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排序方式: 共有238条查询结果,搜索用时 11 毫秒
11.
Markus R. Meyer Carina Lindauer Jessica Welter Hans H. Maurer 《Analytical and bioanalytical chemistry》2014,406(7):1845-1854
Dimethocaine (DMC, larocaine), a synthetic derivative of cocaine, is a widely distributed “legal high” consumed as a “new psychoactive substance” (NPS) without any safety testing, for example studies of metabolism. Therefore, the purpose of this work was to study its in-vivo and in-vitro metabolism by use of liquid chromatography–(high resolution) mass spectrometry (LC–HRMS n ). DMC was administered to male Wistar rats (20 mg kg?1) and their urine was extracted either by solid-phase extraction after enzymatic cleavage of conjugates or by use of protein precipitation (PP). The metabolites were separated and identified by LC–HRMS n . The main phase I reactions were ester hydrolysis, deethylation, hydroxylation of the aromatic system, and a combination of these. The main phase II reaction was N-acetylation of the p-aminobenzoic acid part of the unchanged parent compound and of several phase I metabolites. The metabolites identified were then used for identification of DMC in rat urine after application of a common user’s dose. By use of GC–MS and LC–MS n standard urine-screening approaches (SUSAs), DMC and its metabolites could be detected in the urine samples. 相似文献
12.
Andersson S Arasa C Yabushita A Yokoyama M Hama T Kawasaki M Western CM Ashfold MN 《Physical chemistry chemical physics : PCCP》2011,13(35):15810-15820
The photodesorption of H(2)O in its vibrational ground state, and of OH radicals in their ground and first excited vibrational states, following 157 nm photoexcitation of amorphous solid water has been studied using molecular dynamics simulations and detected experimentally by resonance-enhanced multiphoton ionization techniques. There is good agreement between the simulated and measured energy distributions. In addition, signals of H(+) and OH(+) were detected in the experiments. These are inferred to originate from vibrationally excited H(2)O molecules that are ejected from the surface by two distinct mechanisms: a direct desorption mechanism and desorption induced by secondary recombination of photoproducts at the ice surface. This is the first reported experimental evidence of photodesorption of vibrationally excited H(2)O molecules from water ice. 相似文献
13.
Inside Cover: Ru‐Catalysed CH Arylation of Indoles and Pyrroles with Boronic Acids: Scope and Mechanistic Studies (Chem. Eur. J. 14/2015) 下载免费PDF全文
14.
Selective Template Removal by Thermal Depolymerization to Obtain Mesostructured Molybdenum Oxycarbide
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Martin Schieder Thomas Lunkenbein Carina Bojer Martin Dulle Julia vom Stein Gudrun Auffermann Tina Löbling Judith Schöbel Holger Schmalz Josef Breu 《无机化学与普通化学杂志》2015,641(10):1829-1834
The carbon content of mesostructured organic‐inorganic hybrid material of a cylindrical block copolymer template of poly(2‐vinylpyridine)‐block‐poly(allyl methacrylate) (P2VP‐b‐PAMA) and ammonium paramolybdate (APM) could be reduced by thermal depolymerization. By calcination in vacuo at 320 °C the PAMA core can be completely removed while the remaining P2VP brush preserves the mesostructure. The P2VP‐APM composite can then be carburized in‐situ to MoOxCy in a second pyrolysis step without any additional carbon source but P2VP. The molybdenum oxycarbide nanotubes obtained, form hierarchically porous non‐woven structures, which were tested as catalyst in the decomposition of NH3. They proved to be catalytically active at temperatures above 450 °C. The activation energy was estimated from an Arrhenius Plot to be 127 kJ · mol–1. 相似文献
15.
Carina R. Martins Lucas C. Ducati Cludio F. Tormena Roberto Rittner 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2009,72(5):1089-1096
The conformational isomerism of 2-chlorocyclopentanone and 2-bromocyclopentanone has been determined through the solvent dependence of the 1H NMR 3JHH coupling constants, theoretical calculations and infrared data, using the solvation theory for the treatment of NMR data. In 2-chlorocyclopentanone, the energy difference (EΨ-e − EΨ-a), in the isolated molecule at B3LYP level of theory, between the pseudo-equatorial (Ψ-e) and pseudo-axial (Ψ-a) conformers is 0.42 kcal mol−1, which decreases in CCl4 and in acetonitrile solutions, in good agreement with infrared data (νCO), despite the uncertainties of the latter method. The conformational equilibrium for 2-bromocyclopentanone is also between the Ψ-e and Ψ-a conformations, with an energy difference (EΨ-e − EΨ-a), in the isolated molecule at B3LYP level of theory, is 0.85 kcal mol−1 which decreases in CCl4 and in acetonitrile solutions, also in good agreement with infrared data. 相似文献
16.
C,C‐ and N,C‐Coupled Dimers of 2‐Aminotetraphenylporphyrins: Regiocontrolled Synthesis,Spectroscopic Properties,and Quantum‐Chemical Calculations 下载免费PDF全文
Dr. Torsten Bruhn Dipl.‐Chem. Franziska Witterauf Dr. Daniel C. G. Götz Carina T. Grimmer Dipl.‐Chem. Max Würtemberger Prof. Dr. Udo Radius Prof. Dr. Gerhard Bringmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):3998-4006
β,β′‐Bisporphyrins are intrinsically chiral porphyrin dimers with fascinating properties. The configurational stability at their axes can be directed by variation of the central metal atoms. Herein, we present a regioselective functionalization of the monomeric 2‐amino‐tetraphenyl‐porphyrin as a versatile substrate for dimerization by oxidative coupling. By simple variation of the reaction conditions (solvent and oxidant), the oxidation selectively gave either the axially chiral C,C‐coupled diaminobisporphyrin in high yields or, under Ullmann conditions, the twofold N,C‐linked achiral dimer, also in good yields. A generalized mechanism for the coupling reaction is proposed based on DFT calculations. The axially chiral β,β′‐coupled porphyrin dimers were isolated as racemic mixtures, but can be resolved by HPLC on a chiral phase. TDDFT and coupled‐cluster calculations were used to explain the spectroscopic properties of the aminoporphyrins and their dimers and to elucidate the absolute configurations of the C,C‐coupled bisporphyrins. 相似文献
17.
Stability and Conversion of Tin Zintl Anions in Liquid Ammonia Investigated by NMR Spectroscopy 下载免费PDF全文
Franziska Fendt Dr. Carina Koch Dr. Maria Neumeier Dr. Stefanie Gärtner Prof. Dr. Ruth M. Gschwind Prof. Dr. Nikolaus Korber 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14539-14544
Homoatomic polyanions of post‐transition main‐group metals, namely, Zintl anions, are precast in analogous Zintl phases and can react in solution to form new materials. Despite comprehensible reaction approaches, the formed products cannot be planned in advance, as hitherto undetected and therefore disregarded side reactions take place. The outcomes and interpretations of the reactions of Zintl anions are so far based mainly on crystal structures, which only allow characterization of the product that has the lowest solubility. Here we present the results of our investigation of the stability of highly charged tin Zintl anions in liquid ammonia, which is not exclusively based on solution effects but also on the oxidative influence of the solvent. This allows for a deeper understanding of the ongoing processes in solution and opens doors to the directed synthesis of transition metal complexes of Sn44?, here shown by its reactivity towards MesCu. 相似文献
18.
Carina Schönherr Sounia Touchene Gaston Wilser Regine Peschka-Süss Giancarlo Francese 《Journal of chromatography. A》2009,1216(5):781-786
In recent decades the use of liposomal preparations as drug delivery systems has become very attractive in pharmaceutical development. Therefore, thorough characterization and quantification of the lipids which form liposomes is wished from both investigators and regulatory authorities when the application in humans is being considered. In this study a new HPLC method for the detection of lipids in liposomal formulations was established using corona charged aerosol detection (CAD) which has the advantage to be independent of the chemical properties of the analytes. The superiority of this method over UV detection was demonstrated. Compared to UV detection no absorption effects of the organic solvent in the mobile phase interfering with the lipid signals were observed with CAD. CAD showed good linearity (R2 > 0.990) for all liposomal compounds. The acceptance criteria for precision including repeatability were met. The average recovery for each of the excipients of the liposomal formulation was in the range of 90.0–110%. 相似文献
19.
Bäcktorp C Börje A Nilsson JL Karlberg AT Norrby PO Nyman G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(31):9549-9554
Pathways for formation of previously observed autoxidation products of ethoxylated surfactants have been studied by DFT (B3LYP). In addition to the established radical-chain reaction, several mechanistic possibilities for intramolecular fragmentation of the intermediate radicals have been characterized concerning reaction barriers and energies of transition states. The results can rationalize the formation of previously observed autoxidation products, including several, which have been implicated as strongly allergenic. 相似文献
20.
We introduce a 1+1-dimensional temperature-dependent model such that the classical ballistic deposition model is recovered as its zero-temperature limit. Its ∞-temperature version, which we refer to as the 0-Ballistic Deposition (0-BD) model, is a randomly evolving interface which, surprisingly enough, does not belong to either the Edwards–Wilkinson (EW) or the Kardar–Parisi–Zhang (KPZ) universality class. We show that 0-BD has a scaling limit, a new stochastic process that we call Brownian Castle (BC) which, although it is “free”, is distinct from EW and, like any other renormalisation fixed point, is scale-invariant, in this case under the 1:1:2 scaling (as opposed to 1:2:3 for KPZ and 1:2:4 for EW). In the present article, we not only derive its finite-dimensional distributions, but also provide a “global” construction of the Brownian Castle which has the advantage of highlighting the fact that it admits backward characteristics given by the (backward) Brownian Web (see [37, 16]). Among others, this characterisation enables us to establish fine pathwise properties of BC and to relate these to special points of the Web. We prove that the Brownian Castle is a (strong) Markov and Feller process on a suitable space of càdlàg functions and determine its long-time behaviour. Finally, we give a glimpse to its universality by proving the convergence of 0-BD to BC in a rather strong sense. © 2022 The Authors. Communications on Pure and Applied Mathematics published by Wiley Periodicals LLC. 相似文献