Synthesis of Sucrose Analogues Modified at Position 4

Abstract

Upon reaction with sodium nitrite, the corresponding triflate 2 of known 1,3,4,6-tetra-O-pivaloyl-β-d-fructofuranosyl 2,3,6-tri-O-pivaloyl-α-d-glucopyranoside (1), afforded the galacto-sucrose 3 in high yield. This compound was converted into 4-deoxy-4-fluorosucrose derivative 4 by treatment with DAST. The reaction of triflate 6, derived from 3, with lithium azide afforded 4-azido-4-deoxysucrose derivative 7 which was transformed into 4-amino-4-deoxysucrose 9. S_N2 Displacement of the triflate of compound 6 with thioacetate ion provided the expected 4-S-acetyl-4-thiosucrose derivative 10 in excellent yield. Deacetylation of 10 afforded a mixture of 4-thiosucrose 11 and 4-thiosucrose disulfide 12.     

Para-hydroxybenzoic acid as an indirect detection buffer in capillary zone electrophoresis

Summary Para-hydroxybenzoic acid (p-HBA) has been used as indirect UV detection buffer in capillary zone electrophoresis (CZE). Being an UV-absorbing dibasic acid, p-HBA provides both the necessary buffering for pH control over a wide range and UV absorbance for indirect detection. With sodium dodecyl sulfate (SDS) as a probe, a CZE method using p-HBA solution as running buffer was developed to analyze anions, especially ones with low electrophoretic mobilities. The method was used to separate homologous series of sulfonates, SDS in a formulation sample, and SDS in a standard.     

Chemoenzymatic Syntheses of Sialylated Oligosaccharides Containing C5‐Modified Neuraminic Acids for Dual Inhibition of Hemagglutinins and Neuraminidases

A fast chemoenzymatic synthesis of sialylated oligosaccharides containing C5‐modified neuraminic acids is reported. Analogues of GM₃ and GM₂ ganglioside saccharidic portions where the acetyl group of NeuNAc has been replaced by a phenylacetyl (PhAc) or a propanoyl (Prop) moiety have been efficiently prepared with metabolically engineered E. coli bacteria. GM₃ analogues were either obtained by chemoselective modification of biosynthetic N‐acetyl‐sialyllactoside (GM₃NAc) or by direct bacterial synthesis using C5‐modified neuraminic acid precursors. The latter strategy proved to be very versatile as it led to an efficient synthesis of GM₂ analogues. These glycomimetics were assessed against hemagglutinins and sialidases. In particular, the GM₃NPhAc displayed a binding affinity for Maackia amurensis agglutinin (MAA) similar to that of GM₃NAc, while being resistant to hydrolysis by Vibrio cholerae (VC) neuraminidase. A preliminary study with influenza viruses also confirmed a selective inhibition of N1 neuraminidase by GM₃NPhAc, suggesting potential developments for the detection of flu viruses and for fighting them.     

Native Electrospray Mass Spectrometry of DNA G-Quadruplexes in Potassium Solution

A commonly used electrolyte in electrospray mass spectrometry (ESI-MS) of biomolecules is ammonium acetate (NH₄OAc). Although some nucleic acid structures such as duplexes require only proper physiological ionic strength (whatever the monovalent ions) to be properly folded in ESI-MS conditions, the folding of some other nucleic acid structures such as DNA G-quadruplexes also depends on direct binding of specific cations. Here, we developed ESI-MS compatible conditions that allow one to observe DNA G-quaduplexes with K⁺ ions specifically bound between G-quartets. NH₄OAc was replaced with trimethylammonium acetate (TMAA), at concentrations up to 150 mM to provide physiological ionic strength, and the solution was doped with KCl at concentrations up to 1 mM. The trimethylammonium ion is too large to coordinate between G-quartets, where only K⁺ ions bind. Compared with the equivalent NH₄OAc/KCl mixtures, the TMAA/KCl mixtures provide cleaner spectra by suppressing the nonspecific adducts, and favor the formation of similar stacking arrangements as in 100 mM KCl (physiologically relevant cation) for the polymorphic human telomeric DNA G-quadruplexes. This new sample preparation method can be exploited to determine the number of potassium binding sites in new sequences, to screen ligand binding to the structures favored in potassium, and to transfer potassium-bound G-quadruplexes to the mass spectrometer for gas-phase structural probing, as illustrated herein with ion mobility spectrometry experiments.

Optimized operating rules for short-term hydropower planning in a stochastic environment

Computational Management Science - To operate a large-scale hydropower production system in an ever-changing environment, operating rules are a convenient way of communication between short-term...     

Chaos in computer performance

Modern computer microprocessors are composed of hundreds of millions of transistors that interact through intricate protocols. Their performance during program execution may be highly variable and present aperiodic oscillations. In this paper, we apply current nonlinear time series analysis techniques to the performances of modern microprocessors during the execution of prototypical programs. Our results present pieces of evidence strongly supporting that the high variability of the performance dynamics during the execution of several programs display low-dimensional deterministic chaos, with sensitivity to initial conditions comparable to textbook models. Taken together, these results show that the instantaneous performances of modern microprocessors constitute a complex (or at least complicated) system and would benefit from analysis with modern tools of nonlinear and complexity science.     

5‐aminothiazolium salts as potential cyclic azomethine ylides: Base‐induced cycloaddition reactions with aryl,alkyl, and benzoyl isothiocyanates

Reactions of the in situ generated thiazoles 2 with aryl and alkyl isothiocyanates appear to be totally regioselective and give the unexpected 5‐(phenylthio)imidazolium‐4‐thiolates 3 . Such rapid interconversion of mesoionic compounds is explained by a 1,3‐dipolar addition to the C=N bond of the heterocumulene followed by tBuNCS elimination. Similar interactions with benzoyl isothiocyanate exclusively proceed on the C=S unsaturation of the heteroallene moiety and produce the 4‐(phenylthio)thiazolium‐5‐amidines 12 . Structural assignment of isolated imidazoles and thiazoles is based on ¹³C NMR data and chemically confirmed by the NaBH₄ reduction of the alkylated derivatives 5 and 13 . Efforts to isomerize the starting mesoionic thiazole 2a without the use of tBuNCS are unsuccessful. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 10:16–26, 2000