Impact of Porous Silica Nanosphere Architectures on the Catalytic Performance of Supported Sulphonic Acid Sites for Fructose Dehydration to 5‐Hydroxymethylfurfural

5‐hydroxymethylfurfural represents a key chemical in the drive towards a sustainable circular economy within the chemical industry. The final step in 5‐hydroxymethylfurfural production is the acid catalysed dehydration of fructose, for which supported organoacids are excellent potential catalyst candidates. Here we report a range of solid acid catalysis based on sulphonic acid grafted onto different porous silica nanosphere architectures, as confirmed by TEM, N2 porosimetry, XPS and ATR‐IR. All four catalysts display enhanced active site normalised activity and productivity, relative to alternative silica supported equivalent systems in the literature, with in‐pore diffusion of both substrate and product key to both performance and humin formation pathway. An increase in‐pore diffusion coefficient of 5‐hydroxymethylfurfural within wormlike and stellate structures results in optimal productivity. In contrast, poor diffusion within a raspberry‐like morphology decreases rates of 5‐hydroxymethylfurfural production and increases its consumption within humin formation

Synthesis, Chemistry and Applications of 5-Hydroxymethyl-furfural And Its Derivatives

The prospect of exciting research activity in the chemistry of furfural derived compounds such as 5-hydroxymethylfurfural (HMF), 2,5-furandicarbaldehyde and 2,5-furan-dicarboxylic acid prompted the writing of this article. As the field of application of these compounds is really enormous, it is no wonder that research in this area, starting at the end of 19th century, is still being developed. Numerous important scientific groups are carrying out studies on the synthesis, and applications of HMF and its derivatives. Notable among these are, Gaset (Toulouse), Descotes (Lyon), Lichtenthaler (Darmstadt), and Gelas (Clermont-Ferrand). Not only academic scientists are interested in this subject, the chemical industry, is represented by sugar companies such as Beghin-Say, and Süddeutsche Zucker. Despite this interest, there are not many comprehensive monographs or reviews covering the chemistry of HMF. Two classic reviews, by Newth and by Feather and Harris, appeared in 1951 and 1973 respectively. Reviews by Gaset et al.,3 Faury et al. and by Kuster are more recent, but they are not detailed. An important review review by Cottier and Descotes6 appeared in 1991. This review is written to update those above, to summarize the contributions of the last 100 years; and to emphasize recent developments especially in electrochemistry, and on dialdehyde and diacid chemistry.HMF is a good starting material for the synthesis of precursors of various pharmaceuticals, thermo-resistant polymers and complex macrocycles. Among these precursors, one can find 2,5- furandicarbaldehyde and 2,5-furandicarboxylic acid; these two compounds are described in detail in this article. The field of their applications is enormous – the dialdehyde offers itself to be the precursor for the synthesis of complexing macrocycles, oxo-porphirines, oxo-annulenes as well as mono- and bis alkenyl and alkynyl furans. The diacid is a building block for numerous polyesters and polyamides; its derivatives were found to be useful in pharmacology. No wonder then, that numerous methods for their preparation have been worked out and published.N/

Primary investigation into the occurrence of Hydroxymethylfurfural (HMF) in a range of smoked products

5-hydroxymethylfurfural (HMF) is produced in foods through many different pathways. Recently, studies have revealed its potential mutagenic and carcinogenic properties. Determination of HMF was originally used as an indicator of both the extent of thermal processing a food had undergone and food quality. It has been identified in a variety of food products such as bread, breakfast cereals, fruit juices, milk and honey. In addition to the thermal processes that lead to the formation of HMF during thermal treatment, food smoking also creates conditions that result in the formation of HMF. This can take place within the food due to the elevated temperatures associated with hot smoking, or by the proximity of the products of the pyrolysis of the wood matrix that is used for smoking (cold smoking). This may lead to further contamination of the product by HMF over and above that associated with the rest of the preparation process. Until now, there have been no studies examining the relation between the smoking procedure and HMF contamination in smoked food. This study is a primary investigation measuring HMF levels in three categories of smoked food products; cheese, processed meat, and fish using HPLC-UV. The amount of HMF found in all three product categories supports our hypothesis that HMF levels are due to both internal pathways during processing and external contamination from smoke generation matrix (wood) employed. The results ranged from 1 ppb (Metsovone traditional Greek smoked cheese) to 4ppm (Hot-smoked ready to eat mackerel). Subsequently for smoked cheese products, a correlation was found between HMF and phenolic compounds generated by the smoking procedures and identified by SPME-GCMS. It was observed that cheese samples that had higher concentrations of HMF were also found to have higher concentrations of syringol and cresols. It is important therefore to understand the smoking procedure’s effect on HMF formation. This will aid in the development of mitigation strategies to reduce HMF formation while retaining the flavour of the smoked products

γ-Al2O3 as acid catalyst for dehydration of glucose to 5-hydroxymethylfurfural

Currently, the search and development of sustainable feedstocks for chemicals derived from petrol have gained worldwide attraction because of the instability of the price of crude oil, the reduction of fossil oil reserves, and the environmental concerns associated to the greenhouse effect caused by CO2 emissions, being biomass one of the world’s most important renewable carbon sources. The major component of plant-derived biomass are carbohydrates, being of great importance to develop efficient and green approaches to their valorization by conversion into high value-added products. Thus, glucose can be transformed by dehydration into 5-hydroxymethylfurfural (HMF), which is a versatile and key intermediate for the production of a wide variety of biobased chemicals and it is attracting much attention in biofuels and chemical industry. Different catalytic systems have been evaluated for HMF production from C6 carbohydrates as glucose, mostly based on heterogeneous catalysis as alternative to the use of liquid mineral acids. On the other hand, the high surface area, large pore size and thermal and hydrothermal stabilities of some mesoporous solids make them suitable for many catalytic processes. In the present work, the dehydration of glucose to HMF has been evaluated by using different mesoporous γ-Al2O3 with acid, neutral or basic character, in a biphasic water–MIBK solvent system to avoid the HMF degradation and its possible reaction with the intermediates from glucose to give soluble polymers and humins or acetalization with glucose. Different experimental parameters, such as reaction temperature and time, as well as the addition of inorganic salts have been studied in order to reach the maximum HMF yield.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. Ministry of Economy and Competitiveness (CTQ2012-38204-C04-02 project), Junta de Andalucía (RNM-1565) and FEDER fund

Effect of thermal treatment and storage on bioactive compounds, organic acids and antioxidant activity of baobab fruit (Adansonia digitata) pulp from Malawi

Bioactive compounds of baobab (Adansonia digitata) pulp from Malawi were investigated. The effect of thermal treatment and storage on selected quality attributes of the juice was also evaluated. Organic compounds were analysed by HPLC; total phenol content (TPC) and total antioxidant activity (FRAP, ABTS and DPPH) were measured by spectrophotometry. Malawi baobab pulp contains high levels of procyanidin B2 (533 ± 22.6 mg/100 g FW), vitamin C (AA + DHA) (466 ± 2.5 mg/100 g FW), gallic acid (68.5 ± 12.4 mg/100 g FW) and (−)-epicatechin (43.0 ± 3.0 mg/100 g FW) and showed a maximum TPC of 1.89 × 103 ± 1.61 mg GAE/100 g FW. The maximum antioxidant activity was 2.81 × 103 ± 92.8 mg TEAC/100 g FW for FRAP, 1.52 × 103 ± 17.1 mg TEAC/100 g FW for ABTS and 50.9 ± 0.43% DPPH for DPPH. Thermal pasteurisation (72 °C, 15 s) retained vitamin C which further showed extended half-life under refrigeration temperature (6 °C). Procyanidin B2, (−)-epicatechin, TPC and antioxidant activity fluctuated during storage. Antioxidant activity was significantly correlated (p ≤ 0.05) with bioactive compounds and TPC

Preyssler Heteropolyacids in the Self-Etherification of 5-Hydroxymethylfurfural to 5,5′-[Oxybis(methylene)]bis-2-furfural Under Mild Reaction Conditions

The synthesis of 5,5′-[oxybis(methylene)]bis-2-furfural (OBMF) from 5-hydroxymethylfurfural (5-HMF) was studied using bulk and alumina-supported Preyssler heteropolyacids (HPAs). The formation of OBMF was related to the amount of Brønsted acid sites, and the lowest yield of OBMF was obtained with supported HPAs. However, the Lewis acidity of the HPA supported on Al2O3 favored the formation of 2,5-dimethylfurane. The effects of solvent, catalyst loading, temperature, and reaction time on the selectivity to OBMF from 5-HMF were studied to optimize OBMF production using bulk Preyssler HPAs; a yield of 84 % to OBMF was obtained at 5 h and 343 K. These results demonstrate that bulk Preyssler HPA is a good candidate for OBMF synthesis under mild reaction conditions.Fil: Páez, Alexander. Universidad Pedagógica y Tecnológica de Colombia; ColombiaFil: Rojas, Hugo A.. Universidad Pedagógica y Tecnológica de Colombia;Fil: Portilla Zúñiga, Omar Miguel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; ArgentinaFil: Sathicq, Angel Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; ArgentinaFil: Afonso, Carlos A. M.. Universidade de Lisboa; PortugalFil: Romanelli, Gustavo Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; ArgentinaFil: Martínez, José J.. Universidad Pedagógica y Tecnológica de Colombia; Colombi

5-Hydroxymethylfurfural Content in Selected Food Products

5-hydroxymethylfurfural (HMF) is a common component of heat treated, drying or stored for a long time food products. It is an intermediate product formed in the Maillard reaction as a result of thermal dehydration of reducing sugars (1-2). HMF is also formed during caramelisation while degradation of carbohydrates at high temperature (3). HMF is responsible for the sensory properties of food, especially for the pleasant flavor. Although it is relatively safe food component, there are reports regarding toxic, mutagenic and carcinogenic properties of HMF, and of 5-sulphoxymethylfurfural especially, an allylic sulfuric acid ester metabolite from HMF (4-6). The content of HMF in the various products vary within a wide range and depends on the food group type as well as the type of processing. In present work, the HMF content in different types of breakfast cereals, cookies and muesli as well as in several types of bakery products commercially available in Poland was determined. In addition, the influence of flavor and taste additives (honey, cocoa, dry fruits) as well as the type of cereals (gluten or gluten-free) on the HMF content in the tested products was examined

Conversion of furan derivatives for preparation of biofuels over Ni-Cu/C catalyst

Conversions of furfural and 5-hydroxymethylfurfural as model components in bio-oil were investigated over Ni-Cu/C catalyst with formic acid as hydrogen donor in isopropanol solvent to produce biofuels. The effects of reaction temperature, feed ratio, and reaction time were studied. A high yield of 2-methylfuran up to 91 mol% was obtained from furfural in 8 h at 200 degrees C, and under same conditions 80 mol% yield of 2,5-dimethylfuran could also be obtained from 5-hydroxymethylfurfural in 6 h. The results verified the catalyst performance and the availability of the reaction conditions for producing biofuels from furan derivatives.</p

Evolution of physicochemical parameters during the thermal-based production of água-mel, a traditional Portuguese honey-related food product

The purpose of this work was to investigate the physicochemical changes occurring during the thermal-based production of água-mel, a traditional Portuguese honey-related food product. The refractive index, color parameters (hue angle, H°; chroma, C*), and the content of total reducing sugars, glucose, fructose, total brown pigments, and 5-hydroxymethylfurfural were monitored along the entire production process, and their evolution was kinetically modelled. Thermal processing caused a gradual decrease in sugars, which was accompanied by the formation of brown pigments and 5-hydroxymethylfurfural, increased concentration of soluble solids as evaluated through refractive index measurements, as well as the appearance of darker colors. In particular, a zero-order kinetic model could explain the changes in H° and reducing sugars, while the evolution of refractive index, brown pigments, 5-hydroxymethylfurfural, C*, fructose, and glucose were best fitted using a first-order kinetics model.This research was funded by FCT—Foundation for Science and Technology (UIDB/04020/2020) and Proyectos de Cooperación Transfronteriza en la Eurorregión Alentejo-Algarve-Andalucia (“Caracterización de mieles y productos derivados (água-mel) en el suroeste de la península ibérica. Estudio de su potencial biológico”)info:eu-repo/semantics/publishedVersio

Development of covalent triazine frameworks as heterogeneous catalytic supports

Covalent triazine frameworks (CTFs) are established as an emerging class of porous organic polymers with remarkable features such as large surface area and permanent porosity, high thermal and chemical stability, and convenient functionalization that promotes great potential in heterogeneous catalysis. In this article, we systematically present the structural design of CTFs as a versatile scaffold to develop heterogeneous catalysts for a variety of chemical reactions. We mainly focus on the functionalization of CTFs, including their use for incorporating and stabilization of nanoparticles and immobilization of molecular complexes onto the frameworks