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101.
Schwarz O Jakupovic S Ambrosi HD Haustedt LO Mang C Müller-Kuhrt L 《Journal of combinatorial chemistry》2007,9(6):1104-1113
Recently, we developed a concept known as biology-oriented synthesis (BIOS), which targets the design and synthesis of small- to medium-sized compound libraries on the basis of genuine natural product templates to provide screening compounds with high biological relevance. We herein describe the parallel solution phase synthesis of two BIOS-based libraries starting from alpha-santonin (1). Modification of the sesquiterpene lactone 1 by introduction of a thiazole moiety followed by a Lewis-acid-mediated lactone opening yielded a first library of natural product analogues. An acid-mediated dienone-phenol rearrangement of 1 and a subsequent etherification/amidation sequence led to a second natural product-based library. After application of a fingerprint-based virtual screening on these compounds, the biological screening of 23 selected library members against 5-lipoxygenase resulted in the discovery of four potent novel inhibitors of this enzyme. 相似文献
102.
Kelly TR Cai X Damkaci F Panicker SB Tu B Bushell SM Cornella I Piggott MJ Salives R Cavero M Zhao Y Jasmin S 《Journal of the American Chemical Society》2007,129(2):376-386
Building on prototype 1, which achieves 120 degrees of phosgene-powered unidirectional rotation to rotamer 6 (see Figure 5 in the full article), 7 was designed to accomplish repeated unidirectional rotation (see Scheme 7). Compound 7 contains an amino group on each blade of the triptycene and a 4-(dimethylamino)pyridine (DMAP) unit to selectively deliver phosgene (or its equivalent) to the amine in the "firing position". The synthesis of 7 is described: the key constructive steps are a benzyne addition to an anthracene to generate the triptycene, a stilbene photocyclization to construct the helicene, and a Stille coupling to incorporate the DMAP unit. The DMAP unit was shown to regioselectively relay 1,1'-carbonyldiimidazole (but not phosgene) to the proximal amino group, as designed, but rotation of the triptycene does not occur. Extensive attempts to troubleshoot the problem led to the conclusion that the requisite intramolecular urethane formation, as demonstrated in the prototype (1 --> 4), does not occur with 7 (to give 85) or 97 (to give 100). We speculate that either (i) hydrogen bonding between the hydroxypropyl group and functionality present in 7 but absent from 1 or (ii) a Bürgi-Dunitz (or similar) interaction involving the DMAP (see 106) prevents achievement of a conformation conducive to intramolecular urethane formation. 相似文献
103.
Martin Pabst Stephan Rupert Fagerer Rudolf Köhling Klaus Eyer Jasmin Krismer Konstantins Jefimovs Alfredo Jesus Ibáñez Renato Zenobi 《Journal of the American Society for Mass Spectrometry》2014,25(6):1083-1086
Drug monitoring is usually performed by liquid chromatography coupled with optical detection or electrospray ionization mass spectrometry. More recently, matrix-assisted laser desorption/ionization (MALDI) in combination with triple quadrupole or Fourier-transform (FT) mass analyzers has also been reported to allow accurate quantification. Here, we present a strategy that employs standard MALDI time-of-flight (TOF) mass spectrometry (MS) for the sensitive and accurate quantification of saquinavir from an extract of blood peripheral mononuclear cells. Unambiguous identification of saquinavir in the mass spectra was possible because of using internal mass calibration and by an overall low chemical noise in the low mass range. Exact mass determination of the constant background peaks of the cell extract, which were used for recalibration, was performed by an initial MALDI-FT-MS analysis. Fast and multiplexed sample analysis was enabled by microarray technology, which provided 10 replicates in the lower nL range for each sample in parallel lanes on a chip. In order to validate the method, we employed various statistical tests, such as confidence intervals for linear regressions, three quality control samples, and inverse confidence limits of the estimated concentration ratios. Figure
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104.
Joan Simó Padial Dr. René de Gelder Dr. Célia Fonseca Guerra Prof. Dr. F. Matthias Bickelhaupt Dr. Jasmin Mecinović 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(21):6268-6271
The through‐space polar–π interactions between pyridinium ion and the adjacent aromatic rings in 2,6‐diarylpyridines affect the pKa values. Hammett analysis illustrates that the basicity of pyridines correlates well with the sigma values of the substituents at the para position of the flanking aryl rings. 相似文献
105.
Caroline Cannizzo Mathieu Wagner Jean-Philippe Jasmin Christine Vautrin-Ul Denis Doizi Christine Lamouroux Annie Chaussé 《Tetrahedron letters》2014
This Letter describes the fast synthesis of a mono-aminated calix[6]arene. The immobilization of this macrocycle onto glassy carbon electrodes via diazonium salt chemistry and the electrochemical characterization of the grafted organic layer are also reported. 相似文献
106.
107.
Jasmin Kemptner Martina Marchetti‐Deschmann Robert Mach Irina S. Druzhinina Christian P. Kubicek Günter Allmaier 《Rapid communications in mass spectrometry : RCM》2009,23(6):877-884
Unambiguous identification of mycotoxin‐producing fungal species as Fusarium is of great relevance to agriculture and the food‐producing industry as well as in medicine. Protein profiles of intact fungal spores, such as Penicillium, Aspergillus and Trichoderma, derived from matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) were shown to provide a rapid and straightforward method for species identification and characterization. In this study, we applied this approach to five different Fusarium spp. strains which are known to affect the growth of different grain plants. To obtain a suitable MALDI matrix system and sample preparation method, thin‐layer, dried‐droplet and sandwich methods and several MALDI matrices, namely CHCA, DHB, FA, SA and THAP dissolved in various solvent mixtures (organic solvents such as ACN, MeOH, EtOH and iPrOH and for the aqueous phase water and 0.1% TFA), were evaluated in terms of mass spectrometric pattern and signal intensities. The most significant peptide/protein profiles were obtained with 10 mg ferulic acid (FA) in 1 mL ACN/0.1% TFA (7:3, v/v) used as matrix system. Mixing the spores with the matrix solution directly on the MALDI target (dried‐droplet technique) resulted in an evenly distributed spores/matrix crystal layer, yielding highly reproducible peptide/protein profiles from the spore surfaces. Numerous abundant ions throughout the investigated m/z range (m/z 1500–15 000) could be detected. Differences in the obtained mass spectral patterns allowed the differentiation of spores of various Fusarium species. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
108.
Jasmin Bullermann Rüdiger Spohnholz Stefan Friebel Tunga Salthammer 《Journal of polymer science. Part A, Polymer chemistry》2014,52(5):680-690
A new synthesis for polyurethane dispersions was developed using both trimellitic anhydride alone and in combination with dimethylol propionic acid as internal emulsifiers. During synthesis of the polyurethane ionomer, Fourier transform infrared spectroscopy was used for monitoring and characterizing both the polyaddition step and the anhydride ring opening process. Depending on the synthesis route, the carboxylic groups are either located at the end of the polymer backbone or additionally statistically distributed within the polymer chain itself. The effect of the carboxylic group's position on the chemical and physical properties, with particular reference to particle size and pH, was analyzed. Three different polyols were used to synthesize the polyurethane dispersions. Driven by the current trend to find renewable alternatives to petrochemical‐based raw materials, one bio‐based polyol was included for the synthesis. The effect of the different structures of the polyurethane dispersions (petrochemical‐ or bio‐based polyols) on mechanical properties and thermal behavior was investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 680–690 相似文献
109.
Spin‐labeling of polymeric micelles and application in probing micelle swelling using EPR spectroscopy 下载免费PDF全文
Yanxiong Pan Sunanda Neupane Jasmin Farmakes Bingqing Liu Wenfang Sun Zhongyu Yang 《Journal of Polymer Science.Polymer Physics》2017,55(23):1770-1782
Polymer structure and conformational dynamics are essential to polymer macroscopic properties, but are challenging to probe. We report here a synthetic pathway to chemically add a nitroxide moiety onto block polymers in a mild, aqueous environment and demonstrate its use in a series of polymeric micelles using Electron Paramagnetic Resonance (EPR) spectroscopy. The micelles were characterized with several analytical approaches and EPR findings were in general consistent with other approaches. Upon exposure to organic solvents, the line shape changes reflected the micelle swelling and EPR spectral simulations revealed structural information of the swelled micelles. The label introduced via our method can be cleaved and replaced with other probes to report different information site‐specifically. The mild conditions facilitate the future use of EPR in solving biopolymer problems. In combination with other labeling approaches, one can perform polymer spin labeling with different chemistry, so that various information about polymers can be obtained site‐specifically. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1770–1782 相似文献
110.
Quantitative determination of alkannins and shikonins in endemic Mediterranean Alkanna species 下载免费PDF全文
Jasmin Tappeiner Alexandra Vasiliou Markus Ganzera Dimitrios Fessas Hermann Stuppner Vassilios P. Papageorgiou Andreana N. Assimopoulou 《Biomedical chromatography : BMC》2014,28(7):923-933
The optical antipodes alkannin/shikonin (A/S) and their esters are potent pharmaceutical substances found in the roots of 150 Boraginaceous species. This study estimated and compared total and free A/S content and A/S enantiomeric ratio in roots of 11 Alkanna species (A. corcyrensis, A. tinctoria, A. pindicola, A. orientalis, A. methanaea, A. calliensis, A. graeca, A. primuliflora, A. stribrnyi, A. sieberi and A. noneiformis) growing wild in various Greek regions, to compare with cultivated species. It also re‐characterized the chirality of A/S commercial samples, since most of them were misnamed by the providers. Several Alkanna species were collected (groups 1 and 3) and botanically identified, whereas some Alkanna species were cultivated from collected seeds (group 2). Free A/S and derivatives were extracted from the dried roots of Alkanna species and analyzed by high performance liquid chromatography‐diode array detection (HPLC‐DAD). For total A/S content the hexane extracts of Alkanna roots were hydrolyzed and analyzed by HPLC‐DAD. Chirality determination and A/S enantiomeric ratio estimation was performed for several commercial samples by polarimetry,chiral LC‐DAD and circular dichroism studies. Quantitative analysis revealed that A/S content varied from one region to another even within the same species. Most of the cultivated samples contained greater amounts of free and total A/S compared with the wild ones, wheras no difference was observed in A/S enantiomeric ratio. All the Alkanna samples tested contain mainly alkannin derivatives. Some of the examined Alkanna species of the Greek flora that are endemic to the Mediterranean area could serve as alternative sources for medicinally valuable A/S derivatives. Most of the commercial A/S samples tested were misnamed in terms of chirality and re‐characterized. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献