超临界流体萃取-胶束电动毛细管色谱法分离测定大黄中蒽醌类组分的含量

采用ＳＴＥ－ＭＥＣＣ法分离测定大黄中的芦荟大黄素，大黄素和大黄酸。萃取条件为压 力４１．４ＭＰａ，温度５０℃，改性剂量０．４ｍＬ。被测组分在１０ｍｉｎ得到全部分离。本法准确、简 便、快速、结果令人满意。     

Solid-phase extraction of iron(III) with an ion-imprinted functionalized silica gel sorbent prepared by a surface imprinting technique

A new Fe(III)-imprinted amino-functionalized silica gel sorbent was prepared by a surface imprinting technique for selective solid-phase extraction (SPE) of Fe(III) prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Compared with non-imprinted polymer particles, the ion-imprinted polymers (IIPs) had higher selectivity and adsorption capacity for Fe(III). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Fe(III) was 25.21 and 5.10 mg g⁻¹, respectively. The largest selectivity coefficient of the Fe(III)-imprinted sorbent for Fe(III) in the presence of Cr(III) was over 450. The relatively selective factor (α_r) values of Fe(III)/Cr(III) were 49.9 and 42.4, which were greater than 1. The distribution ratio (D) values of Fe(III)-imprinted polymers for Fe(III) were greatly larger than that for Cr(III). The detection limit (3σ) was 0.34 μg L⁻¹. The relative standard deviation of the method was 1.50% for eight replicate determinations. The method was validated by analyzing two certified reference materials (GBW 08301 and GBW 08303), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace iron in plants and water samples with satisfactory results.     

Icosahedral gold cage clusters: M@Au12- (M=V, Nb, and Ta)

We report the observation and characterization of a series of stable bimetallic 18-valence-electron clusters containing a highly symmetric 12-atom icosahedral Au cage with an encapsulated central heteroatom of Group VB transition metals, M@Au(12) (-) (M=V,Nb,Ta). Electronic and structural properties of these clusters were probed by anion photoelectron spectroscopy and theoretical calculations. Characteristics of the M@Au(12) (-) species include their remarkably high binding energies and relatively simple spectral features, which reflect their high symmetry and stability. The adiabatic electronic binding energies of M@Au(12) (-) were measured to be 3.70+/-0.03, 3.77+/-0.03, and 3.76+/-0.03 eV for M=V, Nb, and Ta, respectively. Comparison of density-functional calculations with experimental data established the highly symmetric icosahedral structures for the 18-electron cluster anions, which may be promising building blocks for cluster-assembled nanomaterials in the form of stoichiometric [M@Au(12) (-)]X(+) salts.     

光纤生物传感器用于核酸的特异性检测

为了利用光纤传感器实现对细菌核酸分子的特异性和相对快速检测，我们使用直径1mm的石英光纤和635nm激光二极管，利用倏逝波原理制作了光纤生物传感器。光纤经过处理后产生醛基化基团，然后与核酸分子进行共价结合。通过3个实验来验证传感器的特异性和灵敏度。蒌光素溶液直接检测，使用互补模式寡核苷酸分子（25mer)进行核酸杂交模式实验和设计嗜肺军团菌一段特异性探针一 光标记嗜肺军团菌染色体DNA杂交。结果表明：光纤检测荧光素的灵敏度可达0.01mmol/L，而生物芯片扫描仪最低可检测到1nmol/L的荧光素；模式寡 核苷酸杂交表明：光纤传感器可以特异地检出目的核酸分子，灵敏度可达纳克级水平；染色体杂交结果显示在正常检测浓度下，光纤检测军团菌之信噪比达到了6：1，同时具有较好的特异性。检测时间约需要3－4h。我们构建的光纤生物传感器可以用于核酸分子的特异性检测，并且具有较好的灵敏度，对光纤表面修饰、样品处理和杂交过程的优化可望使之应用于实际标本的检测。     

Recognition of single nucleotide polymorphisms using scanning potential hairpin denaturation

Conventional single nucleotide polymorphism (SNP) assays, which based their detection on the stringency or temperature of the washing buffers, have encountered difficulties to distinguish a single base pair mismatch from a perfect match. In this study, scanning potential hairpin denaturation (SPHD) has been developed to detect SNP in a sensitive and reliable manner. Combined with hairpin oligonucleotide probes, scanning surface electric potential was used to induce a dissociation of double-stranded DNA around a unique "melting potential" (Vm), and it generated a high-contrast SNP recognition signal. A 21 base pair p53 gene segment was used to test this novel method. A single nucleotide mismatch to the hairpin probes caused an average of 400-800 mV difference in melting potential against the perfect match, while the error of this assay was lower than 20 mV. Experiments demonstrated that the hairpin stem was critical to the method. The concept of scanning potential hairpin denaturation could also be used extensively in different areas of nucleotide hybridization based assays.     

高多孔度多孔硅自支撑膜的制备与表征

发光多孔硅由于在光电子学方面的应用前景而引起人们极大的关注[1]．最近多孔硅发光二极管的研究方面取得了重大进展[2]。但是，有关多孔硅的发光机制仍然存在着争论[1，3，4]，利由于消除了单晶硅衬底的影响，对脱离了硅衬底的多孔硅自支撑膜能够进行普通多孔硅所不能进行的一     

An extended two‐dimensional copper–molybdate compound with mixed dicarboxyl and organodiamine ligands

The title complex, poly[di‐μ₃‐oxo‐hepta‐μ₂‐oxo‐tetra­oxo­bis(1,10‐phenanthroline)‐μ₄‐terephthalato‐dicopper(II)­tetra­molybdate(VI)], [Cu₂Mo₄(C₈H₄O₄)O₁₃(C₁₂H₈N₂)₂], represents a novel two‐dimensional copper–molybdate compound with mixed ligands. Tetra­nuclear molybdenum oxide clusters are joined through corner‐sharing into a ribbon‐like chain, with [Cu(phen)]²⁺ (phen is 1,10‐phenanthroline) complexes grafted onto either side. The terephthalate ligand lies about an inversion centre and links these chains to form a layer via Cu—O and Mo—O bonds. Face‐to‐face π–π stacking inter­actions between adjacent phen ligands stabilize the structure.     

Synthesis,structures and properties of two novel copper(II) complexes with hydrogen bonding supramolecular networks

Two novel complexes, [Cu(HL)₂(H₂O)]₂(OH)₂(ClO₄)₂·1.5H₂O (1) and [Cu(HL)₂]Cl₂·4H₂O (2), have been prepared by reacting copper salts with the 4-amino-3-ethyl-1,2,4-triazole-5-thione (HL) ligand in neutral solution and in HCl (6 mol L^–1) medium, respectively. They were characterized by FT-IR and u.v.–vis. spectra, and the structures were determined by single crystal X-ray diffraction techniques. In both complexes, the triazole ligand chelated the metal ions through the amine and thione substituents on the five-membered ring. Complex (1) has a square-pyramidal copper(II) ion coordinated by two triazole ligands and one water molecule. Unlike (1), the Cu²⁺ ion in (2) displays its characteristic Jahn–Teller distortion with the distance of the Cl^– anions to metal ion further away than that of the triazole ligands. The most intriguing structural features of the title complexes are that the HL ligands chelate copper(II) ions through the N(1) and S(1) atoms, in a cis mode in (1) and a trans mode in (2). In both cases, self-assembled crystals, by supramolecular contacts simultaneously, form two multi-dimensional frameworks.     

用双表面活性剂为共模板合成中孔分子筛MCM-48

利用水热法以非离子表面活性剂聚乙二醇辛基苯基醚和阳离子表面活性剂十六烷基三甲基溴化铵为共模板合成了中孔分子筛MCM-48.实验中发现利用较强的范德华力和氢键,聚乙二醇辛基苯基醚可在很大程度上降低合成MCM-48所需阳离子表面活性剂的用量,且利于制备有序性好、骨架聚合度高、稳定性好的MCM-48.通过调节聚乙二醇辛基苯基醚与十六烷基三甲基溴化铵的比例,可得到不同物相结构的分子筛.     

ESR Studies on a Friedel‐Crafts Alkylation Reaction in [bmim]Cl‐AlCl3 Ionic Liquid

The paramagnetic complexes formed in Friedel‐Crafts alkylation reaction systems are invistigated by electron spin resonance (ESR) spectroscopy, in room temperature ionic liquids system 1‐butyl‐3‐methyl‐limidazolium chloride‐aluminium chloride ([bmim]Cl‐AlCl₃). The results indicate that ESR spectra observed are due to polycyclic aromatic radical cations formed from their parent hydrocarbons. ESR spectrum of spin adduct is obtained in an ionic liquid system composed of [bmim]Cl‐AlCl₃. In acidic solution the ¹⁴N hyperfine coupling constant of 4‐oxo‐TEMPO, 2.15 mT, is appreciably larger due to an adduct formed with AlCl₃.