系列水溶性磺酸卟啉的制备、表征及催化性能

改进磺化路线制备了5种取代基及取代位置不同的水溶性磺酸卟啉,利用氢核磁共振波谱(1H NMR)、傅里叶变换红外光谱(FTIR)、紫外-可见吸收光谱(UV-Vis)及质谱(MS)等手段对产物进行表征及性质研究.将该系列卟啉作为光催化剂,用于催化氧化1,5-萘二酚的反应,主催化产物为5-羟基-1,4-萘二醌,转化率为78%~95%.实验发现,磺酸基团在苯环上的位置以及取代基的数目、电子效应及立体位阻效应均会对催化结果产生影响,其中磺酸根的位置至关重要.动力学研究结果表明该催化氧化过程为一级反应.探讨了该反应的反应机理.     

光源的选择对水溶性磺酸卟啉光催化对萘二酚类物质催化性能的影响

制备了水溶性磺酸卟啉(TPPS, TMPPS)及其铁配合物(FeTPPS). 以过氧化氢为氧源、 碘钨灯为光源, 水溶性磺酸卟啉可以高效光催化氧化1,5-萘二酚, 产物为5-羟基-1,4-萘二醌. 测定了卟啉的荧光量子产率及寿命, 分析了催化机理. 选择波长在350~650 nm区间内6个波段和功率在0~20 W区间内4种功率的光源, 探索了不同波段及功率的光源对卟啉光催化活性的影响. 研究结果表明, 不同波段的光源对卟啉光催化1,5-萘二酚的催化活性顺序为λ_380—385>λ_360—370>λ_580—585>λ_620—630>λ_492—577>λ_450—470, 该活性顺序与卟啉的紫外-可见吸收密切相关; 当使用相同波段光源时, 卟啉配体催化氧化1,5-萘二酚的反应速率常数与功率呈良好的线性关系; 卟啉铁配合物随着光源功率的增大, 其催化活性与光解程度有直接关系.     

水溶性金属卟啉修饰的阴离子交换树脂类过氧化氢酶的催化活性研究

本文应用Shimadzu UV-240 OPI-4型紫外可见分光光度计研究了对-四-磺酸基卟啉合铁(Ⅲ)(FeTPPS)、对-四-磺酸基苯基卟啉合锰(Ⅲ)(MnTPPS)以及咪唑轴向配位对-四-磺酸基苯基卟啉合铁(Ⅲ)(FeIm_2TPPS)等水溶性金属卟啉修饰的阴离子交换树脂D-261(FeTPPSr、MnTPPSr、FeIm_2TPPSr)作为类过氧化氢酶的催化活性,并考察了温度以及溶液中的咪唑对其催化活性的影响。作为催化剂还考察了MnTPPSr和FeTPPSr的使用寿命。根据实验结果提出了其催化反应机理。     

水溶性磺酸卟啉的合成、性质及光催化2,3-萘二酚

制备了多种水溶性磺酸卟啉,利用多种测试手段如1H NMR,FTIR,UV-Vis及荧光等对该系列卟啉进行了表征及性质研究,测得荧光量子产率及寿命.利用不同氧源(空气、氧气、30%过氧化氢溶液)将该系列水溶性磺酸卟啉用于光催化氧化2,3-萘二酚的反应,反应产物是1,2-苯二甲酸,最高转化率可达91%.发现磺酸基和其它取代基的电子效应会影响卟啉的光催化活性.对该光催化氧化反应进行了动力学研究,并探讨了相应的催化机理.     

哌嗪取代卟啉的合成、表征及其抗癌活性

设计并合成了6个具有抗癌活性的哌嗪取代卟啉化合物,分别为5,10,15,20-四[4-(4'-乙基哌嗪基)苯基]卟啉(TEPPH2,8a),5,10,15,20-四[4-(4'-丁基哌嗪基)苯基]卟啉(TBPPH2,8b),5,10,15,20-四[4-(4'-庚基哌嗪基)苯基]卟啉(THPPH2,8c),5,10,15,20-四[4-(4'-苯基哌嗪基)苯基]卟啉(TPhPPH2,8d),5-[4-(4'-乙基哌嗪基)苯基]-10,15,20-三苯基卟啉(EPTPPH2,8e)和5-[4-(4'-丁基哌嗪基)苯基]-10,15,20-三苯基卟啉(BPTPPH2,8f).这些卟啉化合物都由取代苯甲醛与吡咯缩合而成,每一个卟啉分子中含有一个或四个具有抗癌活性的取代哌嗪结构,结构经元素分析,MS,1H NMR,IR和UV-vis等表征.初步的生物活性研究表明,这些化合物具有一定的抗癌活性,因而在医学上可能具有潜在应用前景.     

5-(对-β-乙酸乙酯基氨基苯基)-10,15,20-三苯基卟啉的合成

以5,10,15,20-四苯基卟啉为原料,经硝化,还原和取代反应合成了新化合物5-(对-β-乙酸乙酯基氨基苯基)-10,15,20-三苯基卟啉,其结构经UV,1H NMR,IR和元素分析表征。     

阴、阳离子型水溶性卟啉的有效合成

以meso-四(4-吡啶基)卟啉和meso-四(4-羟基苯基)卟啉为原料,三乙二醇单甲醚单元取代和锰离子配位作为功能性修饰手段,按照优化的反应条件,高效合成了吡啶基阳离子型和磺酸基阴离子型水溶性卟啉化合物.该类方法操作简单、收率高、反应条件温和,为同类型水溶性卟啉的合成提供了很好的合成方法.     

四磺酸酞菁及其金属配合物的合成、表征及对1,5-萘二酚的光敏催化氧化性能

以4-磺酸钾邻苯二腈为原料合成了水溶性四磺酸酞菁(H₂PcTS)及其金属配合物(ZnPcTS, FePcTS, CoPcTS), 通过透析法提纯得到了纯度较高的产物. 采用傅里叶变换红外光谱(FTIR)、紫外-可见吸收光谱(UV-Vis)、核磁共振氢谱(¹H NMR)及循环伏安(CV)等测试手段表征了四磺酸酞菁及其配合物的结构和性质. 结果表明, 磺酸酞菁在水溶液中存在不同程度的聚集现象, 金属离子的配位会对磺酸酞菁的光谱和电化学性质产生影响. 研究了磺酸酞菁作为光敏剂催化氧化1,5-萘二酚的反应, 发现FePcTS/H₂O₂催化体系对1,5-萘二酚具有良好的催化氧化性能, 氧化产物主要为5-羟基-1,4-萘醌. 比较了不同溶液pH值对FePcTS和H₂PcTS催化能力的影响, 初步探讨了该反应的催化机理.     

金属卟啉的电化学性质与其催化氧化α-蒎烯性能的关系

 采用循环伏安法对一系列四苯基金属卟啉的电化学氧化还原性质进行了研究,考察了四苯基金属卟啉的第一还原电位与其催化氧化α-蒎烯性能的关系. 结果表明,各四苯基金属卟啉催化空气氧化α-蒎烯转化率的大小顺序为 TPPMnⅢCl＞TPPCoⅢCl＞TPPFeⅢCl＞TPPCuⅡ≈TPPNiⅡ≈TPPZnⅡ,除TPPCoⅢCl外,基本与其第一还原电位的大小顺序一致. 随着卟啉环上取代基供电子能力的减弱,各取代基铁卟啉和锰卟啉的第一还原电位E1值均逐渐减小,表现在催化体系中是它们越容易被还原而引发反应,催化氧化α-蒎烯的转化率逐渐升高. 四苯基铁卟啉和锰卟啉的第一还原电位E1与其卟啉环上对位取代基常数σ*之间均有良好的线性关系.     

环己烷并卟啉的合成及光谱和电化学性质研究

合成了三种在中位上具有不同取代苯基的环己烷并卟啉:5,10,15,20-四(4-甲苯基)环己烷并卟啉,5,10,15,20-四苯基环己烷并卟啉和5,10,15,20-四(4-氯苯基)环己烷并卟啉。利用核磁共振及质谱对它们进行了结构表征,研究了它们在二氯甲烷和吡啶溶剂中的紫外-可见光谱和电化学性质,探讨了卟啉大环周边的取代基和溶剂对化合物的光谱和氧化还原电位的影响,发现β-位上的环己烷取代基对化合物的光谱和电化学性质具有显著的影响。     

Axial base‐controlled catalytic activity,oxidative stability and product selectivity of water‐insoluble manganese and iron porphyrins for oxidation of styrenes in water under green conditions

A series of water‐insoluble iron(III) and manganese(III) porphyrins, FeT(2‐CH₃)PPCl, FeT(4‐OCH₃)PPCl, FeT(2‐Cl)PPCl, FeTPPCl, MnT(2‐CH₃)PPOAc, MnT(4‐OCH₃)PPOAc, MnT(2‐Cl)PPOAc and MnTPPOAc, in the presence of imidazole (ImH), F^?, Cl^?, Br^? and acetate were used as catalysts for the aqueous‐phase heterogeneous oxidation of styrenes to the corresponding epoxides and aldehydes with sodium periodate. Also, the effect of various reaction parameters such as reaction time, molar ratio of catalyst to axial base, type of axial base, molar ratio of olefin to oxidant and nature of metal centre on the activity and oxidative stability of the catalysts and the product selectivity was investigated. Higher catalytic activities were found for the iron complexes. Interestingly, the selectivity towards the formation of epoxide and aldehyde (or acetophenone) was significantly influenced by the type of axial base. Furthermore, Br^? and ImH were found to be the most efficient co‐catalysts for the oxidation of olefins performed in the presence of the manganese and iron porphyrins, respectively. The optimized molar ratio of catalyst to axial base was different for various axial bases. Also, the order of co‐catalyst activity of the axial bases obtained in aqueous medium was different from that reported for organic solvents. The use of a convenient axial base under optimum reaction catalyst to co‐catalyst molar ratio in the presence of the manganese porphyrin gave the oxidative products with a conversion of ca 100% in a reaction time of less than 3 h. However, the catalytic activity of the iron porphyrins could not be effectively improved by increasing the catalyst to co‐catalyst molar ratio.     

荧光光谱法研究卟啉与金属离子配位反应机理初探

本文用荧光光谱法初步研究了卟啉与金属离子配位反应机理和部分催化剂的催化机理.实验发现,在一定条件下,卟啉以一种与其主要存在形式不同的变形体H₂P^*存在,根据H₂P^*的存在和产生的条件,对卟啉与金属离子配位反应的一般条件作出了较为满意的阐述.     

金属卟啉-聚乙二醇催化烯烃环氧化反应

研究了聚乙二醇在模拟细胞色素P-450酶、CH_2Cl_2-H_2O两相体系中的相转移催化作用;并和季铵盐类相转移催化作用进行了比较。把PEG-400键联到金属卟啉上,进一步考察了连接大分子后对金属卟啉的催化活性及稳定性的影响;同时比较了键联后的聚乙二醇和自由聚乙二醇所起的相转移催化作用;最后,对反应机理进行了讨论。     

Catalytic Activity of Tetraarylporphyrins in the Oxidation Reactions of Saturated Hydrocarbons

The oxidation of cyclic hydrocarbons by potassium peroxymonosulfate catalyzed by the iron and manganese complexes of tetra-(4-N-butylpyridinium)porphyrin, tetraphenylporphyrin, and mixed porphyrins containing phenyl and butylpyridyl substituents was studied in an aqueous acetonitrile medium. The test catalysts were dissolved in the reaction medium or adsorbed on layered aluminosilicates. It was found that the immobilization of metal complexes on layered aluminosilicates, as well as the bromination of porphyrins, decreased the activity of catalysts in a number of cases, although it improved their stability. The addition of pyridine in an equimolar amount with respect to metal complexes to the reaction mixture increased the activity of dissolved manganese complexes. An increase in the number of butylpyridyl meso-substituents in a porphyrin molecule improved the catalytic activity of a metal complex.     

水溶性四(p-磺酸钠苯基)金属卟啉配合物的合成、光谱性质及催化三氯苯酚的氧化脱氯反应

通过四苯基卟啉(H2TPP)和浓硫酸发生磺化反应及其金属化, 控制反应体系pH并利用透析法纯化, 高效合成了水溶性四(对磺酸钠苯基)卟啉(H2TPPS)及其金属配合物(FeTPPS和ZnTPPS); 采用UV-Vis、荧光、1H NMR和FTIR等光谱手段表征及研究了水溶性卟啉的结构及性质. 结果表明, 磺酸根离子的存在增强了卟啉分子间的π-π作用, 从而使H2TPPS及其金属配合物的分子间聚合作用增强. 研究了FeTPPS对2,4,6-三氯苯酚(TCP)催化氧化脱氯反应, 结果表明, FeTPPS/H2O2催化体系对TCP具备很好的催化氧化脱氯性能, 2,6-二氯对苯醌的转化数达到了766.     

Hydroxylation of cyclohexane with molecular oxygen catalyzed by highly efficient heterogeneous Mn(III) porphyrin catalysts prepared by special synthesis and immobilization method

A novel method to synthesize and immobilize porphyrins as well as manganese porphyrins on crosslinked polystyrene (CPS) microspheres was designed. The chloromethyl groups of chloromethylated CPS microspheres (CMCPS microspheres) were first oxidized to aldehyde groups via Kornblum oxidation reaction, obtaining aldehyde group-functionalized microspheres, and then, the synchronous synthesis and immobilization of porphyrins on CPS microspheres were carried out via the Adler reaction between solid–liquid phases, obtaining three kinds of functional microspheres, on which phenyl porphyrin (PP), p-chlorophenyl porphyrin (CPP) and p-nitrophenyl porphyrin (NPP) were immobilized. Finally, three manganese porphyrin-immobilized microspheres, MnPP–CPS, MnCPP–CPS and MnNPP–CPS, were prepared, these solid catalysts were used in the catalytic hydroxylation reaction of cyclohexane with molecular oxygen as oxidant, and their catalytic performances were mainly investigated in this work. Some surprising experimental results were obtained. The prepared immobilized manganese porphyrin catalysts display amazing catalytic activity and selectivity, and cyclohexane conversion can get up to 45?% and cyclohexanol selectivity in the reaction product can be up to 90–100?%.     

Performance of a biomimetic oxidation catalyst immobilized on silicon wafers: comparison with its gold congener

With the aim of extending the usefulness of an existing biomimetic catalytic system, cobalt porphyrin catalytic units with thiol linkers were heterogenized via chemical grafting to silicon wafers and utilized for the catalytic oxidation of hydroquinone to p-benzoquinone. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used to analyze the morphology and composition of the heterogeneous catalyst. The results of the catalytic oxidation of hydroquinone obtained with porphyrins grafted on silicon were compared with those obtained earlier with the same catalyst in homogeneous phase and immobilized on gold. It was found that the catalysis could run over 400 h, without showing any sign of deactivation. The measured catalytic activity is at least 10 times higher than that measured under homogeneous conditions, but also 10 times lower than that observed with the catalytic unit immobilized on gold. The reasons of this discrepancy are discussed in term of substrate influence and overlayer organization. The silicon-immobilized catalyst has potential as an advanced functional material with applications in oxidative heterogeneous catalysis of organic reactions, as it combines long-term relatively high activity with low cost.