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851.
Zhang Y Jin G Illarionov B Bacher A Fischer M Cushman M 《The Journal of organic chemistry》2007,72(19):7176-7184
Lumazine synthase catalyzes the penultimate step in the biosynthesis of riboflavin. A homologous series of three pyrazolopyrimidine analogues of a hypothetical intermediate in the lumazine synthase-catalyzed reaction were synthesized and evaluated as lumazine synthase inhibitors. The key steps of the synthesis were C-5 deprotonation of 4-chloro-2,6-dimethoxypyrimidine, acylation of the resulting anion, and conversion of the product to a pyrazolopyrimidine with hydrazine. Alkylation of the pyrazolopyrimidine with a substituted ribityl iodide and deprotection of the ribityl chain afforded the final set of three products. All three compounds were extremely potent inhibitors of the lumazine synthases of Mycobacterium tuberculosis, Magnaporthe grisea, Candida albicans, and Schizosaccharomyces pombe lumazine synthase, with inhibition constants in the low nanomolar to subnanomolar range. Molecular modeling of one of the homologues bound to Mycobacterium tuberculosis lumazine synthase suggests that both the hypothetical intermediate in the lumazine synthase-catalyzed reaction pathway and the metabolically stable analogues bind similarly. 相似文献
852.
Talukdar A Illarionov B Bacher A Fischer M Cushman M 《The Journal of organic chemistry》2007,72(19):7167-7175
Lumazine synthase and riboflavin synthase catalyze the last two steps in the biosynthesis of riboflavin. To obtain structural and mechanistic probes of these two enzymes, as well as inhibitors of potential value as antibiotics, a sulfur analogue of the pyrimidine substrate of the lumazine synthase-catalyzed reaction and product of the riboflavin synthase-catalyzed reaction was designed. Facile syntheses of the S-nucleoside 5-amino-6-(D-ribitylthio)pyrimidine-2,4(1H,3H)-dione hydrochloride (15) and its nitro precursor 5-nitro-6-(D-ribitylthio)pyrimidine-2,4(1H,3H)-dione (14) are described. These compounds were tested against lumazine synthase and riboflavin synthase obtained from a variety of microorganisms. Compounds 14 and 15 were found to be inhibitors of both riboflavin synthase and lumazine synthase. Compound 14 is an inhibitor of Bacillus subtilis lumazine synthase (Ki 26 microM), Schizosaccharomyces pombe lumazine synthase (Ki 2.0 microM), Mycobacterium tuberculosis lumazine synthase (Ki 11 microM), Escherichia coli riboflavin synthase (Ki 2.7 microM), and Mycobacterium tuberculosis riboflavin synthase (Ki 0.56 muM), while compound 15 is an inhibitor of B. subtilis lumazine synthase (Ki 2.6 microM), S. pombe lumazine synthase (Ki 0.16 microM), M. tuberculosis lumazine synthase (Ki 31 microM), E. coli riboflavin synthase (Ki 47 microM), and M. tuberculosis riboflavin synthase (Ki 2.5 microM). 相似文献
853.
Rümmeli MH Kramberger C Löffler M Jost O Bystrzejewski M Grüneis A Gemming T Pompe W Büchner B Pichler T 《The journal of physical chemistry. B》2007,111(28):8234-8241
In this Article, we describe a carbon nanotube formation model in which sp2 carbon hemispheres form the embryonic caps from which a nanotube can grow. This requirement leads to a single wall carbon nanotube formation window concomitant with our systematic experimental findings, which show upper and lower diameter limits. Further, the successful formation of a nucleation cap (hemisphere) is governed by catalyst particle volume to surface area considerations. Single wall carbon nanotubes are only obtained when both the nanotube formation window and the precipitating catalyst size distribution cross over. The extent to which these two windows overlap establishes the mean diameter and diameter distribution of the obtained single wall carbon nanotubes. 相似文献
854.
As a main step in the numerical solution of control problems in continuous time, the controlled process is approximated by sequences of controlled Markov chains, thus discretising time and space. A new feature in this context is to allow for delay in the dynamics. The existence of an optimal strategy with respect to the cost functional can be guaranteed in the class of relaxed controls. Weak convergence of the approximating extended Markov chains to the original process together with convergence of the associated optimal strategies is established. 相似文献
855.
856.
Markus Haase 《Positivity》2007,11(1):57-68
We prove pointwise convexity (Jensen-type) inequalities of the form Open image in new window where F is a convex function defined on a convex subset of some Banach space X and T is the X-valued extension of a positive operator on some function space. Examples include the pointwise Hölder inequality T(fg) ≤ (Tf p )1/ p (Tf q )1/ q for a positive sublinear operator T. As applications we consider vector-valued conditional expectation and a ``real'' proof of the Riesz-Thorin theorem for positive operators. 相似文献
857.
Lisa Russelli Francesco De Rose Loredana Leone Sybille Reder Markus Schwaiger Calogero DAlessandria Lorenzo Tei 《Molecules (Basel, Switzerland)》2021,26(19)
In this work, we designed, developed, characterized, and investigated a new chelator and its bifunctional derivative for 89Zr labeling and PET-imaging. In a preliminary study, we synthesized two hexadentate chelators named AAZTHAS and AAZTHAG, based on the seven-membered heterocycle AMPED (6-amino-6-methylperhydro-1,4-diazepine) with the aim to increase the rigidity of the 89Zr complex by using N-methyl-N-(hydroxy)succinamide or N-methyl-N-(hydroxy)glutaramide pendant arms attached to the cyclic structure. N-methylhydroxamate groups are the donor groups chosen to efficiently coordinate 89Zr. After in vitro stability tests, we selected the chelator with longer arms, AAZTHAG, as the best complexing agent for 89Zr presenting a stability of 86.4 ± 5.5% in human serum (HS) for at least 72 h. Small animal PET/CT static scans acquired at different time points (up to 24 h) and ex vivo organ distribution studies were then carried out in healthy nude mice (n = 3) to investigate the stability and biodistribution in vivo of this new 89Zr-based complex. High stability in vivo, with low accumulation of free 89Zr in bones and kidneys, was measured. Furthermore, an activated ester functionalized version of AAZTHAG was synthesized to allow the conjugation with biomolecules such as antibodies. The bifunctional chelator was then conjugated to the human anti-HER2 monoclonal antibody Trastuzumab (Tz) as a proof of principle test of conjugation to biologically active molecules. The final 89Zr labeled compound was characterized via radio-HPLC and SDS-PAGE followed by autoradiography, and its stability in different solutions was assessed for at least 4 days. 相似文献
858.
859.
860.
Markus Antonietti 《Nachrichten aus der Chemie》2004,52(11):1139-1143
Chemische Expertise wirkt immer stärker in die Nachbardisziplinen und bildet die Basis für die Lösung von Problemen der Energieversorgung und des Umweltschutzes. Dies schafft Perspektiven und Märkte, die in nichts denen der Bio‐ und Gentechnologie oder den Informationswissenschaften hintanstehen. Zu diesem optimistisch stimmenden Ergebnis kommt ein kürzlich vorgelegter strategischer Bericht der US‐amerikanischen National Academy of Sciences. 相似文献