Copper(II) tetrafluoroborate as an extremely efficient catalyst for 1,3-dithiolane/dithiane formation from carbonyl compounds under solvent-free conditions at room temperature

Copper(II) tetrafluoroborate hydrate is a new and extremely efficient catalyst for 1,3-dithiolane/dithiane formation from aromatic, heteroaromatic and aliphatic aldehydes and cyclic saturated ketones in 1-5 min under solvent-free conditions at room temperature. The reaction is compatible with other functionalities such as ether, ester, hydroxyl, halide, nitro and cyano groups and exhibits excellent chemoselectivity. α,β-Unsaturated aldehydes/ketones lead to selective formation of 1,3-dithiolanes instead of Michael addition products. For substrates bearing an aldehyde and a ketone carbonyl group, chemoselective dithiolane formation takes place with the aldehyde.     

Synthesis and biological evaluation of new inhibitors of UDP-Galf transferase--a key enzyme in M. tuberculosis cell wall biosynthesis

Two iminosugars have been designed and synthesized as potential inhibitors of UDP-Galf transferase, an enzyme involved in Mycobacterium tuberculosis cell wall biosynthesis. The design is based on a proposed model of the transition state for the transferase reaction. One of the two racemic compounds is the first reported inhibitor of the target enzyme from M. smegmatis.     

Dispersion of nano-silicon carbide (SiC) powder in aqueous suspensions

The dispersion characteristics of nanosize silicon carbide (SiC) suspension were investigated in terms of surface charge, particle size, rheological measurement and adsorption study. Ammonium polycarboxylate has been used as dispersant to stabilize the suspension. It was found that the isoelectric point (iep) of SiC powder was pH_iep (4.9). The surface charge of powder changed significantly in presence of the ammonium polycarboxylate dispersant and iep shifted significantly towards lower acidic pH (3.6). The shift in iep has been quantified in terms of ΔG ⁰ _SP, the specific free energy of adsorption between the surface sites and the adsorbing polyelectrolyte (APC). The values of ΔG ⁰ _SP (−10.85 RT unit) estimated by the electro kinetic data compare well with those obtained from adsorption isotherms (−9.521 RT unit). The experimentally determined optimum concentration of dispersant required for maximizing the dispersion was found to be 2.4 mg/g of SiC (corresponding to an adsorbed amount of 1.10 mg/g), at pH 7.5. This is much below the full monolayer coverage (corresponding to adsorbed amount of 1.75 mg/g) of the particles surface by the dispersant. The surface charge quantity, rheological, pH, electro kinetic and adsorption isotherm results were used to explain and correlate the stability of the nanosize silicon carbide in aqueous media. At pH 7.5, where both SiC surface and APC are negatively charged, the adsorption of APC was low because of limited availability of favourable adsorption sites. In addition, the brush-like configuration of the adsorbed polymer prevented close approach of any additional dispersant; hence stabilization of the slurry happens at a comparatively lower concentration than the monolayer coverage.     

Synthesis of a versatile building block for the preparation of 6-N-derivatized α-galactosyl ceramides: rapid access to biologically active glycolipids

A concise route to the 6-azido-6-deoxy-α-galactosyl-phytosphingosine derivative 9 is reported. Orthogonal protection of the two amino groups allows elaboration of 9 into a range of 6-N-derivatized α-galactosyl ceramides by late-stage introduction of the acyl chain of the ceramide and the 6-N-group in the sugar headgroup. Biologically active glycolipids 6 and 8 have been synthesized to illustrate the applicability of the approach.     

Examining and developing fourth grade children’s area estimation performance

This study explored children’s area estimation performance. Two groups of fourth grade children completed area estimation tasks with rectangles ranging from 5 to 200 square units. A randomly assigned treatment group completed instructional sessions that involved a conceptual area measurement strategy along with numerical feedback. Children tended to underestimate areas of rectangles. Furthermore, rectangle size was related to performance such that estimation error and variability increased as rectangle size increased. The treatment group exhibited significantly improved area estimation performance in terms of accuracy, as well as reduced variability and instances of extreme responses. Area measurement estimation findings are related to a Hypothetical Learning Trajectory for area measurement.     

The 5-deoxy-5-methylthio-xylofuranose residue in mycobacterial lipoarabinomannan. absolute stereochemistry, linkage position, conformation, and immunomodulatory activity

Mycobacteria produce a cell-surface glycoconjugate, lipoarabinomannan (LAM), which has been shown to be a potent modulator of the immune response that arises from infection by these organisms. Recently, LAM from the human pathogens Mycobacterium tuberculosis and M. kansasii has been shown to contain an unusual 5-deoxy-5-methylthio-xylofuranose (MTX) residue as well as its corresponding oxidized counterpart, 5-deoxy-5-methylsulfoxy-xylofuranose (MSX). To date, the absolute configuration of these residues and their linkage position to the polysaccharide are unknown, as is their biological role. Through the combined use of chemical synthesis and NMR spectroscopy, we have established that the MTX/MSX residues in these glycoconjugates are of the d-configuration and that they are linked alpha-(1-->4) to a mannopyranose residue in the mannan portion of the glycan. Conformational analysis of the MTX/MSX residue using NMR spectroscopy showed differences in ring conformation and as well as in the rotamer populations about the C-4-C-5 bond, as compared to the parent compound, methyl alpha-d-xylofuranoside. Two of the synthesized disaccharides, 3 and 34, were tested in cytokine induction assays, and neither led to the production of TNF-alpha or IL-12p70. In contrast, both demonstrated modest inhibitory properties when these same cytokines were induced using a preparation of Interferon-gamma and Staphylococcus aureus Cowan strain (SAC/IFN-gamma). These latter observations suggest that this motif may play a role in the immune response arising from mycobacterial infection.     

Evaluation of a learning trajectory for length in the early years

Measurement is a critical component of mathematics education, but research on the learning and teaching of measurement is limited, especially compared to topics such as number and operations. To contribute to the establishment of a research base for instruction in measurement, we evaluated and refined a previously developed learning trajectory in early length measurement, focusing on the developmental progressions that provide cognitive accounts of the development of children’s strategic and conceptual knowledge of measure. Findings generally supported the developmental progression, in that children reliably moved through the levels of thinking in that progression. For example, they passed through a level in which they measured length by placing multiple units or attempting to iterate a unit, sometimes leaving gaps between units. However, findings also suggested several refinements to the developmental progression, including the nature and placement of indirect length comparison in the developmental progression and the role of vocabulary, which was an important facilitator of learning for some, but not all, children.     

Selectfluor and NFSI exo‐Glycal Fluorination Strategies Applied to the Enhancement of the Binding Affinity of Galactofuranosyltransferase GlfT2 Inhibitors

Two complementary methods for the synthesis of fluorinated exo‐glycals have been developed, for which previously no general reaction had been available. First, a Selectfluor‐mediated fluorination was optimized after detailed analysis of all the reaction parameters. A dramatic effect of molecular sieves on the course of the reaction was observed. The reaction was generalized with a set of biologically relevant furanosides and pyranosides. A second direct approach involving carbanionic chemistry and the use of N‐fluorobenzenesulfonimide (NFSI) was performed and this method gave better diastereoselectivities. Assignment of the Z/E configuration of all the fluorinated exo‐glycals was achieved based on the results of HOESY experiments. Furthermore, fluorinated exo‐glycal analogues of UDP‐galactofuranose were prepared and assayed against GlfT2, which is a key enzyme involved in the cell‐wall biosynthesis of major pathogens. The fluorinated exo‐glycals proved to be potent inhibitors as compared with a series of C‐glycosidic analogues of UDP‐Galf, thus demonstrating the double beneficial effect of the exocyclic enol ether functionality and the fluorine atom.     

Loss of a mycobacterial gene encoding a reductase leads to an altered cell wall containing beta-oxo-mycolic acid analogs and accumulation of ketones

Mycolic acids are essential components of the mycobacterial cell wall. In this study, we show that a gene encoding a reductase involved in the final step of mycolic acid biosynthesis can be deleted in Mycobacterium smegmatis without affecting cell viability. Deletion of MSMEG4722 (ortholog of Mycobacterium tuberculosis Rv2509) altered culture characteristics and antibiotic sensitivity. The DeltaMSMEG4722 strain synthesized alpha-alkyl, beta-oxo intermediates of mycolic acids, which were found esterified to cell wall arabinogalactan. While the precursors could not be isolated directly due to their inherent instability during base treatment, their presence was established by prior reduction of the beta-oxo group by sodium borohydride. Interestingly, the mutant also accumulated unsaturated ketones, similar to tuberculenone from M. tuberculosis, which were shunt products derived from spontaneous decarboxylation of alpha-alkyl, beta-oxo fatty acid precursors of mycolic acids.