Preparation of ZnO colloids by aggregation of the nanocrystal subunits

Colloidal ZnO particles with narrow size distribution were prepared via a sol-gel process by base-catalyzed hydrolysis of zinc acetate. The morphology of ordered arrays of the particles was recorded by SEM. SEM also reveals that these uniform particles were composed of tiny ZnO subunits (singlets) sized of several nanometers. The size of the singlets, which is confirmed by X-ray diffraction and UV-vis absorption spectra, increases as the aging time is prolonged. The size-selective formation of colloids by aggregation of nanosized subunits is proposed to consist of two-stage growth by nucleation of nanosized crystalline primary particles and their subsequent aggregation into polycrystalline secondary colloids. The aggregates are all spherical because the internal rearrangement processes are fast enough. The ZnO colloids, i.e., the aggregates, tend to self-assemble into well-ordered hexagonal close-packed structures. Room-temperature photoluminescence was characterized for green and aged ZnO.     

Determination of Formaldehyde Traces in Fabric and in Indoor Air by a Kinetic Fluorimetric Method

A simple and sensitive kinetic fluorimetric method is reported for the determination of trace amount of formaldehyde. The proposed method is based on the catalytic effect of formaldehyde on the oxidation reaction of rhodamine B with potassium chlorate in sulfuric acid solution. Formaldehyde in the range of 0.020-0.340 µg/mL can be determined with a limit of detection of 5.73 ng/mL. The method has been used to determine trace formaldehyde in fabric and in indoor air. The results thus obtained show good agreement with those determined by acetyl acetone method.     

双亲聚合物分子印迹自组装胶束电化学传感器研究

结合大分子自组装和分子印迹技术制备了分子印迹聚合物胶束, 并通过电沉积将其固载到电极表面得到分子印迹电化学传感器. 首先以甲基丙烯酸二甲氨基乙酯(DMA)、丙烯酸羟乙酯(HEA)、丙烯酸二异辛酯(EHA)和苯乙烯(St)合成了共聚物poly(DMA-co-HEA-co-EHA-co-St), 在其侧链接枝上双键得到可光交联的双亲共聚物. 以水为沉淀剂诱发该双亲共聚物在含有对乙酰氨基苯酚的溶液中自组装, 得到印迹有对乙酰氨基苯酚的聚合物胶束, 利用动态激光光散射(DLS)和透射电镜(TEM)表征其尺寸和形貌. 最后通过电沉积技术诱导印迹胶束在金电极表面组装, 经紫外光辐照交联后, 洗脱模板分子形成分子印迹膜, 制备了对乙酰氨基苯酚分子印迹传感器, 通过循环伏安法、差分脉冲溶出伏安法研究此印迹传感器的性能. 实验结果表明, 该传感器对对乙酰氨基苯酚具有良好的选择性和灵敏度, 浓度响应线性范围为1×10^{-6 到4×10-3 mol/L, 检测限为3.3×10-7 mol/L.}     

庚酸甲酯高温燃烧化学动力学机理的系统简化和分析

采用详细化学反应动力学机理的系统简化方法, 对庚酸甲酯高温燃烧化学动力学机理进行了系统简化. 首先采用两步直接关系图法(Directed relation graph method, DRG)和主成分分析(Principle component analysis, PCA)方法对由1087个物种、4592步可逆反应组成的庚酸甲酯燃烧的详细机理进行框架简化, 得到了包含108个物种, 547步基元反应的框架机理. 在此框架机理基础上, 进一步采用计算奇异值摄动法(Computational singular perturbation, CSP)对框架机理进行时间尺度分析, 再选取30个准稳态物种, 采用准稳态近似(Quasi steady state approximation, QSSA)方法构建了包含78个物种、74步总包反应的全局简化机理. 模拟结果表明, 在较宽的参数范围内, 框架机理和全局简化机理均能重现庚酸甲酯高温燃烧时的点火延迟、物种浓度分布和熄火等燃烧特性. 此外, 基于框架机理阐明了庚酸甲酯高温燃烧的反应路径和对点火有重要影响的基元反应. 与详细机理相比, 框架机理保留了良好的精确性和全局性, 可以很好地反映庚酸甲酯的燃烧特性, 有助于对生物柴油的燃烧过程的理解.     

Spectroscopic Investigation on Sonocatalytic Damage of BSA Molecules by FeIII Complexes with Binary Organic Acid Ligands Under Ultrasonic Irradiation

The interaction between bovine serum albumin (BSA) and Fe^III complexes with three binary organic acid (biorga) ligands, [Fe^III(oxa)(H₂O)₄]⁺ (oxa = oxalic acid), [Fe^III(pra)(H₂O)₄]⁺ (pra = propanedioic acid) and [Fe^III(sua)(H₂O)₄]⁺ (sua = succinic acid), as well as the sonocatalytic damage of BSA in the presence of these three Fe^III–biorga complexes under ultrasonic irradiation, were studied by UV–vis and fluorescence spectra. The experimental results show that the fluorescence quenching process of BSA caused by three Fe^III–biorga complexes are all static quenching and the corresponding quenching rate constants (K _q), equilibrium constants (K _A) and the binding site numbers (n) were calculated. The results reveal that, under ultrasonic irradiation, the BSA molecules were obviously damaged by these Fe^III–biorga complexes. In addition, the effects of several factors on the damage of BSA molecules were examined. The experimental results demonstrate that the damage degree of BSA increased with an increase of ultrasonic irradiation time, Fe^III–biorga complex concentration, and ionic strength. In comparison, [Fe^III(pra)(H₂O)₄]⁺ exhibited higher sonocatalytic activity than [Fe^III(oxa)(H₂O)₄]⁺ and [Fe^III(sua)(H₂O)₄]⁺. Finally, the extent of generation of $ \cdot {\text{O}}_{2}^{ - } $ · O 2 ? and ·OH during sonocatalytic processes was estimated. Perhaps, the results will be significant for promoting sonodynamic treatment (SDT) of tumors at the molecular level.     

A bird nest-like manganese dioxide and its application as electrode in supercapacitors

A novel bird nest-like nanostructured MnO2(BNNS-MnO2) was prepared by a facile and cost-effective strategy. Their structures and morphologies were characterized by field emission scanning electron microscopy, transmission electron microscopy and powder X-ray diffraction. Capacitive behaviors were investigated by cyclic voltammetry and galvanostatic charge-discharge. The obtained nano-MnO2 possesses a well designed loose-assembled hierarchical nanoarchitecture with an appropriate crystallinity which gives rise to excellent performances as an electrode material for supercapacitors. A maximum specific capacitance of 917 F/g has been obtained at a current density of 5 mA/cm2 in 6 mol/L KOH aqueous solution, and a specific capacitance of 210 F/g has been maintained for 500 cycles. As the low cost of MnSO4 and KCr2O7 and the low reaction temperature, the present method avoids the requirements for complicated operations, time/energy-consuming and expensive reagents, and perhaps is ready for the industrialization of nano-MnO2 production.     

基于巯基-烯点击反应制备有机-无机杂化硼酸亲和整体柱用于糖蛋白的选择性富集

发展了以巯基-烯点击反应制备有机-无机杂化硼酸亲和整体柱的新方法。首先以四甲氧基硅烷(TMOS)和巯丙基三甲氧基硅烷(MPTMS)作为反应单体,采用溶胶-凝胶反应制备表面含巯基的硅胶整体柱。然后利用巯基-烯(thiol-ene)的点击反应在整体柱上修饰硼酸配基3-丙烯酰胺基苯硼酸(AAPBA),制成AAPBA-硅胶杂化亲和整体柱。对影响硼酸亲和整体柱性能的条件如TMOS与MPTMS的比例、聚乙二醇和甲醇的用量等进行了优化。并采用扫描电镜、红外光谱等分析仪器对整体柱形貌和机械稳定性能进行了表征。研究了AAPBA-硅胶杂化亲和整体柱的分离性能,结果表明,其在中性条件下对含有顺式二醇的生物小分子核苷具有良好的特异亲和能力,并已成功地应用于卵清蛋白、辣根过氧化物酶等糖蛋白的分离。基于巯基-烯反应的制备方法新颖、可靠,可用于制备多种不同类型的硼酸亲和整体柱,具有较大的应用前景。     

钯催化芳基乙炔对氧/氮杂苯并降冰片烯开环反应研究

过渡金属催化的碳亲核试剂对氧/氮杂苯并降冰片烯的开环反应是合成氢化萘衍生物的有效方法之一. 在该类反应中, 采用末端炔烃作为碳亲核试剂在反应操作、底物适用范围等多个方面都具有已报道的各种有机金属亲核试剂所不具备的优势. 目前, 对末端炔烃与氧/氮杂苯并降冰片烯的开环反应的研究进展有限, 只有Ni(dppe)Cl₂/ZnCl₂/Zn和手性的Rh两种催化体系被应用到该类反应当中, 但都面临一些不足. 为该类反应开发简单有效的新型催化体系仍然具有重要的意义和价值. 我们通过研究发现: PdCl₂与Xantphos的配合物是芳基乙炔对氧/氮杂苯并降冰片烯亲核开环反应的有效催化剂. 在优化后的反应条件下, 该Pd催化剂具有良好的催化活性和底物适应能力, 能够实现各种取代的芳基乙炔对氧/氮杂苯并降冰片烯的亲核加成, 并以较好的收率生成目标开环产物.     

基于β-环糊精主客体识别作用的均相DNA杂交电化学生物分子识别研究

基于β-环糊精(β-CD)和间甲基苯甲酸(mTA)的主客体识别,建立了均相DNA杂交电化学生物传感技术。将主体分子β-CD通过电化学聚合的方法固定在氮乙酰基苯胺修饰的玻碳电极表面,同时将mTA通过酸胺缩合反应标记在探针DNA序列上,与目标DNA在溶液均相中杂交之后,用修饰好的电极对探针DNA上的mTA进行主客体识别。以两种嵌入剂作为电化学指示剂——亚甲基蓝(MB)和道诺霉素(DNM),证实了方法的可行性。MB的电化学信号与完全互补DNA浓度在2.0×10"12～2.0×10"10mol/L之间呈良好线性关系,检出限为7.6×10"13mol/L;DNM的电化学响应与完全互补DNA浓度在1.0×10"12～1.0×10"9mol/L之间呈良好线性关系,检出限可达6.0×10"13mol/L,并表现出良好的重现性和稳定性。