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151.
Abstract Economical syntheses of the Lewis X trisaccharide 8 and sialyl Lewis X tetrasaccharide 18 epitopes and the syntheses of the α-galactosyl epimers 9 and 20 of these structures are described. Thioglycosides 2, 5, 11 and 15 were used as glycosyl donors to construct the desired compounds in a stepwise manner in dimethyl(methylthio)sulphonium triflate promoted couplings. Benzyl 3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-2-acetamido-6-O-benzyl-2-deoxy-α-D-glucopyranoside (4) was a key structure in these syntheses, and was synthesised in multi-gram scale. 相似文献
152.
Jerome Karle (1918–2013) had to overcome adversities before he acquired the education he strived to get. He did pioneering work in modernizing the gas-phase electron diffraction technique of molecular structure determination. Drawing on this experience, he and Herbert Hauptman jointly came to a seminal discovery that solved the phase problem in crystal structure determination by X-ray diffraction. All along, he enjoyed close cooperation with his wife, the most distinguished scientist Isabella Karle. Jerome Karle was a revered colleague and a faithful friend. 相似文献
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A mild process for the selective oxidation of sulfides is in great demand. Therefore, probing the mechanism underlying the biological oxidation of sulfides under ambient conditions may provide valuable insights for the development of such a reaction. Based on porphyrin models of P450 enzymes, evidence of two key intermediates, Int0 and Int1 , in this reaction is provided. Spectroscopic studies indicated the formation of a hydroperoxide‐iron(III) species ( Int0 ) upon addition of H2O2. This intermediate proved to be highly selective for sulfoxide production. By contrast, a defined porphyrin oxoiron(IV) cation radical ( Int1 ) directly reacted with sulfoxides, leading selectively to the corresponding sulfones. Interestingly, the available sulfoxides reversibly act as a new axial ligand for Int0 forming a more active species Int0 SO. The amount of Int0 increased in the presence of alkyl, aryl, or aromatic sulfides, while Int1 formed in the absence of these sulfides. Thus, sulfoxides and sulfones would selectively form under conditions that favor the corresponding intermediates, which elucidate the biological oxidation pathway. 相似文献
156.
Horvath I Weise CF Andersson EK Chorell E Sellstedt M Bengtsson C Olofsson A Hultgren SJ Chapman M Wolf-Watz M Almqvist F Wittung-Stafshede P 《Journal of the American Chemical Society》2012,134(7):3439-3444
Small organic molecules that inhibit functional bacterial amyloid fibers, curli, are promising new antibiotics. Here we investigated the mechanism by which the ring-fused 2-pyridone FN075 inhibits fibrillation of the curli protein CsgA. Using a variety of biophysical techniques, we found that FN075 promotes CsgA to form off-pathway, non-amyloidogenic oligomeric species. In light of the generic properties of amyloids, we tested whether FN075 would also affect the fibrillation reaction of human α-synuclein, an amyloid-forming protein involved in Parkinson's disease. Surprisingly, FN075 stimulates α-synuclein amyloid fiber formation as measured by thioflavin T emission, electron microscopy (EM), and atomic force microscopy (AFM). NMR data on (15)N-labeled α-synuclein show that upon FN075 addition, α-synuclein oligomers with 7 nm radius form in which the C-terminal 40 residues remain disordered and solvent exposed. The polypeptides in these oligomers contain β-like secondary structure, and the oligomers are detectable by AFM, EM, and size-exclusion chromatography (SEC). Taken together, FN075 triggers oligomer formation of both proteins: in the case of CsgA, the oligomers do not proceed to fibers, whereas for α-synuclein, the oligomers are poised to rapidly form fibers. We conclude that there is a fine balance between small-molecule inhibition and templation that depends on protein chemistry. 相似文献
157.
In the main result of this paper, some sharp conditions are obtained for global attractivity in a scalar perturbed linear delay differential equation. The proof of the main theorem is based on a new estimate for the infinite integral of the absolute value of the fundamental solution of a linear delay differential equation. We also derive sufficient conditions for asymptotic stability of a system of linear delay differential equations. 相似文献
158.
Let $\mathfrak{g}$ be a complex semisimple Lie algebra, $\mathfrak{b}$ a Borel subalgebra, and $\mathfrak{h}\subset\mathfrak{b}$ a Cartan subalgebra. Let V be a finite dimensional simple $U(\mathfrak{g})$ module. Based on a principal s-triple (e,h,f) and following work of Kostant, Brylinski (J Amer Math Soc 2(3):517–533, 1989) defined a filtration $\mathcal{F}_e$ for all weight subspaces V μ of V and calculated the dimensions of the graded subspaces for μ dominant. In Joseph et al. (J Amer Math Soc 13(4):945–970, 2000) these dimensions were calculated for all μ. Let δM(0) be the finite dual of the Verma module of highest weight 0. It identifies with the global functions on a Weyl group translate of the open Bruhat cell and so inherits a natural degree filtration. On the other hand, up to an appropriate shift of weights, there is a unique $U(\mathfrak{b})$ module embedding of V into δM(0) and so the degree filtration induces a further filtration $\mathcal{F}$ on each weight subspace V μ . A casual reading of Joseph et al. (J Amer Math Soc 13(4):945–970, 2000) might lead one to believe that $\mathcal{F}$ and $\mathcal{F}_e$ coincide. However this is quite false. Rather one should view $\mathcal{F}_e$ as coming from a left action of $U(\mathfrak{n})$ and then there is a second (Brylinski-Kostant) filtration $\mathcal{F}'_e$ coming from a right action. It is $\mathcal{F}'_e$ which may coincide with $\mathcal{F}$ . In this paper the above claim is made precise. First it is noted that $\mathcal{F}$ is itself not canonical, but depends on a choice of variables. Then it is shown that a particular choice can be made to ensure that $\mathcal{F}=\mathcal{F}'_e$ . An explicit form for the unique left $U(\mathfrak{b})$ module embedding $V\hookrightarrow\delta M(0)$ is given using the right action of $U(\mathfrak{n})$ . This is used to give a purely algebraic proof of Brylinski’s main result in Brylinski (J Amer Math Soc 2(3):517–533, 1989) which is much simpler than Joseph et al. (J Amer Math Soc 13(4):945–970, 2000). It is noted that the dimensions of the graded subspaces of $\rm{gr}_{\mathcal{F}_e} V_{\!\mu}$ and $\rm{gr}_{\mathcal{F}'_e} V_{\!\mu}$ can be very different. Their interrelation may involve the Kashiwara involution. Indeed a combinatorial formula for multiplicities in tensor products involving crystal bases and the Kashiwara involution is recovered. Though the dimensions for the graded subspaces of $\rm{gr}_{\mathcal{F}'_e} V_{\!\mu}$ are determined by polynomial degree, their values remain unknown. 相似文献
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A detailed conformational analysis was performed on simple substituted hydroxylamines using either ab initio (from HF/6-31G* to RQCISD/6-311G**) or popular semiempirical (MNDO, AM1, PM3) methods to ascertain the allowed conformations and to establish the influence of the level of theory on the results. All the ab initio results (provision being made for their expected divergences) are similar and show a simple twofold character for the > N? O? rotational energy, without any appreciable populations of the cis conformer. On the other hand, the predictive value of the semiempirical methods for structural and energetical parameters of molecules bearing > N? O? moieties is limited, a situation like that prevailing for peptide bonds. The inversional barriers for the methyl-substituted hydroxylamines were also calculated and compared to the corresponding rotational energy barriers. Rotation is generally favored over inversion for hydroxylamine and its methylated derivatives. © 1994 by John Wiley & Sons, Inc. 相似文献