提高布里渊光时域反射应变仪测量空间分辨力的等效脉冲光拟合法

由于探测光脉冲宽度受到限制,布里渊光时域反射仪(BOTDR)在对光纤上的应变进行分布式测量时,空间分辨力只能达到1 m。针对布里渊光时域反射仪单次采样接收背向布里渊散射信号(BBS)需要一定的时间,提出了基于等效脉冲光的多洛仑兹拟合法以提高其应变测量的空间分辨力。该方法将探测光脉冲在布里渊光时域反射仪完成单次采样所需的时间上进行积分,将积分函数作为等效脉冲光的表达式,再根据等效脉冲光的形状将布里渊光时域反射仪接收到的背向布里渊散射谱(BBS)细分,并对它进行多洛仑兹迭代拟合,准确求得每个细分布里渊散射谱的中心频率,进而利用光纤中布里渊频移与应变的对应关系,得到光纤中与细分布里渊散射谱对应的细分光纤单元上的应变情况。实验结果表明,利用这种方法,可使布里渊光时域反射仪应变测量的空间分辨力提高至0.05 m。     

Guest-Reaction Driven Cage to Conjoined Twin-Cage Mitosis-Like Host Transformation

We report here a guest-reaction-induced mitosis-like host transformation from a known Pd₄L₂ cage 1 to a conjoined Pd₆L₃ twin-cage 2 featuring two separate cavities. The encapsulation of 1-hydroxymethyl-2-naphthol ( G1 ), a known ortho-quinone methide (o-QMs) precursor, within the hydrophobic cavity of cage 1 is found crucial to realize the cage to twin-cage conversion. Confined G1 molecules within the nanocavity undergo self-coupling dimerization reaction to form 2,2′-dihydroxy-1,1′-dinaphthylmethane ( G2 ) which then triggers the cage to twin-cage mitosis. The same conversion also proceeds, in a much faster rate, via the direct templation of G2 , confirming the induced-fit transformation mechanism. The structure of the ( G2 )₂⊂ 2 host–guest complex has been established by X-ray crystallographic study, where cis- to trans- conformational switch on one bridging ligand is revealed.     

Multivariate optimization and comparison between conventional extraction (CE) and ultrasonic-assisted extraction (UAE) of carotenoid extraction from cashew apple

Carotenoids are an essential component of cashew and can be used in pharmaceuticals, cosmetics, natural pigment, food additives, among other applications. The present work focuses on optimizing and comparing conventional and ultrasound-assisted extraction methods. Every optimization step took place with a 1:1 (w:w) mixture of yellow and red cashew apples lyophilized and ground in a cryogenic mill. A Simplex-centroid design was applied for both methods, and the solvents acetone, methanol, ethanol, and petroleum ether were evaluated. After choosing the extractor solvent, a central composite design was applied to optimize the sample mass (59–201 mg) and extraction time (6–34 min). The optimum conditions for the extractor solvent were 38% acetone, 30% ethanol, and 32% petroleum ether for CE and a mixture of 44% acetone and 56% methanol for UAE. The best experimental conditions for UAE were a sonication time of 19 min and a sample mass of 153 mg, while the CE was 23 min and 136 mg. Comparing red and yellow cashews, red cashews showed a higher carotenoid content in both methodologies. The UAE methodology was ca. 21% faster, presented a more straightforward composition of extracting solution, showed an average yield of superior carotenoid content in all samples compared to CE. Therefore, UAE has demonstrated a simple, efficient, fast, low-cost adjustment methodology and a reliable alternative for other applications involving these bioactive compounds in the studied or similar matrix.     

有机污染物的生物富集因子与拓扑指数的数学模型

依据价连接性指数(xi)、电性拓扑态指数(ej)及电性距离矢量(mk)构建239种有机污染物生物富集因子(FBC)的6参数QSFR(定量结构-生物富集因子相关性)模型, 不仅相关程度高, 而且所用自变量数少. 该模型的传统相关系数(R2)为0.821, LOO(levae-one-out)交互验证系数(Q2)为0.809, 证明具有良好的稳健性及预测能力. 根据进入该模型的6个参数可知, 影响有机污染物FBC的主要结构基团是: —C—、>C—、—O—、—X、—NH2以及分子的柔韧性、折叠程度等空间因素. 可以认为在生物富集过程中,“诱导契合机理”也发挥一定作用. 对自变量集进行正交变换, 既不影响模型的相关性, 又能降低其自相关性.     

Bayesian sequential testing for Lévy processes with diffusion and jump components

We study the Bayesian problem of sequential testing of two simple hypotheses about the Lévy-Khintchine triplet of a Lévy process, having diffusion component, represented by a Brownian motion with drift, and jump component of finite variation. The method of proof consists of reducing the original optimal stopping problem to a free-boundary problem. We show it is characterized by a second order integro-differential equation, that the unknown value function solves on the continuation region, and by the smooth fit principle, which holds at the unknown boundary points. Several examples are presented.     

北京谱仪中性径迹测量误差的确定

首先检查了北京谱仪(BES)桶部簇射计数器(BSC)对γ光子电磁簇射形成的中性径迹的沉积能量和空间位置的测量值;然后,利用辐射Bhabha事例修正了BSC的沉积能量及其误差δE;利用e⁺e^－→γγ(γ)过程确定了BSC测量中性径迹的空间位置的误差,这些研究结果可以减小用运动学拟合方法分析包含中性径迹的物理事例的系统误差,提高BES的测量精度.     

利用拉曼散射测量燃烧场的组分浓度及温度

介绍了利用拉曼散射测量燃烧流场温度及组分浓度的物理方法和实验测量结果。利用可调谐KrF准分子激光激发振动拉曼散射（VRS）测量了甲烷－空气燃烧火焰内不同空间的主要组分分子（CH4、N2、O2、H2O等）浓度及温度,测量误差小于10％;另外用N2的拉曼谱拟合测量了火焰的温度,测量精度高于5％。在实验中采用了偏振技术及波长调谐提高了信噪比和测量精度。     

Effective atomic charges in alanine dipeptide

A new set of effective atomic charges of different conformers of alanine dipeptide is presented. These charges are obtained by fitting the electrostatic potential resulting from the ab initio SCF wave function of the system obtained in a 6-31G basis set. A specific fit procedure is used providing charges weakly dependent on the fit points as well as on the geometry of the molecule. It is shown that these charges retain a reasonable chemical meaning. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 473–482, 1999     

Alternative difference analysis scheme combining R‐space EXAFS fit with global optimization XANES fit for X‐ray transient absorption spectroscopy

Time‐resolved X‐ray absorption spectroscopy (TR‐XAS), based on the laser‐pump/X‐ray‐probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR‐XAS data analysis is generally performed on the laser‐on minus laser‐off difference spectrum. Here, a new analysis scheme is presented for the TR‐XAS difference fitting in both the extended X‐ray absorption fine‐structure (EXAFS) and the X‐ray absorption near‐edge structure (XANES) regions. R‐space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non‐derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR‐XAS difference analysis of Fe(phen)₃ spin crossover complex and yielded reliable distance change and excitation population.