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131.
Ostash B Rix U Rix LL Liu T Lombo F Luzhetskyy A Gromyko O Wang C Braña AF Méndez C Salas JA Fedorenko V Rohr J 《Chemistry & biology》2004,11(4):547-555
A 3 kb DNA fragment from the Streptomyces globisporus 1912 landomycin E (LaE) biosynthetic gene cluster (lnd) was completely sequenced. Three open reading frames were identified, lndGT4, lndZ4, and lndZ5, whose probable translation products resemble a glycosyltransferase, a reductase, and a hydroxylase, respectively. Studies of generated mutants from disruption and complementation experiments involving the lndGT4 gene allowed us to determine that LndGT4 controls the terminal L-rhodinose sugar attachment during LaE biosynthesis and that LndZ4/LndZ5 are responsible for the unique C11-hydroxylation of the landomycins. Generation of the novel landomycins F, G, and H in the course of these studies provided evidence for the flexibility of lnd glycosyltransferases toward their acceptor substrates and a basis for initial structure-activity relationships within the landomycin family of antibiotics. 相似文献
132.
Sem DS Bertolaet B Baker B Chang E Costache AD Coutts S Dong Q Hansen M Hong V Huang X Jack RM Kho R Lang H Ma CT Meininger D Pellecchia M Pierre F Villar H Yu L 《Chemistry & biology》2004,11(2):185-194
Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases. 相似文献
133.
In-lens cryo-high resolution scanning electron microscopy: methodologies for molecular imaging of self-assembled organic hydrogels. 总被引:1,自引:0,他引:1
Robert P Apkarian Elizabeth R Wright Victor A Seredyuk Susan Eustis L Andrew Lyon Vincent P Conticello Fredric M Menger 《Microscopy and microanalysis》2003,9(4):286-295
The micro- and nanoarchitectures of water-swollen hydrogels were routinely analyzed in three dimensions at very high resolution by two cryopreparation methods that provide stable low-temperature specimens for in-lens high magnification recordings. Gemini surfactants (gS), poly-N-isopropylacrylamides (p-NIP Am), and elastin-mimetic di- (db-E) and triblock (tb-E) copolymer proteins that form hydrogels have been routinely analyzed to the sub-10-nm level in a single day. After they were quench or high pressure frozen, samples in bulk planchets were subsequently chromium coated and observed at low temperature in an in-lens field emission SEM. Pre-equilibrated planchets (4-40 degrees C) that hold 5-10 microl of hydrogel facilitate dynamic morphological studies above and below their transition temperatures. Rapidly frozen samples were fractured under liquid nitrogen, low-temperature metal coated, and observed in-lens to assess the dispersion characteristics of micelles and fragile colloidal assemblies within bulk frozen water. Utilizing the same planchet freezing system, the cryoetch-HRSEM technique removed bulk frozen water from the hydrogel matrix by low-temperature, high-vacuum sublimation. The remaining frozen solid-state sample faithfully represented the hydrogel matrix. Cryo- and cryoetch-HRSEM provided vast vistas of hydrogels at low and intermediate magnifications whereas high magnification recordings and anaglyphs (stereo images) provided a three-dimensional prospective and measurements on a molecular level. 相似文献
134.
Density functional theory (DFT), in its current local, gradient corrected, and hybrid implementations and their extensions, is approaching an impasse. To continue to progress toward the quality of results demanded by today's ab initio quantum chemistry encourages a new direction. We believe ab initio DFT is a promising route to pursue. Whereas conventional DFT cannot describe weak interactions, photoelectron spectra, or many potential energy surfaces, ab initio DFT, even in its initial, optimized effective potential, second-order many-body perturbation theory form [OEP (2)-semi canonical], is shown to do all well. In fact, we obtain accuracy that frequently exceeds MP2, being competitive with coupled-cluster theory in some cases. Furthermore, this is accomplished within a relatively fast computational procedure that scales like iterative second order. We illustrate our results with several molecular examples including Ne2,Be2,F2, and benzene. 相似文献
135.
Let H=1/2+V on l2(B), whereB is the Bethe lattice andV(x),x
B, are i.i.d.r.v.'s with common probability distribution. It is shown that for distributions sufficiently close to the Cauchy distribution, the density of states(E) is analytic in a strip about the real axis. 相似文献
136.
Recovery of intact proteins from silver stained gels 总被引:1,自引:0,他引:1
Silver stained proteins of a wide molecular weight (MW) range (20-116 kDa) were successfully recovered by both electroblot and electroelution. The recovery was demonstrated for nanogram loads of proteins separated by SDS-PAGE and visualized by silver staining methods compatible and incompatible with mass spectrometry (MS). It was shown that the alcohol/acid and glutaraldehyde fixation steps present in a number of staining procedures did not prevent recovery of intact proteins from gels. It was found that the recovery of intact proteins from silver stained gels was substantially increased upon pre-equilibration in a buffer containing the reducing agent, dithiothreitol (DTT). The effect of destaining on the recovery of silver stained proteins was also investigated. Comparable recovery of intact proteins within a wide MW range from silver stained gels with and without destaining step was demonstrated. Recovery of model proteins from gels visualized using silver staining method compatible with MS showed 52 to 76% yield of that from the unstained gel, depending upon method of the transfer. Comparison of the recovery of intact proteins from gels visualized using other staining procedures was also made. The above findings have implications as to the supposed irreversible nature of protein "fixation" inside polyacrylamide matrix, and confirm lack of binding of proteins in the gel to metal silver deposited on its surface. This method has the potential to be suitable for direct characterization of proteins by matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) without additional purification steps. 相似文献
137.
Victor Wee Lin Ng 《Journal of organometallic chemistry》2005,690(9):2323-2332
The reaction of [CpCr(CO)3]2 (Cp = η5-C5H5) (1) with 1 mol equivalent of 2,5-dimercapto-1,3,4-thiadiazole (DMcTH2) at ambient temperature led to the isolation of a reddish-brown crystalline solid of CpCr(CO)3(η1-DMcTH) (5) and a green solid of CpCr(CO)3H (2) in yields of ca. 28% and 30%, respectively, along with some [CpCr(CO)2]2 (3) and [CpCr(CO)2]2S (4). The reaction of 1 with 1 mol equivalent of vinylene trithiocarbonate (SCS(CH)2S) (VTTC) at 90 °C led to the isolation of a red crystalline solid of CpCr(CO)2(η2-SCHSC2H2) (6) in ca. 15% yield while the reaction of 1 with isopropylxanthic disulfide ((CH3)2CHOCS2)2 resulted in the formation of CpCr(CO)2(η2-S2COCH(CH3)2) (8) in ca. 80% yield. The complexes 5, 6 and 8 have been determined by single crystal X-ray diffraction analysis. 相似文献
138.
[reaction: see text] A conformationally locked carbocyclic version of puromycin amino nucleoside was synthesized via Mitsunobu coupling of a 3-azido-substituted carbocyclic moiety with 6-chloropurine without interference from the azido group reacting with triphenylphosphine. The requisite 3-azido-substituted carbocyclic pseudosugar was prepared by a double inversion of configuration at C3' (nucleoside numbering) involving a nucleophilic displacement with azide. 相似文献
139.
Tandem cuprate addition-Dieckmann condensation is featured in the construction of the polyketide metabolite tetracenomycin A(2). Thus, cyclization substrate 11 was treated with Gilman cuprate Me(2)CuLi to afford anthracene 12. The phenolic acetate protecting group of 12ensured its chemoselective oxidation to reveal terminal quinone 13, which intercepts the previously reported synthesis of tetracenomycin A(2). 相似文献
140.
Victor N. Khrustalev Mikhail Yu. Antipin Irina V. Borisova Valery V. Lunin Ghassoub Rima 《Journal of organometallic chemistry》2004,689(2):478-483
The reaction of equimolar quantities of LiOCH2CH2NMe2 and E14(OCH2CH2NMe2)2 (E14=Ge, Sn) in ether yielded new ate complexes [LiE14(OCH2CH2NMe2)3]2 (E14=Ge (1), Sn (2)) with bidentate ligands. The compounds 1 and 2 are white crystalline substances which are highly soluble in THF and pyridine and very sensitive to the traces of oxygen and moisture. The structures of these compounds are studied by X-ray diffraction analysis. The ate complexes 1 and 2 are powerful nucleophiles and may be employed as ligands (neutral) in the coordination chemistry of the transition metals. The electronegative O-substituents at the divalent E14 atoms render them less oxidizable than alkyl- or aryl-substituted derivatives, and the bidentate ligands, owing to intramolecular donor-acceptor interactions, make them more thermodynamically stable compared to monodentate ligands. 相似文献