SiO2交联剂交联MMA聚合制备PMMA/SiO2纳米复合材料

用SiO2交联剂(SiO2HPA)交联甲基丙烯酸甲酯(MMA)自由基聚合制备PMMA SiO2纳米复合材料。采用两步法将可聚合乙烯基单体以化学键的形式键接到SiO2表面合成SiO2交联剂,首先利用过量的甲苯2,4二异氰酸酯(TDI)对SiO2纳米粒子表面进行化学修饰合成出表面带有高反应活性NCO基团的功能化SiO2粒子(SiO2TDI),SiO2TDI与丙烯酸羟丙酯(HPA)反应合成SiO2交联剂。系统研究了MMA单体与SiO2交联剂投料比及聚合时间对聚合反应的影响。此外,利用红外光谱(FT IR)、DSC、TGA、可见光光谱仪等实验手段对纳米复合材料进行了表征分析。结果表明,纳米SiO2粒子在复合材料中起着物理交联点和化学交联点作用,复合材料玻璃化转变温度(Tg)明显地高于其纯PMMA的玻璃化转变温度,随着纳米SiO2粒子含量的增加,复合材料玻璃化温度升高,而透明度明显降低。     

烷烃电离能和生成焓的相关性

根据化合物形成过程中价电子能量变化与生成焓之间的关系, 推导出烷烃的生成焓和电离能之间的关系. 以21个烷烃化合物为模型将实验测定的电离能与标准生成焓进行直接关联, 证实了模型方程的适用性, 所得回归方程的相关系数达到0.9999, 估算值与实验值之间的标准偏差仅为0.03 eV. 同时还利用实验测定的标准生成焓对一系列烷烃的电离能作了预测.     

咪唑类配体与双过氧钒配合物相互作用的NMR研究

为探讨咪唑环上取代基团对反应平衡的影响, 在模拟生理条件(0.15 mol·L-1 NaCl溶液)下, 应用多核(1H、13C和51V)、扩散排序谱(DOSY)以及变温NMR等谱学技术研究双过氧钒配合物NH4[OV(O2)2{2-(2’-Pyri-dine)-Imidazole}]·4H2O(简写为bpV(Imi-Py))和咪唑类配体(咪唑、2-甲基鄄咪唑、4-甲基-咪唑和组氨酸)的相互作用, 其从强到弱的顺序为咪唑≈4-甲基-咪唑>2-甲基-咪唑>组氨酸. 研究结果表明, 咪唑环上取代基团空间位阻对反应平衡产生较大影响,同时竞争配位的结果导致新的6 配位过氧物种[OV(O2)2L]-(L 为咪唑类配体)的生成, 当配体为4-甲基-咪唑和组氨酸时, 生成的则是一对异构体.     

Preparation and optical properties of worm-like gold nanorods

A type of worm-like nanorods was successfully synthesized through conventional gold nanorods reacting with Na2S2O3 or Na2S. The generated worm-like gold nanorods comprise shrunk nanorod cores and enwrapped shells. Therefore, a gold-gold sulfide core-shell structure is formed in the process, distinguishing from their original counterparts. The formation of the gold chalcogenide layers was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. Experimental results showed that the thickness of the gold chalcogenide layers is controllable. Since the increase of shell thickness and decrease of gold nanorod core take place simultaneously, it allows one to tune the plasmon resonance of nanorods. Proper adjustment of reaction time, temperature, additives and other experimental conditions will produce worm-like gold nanorods demonstrating desired longitudinal plasmon wavelength (LPW) with narrow size distributions, only limited by properties of starting original gold nanorods. The approach presented herein is capable of selectively changing LPW of the gold nanorods. Additionally, the formed worm-like nanorods possess higher sensitive property in localized surface plasmon resonance than the original nanorods. Their special properties were characterized by spectroscopic methods such as Vis-NIR, fluorescence and resonance light scattering. These features imply that the gold nanorods have potential applications in biomolecular recognition study and biosensor fabrications.     

Two-dimensional TiO2 (001) nanosheets as an effective photo-assisted recyclable sensor for the electrochemical detection of bisphenol A

Electrochemical detection is an efficient method for the detection of Bisphenol A (BPA). Herein, a sensitive photo-electrochemical sensor based on two-dimensional (2D) TiO₂ (001) nanosheets was fabricated and then used for BPA electrochemical detection. Upon light irradiation, the 2D TiO₂ (001) nanosheets electrode provided a lower detection limit of BPA detection compared with an ambient electrochemical determination. The low detection limit is ∼5.37 nmol/L (S/N = 3). Furthermore, profiting from the photoelectric characteristics, the 2D TiO₂ (001) nanosheets electrode exhibits a nice regeneration property. After 45 min of light irradiation, the electrochemical signal was regenerated from 14.7% to 82.9% of the original signal at the 6^th cycle. This is attributed to the non-selective OH mediation produced by the 2D TiO₂ (001) nanosheets mineralizing anodic polymeric products and resuming surface reactive sites. This investigation indicates that photo-assistance is an efficient method to improve the electrochemical sensor for detecting BPA in water environments.     

5-(4-羟基-3-硝基苯基)-10,15,20-三苯基卟啉结构

基于卟啉为荧光发色团,以2,4-二硝基苯磺酰氯为识别部分,设计并合成了一种具有较高选择性、高灵敏度的近红外苯硫酚荧光探针,其结构经¹H NMR, IR和HR-MS(ESI)表征。并研究了其荧光性能。结果表明：该探针可快速(90 s)、高选择性地检测苯硫酚,在5×10^-6～13×10^-6mol·L^-1呈良好的线性关系,检出限为61 nm。     

Efficient Synthesis of Isoquinolines by AgNO3‐Catalyzed Sequential Imination‐Annulation of 2‐Alkynyl Aldehydes with Ammonium Bicarbonate

An operationally simple approach for the tandem synthesis of isoquinolines by the reaction of o‐alkynylaldehydes with ammonium bicarbonate via Ag‐catalyzed 6‐endo‐dig ring closure is described. The reaction conditions and the scope of the reaction are examined, and a variety of substituted isoquinolines are prepared in moderate to excellent yields.     

碳纳米管上原位沉积钯-钴-镍纳米颗粒及其对乙醇氧化的电活性

以水合肼为还原剂,在水和乙醇的混合溶液中制备多壁碳纳米管(MWCNT)负载的纳米镍(Ni/MWCNT)和纳米镍钴(Ni-Co/MWCNT)颗粒,然后将它们分别与氯化钯溶液反应,形成的钯纳米颗粒原位沉积在MWCNT表面,从而得到MWCNT负载的PdNi/MWCNT和Pd-Ni-Co/MWCNT催化剂。SEM和TEM图像显示,MWCNT上的催化剂颗粒是由5~10 nm的小颗粒团聚而成的30~100 nm的大颗粒,三金属催化剂的粒径比双金属的粒径小,在MWCNT上的分散度更高。ICP和EDS分析显示,Pd直接还原并包覆在纳米镍和纳米镍钴表面;采用循环伏安和计时电流技术,研究了催化剂在碱性溶液中对乙醇氧化的电催化活性,结果表明,Pd-Ni-Co/MWCNT催化剂对乙醇氧化具有强的电催化活性,乙醇氧化对应的峰电流密度达101.8 m A·cm~(-2),并且催化剂催化活性稳定。     

分子结构振动固有频率与链烷烃热力学性质的定量关系

用分子结构固有频率和分子中的甲基数作为分子结构信息指数,建立链烷烃分子结构与热力学性质的双参数QSPR模型.该模型用于18种链烷烃分子的标准生成焓、标准熵和标准生成自由能实验值的回归分析,得到相关程度大于0.999的标准生成焓、标准熵回归方程和相关程度大于0.99的标准生成自由能回归方程.所得方程用于67种链烷烃的标准生成焓、标准熵和标准生成自由能预测,结果与实验值的相关程度均大于0.9950.     

Solution of a Duffing-harmonic oscillator by the method of harmonic balance

The first-order harmonic balance method via first Fourier coefficient is used to construct an approximate frequency-amplitude relation for a Duffing-harmonic oscillator. This relation is in agreement with the result obtained by the Ritz procedure.