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81.
Haijuan Zhi Zhenwei Li Yanping Deng Peng Qi Jinjun Hou Wen Deng Jinle Cheng Wanying Wu Dean Guo 《Biomedical chromatography : BMC》2019,33(2)
Salvia miltiorrhiza, one of the most well‐known herbal medicines, is commonly used for the treatment of coronary heart diseases in China. Besides traditional decoction slices (TDS), another relatively new product of S. miltiorrhiza, ultrafine granular powder (UGP; D90 < 45 μm), is also increasingly being used. In this paper, a UHPLC‐LTQ‐Orbitrap MS technique was developed for a metabolite profile study after oral administration of UGP and TDS of S. miltiorrhiza. The results showed that the number of in vivo absorbed compounds from UGP was much greater than that from TDS, and different types of products from S. miltiorrhiza will have different metabolic processes in vivo. Furthermore, a UHPLC‐Q‐Trap MS/MS method for simultaneously determining four tanshinones (tanshinone IIA, dihydrotanshinone I, tanshinone I and cryptotanshinone) was established and applied to assess the pharmacokinetics of the two types of products. All of the analytes displayed significant higher area under the concentration–time curve and peak concentration after oral administration of UGP than after TDS, indicating that ultrafine powder product could improve the bioavailability and absorption of cryptotanshinon,tanshinone II A,dihydrotanshinonE I and tanshinone I in vivo. The present study provides scientific information for further exploration of the pharmacology of these two types of S. miltiorrhiza and offers a reference for clinical administration of S. miltiorrhiza. 相似文献
82.
83.
Ronald G. Cavell Christo M. Angelov Dean A. Mazzuca 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):625-628
Abstract: Chlorophosphines react with trivalent (silylamino)phosphines via a direct oxidative addition process with elimination of trimethyl silyl chloride to produce phosphino-phosphoranimines with concomitant formation of a P-P bond. Oxidation of the phosphine center with sulfur and an exchange transformation of the phosphine are discussed. 相似文献
84.
Jiamin Gu Reihong Feng Zhiyuan Wu Shuguang Guan Jiling Guo Chunru Cheng Pingping Xu Jingxian Zhang Yang Wang Hua Qu Wei Man Wenbo Yu Yajun Cui Shuhong Guan Dean Guo 《Journal of separation science》2013,36(14):2366-2372
A rapid and convenient method was established to preparatively isolate the three ellagic acid types of compounds, which were the main polyphenols in Euphorbia pekinensis, by flexibly applying solvent extraction combined with counter‐current chromatography (CCC). The total extract (extracted using 95% ethanol) of E. pekinensis was pretreated by two simple steps before CCC isolation, following the procedure: the total extract was extracted by classical solvent extraction using petroleum ether and ethyl acetate, respectively, and then the ethyl acetate extract was suspended using 95% ethanol, after being allowed to stand overnight, the sediment was obtained. Partial sediment (100 mg) was then directly separated by CCC with a two‐phase solvent system composed of chloroform‐95% ethanol‐water‐85% formic acid (50:50:50:5, v/v/v/v). About 22 mg of 3,3′‐dimethoxy ellagic acid (1), 12 mg of 3,3′‐di‐O‐methyl‐4‐O‐(β‐d ‐xylopyranosyl)ellagic acid (2), and 35 mg of ellagic acid (3) with purities of 96.0, 95.2, and 95.4% were obtained respectively in one step within 4 h. After being purified by washing with methanol, the purities of the three compounds obtained were all above 98%. The purities were determined by HPLC and their chemical structures were further identified by 1H and 13C NMR spectroscopy. The recoveries were calculated as 84.6, 85.7, and 89.5%, respectively. The result demonstrated that the present isolation method was rapid, economical and efficient for the preparative separation of polyphenols from E. pekinensis. 相似文献
85.
Rajeev Rajasekharan‐Nair Dean Moore Dr. Kirsten Chalmers Dr. Dawn Wallace Louise M. Diamond Lisa Darby Dr. David R. Armstrong Dr. John Reglinski Dr. Mark D. Spicer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(7):2487-2495
The alkylation reactions of soft scorpionates are reported. The hydrotris(S‐alkyl‐methimazolyl)borate dications (alkyl=methyl, allyl, benzyl), which were prepared by the reaction of TmMe anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C?S versus B? H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo‐μ‐aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ3‐S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S‐alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B? N bond in soft scorpionates, which has implications for their use in more advanced chemistry. 相似文献
86.
Electrostatic drag in the intramolecular Schmidt reactions of azidopropylcyclohexanones is characterized using density functional theory (DFT) calculations and direct dynamics simulations. Despite resulting from enthalpically favorable interactions, electrostatic drag slows down N2 loss during formation of bridged lactam products, an effect with implications for controlling product selectivity. 相似文献
87.
Sylvestre P. J. T. Bachollet Dean C. Cocker Harry Adams Prof. Joseph P. A. Harrity 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(40):12889-12893
The aza‐Diels–Alder cycloaddition of 1,2,4‐triazines with alkynes offers a rapid and convenient method for the synthesis of highly substituted pyridines, but often requires harsh conditions and long reaction times. The present study offers a solution to these limitations by use of a temporary tether established by a Lewis acid–base complexation of in situ generated alkynylboranes and triazines bearing a Lewis basic donor. The cycloaddition reactions take place within 20 min at 40 °C and provide direct access to a broad range of pyridines with complete and predictable regiocontrol. The carbon?boron bond can be further functionalised by cross‐coupling allowing further functionality to be introduced after cycloaddition. 相似文献
88.
Dr. Dean Strotz Dr. Julien Orts Dr. Harindranath Kadavath Dr. Michael Friedmann Dhiman Ghosh Dr. Simon Olsson Dr. Celestine N. Chi Aditya Pokharna Prof. Dr. Peter Güntert Dr. Beat Vögeli Prof. Dr. Roland Riek 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22316-22323
Protein allostery is a phenomenon involving the long range coupling between two distal sites in a protein. In order to elucidate allostery at atomic resoluion on the ligand-binding WW domain of the enzyme Pin1, multistate structures were calculated from exact nuclear Overhauser effect (eNOE). In its free form, the protein undergoes a microsecond exchange between two states, one of which is predisposed to interact with its parent catalytic domain. In presence of the positive allosteric ligand, the equilibrium between the two states is shifted towards domain–domain interaction, suggesting a population shift model. In contrast, the allostery-suppressing ligand decouples the side-chain arrangement at the inter-domain interface thereby reducing the inter-domain interaction. As such, this mechanism is an example of dynamic allostery. The presented distinct modes of action highlight the power of the interplay between dynamics and function in the biological activity of proteins. 相似文献
89.
Dr. S. James Ratnakar Dr. Sara Chirayil Dr. Alexander M. Funk Dr. Shanrong Zhang Prof. João F. Queiró Prof. Carlos F. G. C. Geraldes Prof. Zoltan Kovacs Prof. A. Dean Sherry 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(48):21855-21860
Paramagnetic chemical exchange saturation transfer (paraCEST) agents are well-suited for imaging tissue pH because the basis of CEST, chemical exchange, is inherently sensitive to pH. Several previous pH-sensitive paraCEST agents were based on an exchanging Ln3+-bound water molecule as the CEST antenna but this design often added additional line-broadening to the bulk water signal due to T2 exchange. We report herein a pH-sensitive paraCEST agent that lacks an inner-sphere water molecule but contains one Ln-bound −OH group for CEST activation. The Yb3+ complex, Yb( 1 ), displayed a single, highly shifted CEST peak originating from the exchangeable Yb-OH proton, the frequency of which changed over the biologically relevant pH range. CEST images of phantoms ranging in pH from 6 to 8 demonstrate the potential of this agent for imaging pH. Initial rodent imaging studies showed that Gd( 1 ) remains in the vascular system much longer than anticipated but is cleared slowly via renal filtration. 相似文献
90.
Dr. Takaaki Mitsuhashi Dr. Lena Barra Zachary Powers Volga Kojasoy Andrea Cheng Feng Yang Dr. Yoshimasa Taniguchi Dr. Takashi Kikuchi Prof. Dr. Makoto Fujita Prof. Dr. Dean J. Tantillo Prof. Dr. John A. Porco Jr Prof. Dr. Ikuro Abe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23980-23989
Fungal meroterpenoids are a diverse group of hybrid natural products with impressive structural complexity and high potential as drug candidates. In this work, we evaluate the promiscuity of the early structure diversity-generating step in fungal meroterpenoid biosynthetic pathways: the multibond-forming polyene cyclizations catalyzed by the yet poorly understood family of fungal meroterpenoid cyclases. In total, 12 unnatural meroterpenoids were accessed chemoenzymatically using synthetic substrates. Their complex structures were determined by 2D NMR studies as well as crystalline-sponge-based X-ray diffraction analyses. The results obtained revealed a high degree of enzyme promiscuity and experimental results which together with quantum chemical calculations provided a deeper insight into the catalytic activity of this new family of non-canonical, terpene cyclases. The knowledge obtained paves the way to design and engineer artificial pathways towards second generation meroterpenoids with valuable bioactivities based on combinatorial biosynthetic strategies. 相似文献