Sn-Beta zeolites with borate salts catalyse the epimerization of carbohydrates via an intramolecular carbon shift

Carbohydrate epimerization is an essential technology for the widespread production of rare sugars. In contrast to other enzymes, most epimerases are only active on sugars substituted with phosphate or nucleotide groups, thus drastically restricting their use. Here we show that Sn-Beta zeolite in the presence of sodium tetraborate catalyses the selective epimerization of aldoses in aqueous media. Specifically, a 5 wt% aldose (for example, glucose, xylose or arabinose) solution with a 4:1 aldose:sodium tetraborate molar ratio reacted with catalytic amounts of Sn-Beta yields near-equilibrium epimerization product distributions. The reaction proceeds by way of a 1,2 carbon shift wherein the bond between C-2 and C-3 is cleaved and a new bond between C-1 and C-3 is formed, with C-1 moving to the C-2 position with an inverted configuration. This work provides a general method of performing carbohydrate epimerizations that surmounts the main disadvantages of current enzymatic and inorganic processes.National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-0819762)DuPont MIT Alliance (Graduate Research Fellowship)National Institutes of Health (U.S.) (Grant EB-001960)National Institutes of Health (U.S.) (Grant EB-002026)National Science Foundation (U.S.). Graduate Research Fellowship Program (Grant 1122374

A model for diffusion and competition in cancer growth and metastasis

A master equation formalism is used to model the growth and metastasis of a tumor as a function of the diffusion and absorption of a nutrient. Healthy and cancerous (C-) cells compete to bind the nutrient, which is allowed to diffuse starting from a prescribed region. Two thresholds are defined for the quantity of nutrient bound by the C-cells. If this quantity falls below the lower threshold, the cell dies, while if it increases above the upper threshold, the cell divides according to a predefined stochastic mechanism. C-cells migrate when they record a low concentration of free nutrient in the local environment. The model is formulated in terms of a coupled system of equations for the cell populations and the free and bound nutrient. This system can be solved by using the Local Interaction Simulation Approach (LISA), a numerical procedure that permits an efficient and detailed solution and is easily adaptable to parallel processing. With suitable parameter variation, the model can describe multiple tumor configurations, ranging from the classical spheroid with a necrotic core favored by mathematicians to very anisotropic shapes with inhomogeneous concentrations of the various populations. This is important because the nature of the anisotropy may be crucial in determining whether and how the cancer metastasizes. The effects of stochasticity and the presence of additional nutrients or inhibitors can be easily incorporated

Multilayered Supported Ionic Liquids as Catalysts for Chemical Fixation of Carbon Dioxide: A High-Throughput Study in Supercritical Conditions

Multilayered, covalently supported ionic liquid phase (mlc-SILP)materials were synthesized by using a new approach based on the grafting of bis-vinylimidazolium salts on different types of silica or polymeric supports. The obtained materials were characterized and tested as catalysts in the reaction of supercritical carbon dioxide with various epoxides to produce cyclic carbonates. The material prepared by supporting a bromide bis-imidazolium salt on the ordered mesoporous silica SBA-15 was identified as the most active catalyst for the synthesis of cyclic carbonates and displayed improved productivity compared with known supported ionic liquid catalysts. The catalyst retained its high activity upon reuse in consecutive catalytic runs. This is the first report of the application of mlc-SILP materials as catalysts in a reaction for the fixation of carbon dioxide. Rapid, parallel screening and comparison of the catalysts was performed by means of high-throughput experimentatio

Sali di imidazolio multistrato supportati covalentemente: attività catalitica per la produzione di carbonati ciclici in scCO2 e nuovi supporti per catalizzatori di palladio

I liquidi ionici supportati (SILP) hanno trovato interessanti applicazioni sia nel campo delle reazioni catalizzate da metalli che in organocatalisi [1]. Inoltre, i SILP sono stati efficacemente impiegati in reazioni di apertura di epossidi in CO2 supercritica per fornire carbonati ciclici [2]. I liquidi ionici vengono generalmente supportati covalentemente attraverso la modificazione dei gruppi funzionali presenti sulla superficie del supporto, conducendo in tal modo alla formazione di un monostrato di liquido ionico supportato. Gli esempi di SILP legati covalentemente, in maniera tale da ottenere dei multistrato, sono rari. In questa comunicazione viene riportato un metodo per preparare dei sali di imidazolio supportati covalentemente e il loro impiego come: a) catalizzatori riciclabili per la reazione di epossidi con CO2 supercritica per fornire carbonati ciclici, e b) supporti per nanoparticelle di palladio e l’impiego di tali materiali come catalizzatori riciclabili per la reazione di Suzuki in ambiente acquoso fra acidi boronici e bromuri arilici

PRIMARY MEDIASTINAL B-CELL LYMPHOMA (PMBL): HIGH FREQUENCY OF BCL-6 MUTATIONS AND CONSISTENT EXPRESSION OF THE TRANSCRIPTION FACTORS OCT-2, BOB.1 and PU.1 IN THE ABSENCE OF IMMUNOGLOBULINS

Although primary mediastinal (thymic) large B-cell lymphoma has been primarily studied, its precise phenotype, molecular characteristics, and histogenesis are still a matter of debate. The International Extranodal Lymphoma Study Group collected 137 such cases for extensive pathological review. Histologically, the lymphomatous growth was predominantly diffuse with fibrosis that induced compartmentalized cell aggregation. It consisted of large cells with varying degrees of nuclear polymorphism and clear to basophilic cytoplasm. On immunohistochemistry, the following phenotype was observed: CD45(+), CD20(+), CD79a(+), PAX5/BSAP(+), BOB.1(+), Oct-2(+), PU.1(+), Bcl-2(+), CD30(+), HLA-DR(+), MAL protein(+/-), Bcl-6(+/-), MUM1/IRF4(+/-), CD10(-/+), CD21(-), CD15(-), CD138(-), CD68(-), and CD3(-). Immunoglobulins were negative both at immunohistochemistry and in situ hybridization. Molecular analysis, performed in 45 cases, showed novel findings. More than half of the cases displayed BCL-6 gene mutations, which usually occurred along with functioning somatic IgV(H) gene mutations and Bcl-6 and/or MUM1/IRF4 expression. The present study supports the concept that a sizable fraction of cases of this lymphoma are from activated germinal center or postgerminal center cells. However, it differs from other aggressive B-cell lymphomas in that it shows defective immunoglobulin production despite the expression of OCT-2, BOB.1, and PU.1 transcription factors and the lack of IgV(H) gene crippling mutations