Use of renewables for the production of chemicals: Glycerol oxidation over carbon supported gold catalysts

As a renewable feedstock and due to its high functionality glycerol is an attractive reactant for the production of a large number of valuable compounds. We report on an environmentally friendly alternative to produce chemicals from the glycerol oxidation, which are currently produced either by stoichiometric oxidation processes or by enzymatic routes. We investigate the heterogeneously catalyzed liquid-phase oxidation of glycerol with carbon supported gold catalysts. The prepared nanosized gold catalysts are highly active, so that the reaction could be performed under atmospheric pressure. The influence of the preparation method of the catalysts has been investigated. Moreover, the support effect on the catalytic process has been studied and discussed in terms of pore structure of the investigated carbon materials. The promotor effect of platinum on Au/C catalysts was examined and it could be shown that the presence of Pt increases not only the catalyst activity but also the selectivity. By promoting the gold catalysts with platinum the selectivity to dihydroxyacetone could be increased from 26% (Au/C) to 36% (Au–Pt/C).     

Production of Biomass-Derived Chemicals and Energy: Chemocatalytic Conversions of Glycerol

The growing production of biodiesel as a renewable source-based fuel leads to an increased amount of glycerol. Thus, it is a favorable starting material to obtain highly functionalized products. From a variety of catalytic reactions three examples, namely glycerol oxidation, glycerol hydrogenolysis and aqueous-phase reforming, were chosen for detailed studies in our group. The experimental focus for the oxidation of glycerol was set on preparation and detailed examination of supported Pt–Bi catalysts in batch reactions as well as in continuous experiments using a trickle bed reactor. For aqueous-phase reforming of glycerol to hydrogen the addition of tin to supported platinum catalysts was investigated. Ruthenium and copper based catalysts could be successfully applied in the hydrogenolysis of glycerol to 1,2-propanediol.     

Potential DNA–protein cross-link products formed by sugar degradation products: identification of N 6-[2-(N 2-2′-deoxyguanosyl)propionyl]lysine

Sugar degradation products are formed during heat treatment of food as well as endogenously in vivo. As reactive carbonyl compounds, they react readily with proteins or DNA to form protein- or DNA-bound advanced glycation end products (glycation reaction or Maillard reaction). In this study, we investigated the formation of potential DNA–protein cross-link products from sugar degradation products. 2-Deoxyguanosine, l-lysine and different carbohydrates were incubated at 37 °C. The sugar degradation products dihydroxyacetone and d,l-glyceraldehyde lead to the formation of two new cross-link products. The new compounds were isolated by preparative high-performance liquid chromatography and identified by spectral data as the two diastereomers of N⁶-[2-(N²-2-deoxyguanosyl)propionyl]lysine. In this structure, the -amino group of lysine and the exocyclic amine group of 2-deoxyguanosine are linked via a carboxyethyl group, derived from the carbohydrate component. The binding sites and the binding types were confirmed by synthesis of the analogous products from N²-(1-carboxyethyl)guanosine and N-acetyllysine methyl ester.Dedicated to Professor Th. Severin on the occasion of his 75^th birthday     

Formation of pyrazines in dihydroxyacetone and glycine Maillard reaction: A computational study

Based on the electronic and Gibb’s free energy changes, the possibility of the formation of 2,5-dimethyl pyrazine (25Pz) as one of the probable final products in dihydroxyacetone (DHA) and glycine Maillard reaction under different pH conditions is described. Mechanisms for the reaction have been proposed following the Hodge-scheme. Density functional computational calculations at the standard state have been performed on the proposed mechanisms of the reaction. Electronic and Gibb’s free energy changes for the formation of different compounds have been estimated by following the total mass balance for different steps of the reaction. The possible order of feasibility for the production of 25Pz has been found as DHA + deprotonated glycine (DGly) gaseous > DHA + DGly aqueous > DHA + unprotonated glycine (UGly) gaseous > DHA + glycine zwitterion (GlyZ) gaseous > DHA + UGly aqueous > DHA + GlyZ aqueous > DHA + protonated glycine (PGly) aqueous > DHA + PGly gaseous phase reactions. Amino-acetone has been found to be the most likely precursor of the pyrazine ring. Oxidation plays an important role during the production of 25Pz. Water has been found as a by-product during the formation of 25Pz.     

Formation of the Heyns rearrangement products in dihydroxyacetone and glycine Maillard reaction: A computational study

Density functional theory computations at the standard state on the proposed mechanisms of dihydroxyacetone and glycine Maillard reaction under different pH conditions have revealed that dihydroxyacetone + deprotonated glycine and dihydroxyacetone + unprotonated glycine reactions are more favorable than dihydroxyacetone + protonated glycine and dihydroxyacetone + glycine zwitterion reactions for the formation of the Heyns rearrangement products (HRPs). The gaseous phase reaction is assumed more feasible than the aqueous phase reaction for the production of HRPs. Due to the possibility of the production of both of the enol and keto forms of HRPs, the rate of browning in the dihydroxyacetone + deprotonated glycine reaction is assumed higher than that of the others. Dihydroxyacetone + protonated glycine and dihydroxyacetone + glycine zwitterion reactions are not favorable for the formation of HRPs and, therefore, the reaction is assumed hindered under these conditions and the rate of browning is supposed to be lower than that of the others. Possibilities for the conversion of dihydroxyacetone to glyceraldehyde and formation of hydroxyacetaldehyde from dihydroxyacetone as a C2-fragmentation product have also been evaluated.     

Purification and properties of dihydroxyacetone reductase and 2,3-butanediol dehydrogenase from Candida utilis CBS 621

Candida utilis CBS 621 contained four different enzymes capable of reducing carbonyl compounds such as dihydroxyacetone, acetoin, diacetyl, acetol, methylglyoxal and acetone, namely alcohol dehydrogenase, acetone reductase, dihydroxyacetone reductase and 2,3-butanediol dehydrogenase. The dihydroxyacetone reductase of C. utilis did not oxidize glycerol, thus providing evidence that this enzyme cannot function as a glycerol-2-dehydrogenase during growth of the yeast on glycerol. This enzyme may, however, play a role in the assimilation of 2,3-butanediol by C. utilis. The organism also contained a separate 2,3-butanediol dehydrogenase which was unable to reduce dihydroxyacetone. Both dihydroxyacetone reductase and 2,3-butanediol dehydrogenase were present at very high activities during growth of C. utilis on a variety of substrates, including 2,3-butanediol.     

脱除苯酚中微量杂质的工艺技术进展

简要介绍了苯酚精制过程中含有微量的有机杂质异亚丙基丙酮、羟基丙酮、苯并呋喃的形成机理,及其对苯酚产品质量的影响,并概述了分别使用水滑石型材料（HTM）、ⅥA族金属改性的氧化铝、沸石、酸性离子交换树脂为催化剂的一步苯酚精制法和使用酸性树脂＋闪蒸法和两步固体酸法的两步精制法脱除苯酚中羟基丙酮、亚丙基丙酮、苯并呋喃等微量有机杂质的生产技术的新进展。     

Formation of methyl glyoxal in dihydroxyacetone and glycine Maillard reaction: A computational study

By considering the formation of methyl glyoxal as one of the possible intermediates, mechanisms for the intermediate stage of the Maillard reaction of dihydroxyacetone and glycine under different pH conditions have been proposed, following the Hodge-scheme. Density functional theory calculations have been performed at the standard state on the proposed mechanisms to calculated the Gibb’s free energy changes for the formation of different compounds in different steps of the reaction. Thus, the possibility for the formation of different compounds in the proposed mechanisms has been evaluated. Electronic energy changes for the formation of different compounds in the proposed mechanisms have been calculated to observe the internal energy changes of the reaction. The total mass balance has been followed during the calculation of electronic and Gibb’s free energies. The result reveals that methyl glyoxal is one of the most likely intermediates in the reaction, and dihydroxyacetone + deprotonated glycine and dihydroxyacetone + unprotonated glycine reactions are assumed favorable for the production of methyl glyoxal. The gaseous phase reaction is supposed to be more feasible than the aqueous phase reaction for the production of methyl glyoxal. Glyceraldehyde + protonated glycine and glyceraldehyde + glycine zwitterion reactions are postulated as less feasible for the formation of methyl glyoxal.