四(对甲氧基苯基)卟啉锌的合成及其与牛血清白蛋白的相互作用

合成了四(对甲氧基苯基)卟啉锌,利用荧光光谱法分别研究了pH值、溶剂和四(对甲氧基苯基)卟啉锌的浓度对四(对甲氧基苯基)卟啉锌与牛血清白蛋白相互作用的影响.由实验数据计算出了该卟啉与牛血清白蛋白的双分子猝灭过程速率常数Kq=4.23×1012L.mol-1.s-1、结合常数KA=3.48×105L.mol-1和结合数n=1.19.结果表明,四(对甲氧基苯基)卟啉锌与牛血清白蛋白之间发生了荧光猝灭作用.     

Trans-membrane controlling of an amphiphilic metalloporphyrin

In order to perform a transfer process of the porphyrin moiety across membrane media, an amphiphilic porphyrin 5,10,15-tri(4-hydroxyphenyl)-20-(4-hexadecyloxy-phenyl) porphyrin (P₁) and its metalloporphyrin (P₁Zn) were selected to be solubilized in cetyltrimethyl ammonium bromide (CTAB) micellar solutions. By taking advantage of the microenvironment sensitivity of their Soret band, UV-Vis spectra were used to study the dependence of location of the porphyrins in CTAB micellar media on the bulk pH value or the salt concentration of bulk solutions. The red shift of the Soret band, the decrease of its absorbance and the increase of the full width at half-maximum (FWHM) of P₁Zn and P₁ with pH titration process from neutral to weak basicity were attributed to the transfer process of the porphyrin moiety from the inner core to the outer surface of the micelles. In the pH sensitive area of the Soret band of P₁Zn and P₁, the blue shift of the Soret band, the increase of its absorbance and decrease of FWHM were observed on decreasing the bulk pH value or increasing the salt bulk solution concentration, indicating that the porphyrin moiety was pushed into the inner core again. Therefore, we can control the trans-membrane transfer process of porphyrin moiety by changing the pH value or the salt concentration of the bulk solutions.     

咪唑基尾式卟啉的新法合成

报道了合成以烷烃链连接的咪唑基尾式卟啉的一种新方法。首先合成溴烷基咪唑盐酸盐,再以5－（对－羟基）苯基－10,15,20－三苯基卟啉与溴烷基咪唑直接反应合成咪唑基尾式卟啉。避免了合成过程中副产物卟啉二聚体的生成,提高了咪唑基尾式卟啉的产率,还降低了合成过程中产物分离纯化的难度。     

新型卟啉衍生物的合成与表征(英文)

以1-溴-2,3,4,6-O-乙酰-D-葡萄糖(1)或氯乙醇分别与5-(对-氨基苯基)-10,15,20-三苯基卟啉(2)反应,制备5-(对-(-D- 葡萄糖氨基苯基)-10,15,20-三苯基卟啉(3)或5-(对-羟乙基氨基苯基)-10,15,20-三苯基卟啉(4)．该方法的反应条件温和,合成路线短,纯化方法简单．     

5,10,15,20-四[4-(2,3-环氧丙氧基)苯基]卟啉的合成与表征

以正丙酸、冰乙酸和硝基苯为混合溶剂, 以对羟基苯甲醛和吡咯为原料, 合成了5,10,15,20-四(4-羟基苯基)卟啉(THPP)．然后以THPP与环氧氯丙烷为原料,在异丙醇中以氢氧化钠为催化剂合成了5,10,15,20-四[4-(2,3-环氧丙氧基)苯基]卟啉(TEPPP)．利用傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(NMR)、紫外可见分光光度计(UV-Vis)和荧光分光光度计分别对THPP和TEPPP的化学结构和光学性质进行了表征与测试．结果表明:1 349 cm-1和916 cm-1处为TEPPP卟啉环中C = N键伸缩振动吸收峰和环氧化物环的(C―O―C键)不对称伸缩振动吸收峰．TEPPP的1H NMR谱图中,在δ 2.92～4.60内5个位移峰峰面积比为1:1:1:1:1,与TEPPP中环氧基团的不同氢原子数比相一致．TEPPP的UV-Vis谱图具有与卟啉结构相符合的吸收峰．通过荧光光谱研究了THPP和TEPPP的荧光性质,并计算得到了二者的荧光量子产率分别为0.08和0.16．     

高产率合成5-(4-氨基-苯基)-10,15,20-三苯基卟啉

报道了一种非常重要的中间体:5-(4-氨基-苯基)-10,15,20-三苯基卟啉的高产率合成方法,产率达95.2%(以5-(4-硝基-苯基)-10,15,20-三苯基卟啉计),总产率为19.5%(以吡咯计).通过红外光谱、紫外-可见光谱、元素分析对目标产物进行了表征,并且讨论了影响目标产物产率的因素.     

新型手性卟啉的制备与识别

利用四苯基卟啉meso位的可调性合成一种新型不对称卟啉, 通过酯键连接叔丁氧羰基(BOC)保护的L-苯丙氨酸(L-BOC-Phen-OH)而使卟啉具有手性识别的能力, 并研究了该手性卟啉对L-丙氨酸甲酯和D-丙氨酸甲酯分子识别能力的不同. 结果表明, 该手性卟啉对D-型氨基酸甲酯的识别能力较强.     

基于羟基苯基卟啉骨架的二聚卟啉合成及性能

以1,4-二氯-2,5-二硝基甲苯为桥联剂, 通过一步合成法制备H-2MHTPP卟啉二聚体, 用MALDI-TOF质谱表征卟啉二聚体的结构, 并研究卟啉二聚体的电化学和光化学性质以及表面光电压光谱（SPS）. 结果表明, H-2MHTPP卟啉二聚体是一种p型半导体.     

Fluorescent detection of singlet oxygen: Amplifying signal transduction and improving sensitivity based on intramolecular FRET of anthryl appended porphyrins

Two new anthryl-appended porphyrin dyads have been synthesized and used as highly selective and sensitive fluorescence probes for singlet oxygen ( 1O2 ). The design strategy for the probes is directed by the idea of intramolecular fluorescence resonance ener- gy transfer (FRET) interactions and carried out by incorporation of an electron-rich fluorophore (porphyrin) with a reactive anthracene for 1O2 . The molecular recognition is based on the specific interaction of 1O2 with the inner anthracene moiety, an...     

Synthesis of novel tailed porphyrins with covalently linked saccharide

The reaction of 5-(p-hydroxyphenyl)-10,15,20-(p-methoxy phenyl) porphyrin with Br(CH2)4Br produced monobromo substituted porphyrin 1. The tailed porphyrins 2-4 were synthesized by the reactions of 1 with small molecular offering biological activities such as D-glucose, D-glucuronic acid. These new compounds were confirmed by 1H NMR, IR, UV-vis and element analyses.     

基于羟基苯基卟啉骨架的二聚卟啉合成及性能

以1,4-二氯-2,5-二硝基甲苯为桥联剂, 通过一步合成法制备H-2MHTPP卟啉二聚体, 用MALDI-TOF质谱表征卟啉二聚体的结构, 并研究卟啉二聚体的电化学和光化学性质以及表面光电压光谱（SPS）. 结果表明, H-2MHTPP卟啉二聚体是一种p型半导体.     

一种新型卟啉席夫碱的合成

合成了一种未见报道的卟啉席夫碱5-(4-氨基苯基)-10,15,20-三苯基卟啉缩1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮,并通过红外光谱、紫外-可见光谱、元素分析和质谱对目标产物进行了表征,并着重讨论了其紫外-可见光谱.     

一种用于光动力治疗的新型Corrole化合物发光特性研究

 通过稳态光谱和皮秒时间分辨的瞬态光谱技术详细研究了一种用于光动力治疗的新型化合物－5,10,15-三（五氟苯基）Corrole（F₁₅TPC）的发光性质。结果表明：F₁₅TPC具有双荧光发射特性;与卟啉相比,F₁₅TPC的S₂态荧光量子产率低,S₁态荧光量子产率高,F₁₅TPC的S₁态荧光寿命为4.8 ns,F₁₅TPC的S₁态具有荧光量子产率高、荧光寿命短的特点。这是由Corrole和卟啉发色团本身的电子结构以及其空间结构和对称性差异引起的。根据实验结果及Corrole和卟啉在光学性质方面的相似性,对Corrole的S₂态电子转移过程进行了类似的讨论。     

卟啉化合物的电化学性质

合成2种在苯环对位连接性质不同取代基的卟啉单体和4种桥联基团性质各异的卟啉低聚物, 并利用循环伏安法研究上述卟啉单体和卟啉低聚物的电化学性质. 结果表明: 卟啉单体周边连接推电子取代基与连接吸电子取代基的卟啉单体相比电极电势正移; 比较卟啉低聚物电化学性质发现, 桥连基团的性质及整个卟啉分子的共轭程度对其电化学性质均有不同程度的影响.     

卟啉单体和卟啉二聚体的光限幅性质

采用Alder法合成了3种在苯环对位连接性质不同取代基的卟啉单体和3种桥联基团性质各异的卟啉二聚体, 并研究卟啉单体和卟啉二聚体的Z-扫描
曲线和光限幅性质. Z-扫描研究结果表明, 卟啉测试样品的Z-扫描曲线相似, 均出现反饱和吸收和光限幅性质, 其中卟啉化合物4的光限幅效果明显, 入射光的透过率约为7%.     

Solvent effects on photophysical properties of copper and zinc porphyrins

The photophysics of Zn（tetraphenylporphyrin,TPP）, Zn（tetra-2,4,6-trimethylphenyl porphyrin, TMP）, Zn （tetra-（o-dichlorophenyl） porphyrin, TPPCI8）, Cu（tetraphenylporphyrin,TPP）, Cu（tetra-2,4,6-trimethyl- phenyl porphyrin,TMP）, and Cu（tetra-（o-dichlorophenyl） porphyrin, TPPCIE, TPPCI8） in several solvents have been investigated on steady state and time-resolved spectroscopy. The Cu（TPPCI8 ） is normal and shows no evidence of CT transition in the visible or near UV regions in nonpolar solvent. However, Cu（TPPCI8）shows a blue shift in the absorption spectrum and intramolecular CT bands at absorption spectra in polar solvent, which shows a fluorescence maximum emission at 650 nm and 8.4 ns lifetime. The reason can be attributed to two points. Firstly, the increase of solvent polarity can enlarge outer reorganisational energy, which is favorable to reduce the activation free energy of charger-transfer transition based on Marcus theory of electron transfer. Moreover, the internal heavy-atom effect on Cu（TPPCIE） is encouraging to stabilize the 2T1 state also, which increases the possibility of population to CT band from 2T1 state. This result is in accord with an earlier estimate of a 10 ns lifetime and CT absorption at 640 nm bands for the CT state of Cu （11） octethylporphyrins. Other possible reasons arousing unusual fluorescence like H-bonding, axial ligands, molecular aggregation are excluded.     

卟啉低聚物的合成与表征

以单体5-(4-羟基苯基)-10,15,20-三苯基卟啉(H2MHTPP)与5,15-二(4-羟基苯基)-10,20-二苯基卟啉(trans-H2DHDPP)做单体,1,3-二溴丙烷做桥连剂,合成了一种一维纳米卟啉低聚物.通过元素分析、紫外光谱、红外光谱1、H核磁共振等手段对其结构进行了表征,确证了其结构.     

ConformationsofCytochromeP─450Modelsby1Dand2DNMR

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浑球红假单胞菌的卟啉分泌与调节

对浑球红假单胞菌（Ｒｐｓ．ｓｐｈａｅｒｏｉｄｅｓ）Ｐ４菌株的卟啉合成与分泌进行了研究．经过在ＲＣＶＢ培养基中的增殖生长与产卟啉液ＭｉｘｔｕｒｅＩ中的诱导，Ｐ４菌可以产生较高含量的卟啉．通过研究分析各种外界因子对卟啉合成与分泌的影响，确定了有利于Ｐ４菌合成与分泌卟啉的培养条件，包括光照、适当的底物浓度、较低的Ｆｅ２＋浓度以及培养程序和培养时间等．为进一步研究菌叶绿素和细菌色素代谢机理、为Ｐ４菌用于卟啉生产提供了良好的基础．