一种确定整周模糊度搜索空间的方法

模糊度搜索空间的大小是影响模糊度解算效率的关键因素之一.针对传统确定模糊度搜索空间的方法较为保守,致使搜索空间过大,提出了一种基于最小二乘模糊度降相关平差法(LAMBDA)的改进方法.首先对目前模糊度搜索空间确定方法给予了介绍和深入的分析比较,评价了这些经典方法的优缺点.在此基础上,定义了搜索空间的一个影响因子η,并结合LAMBDA方提出了确定模糊度搜索空间的修正公式.基于仿真和实测数据对修正方法进行实验,结果表明方法在保证获得期望模糊度组数的前提下,其确定的模糊度搜索空间包含的整数点个数更小,可保证90%以上实际模糊度组数接近于期望值.     

一种修正的CD共轭梯度法及其全局收敛性

求解无约束优化问题的共轭梯度法,其搜索方向的下降性往往依赖于所采用的线性搜索.将提出一种修正的CD算法,其搜索方向d_k始终满足1-1/u≤(-g_k~Td_k)/(‖g_k‖~2)≤1+1/u(u1),即算法在不依赖任何线性搜索的情况下能始终产生充分下降方向.同时,当采用精确线性搜索时,该修正的CD算法就是标准的CD共轭梯度法.在适当条件下,还证明了修正的CD算法在强Wolfe线性搜索下具有全局收敛性.最后,我们给出了相应的数值结果,说明了算法是一种有效的算法.     

空铁联运网络的模型构建与算法设计

针对空铁联运网络具体联运路径的设计问题,借鉴枢纽航线网络p-枢纽中位问题的研究思想,将非枢纽城市间可以直航考虑进去,以联运网络总成本最低为目标函数,构建了允许直航的空铁联运网络混合整数规划模型,并设计了基于遍历搜索的最短路算法来求解模型.最后选取样本城市对模型和算法进行算例分析,给出了不同参数组合下的最优目标值和具体联运路径,设计了中国14个城市的空铁联运网络.算例结果表明联运总成本大小和联运路径的数目与枢纽数目m、折扣系数ρ紧密相关:m越大,ρ越小,联运总成本越小,联运路径数目越多;反之亦然.     

On Weak and Strong Convergence of the Projected Gradient Method for Convex Optimization in Real Hilbert Spaces

This work focuses on convergence analysis of the projected gradient method for solving constrained convex minimization problems in Hilbert spaces. We show that the sequence of points generated by the method employing the Armijo line search converges weakly to a solution of the considered convex optimization problem. Weak convergence is established by assuming convexity and Gateaux differentiability of the objective function, whose Gateaux derivative is supposed to be uniformly continuous on bounded sets. Furthermore, we propose some modifications in the classical projected gradient method in order to obtain strong convergence. The new variant has the following desirable properties: the sequence of generated points is entirely contained in a ball with diameter equal to the distance between the initial point and the solution set, and the whole sequence converges strongly to the solution of the problem that lies closest to the initial iterate. Convergence analysis of both methods is presented without Lipschitz continuity assumption.     

Barzilai–Borwein method with variable sample size for stochastic linear complementarity problems

A smoothing method for solving stochastic linear complementarity problems is proposed. The expected residual minimization reformulation of the problem is considered, and it is approximated by the sample average approximation (SAA). The proposed method is based on sequential solving of a sequence of smoothing problems where each of the smoothing problems is defined with its own sample average approximation. A nonmonotone line search with a variant of the Barzilai–Borwein (BB) gradient direction is used for solving each of the smoothing problems. The BB search direction is efficient and low cost, particularly suitable for nonmonotone line search procedure. The variable sample size scheme allows the sample size to vary across the iterations and the method tends to use smaller sample size far away from the solution. The key point of this strategy is a good balance between the variable sample size strategy, the smoothing sequence and nonmonotonicity. Eventually, the maximal sample size is used and the SAA problem is solved. Presented numerical results indicate that the proposed strategy reduces the overall computational cost.     

Testing an alternative search algorithm for compound identification with the ‘Wiley Registry of Tandem Mass Spectral Data,MSforID’

A tandem mass spectral database system consists of a library of reference spectra and a search program. State‐of‐the‐art search programs show a high tolerance for variability in compound‐specific fragmentation patterns produced by collision‐induced decomposition and enable sensitive and specific ‘identity search’. In this communication, performance characteristics of two search algorithms combined with the ‘Wiley Registry of Tandem Mass Spectral Data, MSforID’ (Wiley Registry MSMS, John Wiley and Sons, Hoboken, NJ, USA) were evaluated. The search algorithms tested were the MSMS search algorithm implemented in the NIST MS Search program 2.0g (NIST, Gaithersburg, MD, USA) and the MSforID algorithm (John Wiley and Sons, Hoboken, NJ, USA). Sample spectra were acquired on different instruments and, thus, covered a broad range of possible experimental conditions or were generated in silico. For each algorithm, more than 30 000 matches were performed. Statistical evaluation of the library search results revealed that principally both search algorithms can be combined with the Wiley Registry MSMS to create a reliable identification tool. It appears, however, that a higher degree of spectral similarity is necessary to obtain a correct match with the NIST MS Search program. This characteristic of the NIST MS Search program has a positive effect on specificity as it helps to avoid false positive matches (type I errors), but reduces sensitivity. Thus, particularly with sample spectra acquired on instruments differing in their setup from tandem‐in‐space type fragmentation, a comparably higher number of false negative matches (type II errors) were observed by searching the Wiley Registry MSMS. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

Supramolecular optical sensor arrays for on-site analytical devices

Supramolecular optical chemosensors are useful tools in analytical chemistry for the visualization of molecular recognition information. One advantage is that they can be utilized for array systems to detect multiple analytes. However, chemosensor arrays have been evaluated mainly in the solution phase, which limits a wide range of practical applications. Thus, appropriate solid support materials such as polymer gels and papers are required to broaden the scope of the application of chemosensors as on-site analytical tools. In this review, we summarize the actual approaches for the fabrication of solid-state chemosensor arrays combined with powerful data processing techniques and portable digital recorders for real-world applications.     

基于麻雀搜索算法结合深度前馈神经网络的近红外模型转移方法研究

该文提出了一种基于麻雀搜索算法结合深度前馈神经网络（SSA－DFN）的近红外光谱模型转移方法。使用深度前馈神经网络拟合不同仪器采集到的光谱之间的非线性函数映射,并将麻雀搜索算法用于网络各层连接权值和阈值的初始化,通过种群中个体位置的迭代更新,求得连接权值和阈值的最优初始值;通过多次调整深度前馈神经网络模型的超参数,使网络拟合效果趋于最优,最终确定转移函数。为验证方法的有效性,分别从烟叶近红外光谱谱图、主成分投影和预测结果的角度,将SSA－DFN方法与分段直接校正算法（PDS）、典型相关性分析算法（CCA）转移前后的效果进行了对比。结果表明SSA－DFN方法转移后的从机光谱与原主机光谱重合度最高,转移后主、从机总糖、烟碱含量的预测结果差异不显著,预测平均误差从8.32%、9.15%分别降至4.65%、4.82%,预测均方根误差（RMSEP）和决定系数（R2）等指标均优于PDS和CCA,取得了最佳的转移效果,可满足企业需求。结果表明该方法是一种有效的模型转移方法。     

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.