Carbohydrate structure-activity relations of Au-catalysed base-free oxidations: gold displaying a platinum lustre.

This paper describes the base-free gold-catalysed oxidation of four different carbohydrates in a packed bed plug flow reactor. The influence of the carbohydrate structure on the catalytic activity and selectivity was investigated by comparing two neutral sugars (glucose (Glc) and galactose (Gal), both with primary alcohols at C6), with their sugar-acid analogues (glucuronic acid (GlcA) and galacturonic acid (GalA), both with carboxylic acids at C6). The orientation of OH-groups at the C4-position (equatorial in Glc/GlcA and axial in Glc/GlcA), and the C6-functionality (primary alcohols in Gal/Glc and carboxylic acids in GalA/GlcA) has a profound influence on the catalytic activity. When the OH-groups are in an axial position their reactivity was higher compared to the OH-groups in the equatorial position for both the sugars and the sugar acids. In addition the reactivity of carbohydrates over Au-catalysts under base-free conditions is different compared to alkaline conditions, and is more in line with a Pt-catalysed dehydrogenation mechanism.

The effect of me-substituents of 1,4-butanediol analogues on the thermal properties of biobased polyesters.

Biobased 1,4-butanediol analogues are used to tune the glass transition temperature and crystallization in a series of polyesters and allow for the formation of stereocomplexes.

Methyl Perillate as a Highly Functionalized Natural Starting Material for Terephthalic Acid.

Renewable commodity chemicals can be generated from plant materials. Often abundant materials such as sugars are used for this purpose. However, these lack appropriate functionalities and, therefore, they require extensive chemical modifications before they can be used as commodity chemicals. The plant kingdom is capable of producing an almost endless variety of compounds, including compounds with highly appropriate functionalities, but these are often not available in high quantities. It has been demonstrated that it is possible to produce functionalized plant compounds on a large scale by fermentation in microorganisms. This opens up the potential to exploit plant compounds that are less abundant, but functionally resemble commodity chemicals more closely. To elaborate this concept, we demonstrate the suitability of a highly functionalized plant compound, methyl perillate, as a precursor for the commodity chemical terephthalic acid.

Synthesis of Furandicarboxylic Acid Esters From Nonfood Feedstocks Without Concomitant Levulinic Acid Formation.

5-Hydroxymethylfurfural (HMF) is a versatile intermediate in biomass conversion pathways. However, the notoriously unstable nature of HMF imposes challenges to design selective routes to chemicals such as furan-2,5-dicarboxylic acid (FDCA). Here, a new strategy for obtaining furans is presented, bypassing the formation of the unstable HMF. Instead of starting with glucose/fructose and thus forming HMF as an intermediate, the new route starts from uronic acids, which are abundantly present in many agro residues such as sugar beet pulp, potato pulp, and citrus peels. Conversion of uronic acids, via ketoaldonic acids, to the intermediate formylfuroic acid (FFA) esters, and subsequently to FDCA esters, proceeds without formation of levulinic acid or insoluble humins. This new route provides an attractive strategy to valorize agricultural waste streams and a route to furanic building blocks without the co-production of levulinic acid or humins.

Functionalized carbon nanofibers as solid-acid catalysts for transesterification.

Carbon nanofibers (CNFs) were functionalized with aryl sulfonic acid groups using in situ diazonium coupling. The use of diazonium coupling yielded an acidic carbon material, in which the introduced acidic groups are readily accessible to the triglyceride substrate. The material is an efficient catalyst for the transesterification of triolein and methanol, outperforming conventional sulfonated carbons in both stability and activity per acid site. Upon comparing CNFs with varying degrees of functionalization, a linear correlation between sulfonic acid sites and catalytic performance was found.

Waste not, want not: mild and selective catalytic oxidation of uronic acids.

And isn't it uronic: A mild, highly efficient and selective catalytic oxidation of pectin-derived uronic acids to the corresponding aldaric acids is reported. Fast, quantitative conversions (>99%) of the starting materials are achieved with high selectivity (>97%) at room temperature, using supported gold catalysts and air as oxidizing agent.