Reversible DNA condensation induced by a tetranuclear nickel(II) complex

DNA condensing agents play a critical role in gene therapy. A tetranuclear nickel(II) complex, [Ni^II₄(L?2H)(H₂O)₆(CH₃CH₂OH)₂] ? 6NO₃ (L=3,3',5,5'‐tetrakis{[(2‐hydroxyethyl)(pyridin‐2‐ylmethyl)amino]methyl}biphenyl‐4,4'‐diol), has been synthesized as a nonviral vector to induce DNA condensation. X‐ray crystallographic data indicate that the complex crystallizes in the monoclinic system with space group P2₁/n, a=10.291(9), b=24.15(2), c=13.896(11) Å, and β=98.175(13)°. The DNA condensation induced by the complex has been investigated by means of UV/Vis spectroscopy, fluorescence spectroscopy, circular dichroism spectroscopy, dynamic light scattering, atomic force microscopy, gel electrophoresis assay, and zeta potential analysis. The complex interacts strongly with DNA through electrostatic attraction and induces its condensation into globular nanoparticles at low concentration. The release of DNA from its compact state has been achieved using the chelator ethylenediaminetetraacetic acid (EDTA) for the first time. Other essential properties, such as DNA cleavage inactivity and biocompatibility, have also been examined in vitro. In general, the complex satisfies the requirements of a gene vector in all of these respects.     

Microspheres of Mixed Proteins

This paper describes the synthesis of mixed proteinaceous microspheres (MPMs) by the sonochemical method. The current fundamental research follows the research of Suslick and co‐workers who have developed a method by which high‐intensity ultrasound is used to make aqueous suspensions of proteinaceous microcapsules filled with water‐insoluble liquids. 1 By using high‐intensity ultrasound, we have synthesized microspheres made of a few different proteins. The three proteins used in the current experiments are bovine serum albumin (BSA), green fluorescent protein (GFP), and cyan fluorescent protein–glucose binding protein–yellow fluorescent fused protein (CFP‐GBP‐YFP). The two synthesized microspheres made of mixed proteins are BSA‐GFP and BSA‐(CFP‐GBP‐YFP). This paper presents the characterization of the sonochemically produced microspheres of mixed proteins. It also provides an estimate of the efficiency of the sonochemical process in converting the native proteins to microspheres.     

AT‐Specific DNA Binding of Binuclear Ruthenium Complexes at the Border of Threading Intercalation

The binuclear ruthenium complex [μ‐bidppz(phen)₄Ru₂]⁴⁺ has been extensively studied since the discovery of its unusual threading intercalation interaction with DNA, a binding mode with extremely slow binding and dissociation kinetics. The complex has been shown to be selective towards long stretches of alternating AT base pairs, which makes it interesting, for example, as a model compound for anti‐malaria drugs due to the high AT content of the genome of the malaria parasite P. falciparum. We have investigated the effect of bridging ligand structure on threading intercalation ability and found that length and rigidity as well as the size of the intercalated ring system are all factors that affect the rate and selectivity of the threading intercalation. In particular, we discovered a new DNA‐threading compound, [μ‐dppzip(phen)₄Ru₂]⁴⁺, which appears to be just at the border of being capable of threading intercalation and displays even greater selectivity for AT‐DNA than the parent compound, [μ‐bidppz(phen)₄Ru₂]⁴⁺.     

黄酮类化合物结构修饰及抗肿瘤活性研究进展

我国天然药物和中药资源丰富,种类繁多,可作为先导化合物进行修饰以提高可成药性。其中,黄酮类化合物是自然界中一种常见的天然多酚类化合物,在抗肿瘤方面具有其独特的生物活性;对其进行结构修饰与改造,可提高黄酮类化合物的生物利用度和抗肿瘤活性。本文通过查阅并整理近几年国内外的黄酮类化合物的相关文献,对黄酮类化合物的母核位点进行结构修饰与改造所得的101个黄酮类衍生物及其抗肿瘤活性及作用机制进行综述,同时讨论了构效关系,以期为黄酮类衍生物的结构修饰和抗肿瘤研究提供参考和帮助。     

ZnCl2改性离子交换树脂的制备及其催化乙醇和乙酸酯化反应性能

 采用离子交换法制备了 ZnCl2 改性的阳离子交换树脂催化剂, 考察了 ZnCl2 浓度、离子交换时间和溶剂等对催化剂催化乙酸和乙醇微波酯化反应性能的影响. 结果表明, 以去离子水为溶剂, 以 0.15%ZnCl2 溶液进行离子交换 30 h, 所得催化剂的性能较好. 采用酸碱滴定法、紫外-可见光谱、傅里叶变换红外光谱、扫描电镜和 N2 吸附脱附等手段对催化剂进行了表征. 结果表明, 改性后的催化剂 H+交换量约为原来的 1.5 倍, 表面酸强度增加; 树脂骨架结构变化不大; 紫外吸收峰发生蓝移, 吸收强度减小; 比表面积略有减小; 催化剂在含水体系中表现出较高的催化活性, 且重复使用性能大大提高.     

钼硫碘纳米线结构特性和化学改性的理论研究

 采用第一性原理密度泛函理论研究了纳米线结构的钼硫碘材料. 结构的理论模拟结果显示, 钼硫碘纳米线机械性能很高, 且其形变过程中显示出一种特殊的磁滞现象. 形成能、投影态密度以及电荷密度的计算结果显示, 使用电负性接近硫的碳元素可对钼硫碘纳米线化学改性同时不失去其良好的结构性能和电子性能. 该结果为化学改性钼硫碘纳米线材料应用于催化提供了依据. 这些钼硫碘纳米线材料将在纳米电子学、纳米机械学、催化、纳米限域等研究中有潜在应用.     

微波辐照2,6-二(2′-咪唑啉-2′-基)吡啶的合成及其与DNA的相互作用

在微波辐射和无催化剂条件下,由吡啶-2,6-二甲酸与乙二胺反应合成了2,6-二(2′-咪唑啉-2′-基)吡啶,并用红外光谱、质谱、核磁共振、熔点分析测试技术对化合物的组成和结构进行了分析与表征。考察了反应溶剂、反应物比及微波辐射功率。结果表明,不同溶剂对反应产物和副产物的比例有明显影响,最佳溶剂为乙二醇,最佳反应条件为:原料摩尔比1:2.7,微波功率450W,辐射时间65min,温度130℃,总收率71.2%。通过紫外吸收光谱和黏度测定了其与DNA的相互作用,测得键合常数Kb=(9.60±0.05)×104L/mol,较常见的键合常数小。推测化合物与DNA可能是以氢键作用与DNA沟面结合。     

胆固醇修饰富勒烯/γ-环糊精包结复合物的生物活性

采用Bingel-Hirsch反应合成了胆固醇修饰的富勒烯(CHL-C60), 通过核磁共振(NMR)、质谱(MS)、元素分析对CHL-C60的化学结构进行了表征. γ-环糊精(γ-CD)对甾环具有较强的包结能力, 能够与CHL-C60形成包结复合物(CHL-C60/γ-CD), 从而有效提高CHL-C60的水溶性. 紫外-可见吸收光谱和荧光光谱研究结果表明, CHL-C60能够从γ-CD的疏水空腔中解离出来, 与人血清白蛋白(HSA)及牛血清白蛋白(BSA)形成稳定的复合体, 其结合常数分别为5.73×104和7.05×104 L·moL-1. 无氧条件下, CHL-C60/γ-CD通过光诱导电子转移作用断裂pBR322质粒脱氧核糖核酸(DNA), 其效率可达60.5%.     

基于蓝黄磷光二元互补色的高效聚合物白光器件

研究了基于互补色的高效聚合物白光器件,双色材料包括蓝绿光材料双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱(Firpic)和黄光材料三[3-(2,6-二甲基苯氧基)-6-(2-噻吩基)-哒嗪]铱(Fs-1),器件结构为ITO/PEDOT(40 nm)/PVK:OXD-7:Firpic:Fs-1(80 nm)/Ba(4 nm)/Al(120 nm).当发光层材料PVK∶OXD-7∶Firpic∶Fs-1质量比为63∶27∶10∶0.25时,用溶液加工方法得到高效白光器件,此时CIE色坐标为(0.30,0.39),最大电流效率为10.8 cd.A-1,亮度可达到4200 cd.m-2.在此基础上,引入水溶性电子注入材料聚[9,9-二(3′-N,N-二甲基胺基丙基-2,7-芴-2,7-交-(9,9-二辛基芴)](PFN)修饰阴极界面,使载流子注入和传输更平衡,当阴极为PFN(20 nm)/Al(120 nm)时,电流效率获得显著改善,达到13.1 cd.A-1,此时电流密度为4.9 mA.cm-2,亮度可达到6096 cd.m-2,白光器件的色坐标为(0.33,0.39),同时发光光谱稳定.另外通过电致发光(EL)、光致发光(PL)光谱及能级结构图分析了载流子俘获和能量转移在发光中的作用.     

检测痕量Hg~(2+)的DNA电化学生物传感器

通过自组装方法将修饰有二茂铁基团的富T序列DNA分子(DNA-Fc)固定在金电极表面,得到了一种基于DNA修饰电极的电化学汞离子(Hg2+)传感器.当溶液中有Hg2+存在时,Hg2+可与修饰电极上DNA的T碱基发生较强的特异结合,形成T-Hg2+-T发卡结构,使DNA分子构象发生改变,其末端具有电化学活性的二茂铁基团远离电极表面,电化学响应随之发生变化.示差脉冲伏安法(DPV)结果显示:DNA末端二茂铁基团的还原峰在0.26V(vs饱和甘汞电极(SCE))附近,峰电流随溶液中Hg2+浓度的增加而降低;Hg2+浓度范围在0.1nmol·L-1-1μmol·L-1时,电流相对变化率与Hg2+浓度的对数呈现良好的线性关系.该修饰电极对Hg2+的检测限为0.1nmol·L-1,可作为痕量Hg2+检测的电化学生物传感器.干扰实验也表明,该传感器对Hg2+具有良好的特异性与灵敏度.