Synthesis of a novel polyester building block from pentoses by tin-containing silicates

C5-Sugars form a new bio-monomer (trans-2,5-dihydroxy-3-pentenoic acid methyl ester), which can undergo enzymatic copolymerization with E6-HH to form multifunctional polymers.</p

Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (1∶50 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here]

Tin-Containing Silicates: Identification of a Glycolytic Pathway via 3-Deoxyglucosone

We identify a glycolytic pathway through 3-deoxyglucosone using Lewis acid catalysts resulting in the formation of bio-based monomers.</p

Facile and Benign Conversion of Sucrose to Fructose Using Zeolites With Balanced Brønsted and Lewis Acidity

A simple and robust two-step process with zeolites as catalysts converts sucrose in high yield into the versatile monosaccharide fructose.</p

Incorporation of tin affects crystallization, morphology, and crystal composition of Sn-Beta.

During synthesis of Sn-Beta, tin affects the crystallization rate, morphology and is incorporated in an outer shell of the crystal.</p

Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites

Isomerization of sugars is used in a variety of industrially relevant processes and in glycolysis. Here, we show that hydrophobic zeolite beta with framework tin or titanium Lewis acid centers isomerizes sugars, e.g., glucose, via reaction pathways that are analogous to those of metalloenzymes. Specifically, experimental and theoretical investigations reveal that glucose partitions into the zeolite in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center, isomerizes into the acyclic form of fructose, and finally ring closes to yield the furanose product. The zeolite catalysts provide processing advantages over metalloenzymes such as an ability to work at higher temperatures and in acidic conditions that allow for the isomerization reaction to be coupled with other important conversions