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1.
张志华 《光谱实验室》2007,24(2):206-208
研究了在不使用表面活性剂的情况下,新型卟啉吡啶季铵盐溴化5-[4-N-(甲氧基)苄铵基吡啶基]-10,15,20-三(4-N-吡啶基)卟啉对铜(I)的显色反应.结果表明,在pH=1.2时卟啉与Cu2 形成了稳定的配合物,其最大吸收波长为423nm,试剂与Cu2 络合比为1:1,表观摩尔吸光系数为3.24×105L·mol-1·cm-1,铜含量在0-0.8μg/10mL范围内符合比耳定律,该方法应用于环境水样中铜的测定,结果令人满意.  相似文献   

2.
两种新型二氯代苯基卟啉-5-氟尿嘧啶衍生物的合成与表征   总被引:2,自引:0,他引:2  
用5-[4-(5-溴戊氧基)苯基]-10,15,20-三(3,4-二氯苯基)卟啉或5-[4-(6-溴己氧基)苯基]-10,15,20-三(3,4-二氯苯基)卟啉与5-氟尿嘧啶反应,合成了1-[5-(4-戊氧苯基)-10,15,20-三(3,4-二氯苯基)卟啉]-5-氟尿嘧啶(A)和1-[5-(4-己氧苯基)-10,15,20-三(3,4-二氯苯基)卟啉]-5-氟尿嘧啶(B),产率分别为29.92%和30.01%。并通过红外光谱、紫外可见光谱、核磁共振谱和质谱表征了其结构。对目标化合物的合成条件进行了研究,结果表明:以DMF为溶剂,反应温度为115℃,反应时间2h,产率较高;采用硅胶G(200—300目)装柱,以氯仿和氯仿∶乙醚(V∶V=50∶1)为洗脱液,柱层析,再用氯仿:丙酮(V∶V=7∶1)洗脱产品色带,分离效果较好。  相似文献   

3.
合成了-种新型水溶性卟啶卟啉季铵盐即溴化5-[(4-N-芐基)吡啶基]10,15,20-(4-N-吡啶基)卟啉,研究了该试剂与锌的显色反应.在pH2.5的邻苯二甲酸氢钾-盐酸缓冲溶液中,形成了配位比为1:1的配合物,基最大吸收波长λ=424nm,表现摩尔吸光系数ε=2.03×105L·mol-1·cm-1.在0-1.2μg/10mL范围内吸光度与锌质量浓度关系符合比耳定律,该法灵敏度高、选择性好.本法应用于环境水试样中痕量锌离子的分析,结果令人满意.  相似文献   

4.
水溶性阳离子卟啉与ctDNA的相互作用及其聚集行为研究   总被引:1,自引:0,他引:1  
水溶性阳离子卟啉作为多功能DNA结合试剂在光动力学疗法、抗病毒药物等方面得到了越来越多的应用,因此研究阳离子卟啉与DNA的相互作用引起人们极大的兴趣.文章采用吸收光谱、荧光光谱和共振光散射技术研究了meso四(4-三甲铵基苯基)卟啉(TMAP)和5-苯基-10,15,20-三(N-甲基-4-吡啶基)卟咻(TriMPyP)两种水溶性阳离子卟啉在水溶液中的聚集状态及与小牛胸腺DNA(ctDNA)的相互作用.在R>1时(R=cTMAP/cDNA),TMAP在DNA分子表面发生聚集,吸收光谱有明显的减色效应,卟啉的荧光被猝灭.在R<1时,TMAP与DNA以外部结合方式结合,荧光得到增强,共振光信号减弱.DNA的加入,使TriMPyP的聚集程度进一步增加.考察了离子强度对卟啉与DNA相互作用的影响,离子强度增大,卟啉的荧光得到增强,卟啉与DNA的结合方式发生改变.  相似文献   

5.
用L 氨基酸和 5 [邻 (2 溴乙氧基 )苯基 ] 1 0 ,1 5 ,2 0 三苯基卟啉为原料合成了三种新型L 氨基酸尾式卟啉及其锌 (Ⅱ )配合物 ,通过元素分析、红外光谱、紫外光谱、化学分析和质谱等对其进行了结构表征。测试并研究了它们在 4 0 0 0~ 4 0 0cm-1 范围内的傅里叶变换红外光谱 ,对主要谱带进行了经验归属  相似文献   

6.
采用实验与密度泛函理论计算(DFT)相结合,研究了不同电子取代基修饰的5-邻羟基苯基-10,15,20-三苯基卟啉(TPPOH)和5-邻羟基苯基-10,15,20-三(对甲氧基)苯基卟啉[(p-OCH_3)TPPOH]化合物的吸收光谱及其电化学性质。结果表明,相对于TPPOH,由于对位甲氧基(-OCH_3)给电子能力强致使(pOCH_3)TPPOH的卟啉环电子云密度增加,从而引起吸收光谱红移(3 nm)、氧化还原电位发生明显的负移,最高占据分子轨道(HOMO)和最低空轨道(LUMO)能级差降低0.06 eV。DFT理论分析分子前线轨道电子分布结果显示(p-OCH_3)TPPOH的HOMO和LUMO轨道能量均增加,而能级差却比TPPOH能级差小0.05 eV。理论结果与电化学和光谱实验结论一致,并进一步阐明了光谱和电化学性质变化机理,为揭示不同取代基卟啉化合物的设计与应用提供重要依据。  相似文献   

7.
取代基对卟啉类化合物三阶非线性光学特性的影响   总被引:10,自引:2,他引:8  
主要采用吸收光谱、荧光光谱和皮秒Z-扫描等实验方法研究了三种不同取代基的卟啉化合物5,10,15,20-四对羟基苯基卟啉[T(4-HP)P]、5,10,15,20-四对酯基苯基卟啉[T(4-EP)P]和5,10,15,20-四对溴苯基卟啉[T(4-BrP)P]的光学及非线性光学性质,并从离域电子共轭结构理论和共振、非共振增强理论进行了分析。结果表明,强给电子基团取代的T(4-HP)P的吸收和荧光发射带比弱给电子基团取代的T(4-EP)P及吸电子基团取代的T(4-BrP)P有明显红移;三种样品均具有正的三阶非线性极化率χ(3),强的给电子能力和共振增强使得T(4-HP)P的三阶极化率比T(4-BrP)P增强了近两个量级,并在532 nm光激发时,χ(3)具有最大值6.81×10-10esu。  相似文献   

8.
合成了两类新型的单尾卟啉-5-(4-(ω-(1-金刚胺基)烷氧基)苯基)-10,15,20-三苯基钴/镍卟啉(CoPCnA,NiPCnA)做为电子给体,并用荧光光谱研究这两类化合物与作为电子受体的环糊精衍生物单-6-氧-(对硝基苯甲酰基)-环糊精(NBCD)在水溶液中的相互作用.观察到由光诱导电子转移反应引起的荧光淬灭,表明所合成的卟啉衍生物和NBCD组成稳定的超分了体系,并测定了详细的动力学淬灭常数和包合常数.  相似文献   

9.
合成了化合物5,10,15-三苯基-20-[4-(S-乙酰硫基)苯基]卟啉,用红外光谱、核磁、高分辨质谱对标题化合物进行了结构表征.研究了标题化合物的紫外-可见光谱、荧光光谱、电化学循环伏安特性.  相似文献   

10.
在中性磷酸盐缓冲溶液中,以紫外-可见分光光度法和荧光光谱法研究了对称性卟啉[四-(三-甲氧基-四-羟基)苯基]-锌卟啉(简称T(3-MO-4-HP)P-Zn)与α-CD、β-CD、γ-CD三种环糊精之间相互作用形成的超分子体系.结果表明T(3-MO-4HP)P-Zn卟啉与3种环糊精均形成1∶1的包结物.利用双倒数曲线法计算了T(3-MO-4-HP)P-Zn-CD超分子体系的包结常数,结果表明T(3-MO-4-HP)P-Zn与β-CD表现出最强的包结能力.  相似文献   

11.
Three novel porphyrins, 5,10,15-tri-phenyl-20-[4-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-phenyl-10,20-di-[4-(3-phenoxy)-propoxy]phenyl porphyrin and 5-phenyl-10,15,20-tri- [4-(3-phenoxy)-propoxy]phenyl porphyrin, and their corresponding copper(II) complexes were synthesized and characterized spectroscopically. The photocatalytic effects of TiO2 samples impregnated with copper(II) porphyrins was investigated by photodegradation of 4-nitrophenol (4-NP) in aqueous solution under visible light. The photocatalysts were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis spectra and FT-IR spectra. The results indicated that CuPps were successfully loaded and interacted with the surface of TiO2 microsphere, which is crucial to enhance the activity of the catalytic composite under visible light.  相似文献   

12.
A novel water-soluble tetraarylporphyrin-containing polymer has been synthesized by the reaction of bromoalkyl-containing poly(N-isopropylacrylamide) with 5-(4-pyridyl)-10,15,20-tri(4-methoxyphenyl)porphyrin. Some physicochemical properties of the obtained polymers are reported. It has been shown that a strong interaction between the porphyrin units takes place in liquid aqueous medium at temperatures below the lower critical solution temperature (LCST). This phenomenon results in considerable broadening of the Soret band in the absorption spectrum and in strong quenching of fluorescence. Higher than LCST fluorescence enhancement is observed.  相似文献   

13.
The structure of a series of complexes of 3d metals (Co, Ni, and Cu) with substituted porphyrins is studied by X-ray EXAFS spectroscopy. Together with complexes based on tetraphenylporphyrin and octaethylporphyrin with known crystalline structures, new complexes of asymmetrically substituted tetraphenylporphyrin, 5-(4-(((4′-hydroxy-benzo-15-crown-5)-5′-yl)diazo)phenyl)-10,15,20-triphenylporphyrin, are studied. Based on an analysis of experimental spectra with allowance for the contributions of multiple scattering, the coordination parameters of metal atoms at the center of the porphyrin ring are determined: the bond distances and valence angles between them for the first four coordination spheres around metal atoms. The EXAFS spectra are shown to be sensitive to the angular parameters. Differences in the geometric parameters in the series of studied metal-porphyrin complexes are analyzed.  相似文献   

14.
The DNA binding and photocleavage specificities of the Zn(II), Cu(II), Co(III), Mn(III) complexes of 5,10,15-tris(1-methylpyridinium-4-yl)-20-(4-propionoxyphenyl)porphyrin have been studied by using a combination of absorption, fluorescence titration, surface-enhanced Raman spectroscopy (SERS), induced circular dichroism (ICD) spectroscopy, thermal DNA denaturation as well as gel electrophoresis experiment. It is found that Cu(II) porphyrin has comparable binding ability with the free base porphyrin while the axial-coordinated Zn(II), Co(III), and Mn(III) porphyrins have lower Kb because of the molecular steric hindrance. However, those metalloporphyrins with lower Kb have similar DNA cleavage efficiencies with the free base porphyrin. This could be best understood by the enhancement of the 1O2 productivity which may also result from the steric hindrance of the axial-coordinated metalloporphyrins.  相似文献   

15.
The synthesis and characterization of [5-(p-alkacyloxy ) phenyl-10,15,20-tri-phenyl] porphyrin (APTPP) and its lanthanide complexes(lanthanide ions: Ho(III), Dy(III), Er(III), Yb(III)) are reported. They form hexagonal columnar discotic columnar (Colh) liquid crystals over an extended domain of temperature. Luminescence spectra of the compounds are discussed. Quantum yields of Q band are in the region 0.004570-0.05847. The electrochemical property is studied by cyclic voltammetry. The synthesized APTPP and its lanthanide complexes exhibit two one-electron reversible redox reactions and three redox reactions, respectively. The photovoltaic properties and charge-transfer process of the liquid crystalline compounds are investigated by surface photovoltage spectroscopy (SPS) and electric-field-induced surface photovoltaic spectroscopy (EFISPS) techniques, and the bands are analogous with the ultraviolet (Uv) -visible absorption spectra, which reveal that all compounds are P-type semiconductors. All of compounds are nonelectrolytes.  相似文献   

16.
合成尾式丝氨酸卟啉 [5 (p 丝氨酸丁氧苯基 ) 10 ,15 ,2 0 三苯基卟啉及其钴 (Ⅱ )的配合物 (Co[Ser TPP]) ,用元素分析、红外光谱、电子吸收光谱、氢核磁共振谱和激光拉曼光谱等手段对其结构进行了表征。研究了吡啶 (Py)、4 甲基吡啶 (4 MePy)、4 氨基吡啶 (4 AmPy)、4 ,4 联吡啶 (4 ,4 BiPy)、咪唑 (Im)、1 甲基咪唑(1 MeIm)、2 甲基咪唑 (2 MeIm)等化合物对Co[Ser TPP]电子光谱的影响。结果表明 ,在Co[Ser TPP]溶液中加入吡啶类和咪唑类化合物后 ,Co[Ser TPP]的电子光谱发生变化是Co[Ser TPP]与吡啶类和咪唑类化合物发生轴向配位反应生成加合物的缘故。  相似文献   

17.
In order to study the effects of anchoring modes on the properties of porphyrin zinc (ZnP) coupled titanate nanotubes (TNTs), the TNTs coupled with 5,10,15,20-tetraphenylporphyrin zinc (ZnTPP) and 5-(4-hydroxyphenyl)10,15,20-triphenylporphyrin zinc (ZnMOHPP), which were denoted as TNTs-ZnTPP and TNTs-ZnMOHPP, were prepared using a simple refluxing method, respectively. Based on the different experimental phenomena observed during the synthesis process as well as the results of the spectral characterization, thermogravimetric analysis, photocatalysis test and photoelectrochemistry measurement, it was demonstrated that the ZnMOHPP molecules were bonded mainly on the outer surfaces of the TNTs through hydrogen bonds, while the ZnTPP molecules were physically adsorbed into the pore channels of the TNTs via a capillary process. The different anchoring modes of ZnP on the TNTs as well as the special morphology of TNTs resulted in the remarkable distinctions in the thermal stability, photocatalytic and photoelectrochemical properties.  相似文献   

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