Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.     

基于荧光光谱技术的菜籽油氧化状态智能评价

菜籽油在加工及贮藏过程中，易受氧气、温度、光照等因素的影响，产生氧化酸败现象。为准确判断油脂氧化程度，实现不同氧化模式下菜籽油品质的快速判别，采用三维同步荧光光谱技术结合平行因子分析法及BP神经网络法建立菜籽油氧化状态的智能评价模型。以冷榨菜籽油为原料，将样品分别置于常温、Schaal烘箱、高温模式中氧化处理，期间采集菜籽油的三维同步荧光光谱数据及理化指标，当理化指标超出国标限定范围时，停止采集数据。结果表明，菜籽油中荧光物质在不同氧化模式中的演变规律呈显著差异，氧化温度对菜籽油荧光光谱有明显影响。常温氧化350 d与第1 d相比，菜籽油的特征荧光峰位置无变化，仅在激发波长Ex为620和660 nm附近荧光峰强度发生微弱变化；Schaal烘箱氧化26 d后，在激发波长Ex为620和660 nm附近荧光峰强度显著减弱，且在激发波长Ex为350～450 nm之间有新的荧光峰生成；高温氧化48 h后，Ex为620和660 nm处荧光峰消失，在Ex为400～550 nm处产生显著荧光峰，相对Schaal烘箱氧化，荧光波长发生一定程度红移，这是由于高温氧化过程中油脂氧化生成的物质稳定性较差引起的。利用平行因子分析法对三维同步荧光光谱数据进行分解获取有效的二维荧光光谱数据，当组分数为6，Δλ=60 nm时激发波长的载荷值最大，不同样品间差异最显著。选定Δλ=60 nm波段的二维荧光光谱数据用于智能评价，作为BP神经网络模型的输入值，以极性组分作为模型输出值，分别对菜籽油三种氧化模式数据建模训练。实验结果表明，三种氧化模式对应的训练集、验证集、测试集模型相关系数r均能达到0.9以上，其中常温氧化模式中验证集及测试集模型的相关系数r为1，输出值与目标值较接近，模型的预测效果较好；综合三种氧化模式数据建模，对应训练集、验证集、测试集模型的相关系数分别为0.999，0.913和0.988，均方误差均较小，说明该模型能准确判断菜籽油的不同氧化状态。因此，三维同步荧光光谱技术结合平行因子分析法、BP神经网络法建立快速检测模型能实现菜籽油不同氧化状态的判别，为菜籽油的氧化程度的评价提供新方法，同时为其他食用油的品质评价提供参考。     

基于DID模型的ITS对北京交通拥堵改善的研究:评价期的视角

采用双重差分模型,基于智能交通系统(ITS)效用发挥滞后时间为3年,选择2010年和2014年作为评价时点对ITS实施效果和北京交通拥堵之间的相关性进行分析.DID模型计量分析的最终结果显示,ITS效果的发挥明显改善了北京交通拥堵问题.为了验证评价结果的可信度,通过改变评价时点这一参数对评价结果进行稳健性检验,结果仍显示ITS效应发挥对北京交通拥堵改善有很大的促进作用.     

Fast computation of generic bivariate resultants

We prove that the resultant of two “sufficiently generic” bivariate polynomials over a finite field can be computed in quasi-linear expected time, using a randomized algorithm of Las Vegas type. A similar complexity bound is proved for the computation of the lexicographical Gröbner basis for the ideal generated by the two polynomials.     

Synthesis and antitumor and antibacterial evaluation of fluoroquinolone derivatives(Ⅲ):Mono- and bis-Schiff-bases

To further explore an efficient modified route for the shift from an antibacterial fluoroquinolone to an antitumor one,mono-Schiff bases 6a-6h related to ciprofloxacin C3 carbonylhydrazone and bis-Schiff bases 4a-4h corresponding to C3/C7 carbonylhydrazone/hydrazone attached on a skeleton of ciprofloquinolone were designed and synthesized,and their in vitro antitumor activity against CHO,HL60,L1210 cells and antibacterial activity against Staphylococcus aureus and Escherichia coli were also reported.     

Geographical discrimination of Glechomae Herba based on fifteen phenolic constituents determined by LC–MS/MS method combined with chemometric methods

Glechomae Herba (GH) is rich in bioactive phenolic constituents and is widely used for treatment of cholelithiasis, urolithiasis and dropsy. The simultaneous determination of phenolic constituents in GH from different geographical origins is significant for authentication and quality control purposes. In this study, we developed a strategy integrating targeted analysis and chemometric methods for quality evaluation and discrimination of GH from different geographical origins. Firstly, an accurate and reliable liquid chromatography–tandem mass spectrometry method was developed for simultaneous quantification of 15 phenolic constituents in GH from different geographical origins. The established method was well validated in terms of desirable specificity, linearity, precision and accuracy. Secondly, the quantitative data were subjected to principal component analysis and orthogonal partial least squares discriminant analysis. Thirdly, a heatmap visualization was employed for clarifying the distribution of 15 phenolic compounds in GH from different geographical origins. These results indicated that GH samples from Shandong province obviously differ from those from other provinces in the content of bioactive phenolic constituents. Collectively, the proposed platform might be a suitable tool for quality evaluation and discrimination of GH from different geographical origins, providing promising perspectives in tracking the formulation processes of traditional Chinese medicine products.     

Two improved formulations for the minimum latency problem

In network problems, latency is associated with the metric used to evaluate the length of the path from a root vertex to each vertex in the network. In this work we are dealing with two applications or variations of the minimum latency problem known as the repairman problem and the deliveryman problem. We have developed two integer formulations for the minimum latency problem and compared them with other two formulations from the literature for the time-dependent traveling salesman problem. The present work highlights the similarities and differences between the different formulations. In addition, we discuss the convenience of including a set of constraints in order to reduce the computation time needed to reach the optimal solution. We have carried out extensive computational experimentation on asymmetrical instances, since they provide the characteristics of the deliveryman and repairman problems in a better way.     

一类综合评价指数编制路径及案例

综合评价指数是一种广义上的统计指数,在讨论了综合评价指数与一般统计指数不同的基础上,引述了综合评价指数一般编制步骤并详细分析研究了综合评价指数编制过程中的权重确定,提出了基于等权设计思想的加权修正综合评价指数编制方法,最后以甘肃省装备制造产业为例进行了展示.     

LDI学生成绩评价方法的构建——以精细化学品化学课程为例

根据我院化工专业精细化学品化学课程改革的实际，围绕以评促学、以评助教，构建了LDI学生课程成绩评价方法。该方法以教师和学生为评价主体，从3个环节（理论学习、课内实验、创新实践）、4个维度（课前自学、课堂学习、课内实验与创新实践、期末考试）入手，将评价内容分为多个项目来引导学生学习、实践，并全面考核学生的知识与能力。该法不仅能提高学生学习的主动性，还能潜移默化地培养学生的创新意识和团队精神。     

轻稀土萃取分离工艺技术经济评价

在传统、三出口、组合联动轻稀土萃取分离工艺研究分析的基础上,设计开发了带模糊分离和置换萃取等技术的组合联动轻稀土萃取分离新工艺流程,并与传统工艺进行了技术经济比较。经比较证明,组合联动轻稀土分离新工艺先进合理,充槽投资更省,生产成本更低,生产废水排放更少。