Synthesis and characterization of multifunctional silica core-shell nanocomposites with magnetic and fluorescent functionalities

Multifunctional core-shell nanocomposites with a magnetic core and a silica shell doped with lanthanide chelate have been prepared by a simple method. First, citric acid-modified magnetite nanoparticles were synthesized by a chemical coprecipitation method. Then the magnetite nanoparticles were coated with silica shells doped with terbium (Tb³⁺) complex by a modified Stöber method based on hydrolyzing and condensation of tetraethyl orthosilicate (TEOS) and a silane precursor. These multifunctional nanocomposites are potentially useful in a variety of biological areas such as bio-imaging, bio-labeling and bioassays because they can be simultaneously manipulated with an external magnetic field and exhibit unique phosphorescence properties.     

对-叔丁基杯[8]芳烃键合硅胶制备及其毛细管电色谱性能研究

以γ-(环氧丙氧)丙基键合硅胶为前体,于硅胶表面键合环氧基,在催化剂存在下以杯芳烃钠盐开环制备杯芳烃键合硅胶固定相.该方法反应条件温和,适用性强.将这个新方法首次用于制备对-叔丁基杯[8]芳烃电色谱键合固定相(C8BS),采用加压电色谱初步评价其电色谱性能.研究结果表明,C8BS电渗流(Electrosmoticflow,EOF)较小,但通过控制键合反应及使用压力辅助电色谱可部分弥补上述不足.该固定相的EOF受流动相pH影响小(pH=3-8),同时大环配体屏蔽效应能有效地克服硅羟基引起的碱性化合物拖尾现象,这对电色谱分离具有重要意义.通过分步封尾研究EOF的来源发现,杯芳烃酚羟基对EOF有弱的贡献,这与报道的杯芳烃涂层具有径向电渗流调控能力相一致.     

蒙药新-Ⅱ中微量硒的测定

采用硒 -硫氰酸钾 -罗丹明 B-明胶 - OP体系分光光度法测定蒙药新 - 中微量硒。其含量为 6 .6—7.3μg· g-1 ,回收率为 94 %— 95 %。     

天然磷脂的色谱法分离、纯化研究进展

天然磷脂是一类含磷酸根的类脂化合物的总称,在医药学、营养学、化妆品和生命科学领域等有重要的应用价值。本文综述了不同原料样品中磷脂种类和其各分子的色谱法分离、纯化。着重讨论高效液相色谱法分离技术及其影响因素。最后概述了有助于提高分离选择性、检测灵敏度的化学衍生化方法。     

Increasing charge while preserving noncovalent protein complexes for ESI-MS

Increased multiple charging of native proteins and noncovalent protein complexes is observed in electrospray ionization (ESI) mass spectra obtained from nondenaturing protein solutions containing up to 1% (vol/vol) m-nitrobenzyl alcohol (m-NBA). The increases in charge ranged from 8% for the 690 kDa α₇β₇β₇α₇ 20S proteasome complex to 48% additional charge for the zinc-bound 29 kDa carbonic anhydrase-II protein. No dissociation of the noncovalently bound ligands/subunits was observed upon the addition of m-NBA. It is not clear if the enhanced charging is related to altered surface tension as proposed in the “supercharging” model of Iavarone and Williams (Iavarone, A. T.; Williams, E. R. J. Am. Chem. Soc. 2003, 125, 2319–2327). However, more highly charged noncovalent protein complexes have utility in relaxing slightly the mass-to-charge (m/z) requirements of the mass spectrometer for detection and will be effective for enhancing the efficiency for tandem mass spectrometry studies of protein complexes.     

Homogeneous and heterogeneous olefin epoxidation catalyzed by a binuclear Mn(II)Mn(III) complex

The synthesis and characterization of a binuclear carboxylated bridged manganese complex containing the heptadentate ligand N,N′-bis(2-hydroxybenzyl)-N,N′-bis(2-methylpyridyl)-2-ol-1,3-propanediamine (H₃bbppnol) is reported. This complex was characterized by elemental analysis; infrared, electronic (UV–vis) and EPR spectroscopy; and conductivity measurements. The complex was immobilized on silica by either adsorption or entrapment via a sol–gel route. The obtained solids were characterized by thermogravimetric analyses (TG and DSC), UV–vis and infrared spectroscopy, and X-ray diffraction. The catalytic performance of the binuclear manganese complex in epoxidation reactions was evaluated for both homogeneous and heterogeneous systems. The catalytic investigation revealed that the complex performs well as an epoxidation catalyst for the substrates cyclohexene (26–39%) and cyclooctene (29–74%). The solids containing the immobilized complex can be recovered from the reaction medium and reused, maintaining good catalytic activity.     

Immobilization of anionic iron(III) porphyrins into ordered macroporous layered double hydroxides and investigation of catalytic activity in oxidation reactions

The first generation anionic iron(III) porphyrin [Fe(TSPP)] and the second generation anionic complexes [Fe(TDFSPP)], [Fe(TCFSPP)], and [Fe(TDCSPP)] were immobilized into three-dimensionally macroporous layered double hydroxide (3DM-LDH), using the direct reconstruction of 3DM-LDH from macroporous mixed oxides MOX or the anionic exchange on DDS intercalated 3DM-LDH. The macroporous layered double hydroxides were obtained at the surface of nanometric polystyrene spheres, which were synthesized by an inverse opal method. Polystyrene was removed after calcination in oxidizing atmosphere, nanostructured mixed oxides (3DM-MOX) were obtained, which after reconstruction give origin to macroporous layered double hydroxide (3DM-LDH). Following metalloporphyrin immobilization, the resulting materials were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), UV–vis (glycerin mull) spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FTIR), and electron paramagnetic resonance (EPR). Results revealed that the complexes are either immobilized at the surface of the macroporous layered double hydroxide or intercalated between the layers, displacing some dodecylsufate anions. The obtained materials were investigated as catalysts for oxidation reactions, to find out whether they function as cytochrome P-450 models.     

RNA unrestrained molecular dynamics ensemble improves agreement with experimental NMR data compared to single static structure: a test case

Nuclear magnetic resonance (NMR) provides structural and dynamic information reflecting an average, often non-linear, of multiple solution-state conformations. Therefore, a single optimized structure derived from NMR refinement may be misleading if the NMR data actually result from averaging of distinct conformers. It is hypothesized that a conformational ensemble generated by a valid molecular dynamics (MD) simulation should be able to improve agreement with the NMR data set compared with the single optimized starting structure. Using a model system consisting of two sequence-related self-complementary ribonucleotide octamers for which NMR data was available, 0.3 ns particle mesh Ewald MD simulations were performed in the AMBER force field in the presence of explicit water and counterions. Agreement of the averaged properties of the molecular dynamics ensembles with NMR data such as homonuclear proton nuclear Overhauser effect (NOE)-based distance constraints, homonuclear proton and heteronuclear ¹H–³¹P coupling constant (J) data, and qualitative NMR information on hydrogen bond occupancy, was systematically assessed. Despite the short length of the simulation, the ensemble generated from it agreed with the NMR experimental constraints more completely than the single optimized NMR structure. This suggests that short unrestrained MD simulations may be of utility in interpreting NMR results. As expected, a 0.5 ns simulation utilizing a distance dependent dielectric did not improve agreement with the NMR data, consistent with its inferior exploration of conformational space as assessed by 2-D RMSD plots. Thus, ability to rapidly improve agreement with NMR constraints may be a sensitive diagnostic of the MD methods themselves.     

基于集合卡尔曼变换的东中国海声学 敏感区判定方法*

为改善海洋与水声环境预报质量,针对常规观测成本高、资料利用率低等问题,将适应性观测方法应用于海洋声学领域。结合海洋-声学耦合模式与集合卡尔曼转换敏感区诊断方法,以东中国海宫古海峡北部区域为验证区,计算并分析不同条件下海洋环境敏感区与声学敏感区分布,通过观测系统模拟试验验证适应性观测对验证区预报的提升效果。结果表明,两种敏感区位置随时间间隔增加均向验证区上游移动,海洋环境敏感区相比于声学敏感区分布更为集中,且平移特征更明显;对海洋环境敏感区和声学敏感区添加适应性观测均能提升海洋与水声环境的预报质量,提升效果随时间间隔增加而减小,在某种类型敏感区的适应性观测对相对应参数的预报质量提升效果优于对其他类型敏感区进行观测的效果。     

Imaging and manipulation of biological structures with the AFM

Many biologists have dreamt of physically touching and manipulating the biomolecules they were investigating. With the invention of the atomic force microscope (AFM), this dream has come true. Here, recent applications of the AFM to image and to manipulate biological systems at the nanometer scale are reviewed. Macromolecular biological assemblies as well as individual biomolecules can be subjected to controlled nanomanipulation. Examples of AFM application in imaging and nanomanipulation include the extraction of chromosomal DNA for genetic analysis, the disruption of antibody--antigen bonds, the dissection of biological membranes, the nanodissection of protein complexes, and the controlled modulation of protein conformations. Also reviewed is the novel combination of single molecule imaging and force spectroscopy which allows biomolecules to be imaged, and inter- and intramolecular forces to be measured. Future application of these nanotechniques will reveal new information on the structure, function and assembly of biomolecules.