基于电化学老化衰退模型的锂离子动力电池外特性

当前锂离子动力电池电化学模型存在模型复杂、建模难度大、计算效率低、老化评估效果差的问题,本文提出一种考虑电池衰退老化的机理模型(ADME).本文首先通过有限差分法对伪二维(P2D)电化学模型进行离散降阶处理,得到简化伪二维(SP2D)模型.在SP2D模型的基础上,基于阴阳两极发生的副反应导致的衰退老化现象,提出一种考虑电池衰退老化的机理模型.其次,使用多变量偏差补偿最小二乘法实现模型参数辨识.最后通过动力电池衰退老化性能循环实验,对比分析了恒流、脉冲工况下SP2D模型和ADME模型的终端电压输出.结果表明:ADME模型较为简单、计算效率和估算精度高,可以有效评估电池容量老化衰退,得到理想的锂离子动力电池外特性曲线.     

Metabolite identification of tanshinol borneol ester in rats by high‐performance liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight mass spectrometry

Tanshinol borneol ester (DBZ) is a potential drug candidate composed of danshensu and borneol. It shows anti‐ischemic and anti‐atherosclerosis activity. However, little is known about its metabolism in vivo. This research aimed to elucidate the metabolic profile of DBZ through analyzing its metabolites using high‐performance liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight mass spectrometry. Chromatographic separation was performed on an Agilent TC‐C₁₈ column (150 × 4.6 mm, 5.0 μm) with gradient elution using methanol and water containing 0.2% (v/v) formic acid as the mobile phase. Metabolite identification involved analyzing the retention behaviors, changes in molecular weights and MS/MS fragment patterns of DBZ and its metabolites. As a result, 20 potential metabolites were detected and tentatively identified in rat plasma, urine and feces after administration of DBZ. DBZ could be metabolized to O‐methylated DBZ, DBZ‐O‐glucuronide, O‐methylated DBZ‐O‐glucuronide, hydroxylated DBZ and danshensu. Danshensu, a hydrolysis product of DBZ, could further be transformed into 12 metabolites. The proposed method was confirmed to be a reliable and sensitive alternative for characterizing metabolic pathways of DBZ and providing valuable information on its druggability.     

Contingent derivatives and regularization for noncoercive inverse problems

Abstract

We study the inverse problem of parameter identification in noncoercive variational problems that commonly appear in applied models. We examine the differentiability of the set-valued parameter-to-solution map using the first-order and the second-order contingent derivatives. We explore the inverse problem using the output least-squares and the modified output least-squares objectives. By regularizing the noncoercive variational problem, we obtain a single-valued regularized parameter-to-solution map and investigate its smoothness and boundedness. We also consider optimization problems using the output least-squares and the modified output least-squares objectives for the regularized variational problem. We give a complete convergence analysis showing that for the output least-squares and the modified output least-squares, the regularized minimization problems approximate the original optimization problems suitably. We also provide the first-order and the second-order adjoint method for the computation of the first-order and the second-order derivatives of the output least-squares objective. We provide discrete formulas for the gradient and the Hessian calculation and present numerical results.     

振型归一化对梁结构柔度曲率损伤指标的影响

结构柔度矩阵需由质量矩阵归一化振型获得,而质量矩阵归一化振型难以直接测得,限制了柔度曲率类损伤指标的应用。为分析振型归一化方法对梁结构柔度曲率类损伤指标的影响,根据梁结构的刚度、弯矩和位移曲率的关系,建立了均布荷载作用下结构损伤前后位移曲率与损伤程度的理论表达式,实现定量分析均匀荷载面曲率结构损伤程度。提出P-范数振型归一化方法,通过均匀荷载面曲率指标推导了振型质量矩阵归一化系数差x_α与损伤程度的关系。以三跨连续梁算例对理论进行了验证,结果表明,损伤程度定量指标效果良好,不同P-范数振型归一化方法下,损伤程度的偏差可由2x_α估算;2-范数振型归一化方法的损伤识别结果与质量矩阵振型归一化结果最接近,故当无法获得质量矩阵归一化振型时,可采用2-范数归一化振型代替。     

基于改进克隆选择算法的统一混沌系统同步控制与参数辨识

提出一种改进的克隆选择算法用于解决混沌系统的参数辨识问题.该算法利用抗体的高频变异和受体编辑两种机制有效平衡算法的全局探索与局部开发，并引入向精英抗体学习策略进一步提高算法的收敛质量.对10个优化问题的实验表明：所提出算法在求解精度、收敛速度以及稳定性方面具有更好的性能.以参数未知统一混沌系统的同步控制为研究对象，合理设计同步控制器，并对同步系统的稳定性进行理论分析.通过对同步比例因子的设置，实现统一混沌系统的完全同步、反同步、投影同步等多种同步方式.仿真实验结果表明该方法能够实现对未知系统参数的精确辨识以及驱动-响应系统的有效同步控制，验证了所提方法的可行性与有效性.     

基于改进云推理算法的塔架结构损伤识别

为了解决塔架结构的损伤识别问题,提出了基于应变能和改进云推理算法的损伤识别方法。首先描述了云模型的基本理论和数字特征,并给出了模态应变能的基本公式;然后分析了X条件云发生器和Y条件云发生器的基本算法和运行步骤,借助灰云模型建立相应的前件云和后件云规则,考虑了测量噪声的影响,利用云发生器生成多组云滴,并利用多模式下云滴的确定度和生成值构建了基本云推理算法及其损伤识别指标。基本云推理算法中常会产生不均匀发散的云滴,从而使计算结果产生一定的偏差,为了降低云滴发散产生的偏差影响,提出了基于损伤模式数量加权的云推理改进策略。计算结果表明:云推理算法可以较好地应用于塔架结构的损伤识别,其识别结果明显优于传统的应变能耗散率指标方法;而改进云推理算法进一步提高了识别的精度,优于基本云推理算法。     

基于流量测点的热网变动阻力系数优化辨识

随着供热计量系统的普及，系统可以根据负荷的变化进行调整，管网的阻力系数随即发生变化。对变动阻力系数进行优化辨识是了解供热管网实时运行状况的有效手段。提出一种基于流量监测数据的供热管网变动阻力系数优化辨识方法，并利用遗传算法进行求解。对洛阳市某小区供暖季管网实际运行数据进行验证，辨识结果的相对误差在5%以内。结果表明：该方法可以在只有流量观测数据时得到精度较高的供热管网变动阻力系数，为供热系统的运行调节提供指导。     

Serum pharmacochemistry combined with multiple data processing approach to screen the bioactive components and their metabolites in Mutan Cortex by ultra‐performance liquid chromatography tandem mass spectrometry

Root cortex of Paeonia suffruticosa Andrews (Paeoniaceae), known as Moutan Cortex (MC), is known to have anti‐allergic and anti‐inflammatory properties. However, the constituents absorbed into blood after oral administration of MC remain unknown. A sensitive and rapid method by ultra‐high‐pressure liquid chromatography–electrospray ionization–quadrupole‐time‐of‐flight mass spectrometry (UPLC‐ESI‐Q‐TOF‐MS) technology and the MetaboLynx^TM software combined with multiple data processing approach (Mdpa) was established to investigate the absorbed constituents in rats after oral administration of MC, providing unique high‐throughput capabilities for drug metabolism study. A hyphenated electrospray ionization and quadrupole‐time‐of‐flight analyzer was used for the determination of accurate mass of the fragment ion in negative mode, with excellent MS mass accuracy and enhanced data acquisition. This rapid automated analysis method was successfully applied for screening and identification of the constituents absorbed and metabolized studies of MC after oral administration to rats. A total of 46 peaks were obtained from MC, 41 of which were tentatively characterized. In the VIP‐plot of orthogonal partial least‐squares discriminant analysis, 23 interesting ions in serum samples were extracted, and 16 parent components and seven metabolites were detected in vivo. The integrative serum pharmacochemistry technique, UPLC‐ESI‐Q‐TOF‐MS, and Mdpa method were successfully applied for rapid discovery of multiple components from MC. Copyright © 2013 John Wiley & Sons, Ltd.     

基于多特征算法选择的太赫兹时域光谱用于水稻种子掺假研究

该文提出了一种基于太赫兹时域光谱的水稻种子模式识别方法。实验以10种不同品牌混合掺假的水稻种子为样本,基于采集的样本太赫兹时域光谱数据,通过建立Relief、随机森林（RF）、支持向量机递归特征消除（SVM-RFE）和最大相关最小冗余（mRMR）模型分别对样本光谱波长进行特征选择,最后设计分类器对4种特征选择方法处理后的样本进行分类识别。结果表明,基于布谷鸟算法（CS）优化的极限学习机模型对经RF特征选择算法提取后的样本光谱数据具有最佳识别效果,其准确率可达100%,实验对于法庭科学领域内种子的掺假鉴定具有一定的借鉴意义。     

Identification strategies for flame retardants employing time‐of‐flight mass spectrometric detectors along with spectral and spectra‐less databases

In the past, the preferred strategy for the identification of unknown compounds was to search in an appropriate mass spectral database for spectra obtained using either electron ionisation (GC‐MS analyses) or collision‐induced dissociation (LC‐MS/MS analyses). Recently, an increase has been seen in the use of accurate mass instruments and spectra‐less databases, based on monoisotopic accurate mass alone. In this article, we describe a systematic workflow for the screening and identification of new flame retardants. This approach utilises LC‐quadrupole‐time‐of‐flight MS and spectra‐less databases based only on monoisotopic accurate mass for the identification of ‘unknowns’. An in‐house database was built, and the input parameters used in the data analysis process were optimised for flame retardant chemicals, so that it can be easily transferred to other laboratories. The procedure was successfully applied to dust, foam and textiles from car interiors and indoor consumer products. The developed method was demonstrated for the main new flame retardant present in Antiblaze V6 and for the three unreported reaction by‐products/impurities present in the same technical mixture. Copyright © 2015 John Wiley & Sons, Ltd.