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.     

Characterization and tentative identification of new flunitrazepam metabolites in authentic human urine specimens using liquid chromatography‐Q exactive‐HF hybrid quadrupole‐Orbitrap‐mass spectrometry (LC‐QE‐HF‐MS)

Flunitrazepam (FNZ) is a potent hypnotic, sedative, and amnestic drug used to treat severe insomnia. In our recent study, FNZ metabolic profiles were investigated carefully. Six authentic human urine samples were purified using solid phase extraction (SPE) without enzymatic hydrolysis, and urine extracts were then analyzed by liquid chromatography‐Q exactive‐HF hybrid quadrupole‐Orbitrap‐mass spectrometry (LC‐QE‐HF‐MS), using the full scan positive ion mode and targeted MS/MS (ddms2) technique to make accurate mass measurements. There were 25 metabolites, including 13 phase I and 12 phase II metabolites, which were detected and tentatively identified by LC‐QE‐HF‐MS. In addition, nine previously unreported phase II glucuronide conjugates and four phase I metabolites are reported here for the first time. Eight metabolic pathways, including N‐reduction and O‐reduction, N‐glucuronidation, O‐glucuronidation, mono‐hydroxylation and di‐hydroxylation, demethylation, acetylation, and combinations, were implicated in this work, and 2‐O‐reduction together with dihydroxylation were two novel metabolic pathways for FNZ that were identified tentatively. Although 7‐amino FNZ is widely considered to be the primary metabolite, a previously unreported metabolites (M12) can also serve as a potential biomarker for FNZ misuse.     

高压下L-丝氨酸的拉曼光谱研究

压力可以引起蛋白折叠与变性。作为蛋白质的基本构成单位，氨基酸在高压下的变化近来年备受关注。在常见的20种氨基酸中，学者们利用高压拉曼技术已研究了多种氨基酸在高压下的变化，研究的最高压力达到30 GPa。为了探究L-丝氨酸(C₃H₇NO₃)在极高压力下的结构变化情况，采用原位高压拉曼技术在常温下对L-丝氨酸晶体进行研究，最高压力达到22.6 GPa。研究发现，当压力达到2.7 GPa时，在102 cm-1处出现新峰，在1 123 cm-1(NH₃反对称摇摆振动)处的特征峰出现劈裂；当压力达到5.4 GPa时，L-丝氨酸晶体在574 cm-1处出现新峰，同时原来164 cm-1处峰消失；当压力达到6.0 GPa时，位于226，456，770和2 968 cm-1(CH₂伸缩振动)等处出现新峰，877 cm-1处的CC伸缩振动峰发生劈裂，产生894 cm-1新峰；当压力达到7.9 GPa时，在145，151和2 946 cm-1等出现新峰，同时原在CO₂摇摆振动峰的肩峰531 cm-1消失；当压力达到11.0 GPa时，位于249 cm-1处的振动峰开始劈叉，在241 cm-1处形成新峰，位于2 956 cm-1(CH₂伸缩振动)同时原位于391和431 cm-1处的峰消失；当压力达到17.5 GPa时，在200 cm-1处出现新峰。通过进一步分析L-丝氨酸的拉曼波数随压力的变化，发现很多拉曼峰在1.37，2.2，5.3，7.46和11.0 GPa以及15.5 GPa等压力点处都出现了拐点。其结果表明：L-丝氨酸在0.1～22.6 GPa之间共发生7处结构相变，分别位于压力区间0.1~1.37，2.2~2.7，5.3，6.0，7.46~7.9，10.1~11.0和15.5~17.5 GPa之间。而且，在6.0 GPa新的相变点在之前文献中未论述过。由于L-丝氨酸晶体在6.0 GPa时CC伸缩振动峰发生劈裂，这现象可能是由于压力引起L-丝氨酸晶体分子发生重排导致的，同时L-丝氨酸晶体分子重排导致氢键发生重排，使得L-丝氨酸晶体出现新的CH₂伸缩振动峰。L-丝氨酸晶体在10.1~11.0 GPa之间的拉曼光谱变化主要集中在低波数段，该波数段的拉曼振动模式主要与晶体晶格振动等低能量振动有关。同时在高波数段出现新的CH₂峰，由此可推测在10.1~11.0 GPa之间，L-丝氨酸晶体的晶格振动发生变化，产生了新的氢键，从而导致了L-丝氨酸晶体结构的改变。L-丝氨酸晶体在15.5~17.5 GPa之间，由于没有发现直接证据证明其发生结构相变，只是在拉曼波数随压力变化中，发现其在17.5 GPa时出现拐点，因此推测L-丝氨酸晶体在15.5~17.5 GPa之间可能发生结构相变。     

氢气浸泡辐照加速方法在3DG111器件上的应用及辐射损伤机理分析

本文以~(60)Co为辐照源,针对3DG111型晶体管,利用半导体参数分析仪和深能级缺陷瞬态谱仪,研究高/低剂量率和有/无氢气浸泡条件下,电性能和深能级缺陷的演化规律.试验结果表明,与高剂量率辐照相比,低剂量率辐照条件下,3DG111型晶体管的电流增益退化更加严重,这说明该器件出现了明显的低剂量率增强效应;无论是高剂量率还是低剂量率辐照条件下,3DG111晶体管的辐射损伤缺陷均是氧化物正电荷和界面态陷阱,并且低剂量率条件下,缺陷能级较深;氢气浸泡后在高剂量率辐照条件下,与未进行氢气处理的器件相比,辐射损伤程度明显加剧,且与低剂量率辐照条件下器件的损伤程度相同,缺陷数量、种类及能级也相同.因此,氢气浸泡处理可以作为低剂量率辐射损伤增强效应加速评估方法的有效手段.     

一种刺松藻来源的硫酸阿拉伯聚糖的制备及特征结构表征

刺松藻(Codium fragile)经水提-醇沉获得粗多糖, 进一步将刺松藻粗多糖(CFP) 通过Q-Sepharose Fast Flow(QFF) 阴离子交换柱纯化得到6个多糖组分CFP1CFP6, 其中, 在CFP6中发现纯度较高的阿拉伯聚糖. 采用高效凝胶渗透色谱与十八角激光散射仪联用法和1-苯基-3-甲基-5-吡唑啉酮(PMP)柱前衍生高效液相色谱法对CFP6的分子量及单糖组成进行了分析. 结果表明, CFP6是一种分子量为79290的多糖, 由阿拉伯糖(Ara)和半乳糖(Gal)组成, 二者摩尔比为14.8:1.0. 通过多维核磁共振波谱、 液相色谱-质谱联用及二级质谱等方法对CFP6的糖苷键连接方式及其寡糖序列结构进行表征, 进一步阐明了该复杂多糖的特征结构. 经判断, CFP6主链由Ara组成, 通过 β-(1→3)糖苷键连接, 在Ara的C2位存在分支结构, 硫酸基位于Ara的C4或C2位.     

NPK 2.0: Introducing tensor decompositions to the kinetic analysis of gas–solid reactions

A method for deriving kinetic models of gas–solid reactions for reactor and process design is presented. It is based on the nonparametric kinetics (NPK) method and resolves many of its shortcomings by applying tensor rank-1 approximation methods. With this method, it is possible to derive kinetic models based on the general kinetic equation from any combination of experiments without additional a priori assumptions. The most notable improvements over the original method are that it is computationally much simpler and that it is not limited to two variables. Two algorithms for computing the rank-1 approximation as well as a tailored initialization method are presented, and their performance is assessed. Formulae for the variance estimation of the solution values are derived to improve the accuracy of the model identification and to provide a tool for diagnosing the quality of the kinetic model. The methods effectiveness and performance are assessed by applying it to a simulated data set. A Matlab implementation is available as Supporting Information.     

A computational foray into the mechanism and catalysis of the adduct formation reaction of guanine with crotonaldehyde

Crotonaldehyde, a common environmental pollutant and product of endogenous lipid peroxidation, reacts with guanine to form DNA adducts with pronounced genotoxicity and mutagenicity. Here, we explore the molecular mechanism of this adduct formation using double-hybrid density functional theory methods. The reaction can be envisaged to occur in a two-step fashion via an aza-Michael addition leading to an intermediate ring-open adduct followed by a cyclization reaction giving the mutagenic ring-closed adduct. We find that (i) a 1,2-type addition is favored over a 1,4-type addition for the aza-Michael addition, and (ii) an initial tautomerization of the guanine moiety in the resulting ring-open adduct significantly reduces the barrier toward cyclization compared to the direct cyclization of the ring-open adduct in its keto-form. Overall, the aza-Michael addition is found to be rate-determining. We further find that participation of a catalytic water molecule significantly reduces the energy barriers of both the addition and cyclization reaction. © 2018 Wiley Periodicals, Inc.     

尾流激励的叶片气动力降阶模型

气动力降阶模型是研究叶片气动弹性振动快速高效的新方法。现有气动力降阶模型的研究主要集中在叶片颤振方面，没有涉及更为常见的上游尾流激励的叶片振动问题。本文提出基于Volterra级数的尾流激励叶片气动力降阶模型，为尾流激励下叶片振动和动静叶干涉振动研究提供了新的思路。采用行波法简化尾流的参数个数，用阶跃信号法识别降阶模型的核函数。二维叶片的算例结果表明，本文方法可以较准确地描述尾流激励引起的叶片气动力振荡，而且计算效率极高。