Relaxation oscillations in a slow–fast modified Leslie–Gower model

In this paper, we prove the existence and uniqueness of relaxation oscillation cycle of a slow–fast modified Leslie–Gower model via the entry–exit function and geometric singular perturbation theory. Numerical simulations are also carried out to illustrate our theoretical result.     

An empirical formula for scattered neutron components in fast neutron radiography

Scattering neutrons are one of the key factors that may affect the images of fast neutron radiog- raphy. In this paper, a mathematical model for scattered neutrons is developed on a cylinder sample, and an empirical formula for scattered neutrons is obtained. According to the results given by Monte Carlo methods, the parameters in the empirical formula are obtained with curve fitting, which confirms the logicality of the empirical formula. The curve-fitted parameters of common materials such as <'6>LiD are given.     

High‐energy collision‐induced dissociation of [M+Na]+ ions desorbed by fast atom bombardment of ceramides isolated from the starfish Distolasterias nipon

Ten ceramides and four cerebrosides were extracted from the starfish Distolasterias nipon by solvent extraction, silica gel column chromatography and reversed‐phase high‐performance liquid chromatography. Structural identification was conducted using tandem mass spectrometry of monosodiated ions desorbed by fast atom bombardment. The complete structures of four cerebrosides were determined by a previously reported method. The high‐energy collision‐induced dissociation (CID) spectral characteristics of ceramides with various structures depend on the number and positions of double bonds on both the N‐acyl and sphingoid chains, the presence of a hydroxyl group or a double bond at the C‐4 position of the sphingoid chain and the presence of an α‐hydroxy group on the N‐acyl chain. The high‐energy CID of the monosodiated ion, [M+Na]⁺, of each ceramide molecular species generated abundant ions, providing information on the composition of the fatty acyl chains and sphingoid long‐chain bases. Each homologous ion series along the fatty acyl group and aliphatic chain of the sphingoid base was used for locating the double‐bond positions of both chains and hydroxyl groups on the sphingoid base chain. The double‐bond positions were also confirmed by the m/z values of abundant allylic even‐ and odd‐electron ions, and the intensity ratio of the T ion peak relative to the O ion peak. This technique could determine the complete structures of ceramides and cerebrosides in an extract mixture and has great potential for determining other sphingolipids isolated from various biological sources. Copyright © 2013 John Wiley & Sons, Ltd.     

Fast polarisation-insensitive optical shutter supported by backflow in dichroic dye-doped dual-frequency liquid crystal

This paper describes a novel implementation of a dual-frequency liquid crystal optical shutter of the guest–host type. The transmissive state of the filter is obtained by applying a low-frequency electric field that brings the dichroic dye in a homeotropic orientation. The light-absorbing state is realised by a twisted planar configuration for which the absorption is quasi-independent of the polarisation. Switching between the two states occurs in about 1 ms and the devices show no scattering for wavelengths inside or outside the absorption band of the dichroic dye. Simulations and experiments reveal how a twisted state is obtained through the backflow phenomenon.     

Design of a reaction field using a linear‐combination‐based isotropic periodic sum method

In our previous study (Takahashi et al., J. Chem. Theory Comput. 2012, 8, 4503), we developed the linear‐combination‐based isotropic periodic sum (LIPS) method. The LIPS method is based on the extended isotropic periodic sum theory that produces a ubiquitous interaction potential function to estimate homogeneous and heterogeneous systems. The LIPS theory also provides the procedure to design a periodic reaction field. To demonstrate this, in the present work, a novel reaction field of the LIPS method was developed. The novel reaction field was labeled LIPS‐SW, because it provides an interaction potential function with a shape that resembles that of the switch function method. To evaluate the ability of the LIPS‐SW method to describe in homogeneous and heterogeneous systems, we carried out molecular dynamics (MD) simulations of bulk water and water–vapor interfacial systems using the LIPS‐SW method. The results of these simulations show that the LIPS‐SW method gives higher accuracy than the conventional interaction potential function of the LIPS method. The accuracy of simulating water–vapor interfacial systems was greatly improved, while that of bulk water systems was maintained using the LIPS‐SW method. We conclude that the LIPS‐SW method shows great potential for high‐accuracy, high‐performance computing to allow large scale MD simulations. © 2014 Wiley Periodicals, Inc.     

Ultra‐fast LC–ESI‐MS/MS method for the simultaneous determination of six highly toxic Aconitum alkaloids from Aconiti kusnezoffii radix in rat plasma and its application to a pharmacokinetic study

A fast, sensitive, and efficient ultra‐fast LC–ESI‐MS/MS method was developed for the simultaneous quantitation of six highly toxic Aconitum alkaloids, that is, aconitine, mesaconitine, hypaconitine, benzoylaconine, benzoylmesaconine, and benzoylhypaconine, in rat plasma after oral administration of crude ethanol extracts from Aconiti kusnezoffii radix by ultrasonic extraction, reflux extraction for 1 h, and reflux extraction for 3 h, respectively. The separation of six Aconitum alkaloids and aminopyrine (internal standard) was performed on an InertSustain® C₁₈ column, and the quantification of the analytes was performed on a 4000Q ultra‐fast LC–MS/MS system with turbo ion spray source in the positive ion and multiple‐reaction monitoring mode. Absolute recoveries ranged within 65.06–85.1% for plasma samples. The intra‐ and interday precision and accuracy of analytes were satisfactory. The methods were validated with sensitivity reaching the lower LOQ for aconitine, mesaconitine, hypaconitine, benzoylaconine, benzoylmesaconine, and benzoylhypaconine, which were 0.025, 0.025, 0.050, 0.025, 0.025, and 0.100 ng/mL, respectively. The method was successfully applied to a pharmacokinetic study of six Aconitum alkaloids in rat plasma after oral administration of crude ethanol extracts from the raw root of Aconitum kusnezoffii Reichb. by three different extraction processes.     

Fast Li-Ion Conduction in Spinel-Structured Solids

Spinel-structured solids were studied to understand if fast Li⁺ ion conduction can be achieved with Li occupying multiple crystallographic sites of the structure to form a “Li-stuffed” spinel, and if the concept is applicable to prepare a high mixed electronic-ionic conductive, electrochemically active solid solution of the Li⁺ stuffed spinel with spinel-structured Li-ion battery electrodes. This could enable a single-phase fully solid electrode eliminating multi-phase interface incompatibility and impedance commonly observed in multi-phase solid electrolyte–cathode composites. Materials of composition Li_1.25M(III)_0.25TiO₄, M(III) = Cr or Al were prepared through solid-state methods. The room-temperature bulk Li⁺-ion conductivity is 1.63 × 10⁻⁴ S cm⁻¹ for the composition Li_1.25Cr_0.25Ti_1.5O₄. Addition of Li₃BO₃ (LBO) increases ionic and electronic conductivity reaching a bulk Li⁺ ion conductivity averaging 6.8 × 10⁻⁴ S cm⁻¹, a total Li-ion conductivity averaging 4.2 × 10⁻⁴ S cm⁻¹, and electronic conductivity averaging 3.8 × 10⁻⁴ S cm⁻¹ for the composition Li_1.25Cr_0.25Ti_1.5O₄ with 1 wt. % LBO. An electrochemically active solid solution of Li_1.25Cr_0.25Mn_1.5O₄ and LiNi_0.5Mn_1.5O₄ was prepared. This work proves that Li-stuffed spinels can achieve fast Li-ion conduction and that the concept is potentially useful to enable a single-phase fully solid electrode without interphase impedance.     

Novel Fast Chromatography-Tandem Mass Spectrometric Quantitative Approach for the Determination of Plant-Extracted Phytosterols and Tocopherols

Phytosterols and tocopherols are commonly used in food and pharmaceutical industries for their health benefits. Current analysis methods rely on conventional liquid chromatography, using an analytical column, which can be tedious and time consuming. However, simple, and fast analytical methods can facilitate their qualitative and quantitative analysis. In this study, a fast chromatography-tandem mass spectrometric (FC-MS/MS) method was developed and validated for the quantitative analysis of phytosterols and tocopherols. Omitting chromatography by employing flow injection analysis—mass spectrometry (FIA-MS) failed in the quantification of target analytes due to analyte-to-analyte interferences from phytosterols. These interferences arise from their ambiguous MS fingerprints that would lead to false identification and inaccurate quantification. Therefore, a C18 guard column with a 1.9 µm particle size was employed for FC-MS/MS under isocratic elution using acetonitrile/methanol (99:1 v/v) at a flow rate of 600 µL/min. Analyte-to-analyte interferences were identified and eliminated. The false peaks could then be easily identified due to chromatographic separation. In addition, two internal standards were evaluated, namely cholestanol and deuterated cholesterol. Both internal standards contributed to the observed analyte-to-analyte interferences; however, adequate shift in the retention time for deuterated cholesterol eliminated its interferences and allowed for an accurate quantification. The method is fast (1.3 min) compared to published methods and can distinguish false peaks observed in FIA-MS. Seven analytes were quantified simultaneously, namely brassicasterol, campesterol, stigmasterol, β-sitosterol, α-tocopherol, δ-tocopherol, and γ-tocopherol. The method was successfully applied in the quantitative analysis of phytosterols and tocopherols present in the unsaponifiable matter of canola oil deodorizer distillate (CODD). β-sitosterol and γ-tocopherol were the most abundant phytosterols and tocopherols, respectively.     

快中子照相模拟分析与实验验证

首次系统地推导出快中子照相像素值形成解析式, 建立图像反差不等式, 并利用该不等式首次对图像对比度与源强、照射时间和散射之间的关系进行说明. 并在像素值解析式基础上编制快中子照相模拟程序, 利用该程序对空间分辨率和图像对比度进行模拟, 并与实验对照, 研究结果表明空间分辨率模拟效果好于实验, 图像对比度模拟效果与实验相当. 最后通过对狭缝、方孔以及多材质组成的复杂样品模拟并与实验对照, 结果显示模拟效果与实验照片在反差灵敏度效果上非常一致, 该模拟计算方法可为实验设计和工程应用提供参考.     

On the reactivity of naphthalene and biphenyl dianions: tying up loose ends concerning an SN2‐ET dichotomy in alkylation reactions

Naphthalene and biphenyl dianions are interesting compounds that can be obtained by double reduction of the corresponding arenes in solution with certain alkali metals. These dianions are highly reactive and rather elusive species with very high laying and highly delocalized electrons. They share many aspects of the reactivity of the alkali metal they originated from and consequently behave primarily as strong electron transfer (ET) reagents. We report here kinetic evidence for a different type of reactivity in their alkylation reactions with alkyl fluorides. By using cyclopropylmethyl fluoride (c‐C₃H₅CH₂F) as a very fast radical probe, we were able to settle that this alkylation does not involve the classical electron transfer reaction followed by radical coupling between diffusing radicals, but supports the alternative S_N2 concerted mechanism, discerning thus this mechanistic S_N2‐ET dichotomy. Copyright © 2015 John Wiley & Sons, Ltd.