具有聚集诱导发光效应的咔唑基三苯乙烯衍生物单体及聚合物

合成了一类新的咔唑基三苯乙烯衍生物单体及其聚合物.利用示差扫描量热法(DSC)、热重分析法(TGA)、紫外可见分光光度法和荧光分光光度法等对单体和聚合物的性能进行了初步的表征.实验结果表明,该单体和聚合物具有较高的玻璃化转变温度(Tg),分别为210℃和229℃;单体和聚合物均具有很高的热稳定性,热失重5%的温度分别为466℃和467℃;单体具有明显的聚集诱导发光性能(AIE),而聚合物则具有聚集诱导增强发光性能(AIEE);所合成的单体和聚合物有望在OLED器件以及化学传感器上得到应用.     

Ni(111)表面上N原子对C原子电子结构的影响

N是金刚石中的主要杂质之一, 为了研究金刚石生长过程中杂质N对C电子结构转化的影响, 用密度泛函理论研究了Ni(111)表面上C与N共吸附的三个不等价模型, 同时建立了三个C吸附模型作为比较. 计算结果表明, N原子的出现使得吸附体系相对不稳定, 吸附原子之间的相互作用不能忽略; 通过比较相互作用能可以看出, 相同的吸附位下C-C相互作用比C-N 相互作用强. 通过比较不同模型中C原子分波态密度可以看出, N-C相互作用一定程度上增加了Ni的催化活性, 但是与C-C自身的相互作用比较起来效果并不明显. 吸附几何结构和分波态密度还表明, 当吸附的原子过于紧密以致占有同一个Ni(111)-(1×1)晶胞表面时, 就会形成CN化合物或者类石墨杂质.     

柱前衍生化-HPLC测定仲丁胺对映体的纯度

用3, 5-二硝基苯甲酸对仲丁胺进行柱前衍生, 将其衍生物在CHIRALCEL OD-H手性固定相上拆分, 并通过二极管阵列紫外检测器对其衍生物进行检测, 建立了一种拆分仲丁胺消旋体、测定仲丁胺光学纯度的新方法. 以正己烷和乙醇或异丙醇为流动相, 在CHIRALCEL OD-H手性固定相上对仲丁胺衍生物进行了拆分, 并考察了流动相组成和柱温对该对映体衍生物分离的影响, 获得较好的分析条件, 分离因子大于1.2. 非手性试剂柱前衍生化法测定仲丁胺光学纯度与旋光度方法比较, 结果一致. 方法可用于仲丁胺对映体的质量控制.     

卤素双原子分子部分电子态的完全振动能谱和离解能

用代数方法(AM)可以获得双原子分子包含最高振动能级在内的所有高阶振动能级的完全振动能谱; 基于Leroy和Bernstein的能级表达式, 研究了卤族元素双原子分子Cl2-A’3∏(2u)、Br2-X1∑+g和I2-0+u电子态的完全振动能谱和离解能, 得到的理论结果与实验符合得很好.     

An Integrated Market for Electricity and Natural Gas Systems with Stochastic Power Producers

In energy systems with high shares of weather-driven renewable power sources, gas-fired power plants can serve as a back-up technology to ensure security of supply and provide short-term flexibility. Therefore, a tighter coordination between electricity and natural gas networks is foreseen. In this work, we examine different levels of coordination in terms of system integration and time coupling of trading floors. We propose an integrated operational model for electricity and natural gas systems under uncertain power supply by applying two-stage stochastic programming. This formulation co-optimizes day-ahead and real-time dispatch of both energy systems and aims at minimizing the total expected cost. Additionally, two deterministic models, one of an integrated energy system and one that treats the two systems independently, are presented. We utilize a formulation that considers the linepack of the natural gas system, while it results in a tractable mixed-integer linear programming (MILP) model. Our analysis demonstrates the effectiveness of the proposed model in accommodating high shares of renewables and the importance of proper natural gas system modeling in short-term operations to reveal valuable flexibility of the natural gas system. Moreover, we identify the coordination parameters between the two markets and show their impact on the system’s operation and dispatch.     

荧光共振能量转移测定牛血清白蛋白的研究

随着生物分析技术进入了后基因组时代,生命科学领域里的研究课题不断深入,DNA、RNA、蛋白质和其他生物大分子的检测技术发展十分迅速,生命科学中单分子分析技术不断揭示出生命活动的客观规律.相关的新的分析方法和仪器不断取得进展,成为生命科学的前沿领域.     

球磨法制备异质结型光催化剂ZnO/Bi_4Ti_3O_(12)及催化性能

本文用水作为分散介质,掺杂一定量的ZnO于Bi_4Ti_3O_(12)中,采用高能球磨法制备了异质结型光催化剂ZnO/Bi_4Ti_3O_(12).利用UV-Vis、XRD、SEM和PL等仪器对样品进行了分析与表征.以375 W中压汞灯为光源,通过对亚甲基蓝的氧化来研究其光催化活性.结果表明,对于光氧化亚甲基蓝(MB),异质结型光催化剂ZnO/Bi_4Ti_3O_(12)光催化活性高于钛酸铋的光催化活性.当ZnO的掺杂量分别是0.0和0.5wt.%,异质结型光催化剂ZnO/Bi_4Ti_3O_(12)对亚甲基蓝光氧化率分别达到50.2和80.3 %.     

5-氟胞嘧啶气相及水助质子转移异构化的理论研究

采用密度泛函B3LYP/6-311G**方法,对6种5-氟胞嘧啶异构体孤立分子的稳定性及质子转移引起的酮式-烯醇式、氨基式-亚胺式互变异构反应机理进行了计算研究,获得了零点能、吉布斯自由能及质子转移过程的反应焓、活化能、活化吉布斯自由能和速率常数等参数.计算结果表明,气相中烯醇-氨基式FC4是最稳定的异构体.分子内质子转移设计了FC1→FC2和FC1→FC6两条通道,分别标记为P(1)和P(2),各通道速控步骤的活化能和速率常数分别为155.9 kJ·mol-1,4.70×10-15 s-1和173.1 kJ·mol-1,1.41×10-18 s-1.水助催化时,相应通道P(3) 和P(4) 速控步骤的活化能和速率常数分别为51.0 kJ·mol-1,1.41×103 s-1和88.2 kJ·mol-1,4.53×10-3 s-1.可见,水分子的加入极大地降低了质子转移的活化能垒.另外发现,水分子参与形成协同的双质子转移机理比水助单质子转移机理更利于降低活化能垒.     

高效液相色谱法测定胶粘剂中的游离甲醛

建立了胶粘剂中游离甲醛的高效液相色谱检测方法,对提取方法、衍生化条件及色谱条件进行了研究。结果表明,采用超声波萃取法代替经典的水蒸气蒸馏法能更快速、高效地提取目标物。液相色谱法对甲醛的检出限为0．024μg／mL,在0．1～12μg／mL范围内,线性相关系数R^2=0．9995,在1、2、8μg／mL三个添加水平下,回收率在98．73％～101．68％之间。五个实验室间的相对标准偏差为2．6％。对某白乳胶样品的测定结果表明,本法在定性检测、抗干扰能力及稳定性上都高于常用的乙酰丙酮比色法。     

Cations of halogenated methanes: adiabatic ionization energies, potential energy surfaces, and ion fragment appearance energies

The DFT-B3LYP and G3X model chemistry were used to predict the cation structures and energetics of fluorinated, chlorinated, and brominated methanes. Ion–complex structures between methylene cations and HX (X = F, Cl, Br) were found for all H-containing cations, and [CHF–FH]⁺, [CF₂–FH]⁺, [CCl₂–ClH]⁺, and [CCl₂–FH]⁺ structures are more stable than their normal tetravalent structures. Several cations should also be better described as ion–complex structures between methyl cations and halogen atoms, e.g., [CF₃–Br]⁺. Transition states connecting normal and ion–complex structures were also located, and potential energy diagrams were constructed for decomposition of methane cations and to predict the fragmentation pathways. The G3X energies were used to predict the adiabatic ionization energies (IE_as) and ion fragment appearance energies (AEs) from methanes. Many of the experimental AEs correspond to the energies of transition states instead of the thermodynamic dissociation limits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.