侧链键合锰卟啉的线型聚甲基丙烯酸缩水甘油酯的制备及其谱学性质

采用Adler法合成了Meso-四(对羟基苯基)卟啉(THPP), 在均相体系中使聚甲基丙烯酸缩水甘油酯(PGMA)与THPP发生开环反应, 得到侧链键合有羟基苯基卟啉的线型PGMA(HPP-PGMA); 进一步使HPP-PGMA与锰离子发生配合作用, 得到侧链键合有锰卟啉(MnP)的线型PGMA(MnP-PGMA), 测定了HPP-PGMA的1H NMR谱, 表征了其化学结构; 测定了HPP-PGMA与MnP-PGMA的UV-Vis光谱及荧光发射光谱, 考察了其光物理行为. 实验结果表明, 通过THPP外环上羟基与PGMA侧基环氧键的开环成醚反应, 可以顺利地将羟基苯基卟啉及其锰配合物键合在PGMA的侧链上. HPP-PGMA具有THPP的特征电子吸收光谱与荧光发射光谱, 且随着THPP键合度的增加, 光谱的强度增强. MnP-PGMA具有小分子锰卟啉的特征电子吸收光谱与荧光特征, 其Soret吸收带发生显著红移(红移58 nm), Q吸收带的数量减为3个吸收峰; 实验发现, MnP-PGMA与小分子锰卟啉类似, 在Q发射带没有荧光发射.     

通过轴向配位反应实现4-乙烯基吡啶聚合物的卟啉功能化

通过轴向配位反应,将四苯基卟啉锌(ZnTPP)键合在4-乙烯基吡啶(4VP)与苯乙烯(St)共聚物P(4VP-co-St)的侧链,制得了卟啉功能化的大分子ZnTPP-P(4VP-co-St).通过FTIR与1H-NMR对其化学结构进行了表征,重点研究了时间、温度对轴配过程的影响,以及大分子轴配化合物ZnTPP-P(4VP-co-St)的谱学性能,对其光物理行为进行了较为深入的分析.研究结果表明,以共聚物P(4VP-co-St)的吡啶侧基为配体,通过轴向配位反应可顺利地制备卟啉功能化的大分子ZnTPP-P(4VP-co-St),且温度越低,键合量越大.该大分子具有类似于ZnTPP的特征电子吸收光谱与荧光发射光谱,同时也显示出轴向配位的特征.与小分子ZnTPP相比,ZnTPP-P(4VP-co-St)的吸收光谱和发射光谱都发生了明显的红移.大分子轴配化合物ZnTPP-P(4VP-co-St)的光物理行为也呈现出一定程度的高分子效应,随着大分子链中ZnTPP键合量的增大,相近的ZnTPP侧链单元之间会发生能量转移,使荧光发射强度有所减弱.     

在聚合物微球 GMA/MMA 表面同步合成与固载卟啉及固载化金属卟啉的催化氧化性能

 制备了甲基丙烯酸缩水甘油酯 (GMA) 与甲基丙烯酸甲酯 (MMA) 共聚微球 GMA/MMA, 并通过键合有对羟基苯甲醛 (HBA) 的改性微球 HBA-GMA/MMA 与苯甲醛 (或取代苯甲醛) 以及吡咯间的 Adler 反应, 实现了卟啉在共聚微球 GMA/MMA 表面的同步合成与固载, 制得了固载有苯基卟啉 (PP)、对氯苯基卟啉 (CPP)、对硝基苯基卟啉 (NPP) 的功能化微球 PP-GMA/MMA, CPP-GMA/MMA 和 NPP-GMA/MMA. 重点考察了影响卟啉同步合成与固载过程的因素. 制备了固载有钴卟啉的催化剂, 并以分子氧氧化乙苯为模型反应, 考察了催化剂的活性. 结果表明, 苯甲醛取代基的结构、催化剂的酸性和溶剂的极性对卟啉的同步合成与固载都有较大的影响; 钴卟啉催化剂对分子氧氧化乙苯反应具有较高的催化活性, 且当钴卟啉外环上含有强吸电子基团硝基时, 催化剂活性最高.     

具有圆偏振光特性的卟啉衍生物的合成、表征和CD光谱研究

合成了一组不同碳链的胆甾醇酯侧链卟啉配体和金属Zn配合物. 研究了它们的吸收光谱和发射光谱. 将这些卟啉配体以一定浓度掺杂在聚甲基丙烯酸甲酯(PMMA)中制成固体薄膜, 发现由于在卟啉环上引入了手性的胆甾醇酯侧链, 卟啉化合物在soret带和Q带均有较强的CD吸收, 这种现象可能是卟啉环上的四个手性胆甾醇酯侧链与四苯基卟啉环发生偶合作用. 进一步还发现这些卟啉化合物的圆偏振吸收性质与在PMMA中的浓度有关.     

在交联聚苯乙烯微球表面实现苯基卟啉的同步合成与固载

以键合有对羟基苯甲醛(HBA)的交联聚苯乙烯(CPS)微球HBA-CPS、苯甲醛和吡咯为反应物, 采用Adler方法, 实现了苯基卟啉(PP)在CPS表面的同步合成与固载, 制得了固载有苯基卟啉的微球PP-CPS. 研究了卟啉同步合成与固载过程的影响因素, 同时进行了微球PP-CPS与钴盐的配合反应, 制备了固载有钴卟啉(CoP)的功能微球CoP-CPS, 初步考察了其对分子氧氧化乙苯的催化活性. 实验结果表明, 在苯基卟啉同步合成与固载的反应过程中, 催化剂的酸性与溶剂的极性是两个主要的影响因素, 使用强极性溶剂与pKa在2.8~3.4范围的酸, 微球PP-CPS表面的苯基卟啉固载量高. 微球CoP-CPS对分子氧氧化乙苯的反应具有明显的催化活性.     

新型meso-四(4-十四氨基磺酰苯基)卟啉及其配合物的合成与液晶性能

以吡咯和苯甲醛为原料制得meso-四苯基卟啉(1);1经氯磺化得meso-四(4-氯磺苯基)卟啉(2);2与十四胺反应制得meso-四(4-十四氨基磺酰苯基)卟啉(3);3与醋酸镉经配位反应合成了meso-四(4-十四氨基磺酰苯基)镉卟啉(4)。3和4为新化合物,其结构经UV-Vis,1H NMR和IR表征。偏光显微镜和DSC检测结果表明:3和4均具有液晶性能。     

新型-meso-四(4-十四氨基甲酰苯基)卟啉及其-金属（Co）配合物的合成与液晶性能

对羧基苯甲醛和吡咯经缩合反应制得meso-四(4-羧基苯基)卟啉(1); 1与氯化亚砜反应得meso-四(4-氯甲酰基苯基)卟啉(2); 2与n-十四胺反应制得meso-四(4-十四氨基甲酰苯基)卟啉(3); 3与CoC_l2经配位反应合成了meso-四(4-十四氨基甲酰苯基)卟啉钴(4)。 3和4为新化合物,其结构经U-Vis, ¹H NMR和IR表征。偏光显微镜和DSC检测结果表明： 3和4具有液晶性能。     

对烷氧基苯基苯并卟啉的新法合成及性能研究

采用先接链后合环密闭熔融新方法，合成了５个系列２５种对烷氧基苯基苯并卟啉，通过紫外，红外，质谱和元素分析等手段进行了表征，初步研究了１０种新型卟啉的性能。     

新型4-{4,5-二[(E)-苯乙烯]-1H-咪唑-2-基}苯甲醛共价键连单羟基四苯基卟啉化合物的合成及其分子内能量转移性能

以2,3-丁二酮为原料,依次与苯甲醛和对苯二甲醛经缩合反应制得4-{4,5-二[(E)-苯乙烯]-1H-咪唑-2-基)苯甲醛}(2);以对二氯苄作为连接链,2与其经取代反应制得4-{1-[4-(氯甲基)苄基]-4,5-二[(E)-苯乙烯]-1H-咪唑-2-基}苯甲醛(3);3与单羟基四苯基卟啉(4)连接合成了4-{4,5-二[(E)-苯乙烯]-1H-咪唑-2-基}苯甲醛共价键连单羟基四苯基卟啉化合物(5),其中2,3和5为新化合物,其结构经1H NMR,MS和元素分析表征。用荧光光谱研究了5中基团3与基团4之间的能量转移过程。结果表明,当激发取代基团3时,能量能够从基团3转移至基团4上。     

卟啉试剂键合硅胶对蛋白质吸附行为的研究

报道了几种卟啉试剂键合硅胶的合成并研究了它们对蛋白质的吸附行为。结果表明 meso-四苯基卟啉键合硅胶 ( TPP· SG)对人血清白蛋白 ( HSA)的最大吸附容量为 1 3.4mg/g,最大吸附率达 92 % ,吸附平衡时间为 60 mi     

对微环境敏感的系列双亲卟啉的光谱研究

研究了系列双亲卟啉(四苯酚基卟啉P₀及其烷氧基衍生物P₁,P₂,P₃)在不同微环境下的电子吸收光谱和荧光发射及荧光激发光谱.研究发现,卟啉在THF溶液中以单体形式存在,并且其侧链取代基对卟啉电子态的影响很小;然而卟啉在CTAB胶束溶液中的光谱特性却表现出很大差异,由此分析了不同侧链取代基对卟啉分子聚集行为和定位性质的影响,初步解释了卟啉在CTAB胶束溶液中随体系pH值改变而发生的荧光猝灭现象.     

Gas‐Phase Spectroscopy of Ferric Heme?NO Complexes

Weakly bound complexes between ferric heme cations and NO were synthesised in the gas phase from ion–molecule reactions, and their absorption measured based on photodissociation yields. The Soret band, which serves as an important marker band for heme‐protein spectroscopy, is maximal at 357±5 nm and significantly blue‐shifted compared to ferric heme nitrosyl proteins (maxima between 408 and 422 nm). This is in stark contrast to the Q‐band absorption where the protein microenvironment is nearly innocent in perturbing the electronic structure of the porphyrin macrocycle. Photodissociation is primarily through loss of NO. In contrast to the Q‐band region, two‐photon absorption was seen in the Soret band despite NO loss only requiring ～1 eV. A model based on intersystem crossing to a long‐lived triplet state where a barrier has to be surmounted is suggested. Finally, we summarise the measured absorption maxima of heme and its complexes with amino acids and NO.     

Synthesis and characterization of 5,10,15,20-tetra[3-(3-trifluoromethyl)phenoxy] porphyrin

The newly synthesized 5,10,15,20-tetra[3-(3-trifluoromethyl)phenoxy]porphyrin, TTFMPP, has been characterized using mass spectroscopy, 1H-, 13C- and 19F-NMR, MALDI-TOF mass spectrometry, UV-Vis and fluorescence spectrophotometry, and cyclic voltammetry. The NMR confirmed the structure of the compound and the mass spectrum was in agreement with the proposed molecular formula. The UV-Vis absorption spectrum of TTFMPP shows characteristic spectral patterns similar to those of tetraphenyl porphryin, with a Soret band at 419 nm and four Q bands at 515, 550, 590, and 648 nm. Protonation of the porphyrin with TFA resulted in the expected red shift of the Soret band. Excitation at 419 nm gave an emission at 650 nm. The quantum yield of the porphyrin was determined to be 0.08. Cyclic voltammetry was used to determine the oxidation and reduction potentials of the new porphyrin. Two quasi-reversible one-electron reductions at -1.00 and -1.32 V and a quasi-reversible oxidation at 1.20 V versus the silver/silver chloride reference electrode with tetrabutylammonium tetrafluoroborate as the supporting electrolyte in methylene chloride were observed.     

Flexible Tuning of Unsaturated β‐Substituents on Zn Porphyrins: A Synthetic,Spectroscopic and Computational Study

A series of zinc porphyrins substituted at adjacent β‐positions with a CN group and para‐substituted ethenyl/ethynyl‐phenyl group have been studied using electronic absorption spectroscopy, resonance Raman spectroscopy and DFT calculations. The oxidative nucleophilic substitution of hydrogen was utilized for the introduction of a cyano substituent on the porphyrin ring. This modification has a remarkable electronic effect on the ring. The resulting porphyrin cyanoaldehyde was further modified in Wittig condensations to give series of arylalkene‐ and arylalkyne‐substituted derivatives. This substitution pattern caused significant redshifting and broadening of the B band, tuning from 433–446 nm. Additionally the Q/B band intensity ratios show much higher values than observed for the parent porphyrin ZnTPP (0.20 vs. 0.03). Careful analysis of the electronic transitions using DFT and resonance Raman spectroscopy reveal that the substituent does not significantly perturb the electronic structure of the porphyrin core, which is still well described by Gouterman’s four‐orbital model. However, the substituents do play a role in elongating the conjugation length and this results in the observed spectral changes.     

Preparation of two kinds of porphyrin‐functionalized polymeric materials based on poly(glyceryl methacrylate)

Poly(glyceryl methacrylate) (PGMA) was reacted with meso‐tetra(4‐hydroxylphenyl)porphyrin (THPP) in a homogeneous system via the ring opening reaction between epoxy and hydroxyl groups, which exist on the side chain of PGMA and the outside ring of THPP, respectively. Porphyrin‐functionalized PGMA with line‐type (denoted as HPP‐PGMA), on whose side chains hydroxylphenyl porphyrin (HPP) was bonded, was obtained. Grafting particles PGMA/SiO₂ were also reacted with THPP, and the porphyrin‐immobilized particles (denoted as HPP‐PGMA/SiO₂), on which HPP was supported, were produced. The above two target products were characterized using spectroscopy methods, such as infrared (IR), nuclear magnetic resonance (¹H‐NMR), electronic absorption, and fluorescence emission. The effects of various factors on the bonding and immobilization reactions of HPP were studied in detail. The experimental results show that the soluble HPP‐PGMA has all the spectral characteristics of porphyrins and the absorption or emission intensity is increased with the increase in the bonding degree of HPP. In the preparation process of HPP‐PGMA, in order to avoid the occurrence of the crosslinking reaction and to obtain HPP‐PGMA with complete line‐type, the catalyst should be selected and the reaction time should be controlled. NaHCO₃ is an appropriate catalyst. In the immobilization process of HPP on the grafting particle PGMA/SiO₂, the greater the used amount of the catalyst triethylamine (TEA), the more rapid is the rate of ring opening reaction, resulting in higher immobilization amount of HPP. Besides, the immobilization amount of HPP is increased with the enhancement of the reaction temperature. Copyright © 2008 John Wiley & Sons, Ltd.