综述了:新型卟啉衍生物的合成及在催化科学中的应用;新型卟啉衍生物的合成及在光电材料科学中的应用;新型卟啉化合物的合成及在医药学中的应用。并对卟啉化学的发展进行了展望。     

Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations

Disproportionation of oxoiron(IV) porphyrin (Compound II) to oxoiron(IV) porphyrin radical cation (Compound I) was studied in three P450 model systems with different electronic structures. Direct conversion of Compound II to Compound I has been observed for 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP) in acid-catalyzed reactions in a mixed solvent of acetonitrile and water (1:1, v/v) containing excess m-CPBA oxidant, with a second-order rate constant of (1.3 ± 0.2) × 10(2) M(-1) s(-1). The acid-catalyzed disproportionation heavily depends on the electron demand of the substituted aryl groups on the porphyrin macrocycle. The disproportionation equilibrium constants show drastic change for the three porphyrin systems.     

5-(4'-羟基苯基)-10,15,20-三(4'-三甲硅基苯基)卟啉的合成

以4-羟基苯甲醛、4-三甲硅基苯甲醛、吡咯(物质的量比1∶3∶4)为原料,借鉴Lindsey方法合成了5-(4'-羟基苯基)-10,15,20-三(4'-三甲硅基苯基)卟啉。研究了提纯该化合物的手段,最终得到了分离效果好的分离方法。其结构由1HNMR、质谱、紫外等表征。     

四苯基卟啉及其衍生物的合成和可见光谱的研究

采用简便易行的方法合成了4种卟啉化合物：四苯基卟啉(TPP)、Meso-四(对磺酸基苯基)卟啉(TPPS4)、Meso-四(对羟基苯基)卟啉[T(OH)4PP]Meso-四(对甲氧基苯基)卟啉[T(OCH3)PP]。可见光谱分析表明苯环上对位取代基的引入和溶剂的极性可使光谱发生不同程度的蓝移或红移，这对改善卟啉化合物的光吸收性能有着重要的指导意义。     

Novel meso-substituted porphyrins: Synthesis, characterization and photocatalytic activity of their TiO2-based composites

Two series of novel meso-substituted porphyrins, namely 5,10,15,20-tetra[4-(3-phenoxy)-propoxy]phenyl porphyrin, the structural analogue 5,10,15,20-tetra[2-(3-phenoxy)-propoxy]phenyl porphyrin and their Co(II) Cu(II) and Zn(II) complexes were synthesized. The compounds were characterized using various spectroscopic techniques and their molecular structure was proposed based on density functional theory calculations. The diverse properties of the porphyrin derivatives result from the different stereochemistry of the particular substituents at the meso site on the macrocycle and are controlled also by the coordinated metal. The ¹H NMR spectrum of the free-base porphyrin showed a complicated spin-splitting. The photocatalytic activities in degradation of 4-nitrophenol were investigated using polycrystalline TiO₂ impregnated with the porphyrins and metalloporphyrins. The Cu(II) porphyrin was a more effective sensitizer than other metal containing compounds (M = Co, Zn) as well as the free-base. Photocatalytic activity was also influenced by spatial positions of the substitutions on the porphyrin molecules.     

卟啉分子整流器件的理论研究

使用密度泛函理论（DFT）与非平衡态格林函数（NEGF）相结合的方法研究了卟啉-烷（porphyrin-alkyl）、卟啉-苯（porphyrin—phenyl）、卟啉-炔（porphyrin—alkyne）三种分子的电压-电流曲线、分子隧穿谱等电学性质。结果显示,卟啉一炔分子的电子传递能力最强,其次是卟啉-苯分子,而卟啉-烷分子的导电性最差;但是,卟啉-烷和卟啉一苯分子具有明显的整流特性,而卟啉-炔分子几乎没有整流效果。     

卟啉类显色剂在铅光度分析中的研究进展

介绍了近十年来卟啉试剂在铅的光度分析当中的研究进展,总结了目前国内显色体系改善方法,简述了卟啉试剂的合成现状,同时展望了卟啉试剂在铅的光度分析当中的发展方向。     

金属卟啉配合物的性能及应用研究进展

金属卟啉配合物是卟啉衍生物中的主体化合物,因其具有优异性能而被广泛地研究与应用.分别从仿生体系、分子识别、催化、材料、有机合成和医疗等方面简要介绍了金属卟啉配合物的优异性能及其应用,旨在让人们了解并熟悉金属卟啉配合物的性能及用途.     

卟啉化合物的合成与应用研究进展

卟啉化学是现代化学领域中重要的研究分支之一,文章综述了卟啉化合物的合成方法,以及卟啉化合物在生物医学、材料科学及催化化学等领域的应用.     

卟啉金属有机框架材料在光催化领域的最新应用

金属卟啉有机框架有机框架材料是一种由卟啉或金属卟啉作为结构单元构筑的新型周期性网状结构材料，既具有卟啉拓宽光谱响应范围、降低光生电子-空穴复合率的独特优势，又具有MOFs材料的多孔道、孔道尺寸可调节、比表面积大的双重优势，成为目前具有良好光电性质的新型光催化剂。近年来，许多科学家们致力于新型光催化剂的开发与应用。尤其是近几年来，随着材料科学的发展，新型光催化剂金属卟啉MOFs成为光催化剂的研究热点并取得了令人欣慰的成果。本文主要综述了近十年来卟啉/金属卟啉MOFs在二氧化碳还原、裂解水制氢、光降解有机染料等领域的最新应用，并对未来MPFs在光催化领域的发展进行了展望.     

卟啉锌/锰配合物的合成与表征

用5,10,15,20-四(4氯苯基)卟啉或5-(4-羟基苯基)-10,15,20三(4-氯苯基)卟啉与四水氯化锰、醋酸锌反应,合成了5,10,15,20-四(4-氯苯基)卟啉锌、5,10,15,20-四(4-氯苯基)卟啉锰、5-(4-羟基苯基)-10,15,20-三(4-氯苯基)卟啉锌、5(4-羟基苯基)-10,15,20-三(4-氯苯基)卟啉锰四种金属卟啉,并用UV-Vis、IR对其结构进行了表征。     

P-450 Type Activation of Dioxygen by Heterogenized Metal Porphyrins: Comparison with the Corresponding Homogeneous Systems

The protons of silanol groups on a silica or silica-alumina surface are replaced by metal(III) porphyrin cations, FeTPP⁺, MnTPP⁺, and CoTPP⁺ (TPP = tetraphenylporphyrin). The heterogenized iron(III) or manganese(III) porphyrin supported on silica thus prepared can activate dioxygen in the presence of excess amounts of NaBH₄ and cyclohexene, affording cyclohexanol and cyclohex-2-ene-1-ol in a 4:1 ratio, which is the same as the ratio observed in the known P-450 type oxidation of cyclohexene catalyzed by a homogeneous manganese porphyrin (MnTPPCl) in the presence of NaBH₄ used as an electron source. The heterogenized iron(III) porphyrin shows a reactivity comparable with that of the corresponding heterogenized manganese(III) porphyrin. On the other hand, substitution of the heterogenized iron(III) porphyrin by the corresponding homogeneous catalyst, FeTPPCl, results in drastic change in the product ratio; the ratio of cyclohexanol to cyclohex-2-ene-l-ol is reversed, suggesting that the oxidation of cyclohexene proceeds via radical chain autoxidation reactions. The catalytic activity for the P-450 type oxidation is diminished while FeTPPCl is converted to the μ-oxo-dimer (FeTPP)₂O. Cobalt(III) porphyrin in a homogeneous system also affords the autoxidation products. Such a mechanistic difference between the homogeneous and heterogeneous metal porphyrins in the oxidation of cyclohexene by dioxygen has been confirmed by kinetic studies in which the P-450 type oxidation and autoxidation obey different kinetics.     

金属卟啉配合物在催化空气氧化环己烷反应中的应用

以四苯基卟啉和乙酸盐为原料,合成了4种简单过渡金属配合物,并应用紫外-可见光谱仪（UV-vis）和傅里叶变换红外光谱仪（FTIR）对所得产物进行表征,获得了同周期过渡金属卟啉配合物吸收光谱的重要信息。研究表明,通过紫外-可见及红外光谱对过渡金属卟啉配合物中心离子的价态及其在周期表中的位置进行初步判断是可行的。以空气氧化环己烷制备环己醇和环己酮为探针反应,在不加入任何溶剂或助催化剂的条件下考察了金属卟啉用量、反应温度、压力、时间等对其催化活性的影响。结果发现,锰卟啉催化活性最好,在最佳反应条件下,环己烷转化率最高可达15.37%,环己醇和环己酮的总选择性约为93.94%。     

环己烷仿生催化工艺初探

金属卟啉是根据末端氧化酶的分子结构进行人工合成的。通过金属卟啉催化氧化环己烷连续性实验研究，初步探讨了温度、催化剂等因素对催化氧化结果的影响，认为该工艺具有工业化的可能。     

Adsorption of tetrakis(p-sulfonatophenyl)porphyrin on kaolinite

The surface modification of kaolinite to introduce the adsorption sites for anionic species was reported. The introduction of an anion exchange site was as follows; intercalation of 2-aminoethanol into kaolinite by using dimethyl sulfoxide-kaolinite intercalation compound as a precursor and subsequent hydrochlorination of 2-aminoethanol-kaolinite in 1,4-dioxane. The hydrochlorination of 2-aminoethanol-kaolinite was confirmed by the increase in the basal spacing (0.2 nm, corresponding to the diameter of chlorine) and the appearance of the infrared absorption bands due to ammonium groups. The modified kaolinite adsorbed an anionic dye, tetrakis(p-sulfonatophenyl)porphyrin, from a N,N-dimethylformamide solution. Initial slope of the adsorption isotherm of tetrakis(p-sulfonatophenyl)porphyrin on the hydrochlorinated 2-aminoethanol-kaolinite was steep, showing strong adsorbate-adsorbent interactions. The gallery height after the adsorption of tetrakis(p-sulfonatophenyl)porphyrin was close to the thickness of the porphyrin ring, suggesting that tetrakis(p-sulfonatophenyl)porphyrin was intercalated as a monomolecular layer and that chlorine simultaneously deintercalated.     

卟啉及其衍生物的合成研究进展

按卟啉母核的不同合成方法,介绍了从各种小分子的缩合而合成卟琳的方法包括经典的Alder-Long法、Lindsey法和新颖的[2 2]法、[3 1]法、线形四吡咯出发合成卟啉、2_位取代吡咯合成卟啉,这些方法能够合成许多不同结构的卟啉化合物.