Raman Optical Activity of N-Acetyl-L-Cysteine in Water and in Methanol: The “Clusters-in-a-Liquid” Model and ab Initio Molecular Dynamics Simulations

Raman and Raman Optical Activity (ROA) spectra of N-acetyl-L-cysteine (NALC), a flexible chiral molecule, were measured in water and in methanol to evaluate the solvent effects. Two different solvation approaches, that is, the DFT based “clusters-in-a-liquid” solvent model and the ab initio molecular dynamics (AIMD) simulations, were applied to simulate the Raman and ROA spectra. Systematic conformational searches were carried out using a recently developed conformational searching tool, CREST, with the inclusion of polarizable continuum model of water and of methanol. The CREST candidates of NALC and the NALC-solvent complexes were re-optimized and their Raman and ROA simulations were done at the B3LYP−D3BJ/def2-TZVP and the B3LYP-aug-cc-pVDZ//cc-pVTZ levels. Also, AIMD simulations, which includes some anharmonic effects and all intermolecular interactions in solution, were performed. By empirically weighting the computed Raman and ROA spectra of each conformer, good agreements with the experimental data were achieved with both approaches, while AIMD offered some improvements in the carbonyl and in the low wavenumber regions over the static DFT approach. The pros and cons of these two different approaches for accounting the solvent effects on Raman and ROA of this flexible chiral system will also be discussed.     

基于质子转移反应-飞行时间质谱快速鉴别不同产地闽北水仙茶

采用质子转移反应-飞行时间质谱仪(PTR-TOF-MS), 构建了3个产地(武夷山、建阳、建瓯)113个闽北水仙茶样品香气的化学指纹图谱, 对所得的闽北水仙茶香气指纹图谱进行主成分分析(PCA), 获得了不同产地闽北水仙茶样品的质谱信息特征, 然后采用软独立建模分类法(SIMCA)、K最邻近结点算法(KNN)、偏最小二乘判别分析法(PLS-DA)对闽北水仙茶的质谱信息进行了模式识别.结果表明, PTR-TOF-MS结合分类识别模式能有效区分不同产地的闽北水仙茶.PCA 提取了3个主成分, 累计贡献率为84.66%;3个识别模型的校正集判别正确率分别为89.38%、100.00%和100.00%, 预测集的判别正确率分别为83.18%、 96.46%和95.57%.基于此成功建立了不同产地的闽北水仙茶识别模型.本方法无需样品预处理、分析速度快、灵敏度高、对茶叶无损伤, 为茶叶产地溯源提供了新方法.     

An adaptive nonmonotone global Barzilai–Borwein gradient method for unconstrained optimization

The Barzilai–Borwein (BB) gradient method has received many studies due to its simplicity and numerical efficiency. By incorporating a nonmonotone line search, Raydan (SIAM J Optim. 1997;7:26–33) has successfully extended the BB gradient method for solving general unconstrained optimization problems so that it is competitive with conjugate gradient methods. However, the numerical results reported by Raydan are poor for very ill-conditioned problems because the effect of the degree of nonmonotonicity may be noticeable. In this paper, we focus more on the nonmonotone line search technique used in the global Barzilai–Borwein (GBB) gradient method. We improve the performance of the GBB gradient method by proposing an adaptive nonmonotone line search based on the morphology of the objective function. We also prove the global convergence and the R-linear convergence rate of the proposed method under reasonable assumptions. Finally, we give some numerical experiments made on a set of unconstrained optimization test problems of the CUTEr collection. The results show the efficiency of the proposed method in the sense of the performance profile introduced (Math Program. 2002;91:201–213) by Dolan and Moré.     

Flexible and powerful strategy for qualitative and quantitative analysis of valepotriates in Valeriana jatamansi Jones using high‐performance liquid chromatography with linear ion trap Orbitrap mass spectrometry

Valeriana jatamansi Jones is an important medicinal plant and its quality is closely related to its region of origin. In the current study, we utilized a flexible and powerful strategy for comprehensive evaluation of the quality diversity for 15 regions in China. The method was based on a hybrid linear ion trap‐Orbitrap mass spectrometry platform. For structure characterization, fragmentation patterns were detected by analyzing a series of standard compounds using data dependent multistage mass spectrometry acquisition. A fragment ion database for valepotriates was established, and the acquired data were high throughput filtered by fragment ion search for compound identification. For quantitative purposes, we normalized the mass spectrometry data of 15 samples using SIEVE 2.0 and the differences in composition were analyzed using principal component analysis combined with hierarchical clustering analysis. The results identified a total of 92 compounds from Valeriana jatamansi Jones. Samples from Dali, Kunming, and Baoshan have better qualities and concentrations of the main active constituents. To verify our strategy, we compared the valtrate, acevaltrate, and baldrinal contents using high‐performance liquid chromatography with diode array detector. We developed and validated a comprehensive qualitative and quantitative analytical method to achieve quality control of Valeriana jatamansi Jones.     

Nonmonotone Inexact Newton Method for the Extended Linear Complementarity Problem

This paper presents a nonmonotone inexact Newton-type method for the extended linear complementarity problem (ELCP). We first reformulate the optimization system of the ELCP problem into a system of smoothed equations. Then we solve this system by a nonmonotone inexact Newton-type algorithm. The global convergence is obtained and numerical tests for some classes of ELCP include linear complementarity, horizontal linear complementarity, and generalized linear complementarity problems are also given to show the e?ciency of the proposed algorithm.     

基于射频前端的GPS软件接收机设计与验证

介绍了基于硬件射频前端的GPS软件接收机设计与验证。针对GPS串行的搜索算法速度慢的缺点，采用了高速的并行码相位搜索算法；设计和实现了码跟踪环和载波跟踪环，并用载波环路来辅助码跟踪环路；综合考虑接收机的动态性和噪声影响，采用最优化设计思想，设计了GPS软件接收机最优环路带宽。采用GPS中频信号采样器采集实际GPS数据，对搜索和跟踪算法进行了验证。测试结果证明所设计的搜索和跟踪方法是有效的，使得用户在微弱信号处理、多路径处理和发展新的算法等方面具有更大的灵活性，为实际的高性能硬件GPS接收机设计提供的重要的基础。     

A UNIVERSAL APPROACH FOR CONTINUOUS OR DISCRETE NONLINEAR PROGRAMMINGS WITH MULTIPLE VARIABLES AND CONSTRAINTS

IntroductionExtensive research works have been published for solving nonlinear mathematicprogramming problems.Nonetheless,it is still difficult to find an effective and universalapproach for general programming problems with multiple design variables and …     

双相介质参数反演的混沌搜索方法

混沌运动能在一定的范围内按自身的规律不重复地遍历所有状态。利用这个特点 ,本文将混沌运动引入到双相介质参数反问题的研究中。首先利用边界元方法实现了由介质参数到地表位移的非线性映射 ,然后通过建立合成位移与实测位移的相关函数将参数识别问题归结为优化问题 ,最后利用混沌运动指导优化搜索求得介质参数。算例结果表明了混沌搜索方法用于双相介质参数反演问题的可行性和有效性     

Non-linear dynamics and pattern formation in a vertical fluid layer heated from the side

We study both experimentally and numerically the convective flow in a tall vertical slot with differently heated walls. The flow is investigated for the fluid with the Prandtl number Pr=26, which is large enough to ensure the traveling waves as primary instability and small enough to prevent boundary layer convection. The flow evolution is determined on the base of the visual observations, power spectra and amplitude analysis. In the numerical simulations of two- and three-dimensional flows, we accept an assumption of an infinite fluid layer. The satisfactory agreement with experiment is observed, and the sequence of convection states is discovered. It starts with a plane-parallel flow as primary solution, which becomes unstable to two counter-propagating waves. It is followed by a tertiary three-dimensional flow in the form of wavy traveling waves. As the Grashof number is increased even further, a chaotically oscillating cellular pattern consisting of the pieces of broken waves arises. The formation of a structure in the form of the vertical rolls chaotically modulated along axes concludes this complicated picture.