L—赖氨酸锌配合物结构的理论研究

采用量子化学半经验PM3方法,优化了L-赖氨酸锌配合物的几何结构,对L-赖氨酸锌配合物的结构、电子性质进行了分析,结果表明：计算结果与实验得到的晶体结构基本吻合,证实了L-赖氨酸锌配合物中Zn具有五配位结构,同时对体系的净电荷分布及前线轨道成分进行了分析。     

硫酸锌与L-α-氨基酸配合行为的相化学研究

锌是人体必需的微量元素之一,L－α－氨基酸是人体必需的氨基酸,是组成蛋白质的结构单元．α－氨基酸锌作为添加剂在药物、食品和化妆品中有广阔的应用前景［1.2］．有关氨基酸锌的合成方法前文［3］已述及．用相平衡方法研究锌盐与氨基酸的配合行为的相化学,可提供它们之间能否形成配合物,能形成几种计量比的配合物以及其相区大小和性质等信息,对新型配合物,特别是固液异成分化合物的合成具有指导意义．本文对ZnSO4与3种人体必需而非自生的L－Met,L－Phe和L－His在水中的相化学进行了研究,在相图指导下合成了新化合物并进行了…     

L—赖氨酸锌配合物中锌的五配位奇数结构研究

用化学方法合成了Ｌ－赖氨酸锌配合物,并对其晶体结构进行测定,结果发现锌作为中心离子的配位数为５,此配位数不同于已报道的４配位数和６配位数锌的结构形式,属奇数结构。     

4’－对二甲氨基苯基－2，2’：6’，2″－三联吡啶－锌配合物在含水乙醇介质中对磷酸根离子的高选择性识别研究

合成了一种－2,2’：6’,2″－三联吡啶衍生物,4＇-对二甲氨基苯基－2,2’：6’,2″-三联吡啶（L）,利用L与锌离子形成的稳定配合物（ZnL）．用紫外可见吸收光谱和荧光光谱研究了在无水乙醇和含水乙醇介质中各种阴离子对该配合物ZnL的吸收光谱和荧光发射光谱的影响,发现该配合物能在含水乙醇介质中选择性的识别磷酸根类离子。磷酸根、磷酸氢根与磷酸二氢根离子分别与ZnL配合物以1：1、2：1及2：1结合模式影响体系的吸收和荧光发射,ZnL配合物对磷酸根类离子的识别作用主要源于配合物多余的结合位点。     

天然及非天然氨基酸席夫碱锌配合物的合成与表征

氨基酸席夫碱及其金属配合物具有良好的抗菌、抗癌活性犤１,２犦,对其深入研究不仅对生物无机化学而且对医药均有重要意义。天然氨基酸席夫碱与过渡金属及稀土配合物的报道较多犤４～８犦,一些非天然氨基酸具有非常重要的生物功能,而非天然氨基酸及蛋氨酸席夫碱配合物报道较少犤９,１０犦,γ－氨基丁酸席夫碱配合物尚未见报道,也未见用X射线粉末衍射数据指标化来研究其晶体结构。锌是非常重要的必需微量元素,我们合成了β－丙氨酸、γ－氨基丁酸、DL－蛋氨酸水杨醛席夫碱与锌?的三种新配合物ZnL·nH２O（L＝sal－β－ala、sal－…     

5-氟尿嘧啶卟啉锰/锌配合物的合成、光电性质及抗癌活性

合成了新型5-氟尿嘧啶修饰的自由卟啉5-(2-(5-氟尿嘧啶-3-基)乙氧基苯基)-10,15,20-三苯基卟啉(L)及其锰配合物(MnL)和锌配合物(ZnL)。通过紫外-可见光谱、红外光谱、核磁共振氢谱及高分辨质谱等手段进行了结构表征。研究了它们的荧光性质和电化学性质;应用标准磺酰罗丹明B法(SRB法)测试了目标化合物对人肺癌细胞株A549、人肝癌细胞株Bel-7402和人结肠癌细胞株HCT-8生长的抑制活性。结果表明:相同实验条件下,不同金属离子对配合物的荧光强度存在较大影响:锌配合物具有荧光猝灭的性质,而锰配合物未能观察到明显的荧光发射光谱;与自由卟啉和锌配合物相比,锰配合物除卟啉环发生氧化还原反应外,Mn~(2+)自身也发生了氧化还原反应;抗癌活性测试显示锰配合物较其他2种化合物有较好的抗癌活性。     

甲硫氨酸席夫碱铜、锌、钴配合物合成及抗O·-2性能

合成了邻香草醛甲硫氨酸席夫碱及其铜、锌、钴等配合物,通过元素分析,摩尔电导、红外光谱、电子光谱、热分析及电子顺磁共振等手段对它们进行了表征,并并用ＥＰＲ法探讨了它们对Ｏ＾．－２的清除作用,结果表明,配体与配合物均具有抗Ｏ＾．－２性能,配合物清除能力比配体强,其中铜和钴配合物清除能力最强。     

聚氧乙烯—高氯酸锂配合笺电致变色光窗的研究

以ＷＯ３为电致变色层，ＮｉＯｘ为离子贮存层，具有较好透光性的氧亚甲基连接聚氧乙烯／ＬｉＣｌＯ４配合物为电解质制备了全固态电致变色光窗。电色窗在７００－９００ｎｍ之辜的调制深度超过５０％。     

吡啶甲酸铬衍生物的合成、安全性及降糖活性

合成了4种新型吡啶甲酸铬衍生物并通过单晶衍射、电喷雾质谱、元素分析、电导率及红外光谱等手段对其结构进行了表征。通过循环伏安法研究了配体对配合物氧化还原活性的影响,通过Fenton-like反应观察了配合物诱发产生自由基的程度,发现其中有3个配合物诱发产生的自由基少于市售产品吡啶甲酸铬Cr(pic)3。动物活体实验表明,高剂量配合物3不会对小鼠脏器造成明显损伤,低剂量喂食能降低糖尿病小鼠的空腹血糖及低密度脂蛋白,其效果优于Cr(pic)3。     

示波极谱法直接测定锌电解液中钴的研究

研究了pH5 0的HAc -NaAc介质中 ,存在大量锌时 ,钴 -丁二酮肟 -柠檬酸钠 -氯化铵体系灵敏的配合物吸附波。峰电位 -0 .93V ,在0 0001～0 .1mg/L范围内钴质量浓度与峰电流呈线性关系 ,检出限达8 5×10-10mol/L。方法无须预处理可直接测定电解锌料液中微量钴。对电活性配合物的组成、极谱波性质和电极过程机理也作了研究     

L-赖氨酸锌兔体内生物利用度研究

用原子吸收分光光度法和氨基酸自动分析仪法分别测定兔血清锌浓度和血清L-赖氨酸含量．结果表明．L-赖氨酸锌中锌的相对生物利用度明显优于硫酸锌．而其中的L-赖氨酸的相对生物利用度与L-赖氨酸组比较无明显差异．     

锌镀层P—Mo—V三元杂多酸盐配合物膜的性能和结构

在锌镀层材料表面,磷钼矾(P-Mo-V)三元杂多酸盐具有较好的配位能力,获得了多种具有金属光泽的不溶性彩色配合物膜,有良好的耐蚀性能和装饰效果。加速化学和电化学腐蚀实验(LSV)研究结果表明,Na6(PMo9V3O40).xH2O与锌镀层材料表面反应时,形成的一种新型金黄色杂多酸盐配合物膜(P-Mo-V金黄色配合物膜)的耐蚀性最佳。XPS和AES分析表明,P-Mo-V金黄色配合物膜层中Mo在膜表面的价态为 6,而在膜内层则以 6、 4价共存,其它元素的价态分别为Zn( 2),P( 5),V( 5),从其AES深度剥蚀曲线的组成恒定区求得膜的组成分别为Zn 19.7%,Mo 29.3%,V 21.2%,P 16.1%,O 13.5%;膜层的厚度约为160 nm。     

A zinc carboxylate network containing metal sites with low coordination numbers

A bifunctional m-terphenyl, 2,6-diphenyl-1,4-dibenzoic acid (Ph2BDC), was synthesized and used in the preparation of a 2-D metal-organic coordination polymer. The steric hindrance of the bulky bifunctional linker forces low coordination at the Lewis-acidic zinc center. A zinc carboxylate dimer was prepared as a model compound to examine the unusual tricoordinate geometry at the metal site.     

Switching from bonding to nonbonding: temperature-dependent metal coordination in a zinc(II) sulfadiazine complex

The metal coordination in the mononuclear complex diamminebis(sulfadiazine)zinc shows a unique temperature dependence: High-resolution diffraction data prove that the coordination is almost tetrahedral at 100 K, whereas a fifth longer interaction becomes relevant at 200 K. The change in the geometry is fully reversible and is also reflected in the charge density of the compound.     

Coordination properties of zinc 5,15-di(<Emphasis Type="Italic">ortho</Emphasis>-aminophenyl)octaalkylporphyrin in reactions with mono- an dibasic nitrogen bases

The coordination properties of zinc 5,15-di(ortho-aminophenyl)octaalkylporphyrin in reactions with mono- and dibasic nitrogen bases in benzene are studied by means of computational modeling and spectrophotometric titration. The stability of molecular zinc porphyrinate complexes in solution is estimated and their structure is determined. The correlation between the coordination properties of the compound under investigation and electronic and conformational factors of the macrocycle is established. The base nature is shown to affect the stability of zinc porphyrinate complexes. The correlations between the calculated σ bond energy of the zinc atom with the nitrogen atom of the base (E _b) and the equilibrium constant of the axial coordination reaction are obtained. It is demonstrated that the reaction is accompanied by an increase in steric hindrance and a change in the type of deformation of the porphyrin ligand.     

The identification of new ATAD2 bromodomain inhibitors: the application of combined ligand and structure-based virtual screening

Ligand-based virtual screening (LBVS) and structure-based virtual screening (SBVS) approaches were used to identify new inhibitors for ATAD2 bromodomain. The LBVS approach was used to search 23,129,083 clean compounds to identify compounds similar to an active compound with reported pIC₅₀ equal to 7.2. Based on LBVS results, 19 compounds were selected. To perform SBVS, by applying nine filters on 23,129,083 clean compounds, 1,057,060 compounds were selected. After performing SBVS on these selected compounds with idock software, 16 compounds with the lowest binding energies were selected. More accurate molecular docking analysis was performed on these 35 selected compounds by using iGEMDOCK software and six of them with the lowest binding energies were selected as hit compounds. These compounds were zinc36647229, zinc77969074, zinc13637358, zinc77971540, zinc12991296 and zinc19374204.     

New semiconducting coordination polymers from zinc sulfide clusters and chains

Two new semiconducting zinc coordination polymers, Zn(8)S(SPh)(14)(bpy) (1) and Zn(2)(SPh)(4)(bpy) (2), have been synthesized by a dual-ligand approach. Single-crystal structural analyses indicate that compound 1 has a helical-chain structure with P1 clusters bridging with bipyridyl (bpy) ligands and compound 2 possesses a layered structure with zinc sulfide chains cross-linked with bpy ligands. The diffuse-reflectance spectra reveal that the band gaps of the two compounds are 2.41 eV for 1 and 2.56 eV for 2.     

High-dimensional zinc porphyrin nanoframeworks as efficient radiosensitizers for cervical cancer

Radiotherapy is widely used clinically, but the toxic and side effects of nonselective killing of high-energy radiation limit its application. Finding biocompatible materials to assemble radiotherapy sensitizers and studying their sensitization patterns are of great significance for the clinical application. Here, biocompatible zinc porphyrin was chosen as sub-unit to construct various dimensional coordination frameworks. By employing top-down approach, suitable nanoframeworks with various dimensional zinc porphyrin were synthesized as radiosensitizers. The experimental data showed that high-dimensional zinc porphyrin nanoframeworks exhibit higher X-ray response performance.     

新型单取代两亲性酞菁锌的制备及其光动力活性研究

设计并制备了一种组成和结构单一的新型两亲性酞菁锌光敏剂. 采用固相合成法合成出2-单羧基取代酞菁锌, 并使之与五聚赖氨酸偶联成五聚赖氨酸2-羰基酞菁锌. 综合运用各种分析及光谱方法对所得化合物进行表征和确认. 研究了在光照下五聚赖氨酸2-羰基酞菁锌对3种肿瘤细胞(人源肝癌细胞Bel7402、人源胃癌细胞BGC823和人源白血病细胞K562) 与一种正常细胞(人源胚肺成纤维细胞HELF)的杀灭活性. 该光敏剂不仅克服了酞菁锌在水中溶解度低的问题, 且因所偶联的五聚赖氨酸对肿瘤细胞有靶向作用, 具有较高的杀灭肿瘤细胞活性.     

Quantum dot probes for bacteria distinguish Escherichia coli mutants and permit in vivo imaging

Fluorescent quantum dots coated with zinc(ii)-dipicolylamine coordination complexes can selectively stain a rough Escherichia coli mutant that lacks an O-antigen element and permit optical detection in a living mouse leg infection model.