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Using halloysite clay and vitamin B1 hydrochloride, a novel acidic halloysite-dendrimer catalytic composite has been developed for conversion of fructose to 5-hydroxymthylfurfural. To grow the dendritic moiety on halloysite, it was first functionalized and then reacted with melamine, epichlorohydrin and vitamin B1 hydrochloride respectively. Then, the resulting composite was treated with ZnCl 2 to furnish Lewis acid sites. Use of vitamin B1 as the cationic moiety of ionic liquid obviated use of toxic chemicals and resulted in more environmentally friendly composite. Similarly, dendritic moiety of generation 2 was also grafted on halloysite and the activity of both catalysts for conversion of fructose to 5-hydroxymthylfurfural was investigated to disclose the role of dendrimer generation. For the best catalytic composite, the reaction variables were optimized via RSM and it was revealed that use of 0.035 g catalyst per 0.1 g fructose at 95 °C furnished HMF in 96% yield in 105 min. Turnover numbers (TONs) and frequencies (TOFs) were estimated to be 10,130 and 5788 h -1 , respectively. Kinetic studies also underlined that Ea was 22.85 kJ/mol. The thermodynamic parameters of Δ H ≠ , Δ S ≠ and Δ G ≠ , were calculated to be 23 kJ/mol, - 129.2 J/mol and 72.14 kJ/mol, respectively. Notably, the catalyst exhibited good recyclability and hot filtration approved heterogeneous nature of catalysis., (© 2024. The Author(s).)

Chitin biomass is the second largest biomass resource on Earth but under-utilized. In this study, pretreated shrimp shells were converted into value-added platform chemical 5-hydroxymethylfurfural (HMF) using microwave hydrothermal treatment. Under the combined pretreatment of acid decalcification at room temperature and microwave-assisted alkali deacetylation, the HMF yield could reach 1.8 wt%. The key process parameters, including the holding temperature, holding time, and pH value, were evaluated and optimised. The highest HMF yield of 6.5 wt% was obtained at 202.6°C at a holding time of 5.8 min and a pH value of 1.5. This result demonstrates the potential of synchronously treating waste and recycling it, thereby offering a highly promising valorisation strategy for chitin-biomass utilisation.

A facile biphasic system composed of choline chloride (ChCl)-based deep eutectic solvent (DES) and methyl isobutyl ketone (MIBK) was developed to realize the furfural production, lignin separation and preparation of fermentable glucose from Eucalyptus in one-pot. Results showed that the ChCl/1,2-propanediol/MIBK system owned the best property to convert hemicelluloses into furfural. Under the optimal conditions (MR ChCl:1,2-propanediol  = 1:2, raw materials:DES:MIBK ratio = 1:4:8 g/g/mL, 0.075 mol/L AlCl 3 ·6H 2 O, 140 °C, and 90 min), the furfural yield and glucose yield reached 65.0 and 92.2 %, respectively. Meanwhile, the lignin with low molecular weight (1250-1930 g/mol), low polydispersity (D M  = 1.25-1.53) and high purity (only 0.08-2.59 % carbohydrate content) was regenerated from the biphasic system. With the increase of pretreatment temperature, the β-O-4, β-β and β-5 linkages in the regenerated lignin were gradually broken, and the content of phenolic hydroxyl groups increased, but the content of aliphatic hydroxyl groups decreased. This research provides a new strategy for the comprehensive utilization of lignocellulose in biorefinery process., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The 5-nitro-2-furaldehyde (5-NF) is an aldehyde aromatic organic compound that has been envisaged as an alternative marker for detecting nitrofurazone treatment abuse and to avoid the false positive results induced by the semicarbazide. Analyzing 5-NF presents challenges, and its derivatization reaction with hydrazine reagents is required to enhance the capability of its detection and its identification. This study aims at developping an analytical method for 5-NF determination in trout muscle samples based on chemical derivatization prior to analysis by liquid chromatography-tandem mass spectrometry. Four commercially available hydrazine reagents, namely: N,N-Dimethylhydrazine (DMH), 4-Hydrazinobenzoic acid (HBA), 2,4-Dichlorophenylhydrazine (2,4-DCPH) and 2,6-Dichlorophenylhydrazine (2,6-DCPH) were proposed for the first time as derivatizing reagents in the analysis of 5-NF. The derivatization reaction was simultaneously performed along with the extraction method in acidic condition using ultrasonic assistance and followed by liquid extraction using acetonitrile. The efficiency of the chemical reaction with 5-NF was examined and the reaction conditions including the concentration of hydrochloric acid, pH, temperature, reaction time and the concentration of the derivatizing reagents were optimized. Experiments with fortified samples demonstrated that 2,4-DCPH derivatizing reagent at 20 mM for 20 min of ultrasonic treatment under acidic condition (pH 4) gave an effective sample derivatization method for 5-NF analysis. Under the optimized conditions, the calibration curves were linear from 0.25 to 2 μg kg -1 with coefficient of determination >0.99. The recoveries ranged from 89 % to 116 % and precision was less than 13 %. The limit of detection and quantification were 0.1 and 0.2 μg kg -1 , respectively., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Biobased furans have emerged as chemical building blocks for the development of materials because of their diverse scaffolds and as they can be directly prepared from sugars. However, selective, efficient, and cost-effective scalable conversion of biobased furans remains elusive. Here, we report a robust transaminase (TA) from Shimia marina (SMTA) that enables the scalable amination of biobased furanaldehydes with high activity and broad substrate specificity. Crystallographic and mutagenesis analyses provide mechanistic insights and a structural basis for understanding SMTA, which enables a higher substrate conversion. The enzymatic cascade process established in this study allows one-pot synthesis of 2,5-bis(aminomethyl)furan (BAMF) and 5-(aminomethyl)furan-2-carboxylic acid from 5-hydroxymethylfurfural. The biosynthesis of various furfurylamines, including a one-pot cascade reaction for BAMF generation using whole cells, demonstrates their practical application in the pharmaceutical and polymer industries., (© 2024. The Author(s).)

Pentanediols are substances with significant market potential as the key monomers for advanced polymeric materials. In this study, we successfully achieved directly hydrogenolysis of biomass-based furfural to 1,5-pentanediol with a remarkable yield of 53.4 % using Cu-modified cobalt supported on cerium dioxide catalysts. Through comprehensive characterization techniques, including H 2 -TPR, NH 3 -TPD, XPS, EPR and Raman analysis, the study revealed that the introduction of Cu altered the dispersion of Co species, attenuated the interaction between Co species and cerium dioxide, enhanced its reduction extent, and fostered the formation of plentiful cobalt oxide species and oxygen vacancies on the catalyst's surface. The cooperative influence of Cu and Co heightened the selectivity of the hydrogenolysis reaction. This work provides a novel strategy for the development of greener and more efficient catalytic processes based on non-precious metals that for the selective conversion of biomass-derived furfural to high-value pentanediols., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In this study, the removal of RhB from water by furfural residue (FR) biochar was prepared by hydrothermal carbonization (HTC) and citric acid (CA) modification and named this biochar as CHFR (C refers to citric acid, H refers to hydrothermal carbonization and FR is furfural residue). The CHFR were characterized by SEM, FT-IR and XPS, and CHFR was investigated by the effects of initial concentration, adsorbent dosage, pH, and contact time on the removal of RhB, and the experimental data were analyzed using the adsorption isotherm models, the adsorption kinetic models and thermodynamics, et al. The results showed that CHFR has strong adsorption performance, and the theoretical maximum adsorption capacity of RhB was 39.46 mg·g -1 under the reaction conditions of pH3, the dosage of 1.5 g·L -1 , and 120 min contact time, with a removal efficiency close to 100%. the adsorption of RhB by CHFR is spontaneous and endothermic, which is consistent with the Freundlich adsorption, and the isotherm model fits well with the pseudo-second-order model, and the adsorption rate could still be as high as 92.74% after five regenerations, therefore, CHFR is an environmentally friendly and efficient adsorbent with excellent adsorption regeneration performance.

The baking process has the potential to generate health-risk compounds, including products from lipid oxidation and Maillard reaction. Pre- and post-digestion levels of hydroxymethylfurfural (HMF), malondialdehyde (MDA), glyoxal (GO), and methylglyoxal (MGO) were studied in cakes formulated with hazelnut and sunflower oil, along with their oleogels as margarine substitutes. The concentration of HMF in oil and oleogel-formulated cakes increased after digestion compared to cakes formulated with margarine. The MDA values were between 82 and 120 μg/100 g in oil and oleogel formulated cakes before digestion and a decrease was observed after digestion. The substitution of margarine with oil and oleogels resulted in the production of high amounts of GO and MGO in cakes. However, the highest bioaccessibility as 318.2% was found in cakes formulated by margarine for GO. Oleogels may not pose a potential health benefit compared to margarines due to the formation of HMF, MDA, GO, and MGO., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Pasteurisation and spray drying are critical steps to ensure the safety and shelf-life of formulae, but these treatments also induce formation of some potentially harmful Maillard reaction products. In this study, the occurrence of potentially harmful Maillard reaction products and proximate compositions in different commercial formulae were analysed. Our results showed that infant formulae had significantly higher concentrations of furosine, N ε -(carboxymethyl)lysine (CML) and N ε -(carboxyethyl)lysine (CEL) than follow-on/toddler formula. Specialty formulae had higher concentrations of glyoxal and CML than other types of formulae. Correlation analysis indicated that concentrations of 5-hydroxymethylfurfural, 3-deoxyglucosone, CML and CEL were closely related to fat contents. These results provided insight into concentrations of potentially harmful Maillard reaction products in different types of formulae and provide a theoretical basis for further optimisation of processing., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Recently, there has been a growing interest in using sustainable energy to decrease lignin monomers to generate high-value-added products. Here, we present a protocol for electrocatalytic hydrogenation of 5-hydroxymethylfurfural. We describe steps for catalyst preparation, performing electrocatalytic experiments, high-performance liquid chromatography analysis, and in situ infrared reflection-absorption spectroscopy testing. The synthesized catalyst used in this reaction exhibits enhanced selectivity and Faradaic efficiency in NaClO 4 solution. For complete details on the use and execution of this protocol, please refer to Zhang et al. 1 ., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

The present study aimed to elucidate the pathway of pigment formation and identify the source of antioxidant activity during sugar smoking. Building upon previous research, this investigation replicated the sucrose cleavage process involved in sugar-smoking through model reactions to obtain distinct model reaction products. The products were analyzed using various techniques such as ultraviolet-visible spectrometry, Fourier-transform infrared spectroscopy, high-performance liquid chromatography, and high-performance liquid chromatography-tandem mass spectrometry. The findings revealed that the pyrolysis of sucrose at 330 °C yielded glucose and fructose, with fructose pyrolysis producing significantly more 5-HMF than glucose. Moreover, the antioxidant capacity of 5-HMF was found to make a substantial contribution. The primary source of 5-HMF was identified as fructose resulting from the cleavage of sucrose at 330 °C, while the primary pathway for the formation of the sugar-smoking pigment 5-GGMF was attributed to the intermolecular dehydration of 5-HMF and glucose at 150 °C., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Fabrication of sustainable bio-based malleable thermosets (BMTs) with excellent mechanical properties and reprocessing ability for applications in electronic devices has attracted more and more attention but remains significant challenges. Herein, the BMTs with excellent mechanical robustness and reprocessing ability were fabricated via integrating with radical polymerization and Schiff-base chemistry, and employed as the flexible substrate to prepare the capacitive sensor. To prepare the BMTs, an elastic bio-copolymer derived from plant oil and 5-hydroxymethylfurfural was first synthesized, and then used to fabricate the dynamic crosslinked BMTs through Schiff-base chemistry with the amino-modified cellulose and polyether amine. The synergistic effect of rigid cellulose backbone and the construction of dynamic covalent crosslinking network not only achieved high tensile strength (8.61 MPa) and toughness (3.77 MJ/m 3 ) but also endowed the BMTs with excellent reprocessing ability with high mechanical toughness recovery efficiency of 104.8 %. More importantly, the BMTs were used as substrates to fabricate the capacitive sensor through the CO 2 -laser irradiation technique. The resultant capacitive sensor displayed excellent and sensitive humidity sensing performance, which allowed it to be successfully applied in human health monitoring. This work paved a promising way for the preparation of mechanical robustness malleable bio-thermosets for electronic devices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

A systematic kinetic study was conducted in subcritical water medium in the temperature range from 150 to 200 °C for pure glucose, xylose, proline and aspartic acid as well as binary mixtures of sugars + amino acids to understand the reaction kinetics and interactions among biomass components and to discern the influence of Maillard reaction (MR) on the overall reaction kinetics. The main degradation products identified for glucose and xylose were the respective dehydration products, hydroxymethyl furfural and furfural, yielding an increasing solid residue with temperature (15.9 wt% at 200 °C) with an augmented heating value. The degradation of sugars and amino acids in binary systems was faster compared to pure compounds due to MR and the production of dehydration products was delayed when considering total sugar conversion. Higher relative reactivity in MR was observed for xylose over glucose showing also higher antioxidant activity., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: M.T. Sanz reports financial support was provided by Agencia Estatal de Investigación. M.T. Sanz reports financial support was provided by Junta de Castilla y León (JCyL) and the European Regional Development Fund (ERDF)., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Catalytic transfer hydrogenation (CTH), that employs protic solvents as hydrogen sources to alleviate the use of molecular hydrogen H 2 , has gained great attention. This work, reports multifunctional, metallic Cu nanoparticles supported ZIF-8 material for CTH of furfural to a highly valued fuel additive, 2-methylfuran (2-MF) using 2-propanol. Of all as-synthesized xCu(yM)/ZIF-8 catalysts with varied NaBH 4 concentration (yM) and Cu loading (x), 11Cu(1.5 M)/ZIF-8 exhibited higher catalytic activity with > 99 % FAL conversion and 93.9 % 2-MF selectivity. This is ascribed to its high specific surface area, and existence of optimum amount of Lewis acid-base sites along with Cu 0 species, which are responsible for hydrogenation of furfural to furfuryl alcohol and subsequent hydrogenolysis to produce 2-MF. The present work reports a highly efficient and stable, metal-MOF hybrid material for CTH of FAL to 2-MF, which is one among the best reports available in literature, therewith suggests a promising approach for bio-oil upgradation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Gentianae Radix, an herbal medicine, has been used as a gastrointestinal drug in Japan. In the Japanese Pharmacopoeia 18th Revision, the sublimation test is specified as an identification test for Gentianae Radix. The compound obtained in this sublimation test was believed to be gentisin, a xanthone family compound. However, the compound we identified using liquid chromatography-high-resolution mass spectrometry (LC-HRMS) and 1 H- and 13 C-NMR was 5-(hydroxymethyl)furfural (5-HMF). The same compound was found to be a sublimate of Gentianae Scabrae Radix and Gentianae Macrophyllae Radix, belonging to the same genus as Gentianae Radix. These results indicate the necessity to revise the identification test for Gentianae Radix to a more unique method., (© 2024. The Author(s) under exclusive licence to The Japanese Society of Pharmacognosy.)

Lactose hydrolysed concentrated milk was prepared using β-galactosidase enzyme (4.76U/mL) with a reaction period of 12 h at 4 °C. Addition of polysaccharides (5 % maltodextrin/β-cyclodextrin) to concentrated milk either before or after lactose hydrolysis did not result in significant differences (p > 0.05) in degree of hydrolysis (% DH) of lactose and residual lactose content (%). Three different inlet temperatures (165 °C, 175 °C and 185 °C) were used for the preparation of powders which were later characterised based on physico-chemical and maillard browning characteristics. Moisture content, solubility and available lysine content of the powders decreased significantly, whereas, browning parameters i.e., browning index, 5-hydroxymethylfurfural, furosine content increased significantly (p < 0.05) with an increase in inlet air temperature. The powder was finally prepared with 5 % polysaccharide and an inlet air temperature of 185 °C which reduced maillard browning. Protein-polysaccharide interactions were identified using Fourier Transform infrared spectroscopy, fluorescence spectroscopy and determination of free amino groups in the powder samples. Maltodextrin and β-cyclodextrin containing powder samples exhibited lower free amino groups and higher degree of graft value as compared to control sample which indicated protein-polysaccharide interactions. Results obtained from Fourier Transform infrared spectroscopy also confirmed strong protein-polysaccharide interactions, moreover a significant decrease in fluorescence intensity was also observed in the powder samples. These interactions between the proteins and polysaccharides reduced the maillard browning in powders., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Recently, catalytic valorization of biomass-derived furans has received growing interest. 5-Aminomethyl-2-furancarboxylic acid (AMFC), a furan amino acid, holds great promise in the aeras of polymer and pharmaceutical, but its synthesis remains limited. In this work, we report a chemobiocatalytic route toward AMFC by combining laccase-TEMPO system and recombinant Escherichia coli (named E. coli&#95;TAF) harboring ω-transaminase (TA), L-alanine dehydrogenase (L-AlaDH) and formate dehydrogenase (FDH), starting from 5-hydroxymethylfurfural (HMF). In the cascade, HMF is oxidized into 5-formyl-2-furancarboxylic acid (FFCA) by laccase-TEMPO system, and then the resulting intermediate is converted into AMFC by E. coli&#95;TAF via transamination with cheap ammonium formate instead of costly organic amine donors, theoretically generating H 2 O and CO 2 as by-products. The tandem process was run in a one-pot twostep manner, affording AMFC with approximately 81 % yield, together with 10 % 2,5-furandicarboxylic acid (FDCA) as by-product. In addition, the scale-up production of AMFC was demonstrated, with 0.41 g/L h productivity and 8.6 g/L titer. This work may pave the way for green manufacturing of the furan-containing amino acid., (© 2024 Wiley‐VCH GmbH.)

Nb-based catalysts supported on porous silica with different textural properties have been synthesized, characterized, and tested in the one-pot reaction of furfural to obtain valuable chemicals. The catalytic results reveal that the presence of fluoride in the synthesis, which limits the growing of the porous silica, limits diffusional problems of the porous silica, obtaining higher conversion values at shorter reaction times. On the other hand, the incorporation of NbO x species in the porous silica provides Lewis acid sites and a small proportion of Brönsted acid sites, in such a way that the main products are alkyl furfuryl ethers, which can be used as fuel additives.

The purpose of this study is to design and investigate two coupling processes for acid-catalyzed hydrolysis of corncob, achieving the simultaneous preparation of biomass-based furfural and levulinic acid (LA). Meanwhile, high concentration and yield of LA were obtained through a situ feeding strategy of pretreated furfural residue with high solids loading (20%, w/v). In Scenario A, 2-methyltetrahydrofuran was selected as the solvent for the LA extraction process compared with the neutralization process in Scenario B. Techno-economic assessment results show that Scenario A is technically feasible and cost-competitive, with an internal rate of return of 21.92%, a net present value of 121 million US dollars, a carbon efficiency of 72%, an environmental factor of 4.38, and a process mass intensity of 32.19. This study will provide new insights for fully utilizing lignocellulosic biomass to prepare renewable energy resources, comprehensively evaluating the economic feasibility, and promoting green and low-carbon development., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Maillard reaction is a non-enzymatic thermal reaction during food processing and storage. It massively contributes to the flavor, color, health benefits and safety of foods and could be briefly segmented into initial, intermediate and final stages with the development of a cascade of chemical reactions. During thermal reaction of food ingredients, sugar, protein and amino acids are usually the main substrates, and polyphenols co-existed in food could also participate in the Maillard reaction as a modulator. Polyphenols including flavan-3-ols, hydroxycinnamic acids, flavonoids, and tannins have shown various effects throughout the process of Maillard reaction, including conjugating amino acids/sugars, trapping α-dicarbonyls, capturing Amadori rearrangement products (ARPs), as well as decreasing acrylamide and 5-hydroxymethylfurfural (5-HMF) levels. These effects significantly influenced the flavor, taste and color of processed foods, and also decreased the hazard products' level. The chemical mechanism of polyphenols-Maillard products involved the scavenging of radicals, as well as nucleophilic addition and substitution reactions. In the present review, we concluded and discussed the interaction of polyphenols and Maillard reaction, and proposed some perspectives for future studies.

Modern biocatalysis requires fast, sensitive, and efficient high-throughput screening methods to screen enzyme libraries in order to seek out novel biocatalysts or enhanced variants for the production of chemicals. For instance, the synthesis of bio-based furan compounds like 2,5-diformylfuran (DFF) from 5-hydroxymethylfurfural (HMF) via aerobic oxidation is a crucial process in industrial chemistry. Laccases, known for their mild operating conditions, independence from cofactors, and versatility with various substrates, thanks to the use of chemical mediators, are appealing candidates for catalyzing HMF oxidation. Herein, Schiff-based polymers based on the coupling of DFF and 1,4-phenylenediamine (PPD) have been used in the set-up of a novel colorimetric assay for detecting the presence of DFF in different reaction mixtures. This method may be employed for the fast screening of enzymes (Z' values ranging from 0.68 to 0.72). The sensitivity of the method has been proved, and detection (8.4 μM) and quantification (25.5 μM) limits have been calculated. Notably, the assay displayed selectivity for DFF and enabled the measurement of kinetics in DFF production from HMF using three distinct laccase-mediator systems.

The research on the efficient use of biomass to produce chemical products has received extensive attention. In this work, a novel heterogeneous biocarbon-based heterogeneous catalyst AT-Sn-YB was prepared using yellow bamboo (YB) as a carrier, and its physical properties were proved to be good by various characterization and stability experiments. In the γ-valerolactone/water (3:1, v/v) medium containing 100 mM CuCl 2 , the use of AT-Sn-YB (3.6 wt%) under 170 °C for 20 min was applied to catalyze YB into furfural (80.3% yield), accompanied with 2.8 g/L xylooligosaccharides. The YB solid residue obtained from treatment was efficiently saccharified to reducing sugars (17.2 g/L). Accordingly, comprehensive understanding of efficiently co-producing xylooligosaccharides, furfural and reducing sugars from YB was demonstrated via the pretreatment with biochar-based catalyst. This study innovatively used a new type of solid acid to complete the efficient co-production of chemical products, and realized the value-added utilization of yellow bamboo., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

The coexistence of anthocyanin with the sugar degradation product 5-hydroxymethylfurfural (5-HMF) is inevitable during the processing and storage of anthocyanin-rich juices. It was determined from our study that lower concentrations of 5-HMF have little effect on the stability of Cyanidin-3-O-glucoside (C3G), and even cause a slight increase for a short period of time. As the concentration of 5-HMF increased, the retention of C3G decreased and the color of the solution changed from orange-red to purple-red. The reaction sites of 5-HMF and C3G in its hemiketal form were predicted by quantum chemical calculations in order to investigate the pathways of action of the two. The degradation mechanism of 5-HMF on anthocyanin was verified by Ultraviolet and Visible spectrophotometer and Ultra performance liquid chromatography-mass spectrometry. Therefore, this article provides further theoretical support for the study of the effect of furfural compounds, which are sugar degradation products, on the stability of anthocyanins., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

FtpM from Aspergillus fumigatus was the first carboxyl methyltransferase reported to catalyse the dimethylation of dicarboxylic acids. Here the creation of mutant R166M that can catalyse the quantitative conversion of bio-derived 2,5-furandicarboxylic acid (FDCA) to its dimethyl ester (FDME), a bioplastics precursor, was reported. Wild type FtpM gave low conversion due to its reduced catalytic efficiency for the second methylation step. An AlphaFold 2 model revealed a highly electropositive active site, due to the presence of 4 arginine residues, postulated to favour the binding of the dicarboxylic acid over the intermediate monoester. The R166M mutation improved both binding and turnover of the monoester to permit near quantitative conversion to the target dimethyl ester product. The mutant also had improved activity for other diacids and a range of monoacids. R166M was incorporated into 2 multienzyme cascades for the synthesis of the bioplastics precursor FDME from bioderived 5-hydroxymethylfurfural (HMF) as well as from poly(ethylene furanoate) (PEF) plastic, demonstrating the potential to recycle waste plastic., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

2,5-Diformylfuran, which can be prepared via the oxidation of biobased HMF, has received considerable attention because of its potential applications in producing furan-based chemicals and functional materials, such as biofuels, polymers, fluorescent material, vitrimers, surfactants, antifungal agents and medicines. This work aimed to develop an efficient one-pot process for chemoenzymatic transformation of biobased substrate to 2,5-diformylfuran with deep eutectic solvent (DES) Betaine:Lactic acid ([BA][LA]) catalyst and oxidase biocatalyst in [BA][LA]-H 2 O. Using waste bread (50 g/L) and D-fructose (18.0 g/L) as feedstocks in [BA][LA]-H 2 O (15:85, vol/vol), the yields of HMF were 32.8% (15 min) and 91.6% (90 min) at 150 °C, respectively. These prepared HMF could be biologically oxidized to 2,5-diformylfuran by Escherichia coli pRSFDuet-GOase, achieving a productivity of 0.631 g 2,5-diformylfuran/(g fructose) and 0.323 g 2,5-diformylfuran/(g bread) after 6 h under the mild performance condition. This bioresourced intermediate 2,5-diformylfuran was effectively synthesized from biobased feedstock in an environmentally-friendly system., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In this study, the high-loaded copper-containing catalysts modified with Fe and Al were successfully applied for the hydroconversion of furfural to furfuryl alcohol (FA) or 2-methylfuran (2-MF) in a batch reactor. The synthesized catalysts were studied using a set of characterization techniques to find the correlation between their activity and physicochemical properties. Fine Cu-containing particles distributed in an amorphous SiO 2 matrix, which has a high surface area, provide the conversion of furfural to FA or 2-MF under exposure to high pressure of hydrogen. The modification of the mono-copper catalyst with Fe and Al increases its activity and selectivity in the target process. The reaction temperature strongly affects the selectivity of the formed products. At a H 2 pressure of 5.0 MPa, the highest selectivity toward FA (98%) and 2-MF (76%) was achieved in the case of 35Cu13Fe1Al-SiO 2 at the temperature of 100 °C and 250 °C, respectively.

The electroenzymatic valorization of biomass derivatives into valuable biochemicals has a promising outlook. However, bottlenecks including poor electron transfer between the electrode surface and oxidoreductase, inefficient regeneration of cofactors, and high cost of enzymes and electron mediators hindered the realistic applications of the technique. Herein, to address the above technical barriers, a novel bio-electrocatalytic system that integrates the electrochemical NADH regeneration and enzymatic reaction was constructed, using an orderly assembled composite bioelectrode consisting of an outer immobilized enzyme layer and a sandwiched redox mediator rhodium complex layer. The as-prepared composite bioelectrode was further applied for the highly selective hydrogenation of furfural into furfural alcohol. Results indicated that the enzyme activity was significantly improved, while the furfural valorization was promoted by effective interfacial electron transition and co-factor regeneration on the composite bioelectrode. Considerable high furfural conversion (96.4%) can be achieved accompanied by a furfural alcohol selectivity of 90.0% at -1.2 V ( vs Ag/AgCl). The novel composite bioelectrode also showed good stability and reusability. Up to 85.1% of the original furfural alcohol selectivity can be preserved after 10 times of recycling. This work presents a promising green alternative for the valorization of furfural, which also shows great potential extending to the valorization of other biomass compounds.

Furfurylamine is a key furan-based compound for manufacturing perfumes, fibers, additives, medicines and agrochemicals. It can be obtained by amination of furfural by ω-transaminase (AtAT) from Aspergillus terreus. In this work, site-directed mutant of amino acid residues [Threonine (T) at AT130 was mutated to Methionine (M) and Glutamic acid (E) at AT133 was mutated to Phenylalanine (F)] was used to change in the flexible region of AtAT. The transamination activity and thermostability were significantly improved. In ChCl:MA (30 wt%), furfural (500 mM) was efficiently transformed into furfurylamine (92% yield) with TMEF after 12 h. 101.3 mM of biomass-derived furfural and 129.7 mM of D-xylose-derived furfural were wholly converted into furfurylamine within 5 h, achieving the productivity of 0.465 g furfurylamine/(g xylan in corncob) and 0.302 g furfurylamine/(g D-xylose). This established chemoenzymatic conversion strategy by bridging chemocatalysis and biocatalysis could be utilized in the valorisation of renewable biomass to valuable furans., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

To date, an efficient process for manufacturing valuable furan compounds from available renewable resources has gained great attention via a chemoenzymatic route. In this study, a sulfonated tin-loaded heterogeneous catalyst CLUST-Sn-LS using lobster shell as biobased carrier was prepared to convert corncob (75.0 g/L) into furfural (122.5 mM) at 170 °C for 30 min in methyl isobutyl ketone (MIBK)-H 2 O biphasic system (2:1, v/v). To improve furfurylamine yield, a novel recombinant E. coli TFTS harboring robust mutant Aspergillus terreus ω-transaminase [hydrophilic threonine (T) at position 130 was site-directed mutated to hydrophobic phenylalanine (F)] was constructed to transform 300-500 mM furfural into furfurylamine (90.1-93.6 % yield) at 30 °C and pH 7.5 in MIBK-H 2 O. Corncob was converted to furfurylamine in MIBK-H 2 O with a high productivity of 0.461 g furfurylamine/(g xylan). This constructed chemoenzymatic method coupling bio-based chemocatalyst CLUST-Sn-LS and mutant ω-transaminase biocatalyst in a biphasic system could efficiently convert lignocellulose into furfurylamine., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Currently, there is a great interest in the development of sustainable and green technologies for production of biofuels and chemicals. In this sense, much attention is being paid to lignocellulosic biomass as feedstock, as alternative to fossil-based resources, inasmuch as its fractions can be transformed into value-added chemicals. Two important platform molecules derived from lignocellulosic sugars are furfural and levulinic acid, which can be transformed into a large spectrum of chemicals, by hydrogenation, oxidation, or condensation, with applications as solvents, agrochemicals, fragrances, pharmaceuticals, among others. However, in many cases, noble metal-based catalysts, scarce and expensive, are used. Therefore, an important effort is performed to search the most abundant, readily available, and cheap transition-metal-based catalysts. Among these, copper-based catalysts have been proposed, and the present review deals with the hydrogenation of furfural and levulinic acid, with Cu-based catalysts, into several relevant chemicals: furfuryl alcohol, 2-methylfuran, and cyclopentanone from FUR, and γ-valerolactone and 2-methyltetrahydrofuran from LA. Special emphasis has been placed on catalytic processes used (gas- and liquid-phase, catalytic transfer hydrogenation), under heterogeneous catalysis. Moreover, the effect of addition of other metal to Cu-based catalysts has been considered, as well as the issue related to catalyst stability in reusing studies., Competing Interests: The authors declare no conflict of interest.

5-Hydroxymethylfurfural (5-HMF) represents a well-known class of lignocellulosic biomass-derived platform molecules. With the presence of many reactive functional groups in the structure, this versatile building block could be valorized into many value-added products. Among well-established catalytic transformations in biorefinery, the reductive amination is of particular interest to provide valuable N-containing compounds. Specifically, the reductive amination of 5-HMF with ammonia (NH 3 ) and molecular hydrogen (H 2 ) offers a straightforward and sustainable access to primary furanic amines [i. e., 5-hydroxymethyl-2-furfuryl amine (HMFA) and 2,5-bis(aminomethyl)furan (BAMF)], which display far-reaching utilities in pharmaceutical, chemical, and polymer industries. In the presence of heterogeneous catalysts contanining monometals (Ni, Co, Ru, Pd, Pt, and Rh) or bimetals (Ni-Cu and Ni-Mn), this elegant pathway enables a high-yielding and chemoselective production of HMFA/BAMF compared to other synthetic routes. This Review aims to present an up-to-date highlight on the supported metal-catalyzed reductive amination of 5-HMF with elaborate studies on the role of metal, solid support, and reaction parameters. Besides, the recyclability/adaptability of catalysts as well as the reaction mechanism are also provided to give valuable insights into this potential 5-HMF valorization strategy., (© 2022 Wiley-VCH GmbH.)

The development and transformation of biomass-derived platform compounds is a sustainable way to deal with the fossil fuel crisis. 5-Hydroxymethylfurfural (HMF) can be reduced or oxidized to produce many high-value compounds; however, it is challenging to effectively produce 2,5-diformylfuran (DFF) due to overoxidation. In this work, a carbon-doped V 2 O 5 (C-V 2 O 5 ) material was obtained through pyrolysis of MIL-47(V) nanorods, a typical metal-organic framework material. The X-ray diffraction patterns and X-ray photoelectron spectra showed that the graphitized carbon species were incorporated in C-V 2 O 5 . High-efficiency HMF oxidation, high specific selectivity for DFF and excellent recycling could be achieved with the C-V 2 O 5 catalyst. Fourier-transform infrared spectroscopy combined with density functional theory (DFT) calculation revealed that graphitized carbon weakens the VO bond and promotes the formation of oxygen vacancies in C-V 2 O 5 , thus improving the catalytic activity in the oxidation of furfuryl alcohols. The V 4+ induced by oxygen vacancies will be oxidized by O 2 to form V 5+ , so that the cycle can be realized. It exhibits remarkable selectivity in the oxidation of different alcohols produced from biomass based on the relatively constant active sites in C-V 2 O 5 .

In this work, a series of (x)Hf-β zeolite catalysts were prepared by a simple wet impregnation method and used as bifunctional catalysts with Lewis and Brønsted acid sites for synthesizing 5-hydroxymethylfurfural (5-HMF) from cellulose in H 2 O (NaCl) -THF biphasic system. Characterization analysis of (x)Hf-β zeolite catalysts with ICP-OES, N 2 adsorption-desorption isotherm, XRD, FTIR, SEM, NH 3 -TPD and Py-FTIR indicated that the catalysts possessed favorable pore structure, appropriate acid strength and acidity. A superior 86.3 % cellulose conversion and 53.4 % 5-HMF yield could be obtained at 200 °C for 4 h by using (5 %)Hf-β zeolite as the catalyst. In addition, the catalytic system provided a favorable 5-HMF yield from other carbohydrates, including glucose (85.1 %), sucrose (80.6 %), starch (65.1 %), maltose (65.0 %), dextran (59.9 %), and Moso bamboo (21.9 %). Nevertheless, the recyclability of (5 %)Hf-β zeolite catalyst was unsatisfactory and the 5-HMF yield showed a downtrend from 53.4 % to 24.4 % after 5 cycles. The catalyst has promising potential for converting biomass materials into high-value platform compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Recently, efficient synthesis of furan-based chemicals from biomacromolecule via chemoenzymatic approaches have been widely recognized. In this work, an efficient conversion of biomacromolecule (e.g., xylan in biomass) to furfurylamine (FLA) was developed in a tandem reaction by bridging with chemocatalysis and biocatalysis. Various biomasses (e.g., corncob, bagasse, bamboo shoot shell, corn stalk, rice straw stalk, reed, water bamboo and sunflower stalk) could produce different titer of furfural due to the diverse xylan content in biomass. After being catalyzed by shrimp shell-supported solid acid catalyst (Sn-DAT-SS) in deep eutectic solvent choline chloride:ethylene glycol (ChCl:EG) - water (10:90, v/v) at 170 °C after 30 min, corncob gave the highest furfural yield of 52.4 %. The potential catalytic mechanism for Sn-DAT-SS-catalyzing the conversion of biomass into furfural in ChCl:EG - water was proposed. It was found that by-products (formic acid, levulinic acid, 5-hydroxymethylfurfural) and soluble sugars (glucose, xylose, arabinose, cellobiose) produced during the conversion of biomass to furfural had certain inhibition effects on the biotransamination of furfural to FLA. Biomass-derived furfural (36.7-92.3 mM) could be fully aminated to FLA by E. coli CCZU-XLS160 cells harboring ω-transaminase after 24-72 h. The established chemoenzymatic strategy for converting biomacromolecules into valuable furan-based products was successfully developed in an eco-friendly system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Currently, the production of furan aldehydes from raw biomass suffers from low furfural yield and high energy consumption. In this study, a recyclable and practical method was explored for the preparation of furfural from corn stover by the one-pot reaction by acidic lithium bromide solution (ALBS) without pretreatment and enzymolysis. In the ALBS reaction, the furan aldehydes were generated by the degradation of lignocellulose; however, the products were unstable and were further dehydrated to form humins. So, dehydration reaction was inhibited in this study, and the high yield of furan aldehydes was obtained, in which 2.94 g/L of furfural and 2.78 g/L of 5-hydroxymethyl furfural (5-HMF) were generated with high solid loading (10 wt%), the presence of commercial catalyst ZSM-5 and co-solvent tetrahydrofuran (THF) at 140 °C for 200 min. Via this method, almost 100% of hemicellulose was transformed to furfural, and 40.71% of cellulose was transformed to 5-HMF, which was based on the theoretical yield of HMF (8.35 g) from glucose (29.30 g) produced from cellulose. After the reaction, the catalyst ZSM-5 was the main component in the solid residue and kept a suitable performance. THF azeotrope was easily separated from the slurry by evaporation. During the removal of THF, lignin was precipitated from the liquid phase and showed lower molecular weight and abundant active groups, which was a potential feedstock for producing valuable aromatics and polymers. Thus, in a one-pot reaction, the ideal yield of furan aldehydes from raw biomass was obtained on a lab scale, and the catalyst, THF, and LiBr were easily recycled, which provided an option to realize the economical production of sustainable furan aldehydes from raw biomass., Competing Interests: All authors declare no conflict of interest and have approved the manuscript.

In aqueous mediums, the chemical environment for catalytic reactions is not only comprised of water molecules but also of corresponding ionized species, i.e., hydronium ions, which can impact the mechanism and kinetics of a reaction. Here we show that in aqueous-phase hydrogenation of furfural on Pd/C, increasing the hydronium ion activities by five orders of magnitude (from pH 7 to pH 1.6) leads to an increase of less than one order of magnitude in the reaction rate. Instead of a proton-coupled electron transfer pathway, our results show that a Langmuir-Hinshelwood mechanism describes the rate-limiting hydrogen addition step, where hydrogen atom adsorbed on Pd is transferred to the carbonyl C atom of the reactant. As such, the strength of hydrogen binding on Pd, which decreases with increasing hydronium ion concentration (i.e., 2 kJ mol H2 -1 per unit pH), is a decisive factor in hydrogenation kinetics (rate constant +270%). In comparison, furfural adsorption on Pd is pH-independent, maintaining a tilted geometry that favors hydrogen attack at the carbonyl group over the furan ring., (© 2022. The Author(s).)

The selective photo-oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is important due to its substitute-role in polyester-fabrication. Here, a titanium-cluster based metal-covalent organic framework nanosheet has been synthesized through the covalent-coupling between Ti 6 -NH 2 and benzotrithiophene tricarbaldehyde (BTT). The integration of them endows the nanosheet with a visible-light-adsorption region, effective electron-hole separation-efficiency and suitable photo-oxidation ability. Specifically, its photo-selectivity for HMF-to-FDCA can be >95 % with ≈100 % conversion, which is more than 2, 5, and 10 times higher than MOF-901 (43 %), Ti 6 -NH 2 (19 %) and under-darkness (9 %), respectively. Notably, an O 2 -based mechanism is proposed and the vital roles of Ti 6 -NH 2 and BTT are verified by DFT calculations. This work might facilitate the exploration of porous-crystalline-catalysts for selective biomass-valorization., (© 2022 Wiley-VCH GmbH.)

Hydrogenation and hydrogenolysis are two important reactions for electrochemical reductive valorization of biomass-derived oxygenates such as 5-hydroxymethylfurfural (HMF). In general, hydrogenolysis (which combines hydrogenation and deoxygenation) is more challenging than hydrogenation (which does not involve the cleavage of carbon-oxygen bonds). Thus, identifying factors and conditions that can promote hydrogenolysis is of great interest for reductive valorization of biomass-derived oxygenates. For the electrochemical reduction of HMF and its derivatives, it is known that aldehyde hydrogenation is not a part of aldehyde hydrogenolysis but rather a competing reaction; however, no atomic-level understanding is currently available to explain their electrochemical mechanistic differences. In this study, combined experimental and computational investigations were performed using Cu electrodes to elucidate the key mechanistic differences between electrochemical hydrogenation and hydrogenolysis of HMF. The results revealed that hydrogenation and hydrogenolysis of HMF involve the formation of different surface-adsorbed intermediates via different reduction mechanisms and that lowering the pH promoted the formation of the intermediates required for aldehyde and alcohol hydrogenolysis. This study for the first time explains the origins of the experimentally observed pH-dependent selectivities for hydrogenation and hydrogenolysis and offers a new mechanistic foundation upon which rational strategies to control electrochemical hydrogenation and hydrogenolysis can be developed., (© 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

In recent years, electrocatalysis was progressively developed to facilitate the selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) towards the value-added chemical 2,5-furandicarboxylic acid (FDCA). Among reported electrocatalysts, alloy materials have demonstrated superior electrocatalytic properties due to their tunable electronic and geometric properties. However, a specific discussion of the potential impacts of alloy structures on the electrocatalytic HMF oxidation performance has not yet been presented in available Reviews. In this regard, this Review introduces the most recent perspectives on the alloy-driven electrocatalysis for HMF oxidation towards FDCA, including oxidation mechanism, alloy nanostructure modulation, and external conditions control. Particularly, modulation strategies for electronic and geometric structures of alloy electrocatalysts have been discussed. Challenges and suggestions are also provided for the rational design of alloy electrocatalysts. The viewpoints presented herein are anticipated to potentially contribute to a further development of alloy-driven electrocatalytic oxidation of HMF towards FDCA and to help boost a more sustainable and efficient biomass refining system., (© 2022 Wiley-VCH GmbH.)

5-Hydroxymethyl-2-furfurylamine (5-HMFA) as an important 5-HMF derivative has been widely utilized in the manufacture of diuretics, antihypertensive drugs, preservatives and curing agents. In this work, an efficient chemoenzymatic route was constructed for producing 5-(hydroxymethyl)furfurylamine (5-HMFA) from biobased D -fructose in deep eutectic solvent Betaine:Glycerol-water. The introduction of Betaine:Glycerol could greatly promote the dehydration of D -fructose to 5-HMF and inhibit the secondary decomposition reactions of 5-HMF, compared with a single aqueous phase. D -Fructose (200 mM) could be catalyzed to 5-HMF (183.4 mM) at 91.7% yield by SG(SiO 2 ) (3 wt%) after 90 min in Betaine:Glycerol (20 wt%), and at 150 °C. E. coli AT exhibited excellent bio-transamination activity to aminate 5-HMF into 5-HMFA at 35 °C and pH 7.5. After 24 h, D -fructose-derived 5-HMF (165.4 mM) was converted to 5-HMFA (155.7 mM) in 94.1% yield with D -Ala ( D -Ala-to-5-HMF molar ratio 15:1) in Betaine:Glycerol (20 wt%) without removal of SG(SiO 2 ), achieving a productivity of 0.61 g 5-HMFA/(g substrate D -fructose). Chemoenzymatic valorization of D -fructose with SG(SiO 2 ) and E. coli AT was established for sustainable production of 5-HMFA, which has potential application.

Upgrading furfuralcohols and furfurals to furancarboxylic acids is of great significance for high value-added downstream chemicals synthesis and biomass conversion. Developing an efficient catalyst is the key to acquiring a completely sustainable process. Herein, nitrogen-doped carbon-supported bimetallic AuPd bowl-like catalysts were synthesized. The surface wettability of nitrogen-doped carbon was well adjusted by the nitrification process. Benefiting from the alloying effect of bimetallic AuPd catalyst and the formation of hydroxyl radical initiated by H 2 O dissociation on the hydrophilic surface of nitrated nitrogen-doped carbon, base-free aerobic oxidation of 5-hydroxymethylfurfural (HMF) could produce the highest 2,5-furandicarboxylic acid (FDCA) yield of 93.9 %. In-situ infrared spectroscopy uncovered adsorption configuration of HMF, and the nitrated carbon surface was favorable for HMF and intermediates to enter the active sites, greatly promoting the catalytic oxidation process. Employing other furfuralcohols (furfuryl alcohol, furan-2,5-diyldimethanol, 2,5-bishydroxymethylfuran) as well as furfural and 5-methylfurfural as starting materials, 35.6-95.4 % yield of furancarboxylic acids (FDCA, 2-furoic acid, 5-methyl-2-furoic acid) were also obtained. Moreover, the developed catalysts could maintain excellent stability and activity after four successive runs. This deep insight into the role of bimetallic synergy and surface wettability provides a basis for the rational design of the highly efficient catalysts for the oxidation of furfuralcohols and furfurals and related reactions., (© 2022 Wiley-VCH GmbH.)

Rationally modulating the catalytic microenvironment is important for targeted induction of specific molecular behaviors to fulfill complicated catalytic purposes. Herein, a metal pre-chelating assisted assembly strategy is developed to facilely synthesize the hollow carbon spheres with ultrafine ruthenium clusters embedded in pore channels of the carbon shell (Ru@Shell-HCSs), which can be employed as nanoreactors with preferred electronic and geometric catalytic microenvironments for the efficient tandem hydrogenation of biomass-derived furfural toward 2-methylfuran. The channel-embedding structure is proved to confer the ultrafine ruthenium clusters with an electron-deficient property via a reinforced interfacial charge transfer mechanism, which prompts the hydrogenolysis of intermediate furfuryl alcohol during the tandem reaction, thus resulting in an enhanced 2-methylfuran generation. Meanwhile, lengthening the shell pore channel can offer reactant molecules with a prolonged diffusion path, and correspondingly a longer retention time in the channel, thereafter delivering an accelerated tandem hydrogenation progression. This paper aims to present a classic case that emphasizes the critical role of precisely controlling the catalytic microenvironment of the metal-loaded hollow nanoreactors in coping with the arduous challenges from multifunctional catalyst-driven complex tandem reactions., (© 2022 Wiley-VCH GmbH.)

Bio-based 5-hydroxymethylfurfural (HMF) serves as an important platform for several chemicals, among which 2,5-furan dicarboxylic acid (FDCA) has attracted considerable interest as a monomer for the production of polyethylene furanoate (PEF), a potential alternative for fossil-based polyethylene terephthalate (PET). This study is based on the HMF oxidizing activity shown by Mycobacterium sp. MS 1601 cells and investigation of the enzyme catalysing the oxidation. The Mycobacterium whole cells oxidized the HMF to FDCA (60% yield) and hydroxymethyl furan carboxylic acid (HMFCA). A gene encoding a novel bacterial aryl alcohol oxidase, hereinafter MycspAAO, was identified in the genome and was cloned and expressed in Escherichia coli Bl21 (DE3). The purified MycspAAO displayed activity against several alcohols and aldehydes; 3,5 dimethoxy benzyl alcohol (veratryl alcohol) was the best substrate among those tested followed by HMF. 5-Hydroxymethylfurfural was converted to 5-formyl-2-furoic acid (FFCA) via diformyl furan (DFF) with optimal activity at pH 8 and 30-40°C. FDCA formation was observed during long reaction time with low HMF concentration. Mutagenesis of several amino acids shaping the active site and evaluation of the variants showed Y444F to have around 3-fold higher k cat /K m and ~1.7-fold lower K m with HMF., (© 2022 The Authors. Microbial Biotechnology published by Society for Applied Microbiology and John Wiley & Sons Ltd.)

Lignocellulosic paper waste constitutes a major waste stream globally, which should be valorised for chemical production. However, paper properties (e.g., feedstock composition, cellulosic crystallinity, and thermal stability/degradability) vary with raw materials and pulping processes. This study investigated levulinic acid (LA), hydroxymethylfurfural (HMF), and furfural production by H 2 SO 4 and FeCl 3 catalysed conversion of nine types of paper wastes in a green solvent system (1:1 γ-valerolactone/water). At 160-180 °C for 1-20 min, ∼23-27 wt% LA yield was achieved from sanitary papers, tracing/parchment paper, and paper food box mainly containing crystalline cellulose, while a lower LA yield (∼10-20 wt%) was obtained from other paper wastes with high contents of ash and lignin. A higher selectivity towards HMF (∼12 mol%) was achieved in the presence of FeCl 3 . A furfural yield of ∼ 4-7.5 wt% was also obtained from the hemicellulose content. This study elucidates crucial factors and desirable characteristics of paper waste for catalytic valorisation., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Two sets of four different supported catalyst materials were prepared. One set was obtained by polymerization of a bis-vinylimidazolium salt, which formed a poly(ionic liquid) coating on SiO2, TiO2, boron nitride BN, and carbon nitride C3N4. The other set was, instead, obtained by immobilizing Keggin heteropolyacid H3PW12O40 onto poly-imidazolium functionalized materials. All the catalysts, including the bare supports, were subjected to physical and chemical characterization by XRD, SEM, Specific Surface Area and pore size measurements, TGA, FTIR, and acidity-basicity measurements. The catalytic activity of the materials was tested versus the fructose dehydration in water solution at two different sugar initial concentrations (0.3 and 1 M). Tests lasted 3 h with an amount of catalyst of 2 g∙L−1. The presence of the poly-imidazolium on the surface of the supports increased the catalytic conversion of fructose to 5-hydroxymethylfurfural (the most abundant compound obtained) and was further improved by the contemporary presence of the heteropolyacid, at least for the highest initial fructose concentration. In the latter conditions, the highest yield of 5-hydroxymethylfurfural (>40%) was also obtained.

Owing to the easy over-oxidation, it is a promising yet challenging task to explore renewable carbon resources to control the sunlight-driven selective catalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF), producing important chemical feedstocks, namely, less-oxidized 2,5-diformylfuran (DFF) and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Herein, we have developed a photocatalyst by anchoring a Ru complex on CdS quantum dots, which achieves selective oxidation of HMF toward DFF or HMFCA with high conversion (>81 %) and selectivity (>90 %), based on the controllable generation of two oxygen radicals under different atmospheres. Such selective conversion can also work well outside the laboratory by using natural sunlight. In particular, the selective production of HMFCA through photocatalytic HMF oxidation is achieved for the first time. More importantly, our photocatalyst is applicable for the selective oxidation of other compounds with hydroxyl and aldehyde groups., (© 2022 Wiley-VCH GmbH.)

The alkali-soluble hemicelluloses extracted with 10% KOH solution from corn bran were further isolated with different concentrations of aqueous ethanol solutions. Herein 92.2% of the original hemicelluloses can be obtained and the cellulase enzymatic hydrolysis rate of the alkali treated corn bran can reach to 97.2%. The corn bran hemicelluloses were mainly glucuronoarabinoxylan, in which xylose (48.4-53.8%) and arabinose (27.8-33.2%) were the main components. More linear hemicelluloses with high molecular weight tended to be precipitated in low concentration aqueous ethanol solutions. Furthermore, the relationship between the structural features of these alkali-soluble corn bran hemicelluloses and their furfural yield was investigated in MIBK (methyl isobutyl ketone)/H 2 O biphasic system. Results showed that the hemicelluloses with high xylose content are benefit to the furfural production, and the highest furfural yield of 67.7% was obtained., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Selective conversion of lignocellulosic biomass-derived chemicals is of critical significance for sustainable fine and commodity chemical industries. Cellulose-derived levoglucosenone (LGO) has a promising potential for producing 5-hydroxymethylfurfural (HMF) with a substantial yield under acid conditions, but the mechanism is unidentified. Herein, we disclose the mechanism of LGO conversion to HMF in the aqueous phase without and with H 2 SO 4 as a catalyst by density functional theory (DFT) calculations for the first time. Results showed that LGO first forms 6,8-dioxabicyclo[3.2.1]-octane-2,4,4-triol (DH) via two sequential hydration reactions occurring at the C═C bond and then the ketone group. The use of H 2 SO 4 as a catalyst significantly reduced the free energy barriers of LGO and DH conversion to HMF, with a free energy barrier of 115 kJ/mol for LGO → HMF compared to that of 91 kJ/mol for DH → HMF, demonstrating that DH is easier for HMF formation.

The depletion of fossil resources is driving the research towards alternative renewable ones. Under this perspective, 5-hydroxymethylfurfural (HMF) represents a key molecule deriving from biomass characterized by remarkable potential as platform chemical. In this work, for the first time, the hydrogenation of HMF in ethanol was selectively addressed towards 2,5-bis(hydroxymethyl)furan (BHMF) or 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) by properly tuning the reaction conditions in the presence of the same commercial catalyst (Ru/C), reaching the highest yields of 80 and 93 mol%, respectively. These diols represent not only interesting monomers but strategic precursors for two scarcely investigated ethoxylated biofuels, 2,5-bis(ethoxymethyl)furan (BEMF) and 2,5-bis(ethoxymethyl)tetrahydrofuran (BEMTHF). Therefore, the etherification with ethanol of pure BHMF and BHMTHF and of crude BHMF, as obtained from hydrogenation step, substrates scarcely investigated in the literature, was performed with several commercial heterogeneous acid catalysts. Among them, the zeolite HZSM-5 (Si/Al=25) was the most promising system, achieving the highest BEMF yield of 74 mol%. In particular, for the first time, the synthesis of the fully hydrogenated diether BEMTHF was thoroughly studied, and a novel cascade process for the tailored conversion of HMF to the diethyl ethers BEMF and BEMTHF was proposed., (© 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Mono- and bimetallic Ni-based catalysts were prepared by screening 6 supports and 14 secondary metals for reductive amination of 5-hydroxymethylfurfural (5-HMF) into 2,5-bis(aminomethyl)furan (BAMF), among which γ-Al 2 O 3 and Mn were the best candidates. By further optimization of the reaction conditions at 0.4 g catalyst loading for 0.5 g substrate of 5-HMF and 160 °C of reaction temperature, 10Ni/γ-Al 2 O 3 and 10NiMn(4 : 1)/γ-Al 2 O 3 achieved the highest BAMF yields of 86.3 and 82.1 %, respectively. Although the BAMF yield values were comparable with that over Raney Ni, the turnover frequencies based on the initial BAMF yield and unit weight of Ni for 10NiMn(4 : 1)/γ-Al 2 O 3 , 10Ni/γ-Al 2 O 3 , and Raney Ni were calculated as 0.41, 0.09, and 0.04 h -1 , respectively. X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy showed that the existence of MnO x well dispersed on the γ-Al 2 O 3 support and its electron transfer effect with Ni particles on the surface of the support contributed to the high efficiency and better recyclability for the five-time reused 10NiMn(4 : 1)/γ-Al 2 O 3 catalyst., (© 2022 Wiley-VCH GmbH.)