尾式亮氨酸卟啉锌与吡啶类化合物轴配反应热力学性质研究

研究了尾式亮氨酸卟啉—— 5 -(对亮氨酸丁氧苯基 ) -1 0 ,1 5 ,2 0 -三苯基卟啉锌 ( )配合物 ( Zn[Leu-TPP]与吡啶( Py)、4 -甲基吡啶 ( 4-Me Py)、4 -醛基吡啶 ( 4-CHOPy)、4 -氨基吡啶 ( 4-Am Py)等化合物轴配反应的电子光谱 ,用紫外可见光谱法测定了轴配反应的配位数和平衡常数 ,利用温度系数法测定了体系的标准摩尔焓变△ r H0 m 和标准摩尔熵变△r S0 m。结果表明 ,Zn[Leu-TPP]与吡啶类化合物轴配反应是放热和熵降低的过程。Zn[Leu-TPP]可通过配位键和氢键与 4 -Am Py结合 ,轴配物 Zn[Leu-TPP]· ( 4-Am Py)稳定性最强     

尾式苏氨酸卟啉及其锌配合物的合成和光谱性质

合成了尾式苏氨酸卟啉——[5-(对苏氨酸丁氧苯基)-10，15，20-三苯基卟啉及其锌(Ⅱ)的配合物(Zn[Thr-TPP])，用元素分析、红外光谱、电子吸收光谱和激光拉曼光谱等手段对其结构进行了表征，研究了咪唑(Im)对Zn[Thr TPP]电子吸收光谱的影响。     

β-硝基四苯基卟啉锌的合成及其光谱性质

合成了β-硝基四苯基卟啉[H2TPP（NO2）]及其锌配合物[ZnTPP(NO2)],用元素分析、红外光谱、电子吸收光谱等手段对其组成和结构进行了表征。研究了吡啶4-甲基吡啶、4-甲基吡啶、4-氨基吡啶、4，4-联吡啶、咪唑、1-甲基咪唑、2-甲基咪唑等化合物对ZnTPP(NO2）电子光谱的影响，结果表明，ZnTPP(NO2)溶液中加入吡啶类和咪唑类化合物后，ZnTPP(NO2)的电子光谱发生变化是由于ZnTPP(NO2）与吡啶类和咪唑类化合物发生轴向配位反应而生成加合物的缘故。     

吡啶氧丁氧苯基三甲氧苯基卟啉及其Fe(Ⅲ)配合物的合成与表征

报道了一种新型尾式卟啉化合物 - 5 -对 [4- (间吡啶氧基 )丁氧基 ]苯基 - 1 0 ,1 5 ,2 0 -三对甲氧苯基卟啉及其 Fe( )配合物的合成。并通过元素分析、红外光谱、核磁共振光谱及紫外可见光谱等对其结构进行了表征     

β-取代卟啉及卟啉锰对氧化破坏的稳定性

在假一级条件下,以亚碘酰苯为氧化剂,通过测定β-未取代的四苯基卟啉(TPP),以及不同β-取代的β-Cl8TPP、β-Br8TPP、β-Br4TPP、β-NO2TPP、β-(CH3)8TPP及其金属锰配合物的氧化破坏反应的表观动力学常数,获得了卟啉配体的稳定性顺序为TPP>β-(CH3)8TPP>β-Br8TPP>β-Cl8TPP>β-Br4TPP>β-NO2TPP,β位位阻越大相应的卟啉配体越稳定,并由此推导PhIO由β位进攻卟啉配体。β-取代锰卟啉的稳定性顺序为:Mn(β-Cl8TPP)Cl>Mn(β-Br8TPP)Cl>Mn(β-Br4TPP)Cl>Mn(β-NO2TPP)Cl>Mn(TPP)Cl>Mn[β-(CH3)8TPP]Cl,并与在催化氧化环己烷反应中的稳定性一致,β位吸电子作用越大相应的锰卟啉越稳定,并推导由氧化能力更强的高价金属-氧中间体以位阻较小的面对面方式进攻β-取代锰卟啉。     

两种带吡啶基侧臂的新型不对称卟啉的合成与表征

合成了2种带吡啶基侧臂的新型不对称卟啉,5-[4-(乙烯基氧基)苯基]-10,15,20-三[4-((2-(O-吡啶-3基)乙氧基)氧基)苯基]卟啉和其水溶性阳离子卟啉5-[4-(乙烯基氧基)苯基]-10,15,20-三[4-((2-(O-(N-甲基吡啶)-3基)乙氧基)氧基)苯基]卟啉,并通过红外光谱、质谱、核磁共振氢谱、紫外光谱和荧光光谱对其结构进行了表征。     

Cu~(2+)、吡啶、环烷酸三元配合物的组成研究

通过摩尔比法(饱和法)对Cu~(2+)、吡啶(Py)、环烷酸(R)三元配合物的组成进行了研究,并通过环烷酸铜、Cu~(2+)、Py、R三元配合物和吡啶红外光谱图对Cu~(2+)、Py、R 三元配合物的结构进行了分析,认为此三元配合物的组成为Cu~(2+):吡啶:环烷酸=1:4:2,且为缔合型三元配合物,其结构简式为[Cu(Py)_4]R_2。     

以氢键组装的铜(Ⅱ)、锌(Ⅱ)卟啉超分子构象

考察了 5 -对 - (间羰基苯甲酸 ) -氨基苯基 - 1 0 ,1 5 ,2 0 -三苯基卟啉锌 ( )配合物 ( Zn( m-CPTPP) )、铜 ( )配合物 ( Cu( m- CPTPP) )及 ( Zn( m- CPTPP) )与 5 -对 - (对羰基苯甲酸 ) -氨基苯基 -1 0 ,1 5 ,2 0 -三苯基卟啉铜 ( ) ( Cu( p- CPTPP) )通过氢键的超分子自组装行为。上述两体系都通过氢键自组装成超分子。 Zn( m- CPTPP) - Cu( m- CPTPP)体系存在卟啉环间的π-π堆积作用     

meso-苯基-4-吡啶基取代卟啉混合物的合成规律研究

以苯甲醛、4-吡啶甲醛、吡咯为原料,同时合成6种卟啉化合物,通过改变溶剂、反应物浓度、反应时间、氧化剂用量和原料比例等反应条件,探讨了meso-苯基-4-吡啶基取代卟啉混合物的合成规律。经研究发现,在70 m L溶剂(V(乙酸)∶V(丙酸)=1∶1)、10 m L硝基苯、反应温度为110℃、反应物浓度为0.2 mol/L、反应时间为1.5 h条件下,当n(苯甲醛)∶n(4-吡啶甲醛)=1∶7~7∶1,卟啉的产率为23.4%~31.2%;当n(苯甲醛)∶n(4-吡啶甲醛)=1∶7时,5-(4-吡啶基)-10,15,20-三苯基卟啉的最高选择性为24%,5,10-二(4-吡啶基)-15,20-二苯基卟啉的最高选择性为15%;当n(苯甲醛)∶n(4-吡啶甲醛)=7∶1时,5,15-二(4-吡啶基)-10,20-二苯基卟啉的最高选择性为25%,5,10,15-三(4-吡啶基)-20苯基卟啉的最高选择性为31%。     

光敏氧化还原反应 Ⅲ.在油/水微乳液中光敏还原甲基红的研究

本文报道了在油/水微乳液(石蜡油/正戊醇/十二烷基磺酸钠/水),以叶绿素a(Chl a),锌四苯基卟啉(Zn TPP)和四苯基卟啉(TPP)为敏化剂的抗坏血酸钠盐(Asc)光敏还原甲基红(MR)的研究。Chl a和Zn TPP对上述反应有着明显的敏化作用。但由于Asc和MR暗反应的速率相当高,光敏反应的动力学数据很难测准。     

Acid‐sensitive reactive oxygen species triggered dual‐drug delivery systems for chemo‐photodynamic therapy to overcome multidrug resistance

In clinical treatment, multidrug resistance (MDR) is one of the major obstacles resulting in the failure of chemotherapy. It is still a challenge to overcome MDR. Herein, we fabricated intelligent dextran‐based dual‐drug delivery systems histidine modified dextran conjugated doxorubicin/zinc porphyrin/paclitaxel (DHTD/Zn‐TPP/PTX) via supramolecular metallo‐coordination for synergistic chemo‐photodynamic therapy to overcome cancer drug resistance. In this designed DHTD/Zn‐TPP/PTX, one anticancer drug (doxorubicin, DOX) was conjugated on the dextran backbone through a reactive oxygen species sensitive linker and the other drug PTX was encapsulated into the acid responsive supramolecular micelles formed by the photosensitizer Zn‐TPP and histidine grafted on dextran. DHTD/Zn‐TPP/PTX with excellent stability could be effectively internalized by tumour cells. In the acidic tumour environment, the loaded PTX and Zn‐TPP as photosensitizer could be released; moreover, when irradiated with light the conjugated DOX could be specifically released because the linker broke. As the obtained data indicate, DHTD/Zn‐TPP/PTX exhibited not only an enhanced anticancer therapeutic effect but also significant growth inhibition for drug‐resistant MCF‐7/ADR cells to reverse MDR, having great potential for synergistic treatments of cancer to overcome MDR. © 2020 Society of Chemical Industry     

新型尾式谷氨酸四苯基卟啉锰(Ⅲ)催化烯烃环氧化研究

研究了新型尾式谷氨酸四苯基卟啉锰（Ⅲ）［Ｍｎ（Ｇｌｕ－ＴＰＰ）Ｃｌ］与锌粉（Ｚｎ）、乙酸（ＣＨ３ＣＯＯＨ）、分子氧（Ｏ２）和咪唑（Ｉｍ）组成的氧化模拟体系催化烯烃的环氧化反应。测定了氧化反应体系吸氧动力学曲线。结果表明,体系的最高吸氧速度高达１．５ｍＬ·ｍｉｎ－１,环氧化产物收率（Ｚｎ％）可达５９．２％。     

双卟啉的超共轭效应对其光谱行为的影响

合成了2个双卟啉化合物(简称为(TPP)2p和(TPP)2n)和一个单卟啉化合物(简称TPPa),并进行了核磁共振表征。研究了卟啉环之间的超共轭效应对分子的单、双光子吸收行为的影响,经吸收光谱和荧光光谱证实,发现双卟啉(TPP)2p和(TPP)2n由于存在pπ共轭效应和σπ超共轭效应,使得双卟啉的吸收和荧光强度均比单卟啉TPPa要强得多。并计算三种卟啉在不同溶剂种光物理性质参数。     

克霉唑金属配合物的合成与表征

以无水甲醇为溶剂,以克霉唑为配体分别与二水合氯化铜、无水氯化锌反应,合成了2种新的药物金属配合物。化合物经元素分析、摩尔电导率、IR、TG及UV等分析表征,表明2种配合物的可能结构式为:[Cu(C22H17ClN2)C l2]n,[Zn(C22H17ClN2)2Cl2]。     

四苯基卟啉锶配合物的合成及发光性能

利用醋酸锶与四苯基卟啉反应,合成了四苯基卟啉锶配合物。利用元素分析、红外、核磁共振等对该配合物进行了结构表征。采用紫外-可见吸收光谱、荧光光谱和循环伏安法研究了该配合物的光电性能。四苯基卟啉锶配合物紫外-可见吸收光谱有一个强的吸收峰和一个次强的吸收峰,分别为428、457 nm。荧光光谱有一个强的发射峰和一个弱的发射峰,分别为610、676 nm。循环伏安法测得其氧化峰电位为1.558 V和1.051 V。与四苯基卟啉相比,四苯基卟啉锶紫外吸收发生红移,而荧光发射发生蓝移。     

Synthesis and in Vitro Characterization of Trehalose-Based Inhibitors of Mycobacterial Trehalose 6-Phosphate Phosphatases

α,α′-Trehalose plays roles in the synthesis of several cell wall components involved in pathogenic mycobacteria virulence. Its absence in mammalian biochemistry makes trehalose-related biochemical processes potential targets for chemotherapy. The trehalose 6-phosphate synthase (TPS)/trehalose 6-phosphate phosphatase (TPP) pathway, also known as the OtsA/OtsB2 pathway, is the major pathway involved in the production of trehalose in Mycobacterium tuberculosis (Mtb). In addition, TPP is essential for Mtb survival. We describe the synthesis of α,α′-trehalose derivatives in the forms of the 6-phosphonic acid 4 (TMP), the 6-methylenephosphonic acid 5 (TEP), and the 6-N-phosphonamide 6 (TNP). These non-hydrolyzable substrate analogues of TPP were examined as inhibitors of Mtb, Mycobacterium lentiflavum (Mlt), and Mycobacterium triplex (Mtx) TPP. In all cases the compounds were most effective in inhibiting Mtx TPP, with TMP [IC₅₀=(288±32) μm ] acting most strongly, followed by TNP [IC₅₀=(421±24) μm ] and TEP [IC₅₀=(1959±261) μm ]. The results also indicate significant differences in the analogue binding profile when comparing Mtb TPP, Mlt TPP, and Mtx TPP homologues.     

卟啉与金属卟啉的光电导性能研究

以苯甲醛和吡咯为原料,丙酸和硝基苯为溶剂,合成了四苯基卟啉(TPP),收率达29.8%。TPP与金属ZnCo、Mn盐合成相应的金属卟啉配合物,收率>90%。用核磁和质谱对化合物结构进行了表征。紫外-可见吸收光谱分析结果表明,TPP有强的Soret吸收带和四个Q带,形成金属卟啉后,Q带减少至两个,且Soret带红移。X射线衍射光谱分析显示,TPP和四苯基金属卟啉粉末均有较高的结晶度。分别以这些卟啉化合物为电荷产生材料,制备了功能分离型双层光电导体,并对它们的光电导性能进行了研究。结果表明,四苯基锌、钴卟啉配合物的光敏性明显优于TPP,其光敏度(E2/3)分别为11和10lx·s。     

Chemical Speciation of Trace Zinc in Ordinary Portland Cement Using X-ray Absorption Fine Structure Analysis

Chemical change of trace zinc in ordinary portland cement (205.1 ppm) was investigated in hydration process using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Intensities of the peaks appearing at the same energy of ZnO in XANES spectra were decreased with cement hydration. The interatomic distances and the coordination numbers of the first and the second shells calculated from EXAFS spectra indicated that ZnO hydrolyzed to zincate ion [Zn(OH)₄]²⁻ with cement hydration keeping their fundamental structure of ZnO₄ tetrahedra.     

Transformations of ortho- and pyrophosphates with or without zinc in chemical solutions and major Indian soils

Studies on the formation and identification of the nature of reaction products formed with zinc and ortho- and pyrophosphate fertilizers were carried out in chemical solutions and in contrasting Indian soils having wide pH range from acidic to alkaline. Triammonium pyrophosphate (TPP), a constituent of the newly developed ammonium polyphosphate (APP) and diammonium orthophosphate (DAP), the only orthophosphate fertilizer manufactured and used in the country were taken for these studies. The reaction products (precipitates) formed in the solutions were isolated and identified through X-ray diffraction technique and chemical analysis, and those formed at the sites of fertilizer placement separated and identified only through X-ray diffraction technique. In the study with solutions ZnNH₄PO₄ (orthorhombic) was identified at all levels of Zn applications and at both concentrations of 0.1Mg and 1.0M DAP; whereas, Zn₃(NH₄)₂(P₂O₇)₂.2H₂O was observed only at the lower concentration (0.1 M) of TPP with Zn. Zinc was completely soluble at the higher concentration (1.0M) of TPP indicating the formation of a soluble complex, (NH₄)₆Zn(P₂O₇)₂.6H₂O. In soils, the reaction products obtained with band application of DAP alone and along with Zn fertilizers were CaHPO₄.2H₂O, Ca(NH₄)₂(HPO₄)₂.H₂O (dimorph B), MgNH₄PO₄.6H₂O (struvite), MgHPO₄.3H₂O, FePO₄.2H₂O (metastrengite, monoclinic), AlPO₄.2H₂O (orthorhombic), ZnNH₄PO₄ (orthorhombic) and Zn₃(PO₄)₂.4H₂O. The reaction products with TPP alone and with Zn were Ca(NH₄)₂P₂O₇.H₂O, Mg(NH₄)₂P₂O₇.4H₂O (monoclinic), FeH₂P₂O₇, Ca₂P₂O₇.2H₂O (monoclinic) and Zn(NH₄)₂P₂O₇.H₂O.