Monte Carlo approach to the decay rate of a metastable system with an arbitrarily shaped barrier

A path integral Monte Carlo method based on the fast-Fourier transform technique combined with the important sampling method is proposed to calculate the decay rate of a metastable quantum system with an arbitrary shape of a potential barrier. The contribution of all fluctuation actions is included which can be used to check the accuracy of the usual steepest-descent approximation, namely, the perturbation expansion of potential. The analytical approximation is found to produce the decay rate of a particle in a cubic potential being about 20% larger than the Monte Carlo data at the crossover temperature. This disagreement increases with increasing complexity of the potential shape. We also demonstrate via Langevin simulation that the postsaddle potential influences strongly upon the classical escape rate.     

Rapid determination of six metabolites from multiple cytochrome P450 probe substrates in human liver microsome by liquid chromatography/mass spectrometry: application to high-throughput inhibition screening of terpenoids

A rapid liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed for the determination of six cytochrome P450 (CYP) probe substrate metabolites including paracetamol (PAR) for CYP1A2, 4-hydroxytolbutamide (OHTOL) for CYP2C9, 5-hydroxyomeprazole (OHOMe) for CYP2C19, dextrorphan (DEXM) for CYP2D6, 6-hydroxychlorzoxazone (OHCHL) for CYP2E1 and dehydronifedipine (DNIF) for CYP3A4. The triple-quadrupole mass spectrometer was operated in both positive and negative modes, and selective reaction monitoring was used for quantification. The method was validated over the concentration ranges (0.075/0.04/0.05/0.02/0.1/0.0625 microM to 4.8/2.56/3.2/1.28/6.4/4.0 microM) for PAR/OHTOL/OHOME/DEXP/OHCHL/DNIF analytes with acceptable accuracy and precision. The inhibitory effect on the six CYP enzymes has been verified with their known specific inhibitors. This high-throughput inhibition screening approach has been successfully applied to study the inhibitory effects of 18 terpenoids on CYP enzymes. Among them, tanshinone IIA and cryptotanshinone are found to be potent inhibitors to CYP1A2, while artemisinin is a marginal inhibitor to CYP1A2 and glycyrrhetic acid is a weak inhibitor to CYP2C9.     

Real-time detection of dental calculus by blue-LED-induced fluorescence spectroscopy

Successful periodontal therapy requires sensitive techniques to discriminate dental calculus from healthy teeth. The aim of the present study was to develop a fluorescence-based procedure to enable real-time detection and quantification of dental calculus. Thirty human teeth--15 teeth with sub- and supragingival calculus and 15 healthy teeth--covered with a layer of physiological saline solution or blood were illuminated by a focused blue LED light source of 405 nm. Autofluorescence spectra recorded along a randomly selected line stretching over the crown-neck-root area of each tooth were utilized to evaluate a so called calculus parameter R, which was selected to define a relationship between the integrated intensities specific for healthy teeth and for calculus in the 477-497 nm (S(A)) and 628-685 nm (S(B)) wavelength regions, respectively. Statistical analysis was performed and a cut-off threshold of R=0.2 was found to distinguish dental calculus from healthy teeth with 100% sensitivity and specificity under various experimental conditions. The results of the spectral evaluation were confirmed by clinical and histological findings. Automated real-time detection and diagnostics for clinical use were implemented by a corresponding software program written in Visual Basic language. The method enables cost-effective and reliable calculus detection, and can be further developed for imaging applications.     

Co9S8@CN Composites Obtained from Thiacalix[4]arene-Based Coordination Polymers for Supercapacitor Applications

Metal sulfides have been recognized as promising electrodes for electrochemical energy storage owing to their remarkable electrochemical properties. Here, we demonstrate the preparation of Co₉S₈ nanoparticles anchored on a carbon matrix (denoted as Co₉S₈-X@CN (X=1, 2)) from precursor sources, two 1D infinite coordination polymers 1 and 2 . The two polymers were assembled by linking Co₄-TC4A secondary building blocks (SBUs) with ligands L₁ and L₂, respectively (H₄TC4A=p-tert-butylthiacalix[4]arene, L₁=1,4-bis(2H-tetrazol-5-yl)benzene, L₂=1,3-bis(2H-tetrazol-5-yl)benzene). The composites obtained from 1D polymers showed different morphologies, that is, the Co₉S₈ nanoparticles of Co₉S₈-1@CN are octahedral with a size of ca. 140 nm, while the lamellar Co₉S₈ nanoparticles in Co₉S₈-2@CN possess different sizes (50–150 nm). The Co₉S₈-2@CN immobilized on nickel foam (Co₉S₈-2@CN/NF) show better supercapacitive performance than that of Co₉S₈-1@CN. Co₉S₈-2@CN showed exceptionally high activities, combining higher specific capacitances (445.2 F g⁻¹ at 2 A g⁻¹ and 393.9 F g⁻¹ and 5 A g⁻¹), rate capacity (94.5% retention at 2 A g⁻¹), and long-term stability (79.2% retention at 5 A g⁻¹ over 1000 cycles). The smaller size and larger BET surface area of Co₉S₈-2@CN nanoparticles can improve the electrical conductivity and provide facile pathways for charge transport, thus leading to conspicuous electrochemical performance of Co₉S₈-2@CN compared with its Co₉S₈-1@CN counterpart.     

碘氧化铋光催化剂的合成、改性及净化一氧化氮

光催化技术因其节能、高效、无二次污染等特点,在低浓度一氧化氮(NO)污染治理方面展现出了巨大潜力。在众多半导体材料中,碘氧化铋(BiOI)光催化剂具有窄带隙和独特的层状结构,有利于可见光吸收和电子空穴对分离,展现出了良好的光催化活性和稳定性,近十几年来备受关注。本文综述了BiOI半导体材料光催化净化NO的最新研究进展,阐述了BiOI晶体形貌与晶面调控对其光催化性能的影响;重点介绍了各类改性方法如表面修饰、离子掺杂、异质结构筑等对BiOI光催化活性的提升机制,并提出了该研究方向所面临的挑战与应用前景,旨在为设计高活性BiOI基光催化材料以及高效处理低浓度NO污染提供理论借鉴与技术支撑。     

On optimal proportional reinsurance and investment in a hidden Markov financial market

This paper investigates the optimal reinsurance and investment in a hidden Markov financial market consisting of non-risky (bond) and risky (stock) asset. We assume that only the price of the risky asset can be observed from the financial market. Suppose that the insurance company can adopt proportional reinsurance and investment in the hidden Markov financial market to reduce risk or increase profit. Our objective is to maximize the expected exponential utility of the terminal wealth of the surplus of the insurance company. By using the filtering theory, we establish the separation principle and reduce the problem to the complete information case. With the help of Girsanov change of measure and the dynamic programming approach, we characterize the value function as the unique solution of a linear parabolic partial differential equation and obtain the Feynman-Kac representation of the value function.     

Acetonitrile-dependent oxyphosphorylation: A mild one-pot synthesis of β-ketophosphonates from alkenyl acids or alkenes

An efficient one-pot synthesis of β-ketophosphonates has been developed, via the reaction of α,β-alkenyl carboxylic acids or alkenes with H-phosphonates and air oxygen, catalyzed by CuSO₄·5H₂O in CH₃CN. CH₃CN plays a decisive role, probably by forming an active oxygen complex [(MeCN)_nCu^II-O-O·].     

Validated chiral separation of M9, a Mannich ketone compound, by chiral ligand-exchange chromatography

Enantioseparation of the Mannich ketone M9, a potential antifungal compound, was examined using chiral ligand-exchange chromatography. The chiral mobile phase contained complexes of Cu(II) with the optically active selector L-aspartame (APM) and the organic modifier methanol. The separation was optimized with respect to the concentration of the Cu(II)-(L-APM) complexes, pH of mobile phase, methanol content, and column temperature. A baseline separation (R(s) = 3.08) was achieved for enantiomers of M9 under optimal conditions, and the analysis was accomplished in eleven minutes. The developed method was extensively validated. The sample stability, linearity, precision (method repeatability and intermediate precision) and accuracy, and the limits of detection and quantification of the developed method were studied. The proposed method was shown to be accurate and suitable for the quantitative determination of each enantiomer of M9.     

Multiple ligand detection and affinity measurement by ultrafiltration and mass spectrometry analysis applied to fragment mixture screening

Binding affinity of a small molecule drug candidate to a therapeutically relevant biomolecular target is regarded the first determinant of the candidate's efficacy. Although the ultrafiltration-LC/MS (UF-LC/MS) assay enables efficient ligand discovery for a specific target from a mixed pool of compounds, most previous analysis allowed for relative affinity ranking of different ligands. Moreover, the reliability of affinity measurement for multiple ligands with UF-LC/MS has hardly been strictly evaluated. In this study, we examined the accuracy of K_d determination through UF-LC/MS by comparison with classical ITC measurement. A single-point K_d calculation method was found to be suitable for affinity measurement of multiple ligands bound to the same target when binding competition is minimized. A second workflow based on analysis of the unbound fraction of compounds was then developed, which simplified sample preparation as well as warranted reliable ligand discovery. The new workflow implemented in a fragment mixture screen afforded rapid and sensitive detection of low-affinity ligands selectively bound to the RNA polymerase NS5B of hepatitis C virus. More importantly, ligand identification and affinity measurement for mixture-based fragment screens by UF-LC/MS were in good accordance with single ligand evaluation by conventional SPR analysis. This new approach is expected to become a valuable addition to the arsenal of high-throughput screening techniques for fragment-based drug discovery.     

定碳定硫分析仪检定规程的探讨和修订建议

JJG 395–1997《定碳定硫分析仪检定规程》中的部分技术要求和检定项目已不能满足现代碳硫分析仪器检定/校准的要求。对规程的适用性、称量稳定性、示值误差、标准物质、重复性、分析时间等进行了探讨,并给出了修订建议。探讨了评定仪器检测空白的可能性,提出了依据碳硫测定基准国标方法的仪器检定/校准方法,以评定不同用途的测试仪器,并扩展了仪器检定/校准的范围。为计量部门修订规程提供参考,同时也为实验室合理评价,验收碳硫分析仪,及时掌握仪器的运行状况,保证分析数据的准确性、一致性和溯源性提供借鉴。