2-(4-取代-苯基)-3-异噻唑啉酮抗菌活性的定量构效关系研究

用密度泛函理论和逐步回归分析方法对22种新合成的2-(4-取代-苯基)-3-异噻唑啉酮化合物进行了结构与抗菌活性研究. 通过对平衡几何构型、前线轨道组成和Mulliken电荷分布的分析得出: S(1), N(2)原子是该类化合物的主要活性部位, 且5位氯取代的化合物抗菌活性较好. 通过回归分析, 筛选了影响抗菌活性的主要因素, 建立了定量构效关系方程. 结果表明, 硫原子的亲核前线电子密度、3D-Balaban指数、S(1)-N(2) Wiberg键级和Schultz分子价拓扑指数是影响异噻唑啉酮类化合物抗大肠杆菌活性的主要因素, 所得模型对化合物抗菌活性有较好的预报能力.     

铂粒子修饰单壁碳纳米管/聚苯胺复合膜对甲醛的电催化氧化

在溶有单壁碳纳米管(SWNTs)的苯胺溶液中, 通过电化学共聚合法成功制备了单壁碳纳米管(SWNT)/聚苯胺(PANI)复合膜. 用电沉积法将铂沉积到SWNT/PANI复合膜上. 样品的成分和形貌分别用XRD和SEM表征. 四探针和电化学交流阻抗的研究表明被PANI包裹的SWNTs整齐地排列在复合膜中, 从而提高了复合膜的电导率, 促进了电荷转移. 循环伏安(CV)说明Pt修饰的SWNT/PANI复合膜对于甲醛氧化具有良好的电催化活性及稳定性. 研究结果表明SWNT/PANI复合膜是一种非常好的催化剂载体, 有着广泛的应用前景.     

Correlating Photovoltaic Performance of Dye-Sensitized Solar Cell to the Film Thickness of Titania via Numerical Drift-Diffusion Simulations

The thickness of TiO₂ film is vital to realize the optimization on photovoltaic performance of dye sensitized solar cells (DSSCs). Herein, the process of charge separation in DSSCs was simulated by using a drift-diffusion model. This model allows multiple-trapping diffusion of photo-generated electrons, as well as the back reaction with the electron acceptors in electrolyte, to be mimicked in both steady and non-steady states. Numerical results on current-voltage characteristics allow power conversion efficiency to be maximized by varying the thickness of TiO₂ film. Charge collection efficiency is shown to decrease with film thickness, whereas the flux of electron injection benefits from the film thickening. The output of photocurrent is actually impacted by the two factors. Furthermore, recombination rate constant is found to affect the optimized film thickness remarkably. Thicker TiO₂ film is suitable to the DSSCs in which back reaction is suppressed sufficiently. On the contrary, the DSSCs with the redox couple showing fast electron interception require thinner film to alleviate the charge loss via recombination. At open circuit, electron density is found to decrease with film thickness, which engenders not only the reduction of photovoltage but also the increase of electron lifetime.     

On the limiting factor of impregnation methods for developing Cu/CeO<Subscript>2</Subscript> anodes for solid oxide fuel cells

The efficiency of impregnation methods for making Cu-based solid oxide fuel cells (SOFCs) is qualitatively characterized for the first time through a conformal coating model. It is found that the low-efficiency results from the uneven distribution of Cu instead of the small loading. Most of the Cu deposits form isolated islands, e.g., in a 20.4 vol.% Cu-loaded anode, 81% Cu is isolated from each other. In order to address the limited impregnation efficiency, two different procedures are adopted to fabricate the practical Cu/CeO₂ anodes, namely, simultaneous and sequential impregnation procedures. It is found that CeO₂ works as a solid dispersant, improving the Cu distribution drastically. Compared to the Cu-only anode, more than a threefold improvement of impregnation efficiency is achieved by both methods. The anode made by the sequential impregnation yields the best performance in CH₄ at 700 °C, 170 mW cm^?2, which represents an 18% enhancement over that of the simultaneous impregnation, or 340% over the Cu-only anode. These findings demonstrate that it is of importance to optimize the Cu impregnation to yield a highly active anode, and the sequential impregnation method is a promising procedure to break the efficiency-limiting factor and produce a high-performance anode with minimized fabrication effort.     

Effect of Linear and Ring-like Co-units on the Temperature Dependence of Nucleation and Growth in II-I Phase Transition of Butene-1 Copolymers

The phase transition from tetragonal form II to hexagonal form I was studied for the butene-1/ethylene and butene-1/1,5-hexadiene random copolymers, which have comparable molecular weight but distinct linear ethylene and ringlike methylene-1,3-cyclopentane (MCP) structural co-units, respectively. It is known that this solid phase transition follows the nucleation-growth mechanism, so the stepwise annealing protocol was utilized to investigate the influences of co-units on the optimal nucleation and growth temperatures. Compared with optimal nucleation and growth temperatures of ?10 and 35 °C, respectively, in polybutene-1 homopolymer, two butene-1/ethylene copolymers with 1.5 mol% and 4.3 mol% co-units have the slightly lower optimal nucleation temperature of ?15 °C but much higher optimal growth temperature of 50 °C. Clearly, the effect of ethylene co-unit is more significant on varying optimal temperature for growth than for nucleation. Furthermore, when the incorporated co-unit is ringlike MCP, the optimal nucleation temperature is ?15 °C for 2.15 mol% co-units, the same with above BE copolymers, but ?13 °C for a very low concentration of 0.65 mol%. Interestingly, the optimal growth temperature of butene-1/1,5-hexadiene copolymers with 0.65 mol%?2.15 mol% MCP counits increases to 55 °C, which is also independent on co-unit concentration. These obtained values of optimal temperatures provide crucial parameters for rapid II-I phase transition.     

Syntheses,crystal structures and antibacterial activities of two new Mn(II) complexes based on triaryltriazoles

Two new Mn(II) complexes, trans-[Mn(L1-L2)₂(NCS)₂] (1–2) with triaryltriazole (1, L1 = 3-(p-bromophenyl)-4-phenyl-5-(2-pyridyl)-1,2,4-triazole; 2, L2 = 3,4-bis(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole), have been synthesized and structurally characterized by elemental analysis, FT-IR, ESI-MS, and single-crystal X-ray crystallography. Crystallographic studies revealed that both 1 and 2 contain a distorted octahedral [MnN₆] core with two trans-disposed NCS^? ions. The L1 ligand, 1 and 2, together with four known homologous Mn(II) complexes, trans-[Mn(L3-L6)₂(NCS)₂] (3–6) (3, L3 = 3-(p-methoxyphenyl)-4-(p-chlorophenyl)-5-(2-pyridyl)-1,2,4-triazole; 4, L4 = 3-(p-methoxyphenyl)-4-(p-bromophenyl)-5-(2-pyridyl)-1,2,4-triazole; 5, L5 = 3-(p-chlorophenyl)-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole; 6, L6 = 3,5-bis(2-pyridyl)-4-(p-methylphenyl)-1,2,4-triazole), were tested in vitro for their antibacterial activities against two Gram-positive bacterial strains and two Gram-negative bacterial strains by the MTT method. The results indicate that 1 exhibited better activity than Penicillin and Kanamycin against Pseudomonas aeruginosa and also better than its free L1 ligand.     

串联双柱固相萃取-高效液相色谱-电喷雾多级质谱法测定盐酸二甲双胍制剂中的盐酸二甲双胍及残留物三聚氰胺和双氰胺

建立了串联双柱固相萃取-高效液相色谱-电喷雾多级质谱（HPLC-ESI-MSⁿ）确认及测定盐酸二甲双胍制剂中的盐酸二甲双胍及残留物三聚氰胺和双氰胺的方法。盐酸二甲双胍制剂样品在超声辅助下,采用含0.1%（v/v）乙酸的无水乙醇溶液提取,选择Cleanert PCX-C18串联固相萃取双柱净化富集,以5%（v/v）氨水甲醇溶液为洗脱剂进行洗脱。采用Kromasil-C18色谱柱（100 mm×4.6 mm,3.5 μm）分离,梯度洗脱,在电喷雾多级质谱、选择离子模式下检测,外标法定量。通过比较制剂残留物在不同萃取溶剂、固相萃取柱及洗脱液等条件下的回收率,优化了前处理方法。结果表明,在各自的线性范围内,3种目标物的峰面积与质量浓度呈良好的线性关系,相关系数（r²）≥0.9992;方法的检出限为1.48~13.61 μg/kg,定量限为5.96~45.67 μg/kg。3种目标物在低、中、高加标水平下的平均回收率为65.02%~118.33%,相对标准偏差（RSD）≤13.41%（n=5）。该法操作简单,净化效果好,准确度高,重现性好,适用于检测和分析不同盐酸二甲双胍制剂中盐酸二甲双胍及残留物三聚氰胺和双氰胺。     

基于金银合金薄膜的波长检测型表面等离子体共振传感器

从实验和理论两方面详细研究了金银合金膜表面等离子体共振（SPR）传感器在可见光波段的敏感特性. 实验方面,通过在玻璃基底上溅射50 nm厚的金银合金薄膜制备了一种新型的SPR传感芯片,并且自行搭建了基于Kretschmann 结构的波长检测型SPR传感器测试平台. 利用不同浓度的氯化钠（NaCl）水溶液和浓度为10 μmol·L^-1的牛血清蛋白（BSA）水溶液分别作为折射率样品和分子吸附样品,研究了传感器的折射率灵敏度和吸附灵敏度,并与金膜和银膜SPR传感器进行了对比研究. 结果表明,对于折射率灵敏度的测试,金银合金膜SPR传感器大幅高于金膜SPR传感器,略低于银膜SPR传感器;而对于吸附敏感的研究,金银合金膜SPR传感器的灵敏度与银膜SPR传感器相近,是金膜SPR传感器的3倍. 理论方面,利用菲涅尔公式和等效折射率计算公式仿真计算了这三种薄膜结构的SPR传感器的灵敏度和精确度,结果指出金银合金膜SPR传感器的灵敏度与银膜SPR传感器接近,是常规金膜SPR传感器的2.31倍,而半高峰宽仅为金膜和银膜SPR传感器的1.36 倍. 在稳定性方面,金银合金膜SPR传感器与金膜SPR传感器均具有良好的化学稳定性,而银膜SPR传感器较易氧化,使用寿命低,不常被采用. 综上,金银合金膜在改善传感器灵敏度的同时,不会降低精度,是一种高灵敏、低成本、良好稳定性的SPR传感器敏感材料.     

化妆品中Hg、As和Pb的微波消解－

采用微波消解 -氢化物发生ICP-AES法测定化妆品中的Hg、As和Pb ,加入L_半胱氨酸消除了过渡金属离子的干扰 ,考察了微波消解、氢化物发生的最佳条件。建立的方法简便快速 ,测定Hg、As和Pb的RSD分别为0.59%、1.2%、2.4 % (n=10) ,样品加标回收率分别为98.5%、99.3 %和100.1 %。该法已应用于化妆品的常规测定 ,得到满意的结果。     

Fe掺杂TiO2和Fe2O3量子点共负载催化剂:吸附与光催化协同作用高效降解有机染料

光催化作为节能、清洁的环境处理技术,被广泛应用于污染物处理领域,如室内气体净化、尾气VOCs处理和水体有机污染降解等.在众多光催化剂中,TiO2以其良好的化学稳定性、无二次污染、无刺激性和安全无毒等优势得到广泛研究.然而TiO2是宽禁带材料,仅能吸收太阳光谱的紫外光部分,通常需要用紫外光源来激发,光生电子-空穴易复合,这限制了其应用.过渡金属离子掺杂能在TiO2价带之上形成新的掺杂能级,从而提高其光谱响应范围,提高全光谱反应活性; 与体相TiO2相比,纳米尺寸的TiO2具有更高的光催化活性,尤其小于10 nm的量子点尺寸TiO2有着高活性面积、较短的光生电子-空穴迁移路径和独特的量子尺寸效应; Fe2O3作为吸附材料与TiO2构建复合材料能够发挥吸附与光催化协同作用,从而提高污染物处理效率.我们以构建Fe掺杂TiO2和Fe2O3量子点共负载催化剂为目标,以钛酸四丁酯(TBT)和硫酸亚铁为前驱体,采用常温水解方法将Fe掺杂的TiO2量子点生长在MCM-41分子筛表面,并通过调节硫酸亚铁加入量合成了MCM-41负载的Fe掺杂TiO2和Fe2O3量子点催化剂.采用透射电子显微镜和X射线衍射研究了复合晶体结构,采用X射线光电子能谱、紫外-可见光谱和傅里叶变换红外光谱等表征手段研究了复合量子点材料生长机理和能带结构.结合吸附过程和光降解过程建立了吸附与光催化协同作用与污染物处理效率之间的关联关系.表征结果表明,硫酸亚铁水溶液加速TBT水解成功地在MCM-41表面生长了Fe掺杂TiO2量子点,并且量子点粒径随Fe前驱体量的增加而变大; 前驱体比例Ti/Fe ≤ 3.0时,过量的硫酸亚铁会析出并在焙烧过程中在MCM-41上分解为Fe2O3量子点,Fe2O3量随着硫酸亚铁加入量提高而增多.通过调节Fe前驱体的量,一方面Fe掺杂在二氧化钛价带之上形成了掺杂能级,减小了带隙,拓宽了光响应范围,另一方面引入适量Fe2O3量子点,实现了Fe掺杂TiO2和Fe2O3量子点共负载催化剂的构建.复合材料实现了吸附过程与光催化降解过程的协同作用,Fe2O3将污染物富集于催化剂表面,Fe掺杂TiO2将其有效降解,大大提高了污染物处理能力,其中FT/M-3.0处理效率最高,并在10次循环处理后依然维持较高的吸附能力和光催化降解能力.该工作为高效光催化水处理催化剂的设计和构建提供了新思路和策略.