Isoshamixanthone: a new pyrano xanthone from endophytic Aspergillus sp. ASCLA and absolute configuration of epiisoshamixanthone

Abstract

Isoshamixanthone (1), a new stereoisomeric pyrano xanthone together with the previously known fungal metabolites, epiisoshamixanthone (2), sterigmatocystin (3), arugosin C (4), norlichexanthone (5), diorcinol (6), ergosterol and methyllinoleate, were obtained from the endophytic fungal strain Aspergillus sp. ASCLA isolated from leaf tissues of the medicinal plant Callistemon subulatus. The chemical structure of the new xanthone (1) was elucidated by extensive 1D, 2D NMR, and ESI HR mass measurements, and by comparison with literature data. The constitutions and absolute configurations of 1 and epiisoshamixanthone (2) were additionally confirmed by X-ray crystallography. Compounds 1,2 were evaluated for their potential anticancer activity using the human cervix carcinoma cell line (KB-3-1). The antimicrobial activities of the fungal extract and compounds 1,2 were studied using a panel of pathogenic microorganisms as well.     

Formation of H3+ in Collisions of H2+ with H2 Studied in a Guided Ion Beam Instrument

In order to study collisions between ions and neutrals, a new Guided Ion Beam (GIB) apparatus, called NOVion, has been assembled and tested. The primary purpose of this instrument is to measure absolute cross sections at energies relevant for technical or inter- and circumstellar plasmas. New and improved results are presented for forming H₃⁺ in collisions of H₂⁺ with H₂. Between 0.1 eV and 2 eV, our measured effective cross sections are in good overall agreement with most previous measurements. However, at higher energies, our results do not show the steep decline, recommended in the standard literature. After critical evaluation of all experimental and theoretical data, a new analytical function is proposed, describing properly the dependence of the title reaction on the collision energy up to 10 eV.     

绝对编码光栅的相位细分及其在位移测量中的应用

提出通过光栅条纹相位的精密测量,获取光栅高精度位移信息的方法。具体方法是对光栅图像采用多码道设计,用CCD二维图像传感器获取测量段光栅图像多码道信息。对最低码道图形的周期函数序列进行傅里叶变换、基频滤波和逆傅里叶变换获得光栅截断相位分布,其余码道信息提供相位展开的级次,以此获得测量段光栅的绝对相位分布。用光刻的手段制作了实用的绝对编码光栅,基元码道的尺寸是:27.36μm用于明条纹,27.36μm用于暗条纹,最小基元码道空间周期为54.72μm,光栅长度为14008.32μm。在步长近似3μm的位移测试中,与比对的标准仪器记录值比较,标准偏差为0.2057μm,精度在亚微米量级。重复性实验表明,位置测试的稳定性为0.09μm(标准差),得到600倍以上细分的分辨力。     

金属标记结合高效液相色谱-选择离子监测质谱的蛋白质绝对定量新方法

建立了金属标记结合高效液相色谱-选择性离子监测质谱(SIM)的蛋白质绝对定量新方法。实验考察了金属标记效率、金属标记的稳定性、标记后肽段的色谱保留和质谱行为、新定量方法的线性范围和准确度。实验结果表明金属标记具有标记效率高,稳定性好,色谱保留行为一致等优点。另外,金属标记-选择离子监测质谱绝对定量方法灵敏度高,其定量限低至1 fmol,线性范围为1~500 fmol,线性范围内R2值大于0.99,具有良好的线性关系;经过测量,标准肽段的回收率为117.01%,说明该方法具有较高的准确度。将该方法应用于腾冲嗜热菌中烯醇酶蛋白的定量分析,相对标准偏差为5.47%,表明该方法的精密度高。以上结果表明该方法可以用于生物样本中的蛋白质的绝对定量分析,为比较简单的生物样本中蛋白质的绝对定量方法提供了一种新的选择。     

Determination of the Absolute Configuration of Perylene Quinone‐Derived Mycotoxins by Measurement and Calculation of Electronic Circular Dichroism Spectra and Specific Rotations

Altertoxins I–III, alterlosins I and II, alteichin (alterperylenol), stemphyltoxins I–IV, stemphyperylenol, stemphytriol, 7‐epi‐8‐hydroxyaltertoxin I, and 6‐epi‐stemphytriol are mycotoxins derived from perylene quinone, for which the absolute configuration was not known. Electronic circular dichroism (ECD) spectra were calculated for these compounds and compared with measured spectra of altertoxins I–III, alteichin, and stemphyltoxin III and with reported Cotton effects. Specific rotations were calculated and compared with reported specific rotations. The absolute configuration of all the toxins, except for stemphyltoxin IV, could thus be determined. The validity of the assignment was high whenever reported ECD data were available for comparison, and the validity was lower when the assignment was based only on the comparison of calculated and reported specific rotations. ECD spectra are intrinsically different for toxins with a biphenyl substructure and for toxins derived from dihydroanthracene.     

Development and validation of a HPLC method for the determination of buprenorphine hydrochloride, naloxone hydrochloride and noroxymorphone in a tablet formulation

A simple isocratic reversed-phase high-performance liquid chromatographic method (RP-HPLC) was developed for the simultaneous determination of buprenorphine hydrochloride, naloxone hydrochloride dihydrate and its major impurity, noroxymorphone, in pharmaceutical tablets. The chromatographic separation was achieved with 10 mmol L⁻¹ potassium phosphate buffer adjusted to pH 6.0 with orthophosphoric acid and acetonitrile (17:83, v/v) as mobile phase, a C-18 column, Perfectsil Target ODS3 (150 mm × 4.6 mm i.d., 5 μm) kept at 35 °C and UV detection at 210 nm. The compounds were eluted isocratically at a flow rate of 1.0 mL min⁻¹. The average retention times for naloxone, noroxymorphone and buprenorphine were 2.4, 3.8 and 8.1 min, respectively. The method was validated according to the ICH guidelines. The validation characteristics included accuracy, precision, linearity, range, specificity, limit of quantitation and robustness. The calibration curves were linear (r > 0.996) over the concentration range 0.22-220 μg mL⁻¹ for buprenorphine hydrochloride and 0.1-100 μg mL⁻¹ for naloxone hydrochloride dihydrate and noroxymorphone. The recoveries for all three compounds were above 96%. No spectral or chromatographic interferences from the tablet excipients were found. This method is rapid and simple, does not require any sample preparation and is suitable for routine quality control analyses.     

Variational formulation of the material failure process in solids by embedded discontinuities model

This work presents a variational formulation of the material failure process, idealized as strain or displacement discontinuities, by weak, strong, or discrete embedded discontinuities into a continuum. It is shown that the solution of the proposed variational formulation may be approximated by different types of finite elements with embedded discontinuities. The developed displacement approximation of a finite element split by the discontinuity leads to a symmetric stiffness matrix, which considers not only the continuity of tractions but also the rigid body relative motions of the portions in which the element is split. The variational formulation of a continuum with more than one discontinuity in its interior is developed. It is shown that this formulation may lead to finite elements with embedded discontinuities that can be classified as displacement, force, mixed, and hybrid models. To show the effectiveness of the proposed formulation, the classical example of a bar under tension is solved using one and 2D finite element approximations. © 2008 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2009     

Convergence Properties of Generalized Fourier Series on a Parallel Hexagon Domain

A new Rogosinski-type kernel function is constructed using kernel function of partial sums Sn（f; t） of generalized Fourier series on a parallel hexagon domain Ω associating with threedirection partition. We prove that an operator Wn（f; t） with the new kernel function converges uniformly to any continuous function f（t） ∈ Cn（Ω） （the space of all continuous functions with period Ω） on Ω. Moreover, the convergence order of the operator is presented for the smooth approached function.     

The reaction force. A scalar property to characterize reaction mechanisms

The reaction force is a global property of a chemical reaction that arises when applying the Hellmann–Feynmann theorem to the potential energy surface that links reactants, products and transition states. In the present work, the reaction force is defined rigorously from the cartesian components coming out from all forces exerted over each atom of a molecular system during the chemical reaction; it is demonstrated that the reaction force is a scalar property. An erratum to this article can be found at     

Porous film fabricated by a thermoresponsive polymer poly(N-isopropylacrylamide-co-butylmethacrylate) with enhanced hydrophobicity

In this paper, two charge-neutral and poorly water-soluble bactericides (BC), hexaconazole and triadimenol, were first encapsulated in micelles derived from anionic surfactant, calcium dodecylbenzenesulfonate (DBS), and then were successfully intercalated into the gallery of Mg–Al layered double hydroxides (LDHs) by using ion exchange, coprecipitation and reconstruction methods, respectively, to obtain BC–LDHs nanohybrids. The loading amounts of hexaconazole-LDHs nanohybrids are obviously higher than those of triadimenol-LDHs nanohybrids. The release kinetics of bactericides from the nanohybrids was investigated. It was found that the bactericide release kinetic processes of the nanohybrids can be described with pseudo-second-order model. The initial release rates and equilibrium percent releases of the nanohybrids are obviously dependent of synthesis methods. The nanohybrids can well control the release of bactericides, showing they are a potential pesticide controlled-release formulation.