meso-四(4-N-取代吡啶基)卟啉铜(Ⅱ)配合物的合成及其对O-·2的清除作用

以Ｃｕ２（ＯＨ）２ＣＯ３为原料通过非均相金属插入反应合成ｍｅｓｏ－四（４－Ｎ－甲基吡啶基）卟啉合铜（Ⅱ）（ＣｕＴＭＰｙＰ）和ｍｅｓｏ－四（４－Ｎ－苄基吡啶基）卟啉合铜（Ⅱ）（ＣｕＴＢＰｙＰ）．方法操作方便，产率高．研究表明，在核黄素光照产生Ｏ－·２的体系中，ＣｕＴＭＰｙＰ和ＣｕＴＢＰｙＰ对Ｏ－·２具有明显的清除作用，对人红细胞内血红蛋白具有一定保护作用．     

水溶性卟啉还原甲基紫精动力学的研究

利用跟踪法测定了碘化四－（对甲基异烟酰基苯基）［ＴＭＩａｐｐＩ］等五种水溶性卟啉在还原甲基紫精过程中［ＭＶ＾＋］深度的变化，获得了［ＭＶ＾＋］／［Ｐｏ］～ｔ及［Ｍｖ＾＋］／［Ｍｖ＾２＋］～ｔ的关系曲线。由稳态近似原理推出的动力学方程求得了几种求得了几种卟啉的动态学参数Ａ、诱导时间ｔｉ及起始速率ｖ０。通过稳态转化率得知５种水溶性卟啉的光敏强度有如下顺序：ＺｎＴＭｐｙＰ＞ＺｎＴＭＩＡＰＰＩ＞ＺｎＴＭＮ     

镍（Ⅱ）与meso—四（4—N—甲基吡啶基）卟啉（TMPyP）络合物的伏…

本文用循环伏安法、溶出伏安法和计时库仑法等多种电化学方法研究了合成的镍（Ⅱ）与ｍｅｓｏ－四（４－Ｎ－甲基吡啶基）卟啉（ＴＭＰｙＰ）络合物的电还原行为。结果表明，Ｎｉ（Ⅱ）ＴＭＰｙＰ的还原过程是中心离子Ｎｉ（Ⅱ）和卟啉环同时还原，其中Ｎｉ（Ⅱ）被还原为Ｎｉ（０），总电子转移数为６。比较并讨论了溶解氧对锰、铁钴、镍卟啉的不同影响。     

meso—四（4—N—取代吡啶基）卟啉铜（Ⅱ）配事物的合成及其对O^—2的清除作用

以Ｃｕ２（ＯＨ）２ＣＯ３为原料通过对非均相金属插入反应合成ｍｅｓｏ－四（４－Ｎ－甲基吡啶基）卟啉合铜和ｍｅｓｏ－四（４－Ｎ－苄基吡啶基）卟啉合铜。方法操作方便产率高。研究表明，在核黄素光照产生Ｏ＾－２的体系中，ＣｕＴＭＰｙＰ和ＣｕＴＢＰｙＰ对Ｏ＾－２具有明显的清除作用，对人红细胞内血红蛋白具有一定保护作用。     

金属卟啉－甲基紫精二连体配合物的合成及其光化学行为

本文合成了四（对－氯代甲基）苯基－甲基紫精卟啉及其Ｚｎ，Ｃｏ，Ｍｎ配合物，用元素分析、红外光谱和紫外可见光谱进行了表征。研究了它们的光化学性质。结果表明，在ＴＥＯＡ中光照使Ｍ。ＴＣＭＰＰ－ｍｖ＾２＋发生了分子内从卟啉到甲基紫精的电子迁移反应。在ＺｎＴＣＭＰＰ－ｍｖ＾２＋／ＴＥＯＡ／ＤＭＳＯ－Ｈ２Ｏ体系中可发生光敏化还原ｍｖ＾２＋反应，生成较稳定的ｍｖ＾＋。在Ｍｎ（Ⅲ）ＴＣＭＰＰ－ＭＶ＾２＋／ＣＨ３     

金属卟啉－甲基紫精二连体配合物的合成及其光化学行为

本文合成了四（对－氯代甲基）苯基－甲基紫精卟啉及其Ｚｎ、Ｃｏ、Ｍｎ配合物，用元素分析、红外光谱和紫外可见光谱进行了表征．研究了它们的光化学性质．结果表明．在ＴＥＯＡ中光照使Ｍ·ＴＣＭＰＰ—ｍｖ￣２＋发生了分子内从卟啉到甲基紫精的电子迁移反应．在ＺｎＴＣＭＰＰ－ｍｖ￣２＋／ＴＥＯＡ／ＤＭＳＯ—Ｈ２Ｏ体系中可发生光敏化还原ｍｖ２＋反应，生成较稳定的ｍｖ＋．在Ｍｎ（Ⅲ）ＴＣＭＰＰ－ｍｖ２＋／ＣＨ３ＯＨ／Ｈ２Ｏ体系中可发生光助氧化甲醇反应，并检出了氧化产物甲醛．     

一种新的含杂原子电子受体的双重荧光N, N-二甲基苯胺衍生物4-(N, N-二甲基氨基)苯磺酸钠的光诱导分子内电荷转移

报道了一种新的双重荧光Ｎ,Ｎ－二甲基苯胺（ＤＭＡ）衍生物,４－Ｎ,Ｎ－二甲基氨基 苯磺酸钠（ＳＤＭＡＳ）,其电子受体经硫杂原子联接于电子给体的对位．ＳＤＭＡＳ在强极性 的水中发射双重荧光,在有机溶剂如甲酰胺,甲醇和乙腈中则只发射位于短波长侧的 单重荧光．纯水中 ＳＤＭＡＳ的荧光峰分别位于 ３６５ ｎｍ和 ４７５ ｎｍ处,引入有机溶剂如乙 醇,乙腈和１,４－二氧六环,长波长荧光被猝灭且峰位置蓝移,稳态及皮秒时间分辨荧光 测量表明,ＳＤＭＡＳ的长波长荧光为光诱导的分子内电荷转移（ＣＴ）态所发射,短波长的 荧光为局域激发（ＬＥ）态所发射,并且ＣＴ态产生自ＬＥ态．只能在高极性的水中观察到 ＳＤＭＡＳ的ＣＴ双重荧光发射的实验事实意味着ＣＴ过程具有高的活化能,激发态超快 反应动力学研究证实该活化能（Ｅ_a）高达 １５．３５ ｋＪ· ｍｏｌ~-1, ＳＤＭＡＳ分子中硫原子的 ｄ－轨道 参与磺酸基和苯环的共轭以及二甲基氨基所在平面相对于苯环的强烈扭转和弯折可能 是导致高活化能的原因,ＣＴ过程的热力学参数分析表明伴随着电荷转移ＳＤＭＡＳ的分 子构型发生了变化报道的ＳＤＭＡＳ是具有双重荧光的氨基取代芳香磺酸衍生物。     

Eu^2＋和Mn^2＋在SrMgP2O7中的光致发光及其能量传递

研究了Ｅｕ＾２＋、Ｍｎ＾２＋共激活的ＳｒＭｇＰ２Ｏ７的发光性质、浓度与荧光性质的关系，Ｅｕ＾２＋和Ｍｎ＾２＋的发射光谱分别在４００ｎｍ及６７０ｎｍ附近，它们是Ｅｕ＾２＋的５ｄ－４ｆ跃迁和Ｍｎ＾２＋的＾４Ｔ１（＾４Ｇ）－＾６Ａ１ｇ（＾６Ｓ）跃迁发射，实验结果表明，Ｅｕ＾２＋对Ｍｎ＾２＋的荧光发射有较强的敏化作用，Ｍｎ＾２＋对Ｅｕ＾２＋的荧光寿命和强度也有显著影响。     

Eu^2＋和Mn^2＋在Sr3MgSi2O8中的光致发光研究

研究了Ｅｕ＾２＋和Ｍｎ＾２＋共激活的Ｓｒ３ＭｇＳｉ２Ｏ８的荧光性质。Ｅｕ＾２＋和Ｍｎ＾２＋在４６０ｎｍ和６９０ｎｍ的发射峰分别由Ｅｕ＾２＋的５ｄ→４ｆ跃迁和Ｍｎ＾２＋的＾４Ｔ１（＾４Ｇ）→＾６Ａ１ｇ（＾６Ｓ）跃迁产生。未观察到单掺杂Ｍｎ＾２＋的Ｓｒ３ＭｇＳｉ２Ｏ８的荧光发射，而掺入Ｅｕ＾２＋后则出现了Ｍｎ＾２＋的６９０ｎｍ光致发光峰，表明Ｅｕ＾２＋对Ｍｎ＾２＋有敏化作用。Ｅｕ＾２＋的荧光寿命也受Ｍ     

铬(VI)-O-FPF-CTMAB-酒石酸钠荧光熄灭体系及其应用

铬(ＶＩ)影响人体健康,从而引起人们的注意,近年来建立了许多测定铬(ＶＩ)的新方法。用荧光熄灭法测定铬的方法有:二溴羟基苯基荧光酮 乳化剂ＯＰ[1]、水杨基荧光酮 ＣＴＭＡＢ[2]、二溴苯基荧光酮[3]、间氟苯基荧光酮 ＣＴＭＡＢ[4]等,但以上均为三元体系。本实验发现在ｐＨ4 20～4 80的ＨＡｃ ＮａＡｃ缓冲介质中,Ｃｒ(ＶＩ)与邻氟苯基荧光酮(Ｏ ＦＰＦ)、溴化十六烷基三甲基铵(ＣＴＭＡＢ)及酒石酸钠(Ｔａｒｔｒａｔｅ)可形成一多元混配络合物,使Ｏ ＦＰＦ试剂的荧光显著熄灭。Ｃｒ(ＶＩ) Ｏ ＦＰＦ ＣＴＭＡＢ Ｔａｒｔ荧光体系测定…     

四(4－N-吡啶基)卟啉衍生物的合成及表征

阳离子卟啉配体;配合物;还原电位;四(4－N-吡啶基)卟啉衍生物的合成及表征     

A novel method for the synthesis of regiospecifically sulfonated porphyrin monomers and dimers

A novel method has been developed to regiospecifically synthesize water-soluble sulfonated porphyrin monomers tetrakis(4′-sulfonatophenyl)porphyrin, tetrakis(3′-sulfonatophenyl)porphyrin, tetrakis(2′-sulfonatophenyl)porphyrin, tetrakis(2′,5′-dimethyl-4′-sulfonatophenyl)porphyrin, the dimers of 1,2-bis[5,10,15-tri(4′-sulfonatophenyl)porphyrinyl]benzene and 1,2-bis[5,10,15-tri(2′,5′-dimethyl-4′-sulfonatophenyl)porphyrinyl]benzene in high yields through introduction of the trimethylsilyl group on the phenyl rings and reaction with trimethylsilyl chlorosulfonate in CCl₄ solvent.     

Investigation of the SERS behaviour of porphyrins with different surface concentrations on electrochemically prepared Ag-surface

Surface-enhanced Raman scattering (SERS) spectra, taken with 632.8 nm excitation are reported for the water-soluble tetrakis(3-N-methylpyridyl)porphyrin chloride (TMPyP(3)), tetrakis(4-N-methylpyridyl)porphyrin chloride (TMPyP(4)) and Sn(IV)tetrakis(4-N-methylpyridyl)porphyrin chloride (Sn(IV)TMPyP(4)) using an electrochemically prepared Ag surface with an area ca. 12.56 mm2. It was found that the spectra vary as increasing amounts of the compounds are placed on the surface, with surface concentrations in the approximate range 1000-5 pmol/12.56 mm2. We suggest that the reasons for the changes be that the reaction means between porphyrin molecules and Ag surface is different and the porphyrin macrocyclic molecules adopt different orientation as the surface concentrations decrease.     

高分子键联金属卟啉的合成及催化性能的研究

本文合成了一种新型大环网状高分子聚苯乙烯键联的四(4-吡啶基)卟啉和四(4-氨基苯基)卟啉的金属配合物。考察了它们在正己烷羟基化反应中的催化性能。结果表明: 四(4-吡啶基)卟啉锰和高分子键联后稳定性增加, 且活性有所提高。     

Aggregation properties of hyperporphyrins with hydroxyphenyl substituents

Acidification of tetrakis(4-hydroxyphenyl)porphyrin (THPP) and tetrakis(3,5-dihydroxyphenyl)porphyrin (OHPP) in dichloromethane solutions has been investigated as a function of the nature of the counteranion. These porphyrins exhibit different patterns of behavior, and extended aggregates are formed displaying broad extinction features together with intense components due to resonant light scattering. Especially in the case of haloacids, J-aggregated species are obtained exhibiting large bathochromic shifts both for B- and Q-bands, which extend in the far red region. The optical characteristics of the aggregated and monomeric protonated species are strongly influenced by the nature of the counteranions. A comparison with tetrakis(4-methoxyphenyl)porphyrin (TMPP), which remains always in a monomeric form, demonstrates the key role played by the peripheral hydroxyl groups in stabilizing various porphyrin aggregates.     

Pincer-porphyrin hybrids

[reaction: see text] Starting from tetrakis(3,5-bis(bromomethyl)phenyl)porphyrin, pincer-porphyrin hybrid molecules (tetrakis(ECE-pincer)porphyrin; E = N, P, S) based on a tetraphenylporphyrin skeleton have been prepared in high yields. These multi-ligand site compounds could be selectively metalated at their peripheries, which was shown by X-ray crystallography.     

Synthesis of Vinylene-Co,N-Linked Multi(porphyrin)s by the Addition of Free-Base Porphyrins to a C(2)H(2) Complex of Cobalt(III) Porphyrin and Their Oxidative Rearrangement to Vinylene-N,N'-Linked Multi(porphyrin)s

The nucleophilic addition reaction of a pyrrole nitrogen of free-base porphyrins to a pi-complexed acetylene ligand in a cationic Co(III) porphyrin intermediate afforded good yields of vinylene-Co,N'-linked bis(porphyrin)s, (Por)Co(III)-CH=CH-(N-Por)H(2). N-substituted porphyrin free bases are N-vinylated regioselectively at the pyrrole adjacent to the original N-substituted pyrrole in this reaction. Tris- and tetrakis(porphyrin)s have been prepared by reacting a vinylene-N,N'-linked bis(meso-tetraarylporphyrin) with (OEP)Co(III)(H(2)O)(2)ClO(4) (OEP: octaethylporphyrin dianion) and acetylene. The tetrakis(porphyrin) proved to be a 1:1 mixture of C(i)()- and C(2)-symmetric regioisomers. These organometallic Co(III) complexes underwent facile oxidative migration of the Co-bound vinyl group to a porphyrin pyrrole nitrogen when treated with Fe(III) salts or HClO(4) to provide moderate to good yields of Co(II) vinylene-N,N'-linked multi(porphyrin) complexes. (Vinylene-N,N')bis(porphyrin) free bases with combinations of different porphyrins have been obtained by this procedure. The homobinuclear (2Co(II), 2Cu(II), and 2Zn(II)) and heterobinuclear (Co(II)Cu(II) and Co(II)Zn(II)) complexes have been prepared and characterized spectroscopically. The single-crystal X-ray analysis of (CH=CH-N,N')[(OEP)Co(II)Cl][(TPP)Zn(II)Cl] (TPP: meso-tetraphenylporphyrin dianion) showed a face-to-face structure with an average inter-ring separation of 4.39 ? (triclinic P&onemacr;; Z = 2; a = 14.806(4), b = 18.703(10), c = 13.796(3) ?, alpha = 97.69(3), beta = 99.57(2), gamma = 96.74(3) degrees ).     

四苯基卟啉质子化结构变化的理论研究(Ⅱ)——五氟苯基及吡咯环上氟的取代基效应

卟啉的衍生物在DNA螺旋中的嵌入并堆积具有高选择性.为考察5,10,15,20-四(五氟苯基)卟啉(TF₅-PPH₂)和2,3,7,8,12,13,17,18-八氟-5,10,15,20-四(五氟苯基)卟啉(F₂₈TPPH₂)中F取代基对质子化卟啉结构的影响,在四苯基卟啉研究的基础上,用半经验的AM₁MO方法,并进行合理的对称性限制,计算了TF₅-PPH₂和F₂₈TPPH₂及其质子化二酸(TF₅-PPH₄²⁺)和(F₂₈TPPH₄²⁺)的几种可能的构型.结果表明,由于F取代基的影响,质子化过程中的结构、键电荷布居和前线分子轨道均有明显的变化,二者的质子化二酸与溶液质子的快速交换作用也都变得更加困难.     

CO2电催化还原的研究(Ⅲ)——TPP、TMAP、TMAPI系列金属卟啉的电催化活性

由于CO₂电催化还原有较高的电流效率、较低的过电位和较高的能量转换效率、因而倍受人们的注意。我们系统地研究了以TPP、TMAP和TMAPI为配体的配合物对CO₂电催化还原的活性,这对于开发CO₂的综合利用无疑是有意义的。     

7种中位—四取代苯基卟啉化合物的合成

卟啉是一类结构与生命物质(如血红素和维生素B_(12))相似的化合物,近年来曾被用于人体肿瘤的光动力学治疗;此外,在电化学、光物理学和光化学、放射医学、微量元素测定、纺织品漂洗等领域中的应用也相当广泛,已受到科技工作者的普遍关注和重视。本文按Rothemond法将相应的取代苯甲醛与新蒸吡咯在丙酸中缩合,制得具有酸性、中性和碱