刺玫果总黄酮Zn2+络合物的制备及其体外抗氧化活性研究

探究刺玫果总黄酮Zn^2+络合物的制备工艺及其体外抗氧化活性。以黄酮转化率为指标,通过单因素实验与正交试验优化刺玫果总黄酮Zn^2+络合物的最佳制备工艺,并测定刺玫果总黄酮及其Zn2+络合物对·OH、O2-·、抗脂质体过氧化、ABTS+·的清除能力,评价其体外抗氧化活性。结果表明:刺玫果总黄酮Zn^2+络合物的最佳制备工艺为,氯化锌溶液14 mg/mL、总黄酮溶液8 mg/mL、体系pH=9,50℃恒温振荡3.0 h,离心收集沉淀物,即为刺玫果总黄酮Zn2+络合物,转化率为96.94%,收率为35.76%。Zn2+络合物对·OH、O2-·的清除能力及抗脂质体过氧化能力强于刺玫果总黄酮和VC溶液,对ABTS+·也具有良好的清除能力。因此,刺玫果总黄酮Zn2+络合物具有一定的抗氧化还原能力。

Structures and Photoluminescent Properties of Two Complexes Based on Dipyrido[3,2-a：2？,3？-c]phenazine and 2,4＇-Biphenyldicarboxylic Acid

ABSTRAC Two new complexes [Cd（2,4＇-bpdc）（DPPZ）]2n·n H2O（1） and [Zn（2,4＇-Hbpdc）2（DPPZ）]· H2O（DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, 2,4＇-H2bpdc = 2,4＇-biphenyldicarboxylic acid） have been hydrothermally synthesized. The structure of complex 1 was determined by single-crystal X-ray diffraction diffraction and further characterized by elemental analysis, IR spectrum, powder X-ray diffraction（XRD） and single-crystal X-ray diffraction. Complex 1 has 1D chains, which are further connected by π-π stacking interactions of neighbouring chains, generating a steady 3D supramolecular structure. Complex 2 shows the isolated mononuclear units, which are further extended to a 2D supramolecular layered structure through π-π stacking interactions and hydrogen bonds. Furthermore, complexes 1 and 2 exhibit green photoluminescent properties at room temperature.

基于水杨醛席夫碱锌配合物交联稳定化荧光聚合物胶束的合成及其对铜离子的荧光响应性

以S-十二烷基-S'-(α,α'-二甲基-α″-乙酸)-三硫代碳酸酯(DMAT)为链转移剂、2-羟基-5-乙烯基苯甲醛(HVB)为单体,利用可逆加成-断裂链转移自由基聚合法(RAFT)合成结构明确、数均相对分子质量可控的水杨醛聚合物(PHVB)。将PHVB直接地与单端胺基功能化聚乙二醇(m PEG-NH2)按n(—NH2group)/n(—CHO group)=0.50投料进行醛-胺缩合反应,获得接枝率为50%的两亲性接枝水杨醛席夫碱聚合物PHVB-graft-PEG。采用凝胶渗透色谱仪(GPC)和核磁共振氢谱(1H NMR)对合成的聚合物的数均相对分子质量和结构进行了确证。将PHVB-graft-PEG直接地分散于无水乙醇中,自组装形成以聚乙烯水杨醛席夫碱为核、聚乙二醇为壳的胶束,然后以所得胶束为微反应器,与Zn(OAc)2进行配位反应得到外壳为可溶性链段PEG,内核为发光水杨醛席夫碱锌配合物的PHVB-graft-PEG/Zn^(2+)交联稳定化胶束。通过紫外-可见分光光谱(UV-Vis)、荧光发射光谱(FLL)、动态光散射(DLS)和透射电子显微镜(TEM)分别对胶束的交联稳定化过程进行了表征。研究结果表明,经交联稳定化后,PHVB-graft-PEG/Zn^(2+)胶束在干燥后仍可在水和常见有机溶剂中再分散形成粒径大小约为100 nm、在约460 nm处发射出蓝光荧光的纳米粒子,并且可作为荧光传感器,在水溶液中对Cu^(2+)离子进行选择性识别,其荧光淬灭率与Cu^(2+)离子浓度(0~50μmol/L范围内)呈线性关系,最低检测下限至0.5μmol/L,而其它共存离子如Cd^(2+)、Mg^(2+)、Ni^(2+)、Pb^(2+)、Ca^(2+)、Hg^(2+)、Al3+、Mn^(2+)等对Cu^(2+)离子的荧光响应性没有干扰,即可实现对Cu^(2+)离子进行定量检测。

以三(2-氨基乙基)胺为核的PAMAM与Zn^(2+)的络合作用研究

以三(2-氨基乙基)胺为核,通过发散法合成了不同代数的树状聚酰胺胺(PAMAM),并利用FT-IR、1H NMR等技术对合成的产物进行表征,结果表明所合成产物的分子结构与理论结构相符。合成的PAM-AM具有大量的伯胺、叔胺和酰胺,可以作为Zn2+的络合剂。采用荧光分光光度法研究了PAMAM与Zn2+的络合作用,探讨了PAMAM的代数、Zn2+与PAMAM的摩尔比、溶液pH值、反应时间和温度对络合的影响。结果表明PAMAM的代数越高,所络合的Zn2+数目越多,且与理论值相符;随着Zn2+与PAMAM摩尔比的增加,络合形式发生变化;溶液pH值对络合体系有显著影响,强酸性条件下,PAMAM的伯胺和叔胺被质子化,H+取代Zn2+,Zn2+从络合体系中释放出来,这为PAMAM的循环利用提供了理论依据;另外,反应时间和温度对PAMAM与Zn2+的络合也有一定影响,延长反应时间和升高反应温度均使络合程度增加。

[Ru(bpy)_2tpphz]^(2+)与Zn^(2+)形成的双核配合物的荧光性质研究

The formation of heterobimetallic ruthenium?complex was investigated by absorption and emission spectra. As an intercalator of DNA, the luminescent monometallic ruthenium?complex [Ru(bpy)2tpphz]2+could coordinate with Zn2+to form the nonluminescent heterobimetallic complex [Ru(bpy)2(tpphz)Zn]4+. The emission intensity of complex decreased as increasing the amounts of Zn2+and the luminescence was almost lost at the ratio of / of 1. After binding to DNA, the peripheral coordination site on the tpphz ligand remained accessible for Zn2+, the coordination occurred from the oppsite side of helix with respect to intercalated [Ru(bpy)2tpphz]2+and the nonluminescent heterobimetallic complex was formed. On the other hand, the [Ru(bpy)2(tpphz)Zn]4+also bound to DNA by intercalation and situated the region of the intercalated [Ru(bpy)2tpphz]2+between the base pairs of DNA. The complex looked like a molecular nut (the Zn2+) and bolt (the [Ru(bpy)2tpphz]2+).

γ-Al_2O_3/SiO_2纳米颗粒混合体系表面的酸碱性质及其对重金属离子的吸附行为

运用电位滴定技术研究了γ-Al2O3/SiO2纳米颗粒混合体系的表面酸碱性质;依据滴定数据及表面配位理论恒电容模式,利用WinSGW软件计算得出了γ-Al2O3/SiO2纳米颗粒混合体系表面的酸碱反应平衡常数:≡XOH+H+≡XOH2+(lgK1=5.06±0.05);≡XOH≡XO-+H+(lgK2=-8.45±0.10);在此基础上研究了不同pH条件下重金属离子Cu2+,Pb2+,Zn2+在γ-Al2O3/SiO2纳米颗粒混合体系表面的吸附行为,并用WinSGW软件模拟得出了Cu2+,Pb2+,Zn2+在该混合悬浮液体系中的表面配位常数:≡XOH+M2+≡XOM++H+[lgK=-2.20,-1.72,-2.90(M=Cu,Pb,Zn)].

用双波长缔合光度法测定镀锌废水中的微量Zn^(2+)

在阿拉伯树胶存在下,在pH=5.5的NH4Ac-HAc缓冲溶液中,Zn2+与硫氰化钾和中性红(NR)反应生成稳定的离子缔合物[NR]4[Zn(SCN)6],使NR褪色,在462 nm处出现正吸收峰,575 nm处出现负吸收峰。选定测定波长为462 nm和575 nm,建立了一种测定微量Zn2+的新的双波长光度法。结果表明:锌含量在0～1.0μg/mL内符合比尔定律,表观摩尔吸光系数为5.72×104L/(mol.cm),本方法用于测定镀锌废水中微量Zn2+,结果与5-Br-DMPAP光度法相符,6次测定值的相对标准偏差小于4%,加标回收率为98.7%～101.8%。

DNA碱基(对)及其Zn^(2+)复合物对CO_2,N_2,H_2小分子的吸附

用M062X/6-31+G*方法探讨了腺嘌呤(A)、胸腺嘧啶(T)、鸟嘌呤(G)、胞嘧啶(C)及其碱基对(AT,GC)以及Zn2+复合物(AAA-Zn2+,AAT-Zn2+和GGC-Zn2+)对混合小分子H2,N2,CO2的吸附情况,系统研究了其相互作用模式及吸附强度,预测了常见混合气体分子与碱基(对)及复合物的吸附位置.研究表明,CO2倾向于以氢键的形式结合到碱基(对)的氨基氢或亚氨基氢上,而N2和H2分子则倾向于结合到这些碱基(对)的平面π电子上,以堆垛的形式存在.根据吸附强度大小,预测了由这些碱基为骨架合成的金属有机骨架(MOF)吸附材料对小分子的选择性吸附顺序为H2<N2<CO2.研究表明,以AT对结合金属Zn2+为节点的纯天然碱基对构成的MOF要比实验合成的AA碱基对与Zn2+结合的MOF具备更好的吸附和分离性能.

丙烯酸-马来酸酐共聚物络合超滤分离水溶液中Pb^(2+)和Zn^(2+)的实验研究

采用丙烯酸-马来酸酐共聚物(PMA)为络合剂,研究络合超滤技术对水溶液中Pb2+和Zn2+的分离效果、竞争络合效应以及外加盐对分离效果的影响。以两种金属离子截留率之差表示分离率,以单一金属离子溶液中离子截留率与混合溶液中该离子的截留率之差表示金属离子间的竞争强度。结果表明:随着PMA浓度增加,两种金属离子的分离率先增大后减小,当PMA浓度为200 mg/L时,分离率达到最大值,为54.47%。pH从2增加到6时,分离率先增大后减小,且在pH=4时达到最大,为71.34%。两种金属离子的竞争效应随pH及PMA浓度的增加先增强后减弱,在pH=5,PMA浓度为200 mg/L时,混合溶液中两种离子竞争效应最强。外加Na2SO4对分离率有较大影响,随着n(Na2SO4)增大分离率增加,随后基本保持不变,在n(Na2SO4)=0.06mol/L时,分离率达到最大值,为97.677%。加入Na2SO4减弱了Zn2+的竞争络合能力,有利于两种金属离子的分离。

Synthesis,Crystal Structure and Theoretical Calculations of a Zinc(Ⅱ) Coordination Polymer Assembled by Pyrazine-2,3-dicarboxylic Acid and Bis(imidazol) Ligands

A new metal-organic coordination polymer [Zn（pzdc）（mbix）]n·nH2O（H2pzdc = pyrazine-2,3- dicarboxylic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in monoclinic system, space group P21/n with a = 8.5519（6）, b = 14.8764（10）, c = 16.4108（11） A, β = 103.4520（10）o, V = 2030.5（2）A^3, C（20）H（18）N6O5Zn, Mr = 487.77, Dc = 1.596 g/cm^3, F（000） = 1000, Z = 4, μ（MoK α） = 1.257 mm^-1, the final R = 0.0260 and w R = 0.0706 for 3445 observed reflections（I 〉 2σ（I））. The structure of 1 exhibits a one-dimensional chain-like structure. In addition, natural bond orbital（NBO） analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program. The calculation results show obvious covalent interaction between the coordinated atoms and Zn（Ⅱ） ion.

Proton Transfer Mechanism of Alanine Induced by Zn^(2+): a Theoretical Study

In this paper, proton transfer mechanism of alanine induced by Zn2＋ was investiga- ted by the CCSD/6-31＋＋G＊＊//B3LYP/6-31＋＋G＊＊ method. Six neutral complexes and one ampho- teric complex were optimized, among which the amphoteric complex was the most stable with binding energy of 201.92 kcal·mol-1. In addition, the rotation of intramolecular single bond leads to the neutral configuration conversion, in which the rotation energy barriers of C–C single bonds are lower than 10.51 kcal·mol-1, and those of C–O single bonds range among 9.53~17.50 kcal·mol-1. On the other hand, the proton transfers among the carboxylic oxygen atoms can also result in the neutral configuration conversion, whose energy barriers of forward/back reaction are 53.90 and 32.46 kcal·mol-1, respectively. In detail, the proton transfers from carboxylic group to amino lead to their configuration conversion from neutral to amphoteric. Furthermore, under the catalysis of Zn2＋, there was no energy barrier in this reaction. The conversion route from the most stable neutral configuration Ⅱ to the most stable amphoteric configuration I was： Ⅱ→Ⅱ-Ⅲ→Ⅲ→Ⅲ-Ⅵ→Ⅵ→Ⅴ-Ⅵ→Ⅴ→Ⅰ-Ⅴ→Ⅰ,with the energy barrier to be 64.64 kcal·mol-1.

Thermal Behavior of Zn(Thr)SO_4·H_2O

Solid complex Zn(Thr)SO 4·H 2O was prepared in a water acetone system. Under linearly increasing temperature, the non isothermal kinetics and the decomposition mechanism of Zn(Thr)SO 4·H 2O were studied by means of thermogravimetry and IR spectrometry. The thermal decomposition processes of the complex could be divided into three stages. The non isothermal decomposition mechanism and the kinetics parameters of the ligand lost process were obtained from an analysis to the TG DTG curves at various heating rates of 5 0, 10 0, 15 0 and 20 0 K/min by two integral and three differential methods. The results show that the random nucleation and the subsequent growth mechanism ( n =3/2) controlled the ligand lost process, the corresponding activation energy E and pre exponential constant A are 139 96 kJ/mol and 10 11 32 s -1 , respectively. The empirical kinetics model equation was constructed.

鲢鱼源多肽锌的制备工艺对其抑菌活性的影响

研究了制备工艺中的主要因素对鲢鱼源多肽锌螯合物的抑菌活性影响。以抑菌圈直径为指标,探讨了酶解工艺(蛋白酶种类和酶解时间)和螯合工艺(螯合反应的pH、多肽与氯化锌的质量比、螯合反应的温度和时间)对多肽锌螯合物的抑菌活性影响。结果表明,酶法水解鲢鱼蛋白制备抑菌型多肽锌的最佳条件为风味蛋白酶酶解时间6h、螯合反应pH为6.0、多肽与氯化锌质量比为2:1、反应时间45min、温度30℃,得到的螯合物对大肠杆菌和金黄色葡萄球菌的抑菌圈直径分别为12.50mm和12.66mm,螯合物得率38.67%。因此,鲢鱼源多肽锌螯合物具有较好的抑菌活性,有望作为一种潜在的抗菌剂。