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

Ternary Ag/MgO-SiO2 Catalysts for the Conversion of Ethanol into Butadiene

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Impartial Selection with Additive Approximation Guarantees

Impartial selection has recently received much attention within the multi-agent systems community. The task is, given a directed graph representing nominations to the members of a community by other members, to select the member with the highest number of nominations. This seemingly trivial goal becomes challenging when there is an additional impartiality constraint, requiring that no single member can influence her chance of being selected. Recent progress has identified impartial selection rules with optimal approximation ratios. Moreover, it was noted that worst-case instances are graphs with few vertices. Motivated by this fact, we propose the study of {\em additive approximation}, the difference between the highest number of nominations and the number of nominations of the selected member, as an alternative measure of the quality of impartial selection. Our positive results include two randomized impartial selection mechanisms which have additive approximation guarantees of $\Theta(\sqrt{n})$ and $\Theta(n^{2/3}\ln^{1/3}n)$ for the two most studied models in the literature, where $n$ denotes the community size. We complement our positive results by providing negative results for various cases. First, we provide a characterization for the interesting class of strong sample mechanisms, which allows us to obtain lower bounds of $n-2$, and of $\Omega(\sqrt{n})$ for their deterministic and randomized variants respectively. Finally, we present a general lower bound of $2$ for all deterministic impartial mechanisms.Comment: SAGT 201