Search Results (5)

This work reports the synthesis of two monometallic catalysts, Cu/Al₂O_3, and Pd/Al₂O₃, using a green approach based on Mexican oregano (Lippia graveolens), a common food condiment. Its extract has been largely overlooked as a high-technology reactive for synthesizing catalysts, metallic or oxide nanoparticles, unlike other green leaf plants. The green synthesis was compared with a conventional catalyst synthesis methodology using commercial chemical reducing agents. Oregano extract shows promise for novel applications extending beyond its culinary use, valorizing it as a chemical reducer to produce catalysts. Thus, this kind of application could significantly elevate the value of oregano, empowering communities that rely on its cultivation for economic benefit and transforming the plant from a low-profit agro-industrial product to a high-added-value crop. The reduction kinetics involved in the formation of nanoparticles were monitored up to the first stage of nucleation and a first-order model adequately described the data. Activation energy analysis showed that the chemical reaction mechanism has a dominant role in controlling the reaction, compared to mass transfer effects. Notoriously, the Pd/Al₂O₃ green synthesis catalyst showed the smallest mean particle size (4.85 ± 1.30 nm). These findings underscore the potential of green synthesis as an economically viable and environmentally friendly alternative for producing catalysts. Concerning the 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) as a biomass-derived molecule, its oxidation with H₂O₂ using both Pd/Al₂O₃ catalysts (by green and chemical synthesis methods) exhibited significantly higher selectivity toward 2,5-diformylfuran (DFF) compared to Cu/Al₂O₃ catalysts, suggesting a possible inhibitory effect. Full article

The implementation of cost-effective and sustainable biorefineries to substitute the petroleum-based economy is dependent on coupling the production of bioenergy with high-value chemicals. For this purpose, the US Department of Energy identified a group of key target compounds to be produced from renewable biomass. Among them, 5-hydroxymethylfurfural (HMF) can be obtained by dehydration of the hexoses present in biomass and is an extremely versatile molecule that can be further converted into a wide range of higher value compounds. HMF derivatives include 2,5-bis(hydroxymethyl)furan (BHMF), 5-hydroxymethyl-furan-2-carboxylic acid (HMFCA), 2,5-diformylfuran (DFF), 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA), all presenting valuable applications, in polymers, bioplastics and pharmaceuticals. Biocatalysis conversion of HMF into its derivatives emerges as a green alternative, taking into account the high selectivity of enzymes and the mild reaction conditions used. Considering these factors, this work reviews the use of microorganisms as whole-cell biocatalysts for the production of HMF derivatives. In the last years, a large number of whole-cell biocatalysts have been discovered and developed for HMF conversion into BHMF, FDCA and HMFCA, however there are no reports on microbial production of DFF and FFCA. While the production of BHMF and HMFCA mainly relies on wild type microorganisms, FDCA production, which requires multiple bioconversion steps from HMF, is strongly dependent on genetic engineering strategies. Together, the information gathered supports the possibility for the development of cell factories to produce high-value compounds, envisioning economical viable biorefineries. Full article

The transformation of biomass, a carbon resource presenting a huge potential to produce valuable chemicals, requires the search for sustainable catalytic routes. This work proposes the microwave-assisted oxidation of biomass -derived substrates, such as glycerol and the furfural derivatives 5-(hydroxymethyl)furfural (HMF) and 5-hydroxymethyl-2-furancarboxylic acid (HFCA), using the C-scorpionate dichloro-gold(III) complex [AuCl₂(κ²-Tpm)]Cl (Tpm = HCpz₃; pz = pyrazol-1-yl) as a catalyst, as prepared and supported on graphene, in solvent-free conditions. The unprecedented application of a mechanochemical procedure (in a planetary ball mill, in solid state) to synthesize a C-scorpionate complex, the [AuCl₂(κ²-Tpm)]Cl, is disclosed. The immobilization of [AuCl₂(κ²-Tpm)]Cl on graphene was performed using different methods, including some (e.g., microwave irradiation and liquid assisted grinding) for the first time. The structural properties and the performance of the prepared catalytic materials are presented and discussed. Full article

Enzymatic oxidation of 5-hydroxymethylfurfural (HMF) and its oxidized derivatives was studied using three fungal enzymes: wild-type aryl alcohol oxidase (AAO) from three fungal species, wild-type peroxygenase from Agrocybe aegerita (AaeUPO), and recombinant galactose oxidase (GAO). The effect of pH on different reaction steps was evaluated and apparent kinetic data (Michaelis-Menten constants, turnover numbers, specific constants) were calculated for different enzyme-substrate ratios and enzyme combinations. Finally, the target product, 2,5-furandicarboxylic acid (FDCA), was prepared in a multi-enzyme cascade reaction combining three fungal oxidoreductases at micro-scale. Furthermore, an oxidase-like reaction is proposed for heme-containing peroxidases, such as UPO, horseradish peroxidase, or catalase, causing the conversion of 5-formyl-2-furancarboxylic acid into FDCA in the absence of exogenous hydrogen peroxide. Full article

Extracts from an endophytic fungus isolated from the roots of the Algerian plant Globularia alypum showed prominent antimicrobial activity in a screening for novel antibiotics. The producer organism was identified as Dendrothyrium variisporum by means of morphological studies and molecular phylogenetic methods. Studies on the secondary metabolite production of this strain in various culture media revealed that the major components from shake flasks were massarilactones D (1) and H (2) as well as two new furanone derivatives for which we propose the trivial names (5S)-cis-gregatin B (3) and graminin D (4). Scale-up of the fermentation in a 10 L bioreactor yielded massarilactone D and several further metabolites. Among those were three new anthranilic acid derivatives (5–7), two known anthranilic acid analogues (8 and 9) and three cyclopeptides (10–12). Their structures were elucidated on the basis of extensive spectroscopic analysis (1D- and 2D-NMR), high-resolution mass spectrometry (HRESIMS), and the application of the modified Mosher’s method. The isolated metabolites were tested for antimicrobial and cytotoxic activities against various bacteria, fungi, and two mammalian cell lines. The new Metabolite 5 and Compound 9 exhibited antimicrobial activity while Compound 9 showed cytotoxicity activity against KB3.1 cells. Full article