两种新型卟啉吡啶季铵盐的合成

合成了两种新型卟啉吡啶季铵盐:溴化5-[4-N-(对硝基)苄铵基吡啶基]-10,15,20-三(4-N吡啶基)卟啉和氯化5-[4-N-(对甲氧基)苄铵基吡啶基]-10,15,20-三(4-N-吡啶基)卟啉.这两种化合物尚未见文献报道,它们的结构分别由紫外可见光谱、红外光谱、核磁共振谱、质谱、元素分析得到确证.     

新型L-氨基酸尾式卟啉及其锌(Ⅱ)配合物的合成与光谱性质

用L-氨基酸和5-[邻-(2-溴乙氧基)苯基]-10,15,20-三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4 000～400 cm-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。     

溴化5-[4-(3-吡啶丙氧基苯基)]-10，15，20-三苯基卟啉对铜离子显色反应的研究

本文研究了溴化 5- [4 - (3-吡啶丙氧基苯基 ) ]- 10 ,15,2 0 -三苯基卟啉 ,在 p H=4 .0时与 Cu2 + 的显色反应条件 ,其络合物最大吸收波长为 4 13nm。在相同条件下 ,试剂最大吸收波长为 4 4 4nm,对比度大约30 nm。试剂与铜络合比为 1∶ 1,表观摩尔吸光系数为 2 .9× 10 5L· mol-1·cm-1,铜含量在 0— 6 0 μg/ L范围内符合比耳定律 ,可用于痕量铜的测定。     

新型吡唑并[3,4-d]嘧啶-4-酮类衍生物的结构表征和镇痛活性

本文以2-氰基-3-乙氧基丙烯酸乙酯与3,4-二甲基苯肼为原料,通过多步反应合成了三种新型吡唑并[3,4-d]嘧啶-4-酮类衍生物（A~C）,通过核磁共振（NMR,包括¹H NMR、¹³C NMR）和液相色谱-质谱联用（LC-MS）技术表征确证了其结构,并完整归属了三种化合物的¹H NMR数据．对所合成的化合物1-(3,4-二甲基苯基)-6-甲基-5-[3-(哌啶-1-基)丙氧基]-1,5-二氢-4H-吡唑并[3,4-d]嘧啶-4-酮（A）,通过小鼠脑部质谱成像和福尔马林实验进行了初步的体内镇痛活性评价,我们发现化合物A能透过血脑屏障,并产生显著且剂量依赖的镇痛活性．本研究为以吡唑并[3,4-d]嘧啶-4-酮为骨架的镇痛药物的研发提供了结构和体内活性的基础研究数据．     

[四-(三-甲氧基-四-羟基)苯基]-锌卟啉-环糊精超分子体系研究

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.     

5-（4-乙酰丙氧基）苯基-10,15,20-三苯基卟啉Yb（Ⅲ）配合物的合成及近红外发光性能研究

合成并表征了5-(4-乙酰丙氧基)苯基-10,15,20-三苯基卟啉的Yb3 配合物.配合物经元素分析、1H NMR及UV-VIS吸收光谱表征.配合物呈现七配位特征.在可见光的照射下,Yb3 配合物在950-1050nm范围内给出特征发射.配合物在强配位溶剂及非O-H溶剂如二甲基亚砜中的发射强度比在甲醇中的发射强度高近10倍,半衰期也提高两倍.     

溴化5-［4-(2-吡啶-乙氧基)苯基］-10，15，20-三苯基卟啉对铜离子的显色反应研究

本文研究了溴化 5- [4 - ( 2 -吡啶 -乙氧基 )苯基 ]- 10 ,15,2 0 -三苯基卟啉与 Cu2 +的显色反应条件 ,在 p H=4 .0时 ,其络合物最大吸收波长为 4 13nm,试剂最大吸收波长为 4 4 3.5nm。对比度大约为 30 nm。试剂与铜络合比为 1∶ 1,其络合物表观摩尔吸光系数为 3.4× 10 5L·mol-1· cm-1,铜含量在 0— 0 .5μg/ 10 m L范围内符合比耳定律 ,本研究可用于痕量铜的测定     

新型卟啉吡啶季铵盐对铜(Ⅱ)显色反应的研究

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.     

5,10,15-三苯基-20-[4-(S-乙酰硫基)苯基]卟啉的合成、光谱及电化学性质研究

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.     

取代基对卟啉类化合物三阶非线性光学特性的影响

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。     

Enhanced photoactivity of CuPp-TiO2 photocatalysts under visible light irradiation

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.     

A Novel Porphyrin-Labeled Poly(N-Isopropylacrylamide): Spectral and Luminescent Properties

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.     

水溶性阳离子卟啉与ctDNA的相互作用及其聚集行为研究

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)卟啉(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=c_TMAP/c_DNA),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。     

Photophysical and electrochemical properties of monoporphyrin rare earth liquid crystalline materials

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 (Col_h) 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.     

Synthesis and Characterization of Soluble Cardo Poly(ester-imide)s Derived from 9,9-Bis[4-(3,4-dicarboxybenzoyloxy)phenyl]fluorene

A novel fluorenyl cardo dianhydride-9,9-bis[4-(3,4-dicarboxybenzoyloxy)phenyl]fluorene (BDPF) was synthesized and characterized. A series of fluorenyl cardo poly(ester-imide)s (FCPEIs) were prepared by the polycondensation of BDPF with m-phenylene diamine, 4,4′-oxydianiline (4,4′-ODA), 3,4′-oxydianiline (3,4′-ODA), 2,2-bis[4-(4-amino -phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 1,6-hexamethylenediamine. Most of the FCPEIs exhibited excellent solubility in common organic solvents such as 1,2-dichlorobenzene (o-DCB), chloroform, tetrahydrofuran, N,N-dimethylacetamide (DMAc), dimethyl sulfoxide, N-methyl-2-pyrrolidinone, etc. Intrinsic viscosities of FCPEIs in DMAc, for instance, ranged from 0.29–0.52 dL/g. The glass transition temperature of these polymers was between 199°C and 283°C by differential scanning calorimentry, and the 5% weight loss temperature of all polymers exceeded 400°C in air.     

尾式缬氨酸四苯基卟啉锌与嘧啶轴配反应光谱和热力学

研究了５（４－缬氨酸丁氧苯基）－１０,１５,２０－三（４－氯苯基）卟啉锌与嘧啶在氯仿溶液中轴配反应光谱和热力学性质。用紫外－可见分光光度法测定了轴向配位反应体系的配位数和平衡常数。用温度系数法求得了轴配反应的标准摩尔焓变和标准摩尔熵变。探讨了温度对轴向配位反应的影响。     

氯代5-氟脲嘧啶卟啉的红外光谱特性的研究

本文对新合成的对位及间位两类氯代苯基 5 氟脲嘧啶卟啉的红外光谱吸收峰进行了归属和总结 ,讨论了其红外吸收频率随取代基位置变化的规律。指出了苯环上的取代基为电负性强的基团时 ,由于场效应的存在 ,使被测化合物的羰基伸缩振动吸收峰的相对强度发生改变。同时 ,表明了嘧啶环上N原子发生了取代 ,形成单、双取代 5 氟脲嘧啶卟啉化合物的红外光谱特性。     

Carbon-13 NMR Spectra of Some 6-Chloro-4-Hydroxy-2-Oxopyrano-3-Carboxyl Derivative, 7-Chloro-Pyrano-1, 3-Oxazine and their Morpholine Reaction Products

Carbon-13 chemical shifts of 3-Carboxy, 3-methoxy or ethoxy carbonyl or 3-carboxy analide -6-chloro-4-hydroxy-2-oxo-pyran (1), 7-chloro or 7-morpholino-3-substituted-3,4-dihydro-4, 5-dioxo-2-thio or oxo-2H, 5H-Pyrano [3, 4-e]-1, 3-oxazine (2 or 3) and 2-substituted phenyl carbamoyl-3-morpholino-N, N-glutaconoyl-dimorpholine (4) were assigned using first order and long range CH coupling constant.