Selective and solventless oxidation of organic sulfides and alcohols using new supported molybdenum (VI) complex in microwave and conventional methods

A new dioxo-molybdenum (VI) complex supported on functionalized Merrifield resin ( MR-Mo ) has been synthesized and characterized by elemental, scanning electron mcroscopy, energy-dispersive X-ray analysis, TGA, Brunauer–Emmett–Teller method, powder-X-ray diffraction, Fourier transform infrared, X-ray photoelectron spectroscopy and DRS–UV–vis analysis. The virgin Merrifield resin ( MR ) was functionalized by carbonylation followed by Schiff base formation with ethanolamine ( MR-SB ). Experimental data showed that the Schiff base coordinated with the MoO₂²⁺ moiety via O- and N-atoms. The catalytic activity of MR-Mo was explored under solventless conditions toward the oxidation of organic sulfides and alcohols using 30% aqueous H₂O₂ as oxidant. The oxidation reactions were conducted under microwave and conventional methods. The microwave-assisted oxidation reactions were found to be many times faster than the conventional methods. The oxidation reactions were selective and formed sulfoxides or aldehydes as the sole product with superior TOF values among the molybdenum (VI)-based complexes. Besides these, the MR-Mo was purely heterogeneous in nature and can be recycled for at least five reaction cycles without the loss of catalytic efficiency and product selectivity.     

Enhanced solubility and selective benzoylation of nucleosides in novel ionic liquid

Solubility and benzoylation study of both ribo- and deoxyribonucleosides is reported in a new ionic liquid MoeMIM·TFA; high selectivity for O-benzoylation is achieved.     

Preparation of 4′-Spirocyclobutyl Nucleoside Analogues as Novel and Versatile Adenosine Scaffolds

Despite the large variety of modified nucleosides that have been reported, the preparation of constrained 4′-spirocyclic adenosine analogues has received very little attention. We discovered that the [2+2]-cycloaddition of dichloroketene on readily available 4′-exo-methylene furanose sugars efficiently results in the diastereoselective formation of novel 4′-spirocyclobutanones. The reaction mechanism was investigated via density functional theory (DFT) and found to proceed either via a non-synchronous or stepwise reaction sequence, controlled by the stereochemistry at the 3′-position of the sugar substrate. The obtained dichlorocyclobutanones were converted into nucleoside analogues, providing access to a novel class of chiral 4′-spirocyclobutyl adenosine mimetics in eight steps from commercially available sugars. Assessment of the biological activity of designed 4′-spirocyclic adenosine analogues identified potent inhibitors for protein methyltransferase target PRMT5.     

Similarity in the metabolic profile in macroscopically involved and un-involved colonic mucosa in patients with inflammatory bowel disease: an in vitro proton (H) MR spectroscopy study

Background

The histological extent of inflammatory bowel disease (IBD) is greater than that evident by colonoscopic evaluation. We hypothesized that metabolic profile in macroscopically un-involved colonic mucosa in IBD is similar to that of controls with healthy colon. We thus assessed the differences in metabolic profile in macroscopically involved and un-involved colonic mucosa of IBD patients to further substantiate the extent of disease.

Patients and Methods

Colonic mucosal biopsies were obtained and snap frozen from both the macroscopically un-involved and involved colonic mucosa of IBD patients and macroscopically normal colonic mucosa of controls and were subjected to in-vitro high-resolution proton (¹H) magnetic resonance (MR) spectroscopy and the concentrations of metabolites were determined.

Results

Thirty-two metabolites were assigned in the proton MR spectrum of colonic mucosa of IBD patients. The concentrations of amino acids (isoleucine, leucine, valine, arginine, lysine, glutamine/glutamate, alanine), membrane metabolites (choline, glycerophosphorylcholine/phosphorylcholine), glycolytic product (lactate) and short chain fatty acid (formate) were significantly lower while significantly high level of glucose were observed in the macroscopically un-involved colonic mucosa of IBD patients compared to the macroscopically normal mucosa of controls. There was no significant difference in the concentrations of metabolites in macroscopically involved and un-involved colonic mucosa of IBD patients.

Conclusions

The metabolic profile in macroscopically un-involved colonic mucosa of IBD patients is similar to that of macroscopically involved mucosa but different from colonic mucosa of controls. This suggests that even macroscopically un-involved colonic mucosa is metabolically abnormal and may explain the increase in extent of disease with time.     

MIP reformulations of the probabilistic set covering problem

In this paper, we address the following probabilistic version (PSC) of the set covering problem: where A is a 0-1 matrix, is a random 0-1 vector and is the threshold probability level. We introduce the concepts of p-inefficiency and polarity cuts. While the former is aimed at deriving an equivalent MIP reformulation of (PSC), the latter is used as a strengthening device to obtain a stronger formulation. Simplifications of the MIP model which result when one of the following conditions hold are briefly discussed: A is a balanced matrix, A has the circular ones property, the components of are pairwise independent, the distribution function of is a stationary distribution or has the disjunctive shattering property. We corroborate our theoretical findings by an extensive computational experiment on a test-bed consisting of almost 10,000 probabilistic instances. This test-bed was created using deterministic instances from the literature and consists of probabilistic variants of the set covering model and capacitated versions of facility location, warehouse location and k-median models. Our computational results show that our procedure is orders of magnitude faster than any of the existing approaches to solve (PSC), and in many cases can reduce hours of computing time to a fraction of a second. Anureet Saxena’s research was supported by the National Science Foundation through grant #DMI-0352885 and by the Office of Naval Research through contract N00014-03-1-0133. Vineet Goyal’s research was supported in part by NSF grant CCF-0430751 and ITR grant CCR-0122581.     

A hybrid finite/boundary element method for periodic structures on non-periodic meshes using an interior penalty formulation for Maxwell’s equations

This paper presents a hybrid finite element/boundary element (FEBE) method for periodic structures. Periodic structures have been efficiently analyzed by solving for a single unit cell utilizing Floquet’s theorem. However, most of the previous works require periodic meshes to properly impose the boundary conditions on the outer surfaces of the unit cell. To alleviate this restriction, the interior penalty method is adopted and implemented in this work. Also, the proper treatment of the boundary element part is addressed to account for the non-conformity of the boundary element mesh. Another ingredient of this work is the use of the efficient boundary element computation, accelerated by the Ewald transformation for the calculation of the periodic Green’s function. Finally, the method is validated through examples which are discretized without the constraint of a periodic mesh.     

Spectroscopic properties of Pr(3+) doped in tellurite glass

The absorption and fluorescence spectra of Pr(3+) doped in tellurite glass has been recorded and analyzed in terms of Judd-Ofelt theory. The lifetime of (3)P(0) and (3)P(1) levels has been measured. Fluorescence quenching has been observed for higher concentrations of Pr(3+) ion. The temperature dependence of the fluorescence intensity and the lifetime of the (3)P(0) level has been investigated and found that they decrease with the increase of the temperature.     

Spectroscopy and upconversion of Dy3+ doped in sodium zinc phosphate glass

Optical absorption and fluorescence spectra of Dy3+ doped in sodium zinc phosphate glasses have been reported. Judd-Ofelt theory has been applied to analyze the spectra and determine the optical parameters such as transition probabilities, radiative lifetime, stimulated emission cross-section, etc. The fluorescence intensity of Dy3+ corresponding to 4F9/2-->6H13/2 transition increases with increasing concentration of Dy3+ but at higher concentrations, concentration quenching is observed. The radiative lifetime of the 4F9/2 level at 1 mol% concentration of Dy3+ in this host is found to be 541 micros. Emission corresponding to 4F9/2-->6H13/2 transition (570 nm) is observed on excitation with NIR radiation due to upconversion. An attempt is made to explain this observation.     

Optical transitions of Dy in tellurite glass: observation of upconversion

Dy³⁺ doped tellurite glasses were prepared and its optical absorption, fluorescence and upconversion have been studied. The absorption data has been used to calculate the Judd-Ofelt parameters, oscillator strengths along with transition probability, branching ratio, etc. The lifetime of the level is found to be 0.66 ms for 1.0 mol% of Dy³⁺ doped in tellurite glass. NIR to visible upconversion has been observed at room temperature. The increase in upconversion luminescence at lower temperature indicates that upconversion is not due to a thermally activated process. The quantum efficiency of the transition is found to be ∼0.17 and the upconversion efficiency is ∼0.022. The strong dependence of the upconversion efficiency on the Dy³⁺ concentration reveals that the upconversion is due to energy transfer interaction.