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21.
Cooper SM Laosripaiboon W Rahman AS Hothersall J El-Sayed AK Winfield C Crosby J Cox RJ Simpson TJ Thomas CM 《Chemistry & biology》2005,12(7):825-833
Mupirocin, a polyketide-derived antibiotic from Pseudomonas fluorescens NCIMB10586, is a mixture of pseudomonic acids (PA) that target isoleucyl-tRNA synthase. The mup gene cluster encodes both type I polyketide synthases and monofunctional enzymes that should play a role during the conversion of the product of the polyketide synthase into the active antibiotic (tailoring). By in-frame deletion analysis of selected tailoring open-reading frames we show that mupQ, mupS, mupT, and mupW are essential for mupirocin production, whereas mupO, mupU, mupV, and macpE are essential for production of PA-A but not PA-B. Therefore, PA-B is not simply produced by hydroxylation of PA-A but is either a precursor of PA-A or a shunt product. In the mupW mutant, a new metabolite lacking the tetrahydropyran ring is produced, implicating mupW in oxidation of the 16-methyl group. 相似文献
22.
Iain L. Marr Petra Kluge Laura Main Vincent Margerin Cyrille Lescop 《Mikrochimica acta》1995,119(3-4):219-232
Three sets of samples have been investigated in some detail. One set is from a river polluted by mine workings, containing substantial levels of Fe, Mn,Cu, Zn and Ni with traces of many other metals. The second set consists of typical estuarine sediments contaminated from a wide range of industrial sources, and the third set consists of oily drilling cuttings from the sea bottom in the vicinity of a North Sea oil production platform.These samples have been subjected to treatment 1) with EDTA at two different pH's (extracts) 2) with HNO3/H2O2 3) with HNO3/HCl and 4) with HNO3/HCl/HF (digests). EDTA recoveries, compared toaqua regia digests, are often very reproducible, not dependent on pH, and usually significantly low. Nitric/peroxide andaqua regia digests often give very close results suggesting that these are meaningful values indicating the maximum levels of polluting metals in the sediments. However, the triple acid digest with HF does sometimes give higher values (and reasonable agreement for CRM's such as MESS-1) but with poorer reproducibility. 相似文献
23.
Addition of amines to pyranosyl nitrile oxides, generated by base-induced dehydrochlorination of the corresponding hydroximoyl chloride, affords pyranosyl N-alkyl/aryl-formamide oximes (41-90%). Reaction with amino acid esters yields the corresponding amidoximes and/or 3-pyranosyl-1,2,4-oxadiazin-6-ones. The structure of N-phenyl-C-(2,3,4-tri-O-acetyl-β-D-xylopyranosyl)formamide oxime was established by X-ray crystallography. 相似文献
24.
A computational study has been performed to examine the reactions of a model beta-diketiminatoaluminium (I) complex with the hydrogen atom and with the electron. It was found that the hydrogen atom adds to the metal centre exothermically (DeltaH(rxn)=-202 kJ mol(-1)), and the spin density in the resulting radical resides entirely on the beta-diketiminato ligand. The spin density of the corresponding radical anion is very similar to the H-adduct. 相似文献
25.
Eric A. Gregory Mark R. Buckingham Dawn Z. Clayton Freda J. Wolfenden C.J.S.M. Simpson 《Chemical physics letters》1984,104(4):393-397
Rate constants for the vibrational deactivation of CD4 by the collision partners CD4, He, Ne, Ar, Kr, D2 and O2 have been measured using a laser-fluorescence technique. The results are compared with those for the deactivation of CH4 by the same collision partners and with a modified SSH type theoretical treatment. 相似文献
26.
Chabinyc ML Salleo A Wu Y Liu P Ong BS Heeney M McCulloch I 《Journal of the American Chemical Society》2004,126(43):13928-13929
A method for the fabrication of polymeric thin-film transistors (TFTs) by lamination is described. Poly(dimethylsiloxane) stamps were used to delaminate thin films of semiconducting polymers from silicon wafers coated with a self-assembled monolayer (SAM) formed from octyltrichlorosilane. These supported films were laminated onto electrode structures to form coplanar TFTs. The fabrication process was used to make TFTs with poly(3-hexylthiophene), P3HT, and poly[5,5'-bis(3-dodecyl-2-thienyl)-2,2'-bithiophene], PQT-12. TFTs, where these polymers were laminated onto gate dielectrics coated with SAMs from octyltrichlorosilane, had effective field-effect mobilities of 0.03 and 0.005 cm2/(V s), respectively. TFTs where PQT-12 was laminated onto gate dielectrics that were not coated with a SAM also had mobility of 0.03 cm2/(V s). In contrast, TFTs fabricated by spin-coating PQT-12 onto the same structure had mobilities ranging from 10-3 to 10-4 cm2/(V s). These results suggest that the lower mobilities of polymer TFTs made with hydrophilic gate dielectrics are caused by molecular ordering in the semiconducting film rather than electronic effects of dipolar groups at the interface. 相似文献
27.
RNA targeting is an exciting frontier for drug design. Intriguing targets include functional RNA structures in structurally-conserved untranslated regions (UTRs) of many lethal viruses. However, computational docking screens, valuable in protein structure targeting, fail for inherently flexible RNA. Herein we harness MD simulations with Markov state modeling to enable nanosize metallo-supramolecular cylinders to explore the dynamic RNA conformational landscape of HIV-1 TAR untranslated region RNA (representative for many viruses) replicating experimental observations. These cylinders are exciting as they have unprecedented nucleic acid binding and are the first supramolecular helicates shown to have anti-viral activity in cellulo: the approach developed in this study provides additional new insight about how such viral UTR structures might be targeted with the cylinder binding into the heart of an RNA-bulge cavity, how that reduces the conformational flexibility of the RNA and molecular details of the insertion mechanism. The approach and understanding developed represents a new roadmap for design of supramolecular drugs to target RNA structural motifs across biology and nucleic acid nanoscience.MD simulations and Markov state modeling explore induced fit binding of metallo-helicates to bulges in dynamic TAR RNA, reproduce experimental data, show how RNA conformational flexibility is reduced, and give mechanistic insight into insertion. 相似文献
28.
Merle A. Battiste James M. Coxon Gregory W. Simpson Peter J. Steel Alan J. Jones 《Tetrahedron》1984,40(16):3137-3144
The reaction of endo-tricyclo[3.2.1.02,4]oct-6-ene 1 with methanol in the presence of catalytic amounts of toluene-p-sulphonic acid has been shown to give 2-exo- and endo-methoxybicyclo[3.2.1]oct-3-ene (2c) and (2d) and 2-endo-methoxybicyclo[3.2.1]oct-6-ene (13). The formation of 2-exo- methoxybicyclo[3.2.1]oct-3-ene (2c), the major product of reaction, has been probed by deuterium labelling experiments and a series of 6-exo-7-exo- dideuterobicyclo[3.2.1]oct-3-enes synthesised for 2H, 1H and 13C NMR spectral analysis in order unambiguously to determine the stereochemistry of proton attack on endo-tricyclo[3.2.1 02,4]oct-6-ene (1). The formation of 2-exo-methoxybicyclo[3.2.1]oct-3-ene (2c) has been determined to involve corner protonation of the cyclopropyl moiety and skeletal rearrangement to an allylic cation with a small but measurable memory effect 相似文献
29.
30.
Summary Consider estimating the mean vector from dataN
n
(,
2
I) withl
q
norm loss,q1, when is known to lie in ann-dimensionall
p
ball,p(0, ). For largen, the ratio of minimaxlinear risk to minimax risk can bearbitrarily large ifp
. Obvious exceptions aside, the limiting ratio equals 1 only ifp=q=2. Our arguments are mostly indirect, involving a reduction to a univariate Bayes minimax problem. Whenp, simple non-linear co-ordinatewise threshold rules are asymptotically minimax at small signal-to-noise ratios, and within a bounded factor of asymptotic minimaxity in general. We also give asymptotic evaluations of the minimax linear risk. Our results are basic to a theory of estimation in Besov spaces using wavelet bases (to appear elsewhere). 相似文献