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91.
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Harding DJ Gruene P Haertelt M Meijer G Fielicke A Hamilton SM Hopkins WS Mackenzie SR Neville SP Walsh TR 《The Journal of chemical physics》2010,133(21):214304
The geometric structures of small cationic rhodium clusters Rh(n)(+) (n = 6-12) are investigated by comparison of experimental far-infrared multiple photon dissociation spectra with spectra calculated using density functional theory. The clusters are found to favor structures based on octahedral and tetrahedral motifs for most of the sizes considered, in contrast to previous theoretical predictions that rhodium clusters should favor cubic motifs. Our findings highlight the need for further development of theoretical and computational methods to treat these high-spin transition metal clusters. 相似文献
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Hollenhorst MA Bumpus SB Matthews ML Bollinger JM Kelleher NL Walsh CT 《Journal of the American Chemical Society》2010,132(44):15773-15781
The gene cluster from Pantoea agglomerans responsible for biosynthesis of the dapdiamide antibiotics encodes an adenylation-thiolation didomain protein, DdaD, and an Fe(II)/α-ketoglutarate-dependent dioxygenase homologue, DdaC. Here we show that DdaD, a nonribosomal peptide synthetase module, activates and sequesters N(β)-fumaramoyl-l-2,3-diaminopropionate as a covalently tethered thioester for subsequent oxidative modification of the fumaramoyl group. DdaC catalyzes Fe(II)- and α-ketoglutarate-dependent epoxidation of the covalently bound N(β)-fumaramoyl-l-2,3-diaminopropionyl-S-DdaD species to generate N(β)-epoxysuccinamoyl-DAP (DAP = 2,3-diaminopropionate) in thioester linkage to DdaD. After hydrolytic release, N(β)-epoxysuccinamoyl-DAP can be ligated to l-valine by the ATP-dependent ligase DdaF to form the natural antibiotic N(β)-epoxysuccinamoyl-DAP-Val. 相似文献
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Highly crystalline, nanostructured, three-dimensional β-PbO2 coatings were successfully obtained by galvanostatic deposition from baths containing aqueous lead(II) and methanesulfonic acid (CH3SO3H). This constitutes a much more environmentally friendly methodology compared to plating of β-PbO2 in HNO3. The deposits exhibited high quality and good adherence. The crystallite size was in the range 20–30 nm and AFM imaging revealed very uniform, rough deposits (i.e., 255–275 nm rms). The oxidative destruction of Methyl Orange azo dye was studied by electrochemical advanced oxidation processes (EAOPs). An electro-Fenton process with a high surface area carbon-felt cathode performed better than the single anodic oxidation. Rapid and complete decolorisation was achieved following pseudo first-order kinetics. The stability of the β-PbO2 electrodes during the electrolyses was also demonstrated. 相似文献
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Juliana S Luz Celso RR Ramos Márcia CT Santos Patricia P Coltri Fernando L Palhano Debora Foguel Nilson IT Zanchin Carla C Oliveira 《BMC biochemistry》2010,11(1):22
Background
The archaeal exosome is formed by a hexameric RNase PH ring and three RNA binding subunits and has been shown to bind and degrade RNA in vitro. Despite extensive studies on the eukaryotic exosome and on the proteins interacting with this complex, little information is yet available on the identification and function of archaeal exosome regulatory factors. 相似文献96.
This paper extends the works of Kang and Ramanan (2010) and Kaspi and Ramanan (2011), removing the hypothesis of absolute continuity of the service requirement and patience time distributions. We consider a many-server queueing system in which customers enter service in the order of arrival in a non-idling manner and where reneging is considerate. Similarly to Kang and Ramanan (2010), the dynamics of the system are represented in terms of a process that describes the total number of customers in the system as well as two measure-valued processes that record the age in service of each of the customers being served and the “potential” waiting times. When the number of servers goes to infinity, fluid limit is established for this triple of processes. The convergence is in the sense of probability and the limit is characterized by an integral equation. 相似文献
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Dr. Zhipeng Zheng Youge Pu Prof. Javier Adrio Prof. Patrick J. Walsh 《Angewandte Chemie (International ed. in English)》2023,62(25):e202303069
Aziridines are highly valued synthetic targets in organic and medicinal chemistry. The organocatalytic synthesis of such structures with broad substrate scope and good diastereoselectivity, however, is rare. Herein, we report a broadly applicable and diastereoselective synthetic method for the synthesis of trans-aziridines from imines and benzylic or alkyl halides utilizing sulfenate anions (PhSO–) as the catalyst. Substrates bearing heterocyclic aromatic groups, alkyl, and electron-rich and electron-poor aryl groups were shown to be compatible with this method (33 examples), giving good yields and high diastereoselectivities (trans : cis >20 : 1). Further functionalization of aziridines containing cyclopropyl or cyclobutyl groups was achieved through ring-opening reactions, with a cyclobutyl-substituted norephedrine derivative obtained through a four-step synthesis. We offer a mechanistic proposal involving reversible addition of the deprotonated benzyl sulfoxide to the imine to explain the high trans-diastereoselectivity. 相似文献