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排序方式: 共有105条查询结果,搜索用时 31 毫秒
51.
52.
Thermolysis of several trans-1-isopropenyl-4-methylene-spiro[2.x]- alkanes (x = 4,5) in xylene solution at 130° causes quantitative rearrangement to 1-methylene-2-(3′-methylbut-2′-enyl)cycloalkanes ( – ). 相似文献
53.
Prof. Dr. Ada Yonath 《Angewandte Chemie (International ed. in English)》2010,49(26):4340-4354
High‐resolution structures of ribosomes, the cellular machines that translate the genetic code into proteins, revealed the decoding mechanism, detected the mRNA path, identified the sites of the tRNA molecules in the ribosome, elucidated the position and the nature of the nascent proteins exit tunnel, illuminated the interactions of the ribosome with non‐ribosomal factors, such as the initiation, release and recycling factors. Notably, these structures proved that the ribosome is a ribozyme whose active site, namely where the peptide bonds are being formed, is situated within a universal symmetrical region that is embedded in the otherwise asymmetric ribosome structure. As this symmetrical region is highly conserved and provides the machinery required for peptide bond formation and for ribosome polymerase activity, it may be the remnant of the proto‐ribosome, a dimeric prebiotic machine that formed peptide bonds and non‐coded polypeptide chains. Structures of complexes of ribosomes with antibiotics targeting them revealed the principles allowing for their clinical use, identified resistance mechanisms and showed the structural bases for discriminating pathogenic bacteria from hosts, hence providing valuable structural information for antibiotics improvement and for the design of novel compounds that can serve as antibiotics. 相似文献
54.
Vasco Corti Riccardo Riccioli Ada Martinelli Sofia Sandri Mariafrancesca Fochi Luca Bernardi 《Chemical science》2021,12(30):10233
Currently, conventional reductive catalytic methodologies do not guarantee general access to enantioenriched β-branched β-trifluoromethyl α-amino acid derivatives. Herein, a one-pot approach to these important α-amino acids, grounded on the reduction – ring opening of Erlenmeyer–Plöchl azlactones, is presented. The configurations of the two chirality centers of the products are established during each of the two catalytic steps, enabling a stereodivergent process.A one-pot approach to β-branched β-trifluoromethyl α-amino acids, grounded on the reduction – ring opening of Erlenmeyer–Plöchl azlactones, and complementary to conventional catalytic asymmetric hydrogenation, is presented. 相似文献
55.
This paper develops a model to describe the unequal time correlation between rate of returns of different stocks. A non-trivial fourth order derivative Lagrangian is defined to provide an unequal time propagator, which can be fitted to the market data. A calibration algorithm is designed to find the empirical parameters for this model and different de-noising methods are used to capture the signals concealed in the rate of return. The detailed results of this Gaussian model show that the different stocks can have strong correlation and the empirical unequal time correlator can be described by the model’s propagator. This preliminary study provides a novel model for the correlator of different instruments at different times. 相似文献
56.
Iris Martínez-Salazar Francisco Angel-Bello Ada Alvarez 《The Journal of the Operational Research Society》2015,66(8):1312-1323
In this study, we introduce a routing problem with multiple uses of a single vehicle and service time in demand points, minimizing the sum of clients’ waiting time to receive service. This problem is relevant in the distribution of aid in disaster-stricken communities, in the recollection and/or delivery of perishable goods and personnel transportation, among other situations, where reaching clients to perform service, fast and fair, is a priority. We consider vehicle capacity and travel distance constraints, forcing multiple use of the vehicle during the planning horizon. This paper presents two mixed integer formulations for this problem, based on a multi-level network, as well as a metaheuristic algorithm. The proposed models can solve to optimality instances with up to 30 clients. The proposed metaheuristic algorithm obtains high-quality solutions in short computational times. 相似文献
57.
Gülsüm Ulusoy Ada 《Mathematical Methods in the Applied Sciences》2019,42(18):7528-7536
The paper deals with general Baskakov‐Durrmeyer operators containing several previous definitions as special cases. We construct a new sequence of BaskakovDurrmeyer operators depending on a parameter γ. We present a quantitative Voronovskaya type theorem in terms of weighted modulus of smoothness using sixth‐order central moment. In addition, we studied Grü ss‐type Voronovskaya theorem. All results in this work show that our new operators are flexible and sensitive to the rate of convergence to f, depending on our selection of γ(x). 相似文献
58.
59.
Organocatalytic Asymmetric Conjugate Additions to Cyclopent‐1‐enecarbaldehyde: A Critical Assessment of Organocatalytic Approaches towards the Telaprevir Bicyclic Core
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Dr. Luca Bernardi Dr. Mariafrancesca Fochi Riccardo Carbone Ada Martinelli Dr. Martin E. Fox Dr. Christopher J. Cobley Bhaskar Kandagatla Dr. Srinivas Oruganti Dr. Vilas H. Dahanukar Dr. Armando Carlone 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(52):19208-19222
In the context of a programme directed at the manufacture of telaprevir, eight possible approaches to its bicyclic α‐amino acid core, based on organocatalytic enantioselective conjugate additions to cyclopent‐1‐enecarbaldehyde, were identified and preliminarily explored. Four reactions, delivering advanced intermediates en route to the target amino acid, were selected for a thorough optimisation. Three of this reactions involved iminium ion catalysis with a prolinol catalyst (addition of nitromethane, nitroacetate and acetamidomalonate) and one was based on a Cinchona‐derived phase‐transfer catalyst (addition of glycine imines). A careful choice of additives allowed lowering of the catalyst loading to 0.5 mol % in some cases. The preparation of intermediates that would give access to the core of telaprevir in good yields and enantioselectivities by exploiting readily available substrates and catalysts, highlights the potential of organocatalytic technology for a cost‐effective preparation of pharmaceuticals. 相似文献
60.
Miranda LP Shao H Williams J Chen SY Kong T Garcia R Chinn Y Fraud N O'Dwyer B Ye J Wilken J Low DE Cagle EN Carnevali M Lee A Song D Kung A Bradburne JA Paliard X Kochendoerfer GG 《Journal of the American Chemical Society》2007,129(43):13153-13159
Chemical protein synthesis is important for dissecting the molecular basis of protein function. Here we advance its scope by demonstrating the significant improvement of the multifaceted pharmaceutical profile of small proteins exclusively via a chemical-based approach. The focus of this work centered on CCL-5 (RANTES) derivatives with potent anti-HIV activity. The overall chemical strategy involved a combination of coded and noncoded amino acid mutagenesis, peptide backbone engineering, and site-specific polymer attachment. The ability to alter specific protein residues, as well as precise control of the position and type of polymer attachment, allows for the exploration of specific molecular designs and resulted in novel CCL-5 analogues with significant differences in their respective biochemical and pharmaceutical properties. Using this approach, the complex-interplay of variables contributing to the noncovalent self-association (aggregation) state, CCR-5 specificity, in vivo elimination half-life, and anti-HIV activity of CCL-5-based protein analogues could be empirically evaluated via total chemical synthesis. This work has led to the identification of potent (sub-nanomolar) anti-HIV proteins with significantly improved pharmaceutical profiles, and illustrates the increasing value of protein chemical synthesis in contemporary therapeutic discovery. These antiviral molecules provide a novel mechanism of action for the development of a new generation of anti-HIV therapeutics which are still desperately needed. 相似文献