Free mycophenolic acid determination in human plasma ultrafiltrate by a validated liquid chromatography–tandem mass spectrometry method

The aim of this study was to develop and validate fully the liquid chromatography–tandem mass spectrometry method for free mycophenolic acid (MPA) concentration measurements in plasma ultrafiltrate that will be reliable and simple in preparation with deuterated MPA (MPA‐d3) chosen as an internal standard. The chromatographic separation was made with Zorbax Eclipse XDB‐C18 column (4.6 × 150 mm) using a gradient of two solutions as a mobile phase: (A) water and (B) methanol, each containing 0.1% formic acid and 2.5 mm ammonium acetate. Satisfactory repeatability of retention times was achieved with average values of 7.54 ± 0.20 min and 7.50 ± 0.19 min for MPA and MPA‐d3, respectively. The method was selective, with no carry‐over or matrix effect observed. The analytical range was proven for MPA ultrafiltrate concentrations of 1–500 ng/mL. The accuracy and precision fell within the acceptance criteria for intraday (accuracy: 100.63–110.46%, imprecision: 6.23–7.76%), as well as interday assay (accuracy: 98.81–110.63%; imprecision: 5.36–10.22%). The method was used for free MPA determination in plasma samples from patients treated with mycophenolate mofetil. To the best of our knowledge this is the first liquid chromatography–tandem mass spectrometry method for free MPA monitoring using MPA‐d3 that allows to measure plasma ultrafiltrate concentrations as low as 1 ng/mL.     

Precessional frequency of ferromagnetic elements: Influence of magnetic domain width

A model is presented that semi-quantitatively describes the dependence of precessional frequency on magnetic domain width in ferromagnetic thin film elements. With decreasing domain width an increase of precessional frequency at zero-bias field by a factor of about 1.5 is found experimentally and from the calculations. The modelled value of change of precessional frequency is in agreement with the experimental results. The simple model offers the opportunity to relate the drastic effects of domain structure on the dynamic magnetic properties of soft-magnetic thin films by a straightforward approach.     

A high‐performance liquid chromatography assay with a triazole‐bonded column for evaluation of d‐amino acid oxidase activity

Elution profiles of kynurenic acid (KYNA) and 7‐chlorokynurenic acid (Cl‐KYNA) were examined by high‐performance liquid chromatography (HPLC) using a triazole‐bonded stationary phase column (Cosmosil® HILIC) under isocratic elution of a mobile phase consisting of CH₃CN–aqueous 10 mm ammonium formate between pH 3.0 and 6.0. The capacity factors of KYNA and Cl‐KYNA varied with both the CH₃CN content and the pH of the mobile phase. The elution order of KYNA and Cl‐KYNA was reversed between the CH₃CN‐ and H₂O‐rich mobile phases, suggesting that hydrophilic interactions and anion‐exchange interactions caused retention of KYNA and Cl‐KYNA in the CH₃CN‐ and H₂O‐rich mobile phases, respectively. The present HPLC method using a triazole‐bonded column and fluorescence detection (excitation 250 nm, emission 398 nm) was applied to monitor in vitro production of KYNA from d ‐kynurenine (d ‐KYN) by d ‐amino acid oxidase (DAO) using Cl‐KYNA as an internal standard. A single KYNA peak was clearly observed after enzymatic reaction of d ‐KYN with DAO. Production of KYNA from d ‐KYN was suppressed by the addition of commercial DAO inhibitors. The present HPLC method can be used to evaluate DAO activity and DAO inhibitory effects in candidate drugs for the treatment of schizophrenia. Copyright © 2015 John Wiley & Sons, Ltd.     

基于X3D不规则圆柱体构造算法研究与实现

目前,多边形表面模型是最常用的一种三维几何模型表示方法.然而这种复杂的三维几何模型经常超过了系统的处理能力,既占据大量的存储空间,也不利于互联网传输.针对这一缺陷,文章提供一种使用X3D的Indexed Triangle Strip Set节点构造不规则圆柱体模型的方法.不规则圆柱体采用层数及每一层半径表示方法,并结合曲面精度一同拟合3D几何面.此方法具有模型构建精度高的特点.     

Construction of topological defect networks with complex scalar fields

This work deals with the construction of networks of topological defects in models described by a single complex scalar field. We take advantage of the deformation procedure recently used to describe kinklike defects in order to build networks of topological defects, which appear from complex field models with potentials that engender a finite number of isolated minima, both in the case where the minima present discrete symmetry, and in the non-symmetric case. We show that the presence of symmetry guide us to the construction of regular networks, while the non-symmetric case gives rise to irregular networks which spread throughout the complex field space. We also discuss bifurcation, a phenomenon that appear in the non-symmetric case, but is washed out by the deformation procedure used in the present work.     

Macrocyclization of polymers via ring‐closing metathesis and azide/alkyne‐“click”‐reactions: An approach to cyclic polyisobutylenes

The end‐to‐end cyclization of telechelic polyisobutylenes (PIB's) toward cyclic polyisobutylenes is reported, using either ring‐closing metathesis (RCM) or the azide/alkyne‐“click”‐reaction. The first approach uses bisallyl‐telchelic PIB's (M_n = 1650, 3680, 9770 g mol^?1) and Grubbs 1st‐, 2nd‐, and 3rd‐generation catalyst leading to cyclic PIB's in 60–80% yield, with narrow polydispersities (M_w/M_n = 1.25). Azide/alkyne‐“click”‐reactions of bisalkyne‐telechelic PIB's (M_n = 3840 and 9820 g mol^?1) with excess of 1,11‐diazido‐undecane leads to the formation of mixtures of linear/cyclic PIB's under formation of oligomeric cycles. Subsequent reaction of the residual azide‐moieties in the linear PIB's with excess of alkyne‐telechelic PEO enables the chromatographic removal of the resulting linear PEO‐PIB‐block copolymers by column chromatography. Thus pure cyclic PIB's can be obtained using this double‐“click”‐method, devoid of linear contaminants. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 671–680, 2010     

Enhancement of Mn red emission in CaGa2S4 compounds by co-doping rare-earth elements

When certain trivalent rare-earth ions (Ln's) are co-doped in CaGa₂S₄:Mn²⁺ as sensitizers, the Mn red emission of the compound is strikingly enhanced. In this work, efficiency of each lanthanide is studied. The best efficiencies are achieved with La³⁺-, Pr³⁺-, and Tb³⁺- co-doped compounds, for each of which the effects of concentrations of the co-doped ions on the Mn²⁺ emission are investigated. The energy-transfer mechanisms and the location of electronic energy levels of both the trivalent and the divalent lanthanides in the energy band gap of the host material are discussed. Depending on Ln's, charge transfer or cross-relaxation should be taken into account.     

Fluorescence quenching of 9-cyanoanthracene in presence of zinc tetraphenylporphyrin in a polar liquid medium

Steady-state and time-resolved techniques are used to study photoinduced electron and/or excitational energy transfer processes involved within a novel donor (zinc tetraphenylporphyrin)-acceptor (9-cyanoanthracene) system in a polar liquid medium (acetonitrile) at the ambient temperature (300 K). After photoexcitation of 9-cyanoanthracene, its fluorescence emission as well as lifetime are found to be quenched in presence of zinc tetraphenylporphyrin. The fluorescence quenching is ascribed to be due to the combined effect of electron transfer from zinc tetraphenylporphyrin to 9-cyanoanthracene and energy transfer (radiative as well as non-radiative) from 9-cyanoanthracene to zinc tetraphenylporphyrin. The highly exergonic values of Gibbs free energy change for both forward electron transfer reaction (−1.15 eV) and charge recombination reaction (−1.94 eV) indicate the possibilities of occurrences of these two processes in the Marcus inverted region. The fluorescence quenching rate due to photoinduced electron transfer reaction is found to be close to the diffusion-controlled limit within the present donor-acceptor system upon excitation of the acceptor molecules.