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101.
Metabolic study of paeoniflorin and total paeony glucosides from Paeoniae Radix Rubra in rats by high‐performance liquid chromatography coupled with sequential mass spectrometry
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《Biomedical chromatography : BMC》2018,32(4)
A clear understanding of the metabolism of Traditional Chinese Medicines is extremely important in their rational clinical application and effective material foundation research. A novel and reliable strategy was performed to find more metabolites of paeoniflorin, determine the metabolites of total paeony glucosides (TPG) by means of determining those metabolites of paeoniflorin, and compare the metabolism differences between paeoniflorin and TPG by intragastric administration. This strategy was characterized as follows. Firstly, the rats were divided into two groups (the paeoniflorin group and the TPG group) to find differences in metabolism mechanisms between paeoniflorin and TPG. Secondly, UPLC‐FT‐ICR MS and UPLC‐Q‐TOF MS2 were applied to obtain accurate molecular weight and structural information, respectively. Thirdly, the metabolites were tentatively identified by a combination of data‐processing methods including mass defect screening, characteristic neutral loss screening and product ion screening. Finally, a comparative study was employed in the metabolism of paeoniflorin and TPG. Based on the strategy, 18 metabolites of paeoniflorin (including four new compounds) and 11 metabolites of TPG (including two new compounds) were identified. In all of the identified metabolites of paeoniflorin, two metabolites in rat plasma, four metabolites in rat urine and six metabolites in rat feces were found for the first time after paeoniflorin administration. The results indicate that hydrolyzation of the ester bond and glucosidic band and conjugation with glucuronide were the major metabolic pathways of paeoniflorin. The metabolites of paeoniflorin and TPG in rat plasma, urine and feces have been detected for the first time after intragastric administration. The results may contribute to a better understanding of the metabolism mechanism and provide a scientific rationale for researching the material basis of paeoniflorin and TPG in vivo. 相似文献
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103.
《Optimization》2012,61(4-5):495-505
This paper investigates properties of the optimality equation and optimal policies in discrete time Markov decision processes with expected discounted total rewards under weak conditions that the model is well defined and the optimality equation is true. The optimal value function is characterized as a solution of the optimality equation and the structure of optimal policies is also given. 相似文献
104.
Bernhard Wölfl Dr. Guillaume Mata Prof. Alois Fürstner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):255-259
The macrocyclic core of the cytotoxic marine natural product callyspongiolide ( 1 ) was forged by ring-closing alkyne metathesis (RCAM) of an ynoate precursor using a molybdenum alkylidyne complex endowed with triarylsilanolate ligands as the catalyst. This result is remarkable in view of the failed attempts documented in the literature at converting electron deficient alkynes with the aid of more classical catalysts. The subsequent Z-selective semi-reduction of the resulting cycloalkyne by hydrogenation over nickel boride required careful optimization in order to minimize overreduction and competing dehalogenation of the compound's alkenyl iodide terminus as needed for final attachment of the side chain of 1 by Sonogashira coupling. The required cyclization precursor itself was prepared via Kocienski olefination. 相似文献
105.
Dr. Yusaku Nomura Dr. Frédéric Thuaud Dr. Daisuke Sekine Prof. Dr. Akihiro Ito Satoko Maeda Dr. Hiroyuki Koshino Dr. Daisuke Hashizume Dr. Atsuya Muranaka Dr. Thomas Cruchter Prof. Dr. Masanobu Uchiyama Prof. Dr. Satoshi Ichikawa Prof. Dr. Akira Matsuda Prof. Dr. Minoru Yoshida Prof. Dr. Go Hirai Prof. Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8387-8392
A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B2(pin)2). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity. 相似文献
106.
Dr. Azusa Kondoh Dipl.‐Chem. Alexander Arlt Barbara Gabor Prof. Alois Fürstner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(24):7731-7738
The lichen‐derived glycoconjugate gobienine A is structurally more complex than most glycolipids isolated from higher plants by virtue of the all‐cis substituted γ‐lactone substructure embedded into its macrocyclic frame. A concise entry into this very epimerization‐prone and hence challenging structural motif is presented, which relies on an enantioselective cyanohydrin formation, an intramolecular Blaise reaction, a palladium‐catalyzed alkoxycarbonylation, and a diastereoselective hydrogenation of the tetrasubstituted alkene in the resulting butenolide. This strategy, in combination with ring‐closing olefin metathesis for the formation of the macrocyclic perimeter, allowed the proposed structure of gobienine A ( 1 ) to be formed in high overall yield. The recorded spectral data show that the structure originally attributed to gobienine A is incorrect and that it is not the epimerization‐prone ester site on the butanolide ring that is the locus of misassignment; rather, the discrepancy must be more profound. 相似文献
107.
On-vial immobilized CdSe quantum dots (QDs) are applied for the first time as chemiluminescent probes for the detection of trace metal ions. Among 17 metal ions tested, inhibition of the chemiluminescence when CdSe QDs are oxidized by H2O2 was observed for Sb, Se and Cu. Liquid–liquid–liquid microextraction was implemented in order to improve the selectivity and sensitivity of the chemiluminescent assay. 相似文献
108.
Hiu Yung Lam Rannveig Ingebrigtsen Gaarden Xuechen Li 《Chemical record (New York, N.Y.)》2014,14(6):1086-1099
Daptomycin, the first antibiotic of its class, provides a new structural motif for the development of new antibiotics. Recently, we have completed the total synthesis of daptomycin. The development of the successful synthetic strategy is described here, including the application of serine/threonine ligation mediated peptide cyclization to the daptomycin macrocyclization. 相似文献
109.
110.
Dr. Wei Zhang Dr. Emmanuel Baudouin Marie Cordier Dr. Gilles Frison Dr. Bastien Nay 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8643-8648
A one-pot methodology to synthesize metastable bicyclic 2,5-dihydrooxepines from cyclic 1,3-diketones and 1,4-dibromo-2-butenes through the retro-Claisen rearrangement of syn-2-vinylcyclopropyl diketone intermediates is reported. DFT calculations were performed to understand the reaction selectivity and mechanisms towards [1,3]- or [3,3]-sigmatropic rearrangements, highlighting the crucial influence of the temperature. The reaction was successfully applied to a short protecting group-free total synthesis of radulanin A, a natural 2,5-dihydrobenzoxepine. Moreover, the strong herbicidal potential of this natural product is demonstrated for the first time. 相似文献