拉曼光谱原位表征在有机光电器件中的应用

拉曼原位表征(Raman in situ characterization)就是在不破坏样品的情况下利用拉曼光谱实时监测变化过程,以表征样品在真实环境下的结构性能变化或记录样品在整个过程中的实时信息。在器件的工作时,原位检测化学结构、物理结构的变化,有利于深入了解器件微观结构与光电性能间的关系,帮助我们优化器件结构,提高器件性能。本文主要针对有机光电器件,总结原位观察生长、老化、带电状态的特点和规律,探讨了原位拉曼光谱在有机光电器件原位表征中的应用和发展潜力。     

Fitness of others' evaluation effect promotes cooperation in spatial public goods game

Payoff-driven strategy updating rule has always been adopted as a classic mechanism, but up to now, there have been a great many of researches on considering other forms of strategy updating rules, among which pursuing high fitness is one of the most direct and conventional motivations in the decision-making using game theory. But there are few or no researches on fitness from the perspective of others' evaluation. In view of this, we propose a new model in which the evaluation effect with fitness-driven strategy updating rule is taken into consideration, and introduce an evaluation coefficient to present the degree of others' evaluation on individual's behavior. The cooperative individuals can get positive evaluation, otherwise defective individuals get negative evaluation, and the degree of evaluation is related to the number of neighbors who have the same strategy of individual. Through numerical simulation, we find that the evaluation effect of others can enhance the network reciprocity, thus promoting the cooperation. For a strong dilemma, the higher evaluation coefficient can greatly weaken the cooperation dilemma; for a weak one, the higher evaluation coefficient can make cooperator clusters spread faster, however, there is no significant difference in the level of cooperation in the final stable state among different evaluation coefficients. The cooperation becomes more flourish as the number of fitness-driven individuals increases, when all individuals adopt fitness-driven strategy updating rule, the cooperators can quickly occupy the whole population. Besides, we demonstrate the robustness of the results on the WS small-world network, ER random network, and BA scale-free network.     

超声波-微波协同萃取南五味子木脂素及五味子酯甲的制备

考察了超声波-微波协同萃取南五味子木脂素的工艺条件.采用L9(34)的正交实验考查了萃取剂浓度,萃取时间,微波功率,液固比的影响效果.实验结果表明,优化的提取条件是:萃取剂乙醇浓度为90％,萃取时间为10min,微波功率为70W,液固比为15∶1(mL/g)(超声波功率内置为50W).优化条件下木脂素得率为5.86％.将提取物利用高效液相制备色谱分离纯化,得到了五味子酯甲,产品纯度为98％,得率为0.16％.     

利伐沙班关键杂质的合成

以对溴硝基苯为原料,经偶联、胺基保护、亲核取代、硝基还原、环氧开环、环合、脱保护和胺基酰化反应合成了利伐沙班的二胺杂质--5-氯-N-【【(5S)-2-氧代-3-｛4-［5-氯-噻吩-2-甲酸-N-(2-甲基氨基甲酰基甲氧基乙基)酰胺基］苯基｝-1,3-噁唑烷-5-基】甲基】-2-噻吩甲酰胺,其结构经¹H NMR, ¹³C NMR, DEPT135°, ¹H-¹HCOSY, HSQC, HMBC和MS（ESI）确证。     

分子H_2X(X=O、S、Se)的全对称群Dirac理论研究

本文应用全对称群的Dirac理论计算了分子H_2X(X=O、S、Se)的结构,并与非相对论的结果比较.对比相对论和非相对论的结果,所得到的分子几何差异不大;而所计算的能量,相对论的比非相对论的要低,并能量随质量增加而降低;相对论值的极化率(A~3)和偶极矩更接近实验值.分子的电性状态为费密子共群的不可约表示E_1,明显地体现不可约表示E1的效应.所以,特别对重元素分子,更要应用相对论方法.     

基于核运动效应下的H同位素双原子分子的解析势能函

在加入核运动效应修正下的Born-Oppenheimer近似电子能量的基础上, 采用QCISD(T)/ aug-cc-pvqz方法计算出H同位素双原子分子（H₂, HD, HT, D₂, DT,T₂）的势能函数参数, 获得体现H同位素分子质量差异下的势能函数。 并在此基础上导出H同位素分子的力常数和光谱数据。 同时对于OH, OD和OT分子采用QCISD/aug-cc-pvtz方法计算, 同样获得了这些分子对应的势能函数、 力常数和光谱数据。Based on the correction of the electron energy under Born Oppenheimer approximation using nuclear motion effect, the parameters of potential energy functions for hydrogen isotopic diatomic molecules (H₂, HD,HT,D₂, DT,T₂) are calculated with QCISD (T) method and aug-cc-pvqz basis set,and those potential energy functions that indicate the differences from the masses of hydrogen isotopic atoms are obtained. The force constants and spectroscopic data of those molecules are calculated as well. The potential energy functions, force constants, and spectroscopic data of the isotopic diatomic molecules OH, OD,and OT are also derived using QCISD method and aug-cc-pvtz basis set.     

达格列净呋喃环杂质的合成

以5-溴-2-氯-4′-乙氧基二苯甲烷为原料，与2,3-二-O-叔丁基二甲基硅基-5,6-O-异亚丙基-D-葡糖醛酸-1,4-内酯缩合后，再经还原、脱保护、酯化及水解反应合成了达格列净呋喃环杂质--(1S)-1,4-脱水-1-(4-氯-3-(4-乙氧基苄基)苯基)-D-葡萄糖，总收率29.0%，纯度98.5%，其结构经¹H NMR，¹³C NMR， DEPT135，¹H-¹H COSY， HSQC， HMBC和MS(ESI)确证。     

1-碘-2-锂-邻碳硼烷与环戊二烯衍生物的类Diels-Alder反应的理论研究

运用密度泛函理论的B3LYP方法对1-碘-2-锂-邻碳硼烷与亚甲基环戊二烯衍生物的类Diels-Alder反应进行了理论研究.计算结果显示：1-碘-2-锂-邻碳硼烷与亚甲基环戊二烯衍生物的类Diels-Alder反应为分步过程,需要依次经过脱LiI形成碳硼炔、碳硼炔与亚甲基环戊二烯成键、碳硼烷基1,2-σ迁移和成环四个过程才能形成与Diels-Alder反应形式相同的产物.其中碳硼烷基的1,2-σ迁移过程为整个反应的决速步,在353 K的实验条件下需要越过28.3 kcal•mol^-1的自由能垒才能形成相应的碳硼烷基降冰片烯衍生物,理论预测的反应速率与实验结果较好吻合.自然键轨道理论（NBO）分析结果显示：该反应与正常电子需求的Diels-Alder反应（NEDDA）具有相似的电子结构特征.文中还对反应底物的取代基效应进行了讨论,并得到了与实验数据基本一致的结果.     

锚固岩体参数的等效方法研究

利用岩体中结构体与结构面的刚度系数比较严密地推导了裂隙岩体的等效法向及切向刚度系数;基于岩体小变形、变形可叠加性及强度参数C、φ不相关性假定,利用Coulomb强度理论推导了裂隙岩体等效连续体的等效强度参数C、φ值的表达式.其成果在岩体边坡的整体稳定分析方面具有重要的应用价值,对于推动岩体本构关系的研究具有重要意义.     

区间值模糊推理反向三I约束算法的鲁棒性

给出了区间值模糊推理FMP、FMT反向三I约束算法解的一般表达形式,基于Moore距离证明了区间值反向三I约束算法的鲁棒性。得到了基于区间值Lukasiewicz蕴涵的反向三I约束算法解的灵敏度。