Furfuryl alcohol

Photolysis of atrazine: Role of triplet dissolved organic matter and limitations of sensitizers and quenchers.[Pubmed:33279742]

Water Res. 2020 Nov 20;190:116659.

Atrazine, a widely used herbicide, is susceptible to photolysis. The role of triplet excited states of chromophoric dissolved organic matter ((3)CDOM*) in the photolysis of atrazine, however, is not well understood. The direct photolysis of atrazine under irradiation sources (natural sunlight/environmentally relevant simulated solar light) and its indirect photochemical reactivity with model triplet photosensitizers (benzophenone, 2-acetonaphthone, 3'-methoxy-acetophenone, 4-carboxybenzophenone, rose bengal, methylene blue, and anthraquinone-2-sulphonate) was investigated. The reactivity of the model sensitizers and DOM (Suwannee River natural organic matter, river/lake water, and wastewater effluent), were compared. The direct photolysis quantum yield was determined as 0.0196 mol Einstein(-1) in a solar simulator and 0.00437 mol Einstein(-1) under natural sunlight. Considerable photosensitization was induced by triplet state (n-pi*) model sensitizers, while insignificant effects on atrazine loss were discerned in natural organic matter even when oxygen, a triplet quencher, was removed. The triplet sensitizers benzophenone and 2-acetylnaphthone reacted with L-histidine and 2-propanol that were intended to quench/ scavenge (1)O2 and hydroxyl radical (*)OH, respectively, and benzophenone reacted with NaN3 as a (1)O2 scavenger and Furfuryl alcohol as a (1)O2 trapping agent, indicating quenchers may have unanticipated effects when using model sensitizers. Atrazine loss via reaction with (3)DOM* will be relevant only in selected conditions, and this work provides a more comprehensive view on the use of model photosensitizers to mimic triplet (3)DOM*.

A Resol-assisted Cationic Coordinative Co-assembly Approach to Mesoporous ABO3 Perovskite Oxides with Rich Oxygen Vacancy for Enhanced Hydrogenation of Furfural to Furfuryl Alcohol.[Pubmed:33244843]

Angew Chem Int Ed Engl. 2020 Nov 26.

The design of ABO 3 perovskite oxides with porous mesostructure and unique surface active sites for heterogeneous catalysts holds great promise in various catalytic applications. However, it is still a challenge to get ABO 3 perovskite oxides with favourable crystal phase and well-defined porous structure via existing approaches. Here, we design an effective and versatile strategy to construct mesoporous ABO 3 perovskite oxides with functionalized nanocrystal frameworks and abundant oxygen vacancy sites via a resol-assisted cationic coordinative co-assembly approach. The as-prepared oxygen vacancy-rich mesoporous LaMnO 3 as heterogeneous catalyst exhibits remarkable catalytic activity and stability for hydrogenation of furfural to Furfuryl alcohol, including over 99% conversion and 96% selectivity. Combined with density functional theory calculation, the catalytic mechanism is elucidated, revealing that porous LaMnO 3 nanocrystal framework is conducive to expose oxygen deficiency sites, which can facilitate the interaction between catalyst surface and catalytic substrate, leading to lower barrier in hydrogenation process.

Fully Automated Identification of Coffee Species and Simultaneous Quantification of Furfuryl Alcohol Using NMR Spectroscopy.[Pubmed:33241277]

J AOAC Int. 2020 Apr 1;103(2):306-314.

BACKGROUND: Coffee is a popular beverage with two species, Coffea canephora and C. arabica, being commercially exploited. The quality and commercial value of coffee is dependent on species and processing. C. arabica typically obtains a higher price on the market compared to C. canephora. Coffee beans undergo roasting during processing, resulting in the formation of flavor compounds including Furfuryl alcohol which has been classified by the International Agency for Research on Cancer as possibly carcinogenic to humans (Group 2B). OBJECTIVE: The aim of this study was to identify coffee species and other properties using nuclear magnetic resonance (NMR) spectroscopy, specifically to conduct quantification of the roasting process contaminant Furfuryl alcohol. METHOD: The quantification of Furfuryl alcohol was performed from the NMR spectra using the pulse length-based concentration (PULCON) methodology. Prior to NMR analysis, samples were extracted using deuterated chloroform. RESULTS: Roasting experiments identified the maximum roasting temperature to be the most significant factor in the formation of Furfuryl alcohol. Among the coffee species, C. canephora was found to contain a relatively lower amount of Furfuryl alcohol compared to C. arabica. The roasting of wet processed coffee resulted in higher contents of Furfuryl alcohol. Geographical origin and variety within species had no influence on the Furfuryl alcohol content. CONCLUSION: Validation results show that NMR spectroscopy is fit-for-purpose to obtain targeted information of coffee samples. HIGHLIGHTS: The PULCON NMR methodology allows a simple, rapid and accurate determination of constituents of coffee.

Gas chromatography-mass spectrometry based untargeted volatolomics for smoked seafood classification.[Pubmed:33233272]

Food Res Int. 2020 Nov;137:109698.

With the increase of the demand of low flavouring smoked seafood products, there is a need of methodologies able to distinguish between different seafood treatments, as not all of them are allowed in all markers. Following this objective, in the present work an untargeted volatolomics approach was applied to identify volatile markers that demonstrate that Cold smoked products can be distinguished from Tasteless smoke neither Carbon monoxide treated seafood, which are prohibited in the European Union. The use of dynamic headspace for the volatile extraction followed by thermal desorption in combination with Gas Chromatography (GC) coupled to single quadrupole Mass Spectrometry (MS) has been employed for the determination of volatile composition of smoked fish. Data processing consisted on the use of PARADISe software, applied for GC/MS data treatment, followed by the multivariate analysis with PLS_Toolbox (MATLAB), and finally the creation and validation of statistical classification model. All 107 variables obtained allowed the construction of a model reaching the correct classification of 97% of the blind samples, while a simplified model with only 11 variables correctly classified up to 93% of the blind samples. These 11 compounds were elucidated to develop subsequent target volatolomics approaches, if needed. Ordered according to the importance in the classification model, the elucidated compounds were: 3-methyl-cyclopentanone, ethylbenzene, 2-methyl-2-cyclopenten-1-one, 2-methyl-benzofuran, Furfuryl alcohol, 2-acetylfuran, acetophenone, guaiacol, 1-hydroxy-2-butanone, 4-vinylguaicol and acetoin. The results demonstrated the great potential of untargeted volatolomics for smoked seafood treatments classification.

Investigation on the mitigation effects of furfuryl alcohol and 5-hydroxymethylfurfural and their carboxylic acid derivatives in coffee and coffee-related model systems.[Pubmed:33233124]

Food Res Int. 2020 Nov;137:109444.

The mitigation of Furfuryl alcohol, 5-hydroxymethylfurfural, 2-furoic acid, and 5-hydroxymethyl 2-furoic acid was conducted in two dry model systems mimicking coffee and an actual coffee system by incorporating 14 chemicals, that are categorized to phenolic acids, flavonoids, non-phenolic antioxidants, and non-antioxidant agents. Mitigation effects were determined as the decrease in the levels of the studied furan derivatives after the systems went through a controlled roasting process. Strong mitigation effects in the dry model systems were observed after the application of phenolic acids, quinic acid or EDTA. The mitigation effects of phenolic acids and flavonoids depended on the number and availability of phenolic hydroxyl groups. Certain agents exhibited a furan derivative-specific reducing effect while most of them showed a generalized effect. The mitigation efficacy decreased with the increasing complexity of the tested systems. In the coffee system, mitigation effects were almost completely lost in comparison with dry model systems. Still, taurine and sodium sulfite exerted the strongest mitigation effect in the coffee system.

Ambient Temperature Self-Blowing Tannin-Humins Biofoams.[Pubmed:33213107]

Polymers (Basel). 2020 Nov 17;12(11). pii: polym12112732.

Ambient temperature self-blowing tannin-furanic foams have been prepared by substituting a great part-even a majority-of Furfuryl alcohol with humins, a polyfuranic material derived from the acid treatment at high temperature of fructose. Closed-cell foams were prepared at room temperature and curing, while interconnected-cell foams were prepared at 80 degrees C and curing, this being due to the more vigorous evaporation of the solvent. These foams appear to present similar characteristics as other tannin-furanic foams based only on Furfuryl alcohol. A series of tannin-humins-Furfuryl alcohol oligomer structures have been defined indicating that all three reagents co-react. Humins appeared to react well with condensed tannins, even higher molecular weight humins species, and even at ambient temperature, but they react slower than Furfuryl alcohol. This is due to their high average molecular weight and high viscosity, causing their reaction with other species to be diffusion controlled. Thus, small increases in solvent led to foams with less cracks and open structures. It showed that Furfuryl alcohol appears to also have a role as a humins solvent, and not just as a co-reagent and self-polymerization heat generator for foam expansion and hardening. Stress-strain for the different foams showed a higher compressive strength for both the foam with the lowest and the highest proportion of humins, thus in the dominant proportions of either Furfuryl alcohol or the humins. Thus, due to their slower reactivity as their proportion increases to a certain critical level, more of them do proportionally participate within the expansion/curing time of the foam to the reaction.

Crystal facet-dependent activity of h-WO3 for selective conversion of furfuryl alcohol to ethyl levulinate.[Pubmed:33205795]

Phys Chem Chem Phys. 2020 Dec 7;22(46):26923-26934.

The use of WO3 as an acid catalyst has received extensive attention in recent years. However, the correlation between the catalytic activity and the predominantly exposed surface with varied acidic sites needs further understanding. Herein, the effects of the Bronsted and Lewis acid sites of different crystal facets of WO3 on the catalytic conversion of Furfuryl alcohol (FA) to ethyl levulinate (EL) in ethanol were investigated in detail. A yield of EL up to 93.3% over WO3 with the (110) facet exposed was achieved at 170 degrees C, while FA was mainly converted to polymers over (001) faceted nanosheets and nanobelts with exposed (002) and (100) facets. This was attributed to the different distribution of the acidic sites on different exposed crystal facets. The (110) faceted WO3 possessed abundant and strong Bronsted acid sites, which favored the conversion of FA to EL, while the (100) faceted WO3 with stronger Lewis acid sites and weaker Bronsted acid sites mainly led to the formation of polymers. In addition, the (110) faceted WO3 showed excellent sustainability in comparison with the (100) faceted counterpart.

Collaborative Conversion of Biomass Carbohydrates into Valuable Chemicals: Catalytic Strategy and Mechanism Research.[Pubmed:33196190]

J Agric Food Chem. 2020 Nov 25;68(47):13760-13769.

Levulinate is one of the high added-value biomass-derived chemicals that is primarily produced from hexoses in cellulose and hemicellulose. Producing levulinate from pentoses in hemicellulose that is extensively distributed in biomass is still highly challenging. In this study, biomass materials and carbohydrates (including cellulose, xylan, glucose, fructose, and xylose) were collaboratively converted into levulinates efficiently over various zeolites with ethanol/dimethoxymethane as cosolvents. The key process for converting pentoses into levulinates is the synthesis of intermediates (furfural) into alkoxy methyl furfural via electrophilic substitution or their conversion into Furfuryl alcohol via in situ hydrogenation. The substitution was achieved by the synergic effect between bifunctional catalysts and cosolvents, which promotes conversion of furfural into alkoxy methyl furfural via the electrophilic addition of alkoxy methyl radicals. Hydrogenation of furfural into Furfuryl alcohol was impelled by the cooperative process between in situ generated H-donor from alcohol solvents and zeolite catalysts. Moreover, a favorable yield of 21.05 mol % of levulinates was achieved by simultaneous and collaborative conversion of cellulose and hemicellulose with the one-pot process using ethanol/dimethoxymethane as a cosolvent and the zeolite with B and L acid sites as a catalyst.

Current Approaches to Alkyl Levulinates via Efficient Valorization of Biomass Derivatives.[Pubmed:33195025]

Front Chem. 2020 Oct 15;8:794.

Biomass is a potential non-food, carbon-neutral, and abundant resource, which can be used as an alternative to fossil fuels during the sustainable preparation of various platform chemicals. Alkyl levulinates (ALs) have found widespread application as flavorings, plasticizing agents, and fuel additives, as well as synthetic precursors to various building blocks. Several processes have been investigated to transform biomass and its derivatives into ALs, which mainly include: (i) direct esterification of levulinic acid (LA) with alkyl alcohols and (ii) alcoholysis reactions of renewable biomass feedstocks and their derivatives, including Furfuryl alcohol (FAL), chloromethyl furfural (CMF), and saccharides. This review focuses on illustrating the effects of the biomass pretreatment step, catalyst texture, possible mechanisms, acidities, and intermediates on the synthesis of ALs from sustainable resources covering a wide range of intermediates, including diethyl ether (DEE), 4,5,5-triethoxypentan-2-one (TEP), ethoxymethylfuran (EMF), ethyl-D-fructofuranoside (EDFF), and ethyl-D-glucopyranoside (EDGP).

Catalytic conversion of corncob to furfuryl alcohol in tandem reaction with tin-loaded sulfonated zeolite and NADPH-dependent reductase biocatalyst.[Pubmed:33120059]

Bioresour Technol. 2020 Oct 16;320(Pt A):124267.

In this study, tin-loaded sulfonated zeolite (Sn-zeolite) catalyst was synthesized for catalysis of raw corncob (75.0 g/L) to 103.0 mM furfural at 52.3% yield in water (pH 1.0) at 170 degrees C. This corncob-derived furfural was subsequently biotransformed with recombinant E. coli CG-19 cells coexpressing NADPH-dependent reductase and glucose dehydrogenase at 35 degrees C by supplementary of glucose (1.5 mol glucose/mol furfural), sodium dodecyl sulfate (0.50 mM) and NADP(+) (1.0 mumol NADP(+)/mmol furfural) in the aqueous catalytic media (pH 7.5). Both sodium dodecyl sulfate (0.50 mM) and Sn(4+) (1.0 mM) could promote reductase activity by 1.4-folds. Within 3 h, furfural was wholly catalyzed into Furfuryl alcohol. By combining chemical catalysis with Sn-zeolite and biocatalysis with CG-19 cells in one-pot, an effective and sustainable process was established for tandemly catalyzing renewable biomass into Furfuryl alcohol under environmentally-friendly way.

Preparation and evaluation of mushroom (Lentinus edodes) and mealworm (Tenebrio molitor) as dog food attractant.[Pubmed:33102877]

Heliyon. 2020 Oct 20;6(10):e05302.

Chicken liver is a main protein source to prepare attractant for dog food. However, animal proteins are costly. Seeking high quality and low-cost protein sources has been a goal for the industry. Mushroom Lentinus edodes (L. edodes) and Mealworm Tenebrio molitor (T. molitor) are novel protein sources, showing high potential as raw material of attractants. In this paper, chicken liver, L. edodes, and T. molitor were used as three different protein sources to prepare attractants. Their palatability to dogs were then compared. Firstly, the enzymatic hydrolysis process of three proteins was optimized, with a degree of hydrolysis of 54.82%, 36.10% and 30.14% for chicken liver, L. edodes, and T. molitor respectively. Secondly, volatile compounds of three attractants were identified by HS-SPME/GC-MS and SDE/GC-MS. Using OAV and PLRS method, it was found that bis(2-methyl-3-furyl) disulfide, indole, methional, 2-(methyl thio) phenol, gamma-butyrolacton, Furfuryl alcohol, acetic acid and isovaleraldehyde were the key components. Although both T. molitor and L. edodes attractant showed less palatability than that of chicken liver, they could be readily improved via adding key palatable volatile compounds. The ingestion rate of dog food with attractant showed a similar trend and was higher than that of food without attractant.

Comprehensive utilization of corncob for furfuryl alcohol production by chemo-enzymatic sequential catalysis in a biphasic system.[Pubmed:33010718]

Bioresour Technol. 2021 Jan;319:124156.

A new process for the production of Furfuryl alcohol from corncob was constructed by using deep eutectic solvents and whole cell catalysis in this paper. Firstly, the corncob was treated with deep eutectic solvents to convert the xylan into furfural, and then the pretreated corncob residue was enzymatically hydrolyzed to obtain a glucose-rich enzymatic hydrolysate, which was used to provide NADH for Bacillus coagulans NL01 during the process of furfural reduction. The furfural yield could reach 46% using the selected choline chloride-oxalic acid as catalysts and corncob as substrate under the optimized catalytic condition at 120 degrees C for 30 min. The final Furfuryl alcohol yield of 20.7% was achieved with corncob as substrate. Moreover, this catalytic system realized the recycling of deep eutectic solvents three times, the high-value production of Furfuryl alcohol, and the comprehensive utilization of corncob.

Characterization of the Soluble Products Formed during the Hydrothermal Conversion of Biomass-Derived Furanic Compounds by Using LC-MS/MS.[Pubmed:32954183]

ACS Omega. 2020 Sep 1;5(36):23322-23333.

To reveal the hydrothermal conversion routes of the biomass-derived furanic compounds, the soluble products formed during the hydrothermal conversion of 5-hydroxymethylfurfural (HMF), furfural, and Furfuryl alcohol were analyzed by liquid chromatography-mass spectrometry (LC-MS) and LC-MS/MS. Multiple carbocyclic compounds containing hydroxy group and carbonyl group were detected, with a molecular mass in the range of 154-272 Da and carbon chain of the length 8-15. The formation of these soluble carbocyclic compounds was proposed to involve hydrolytic ring-opening of the furanic ring, intermolecular aldol condensation, intramolecular aldol condensation, and C-C cleavage reaction. The C-C cleavage reaction was proposed to occur on the dicarbonyl structure of the formed primary polymers.

Hydrophobic Formulations Based on Tall Oil Distillation Products for High-Density Fiberboards.[Pubmed:32927923]

Materials (Basel). 2020 Sep 10;13(18). pii: ma13184025.

This study investigates the effect of renewable formulations based on tall oil bio-refinery products on the water vapor sorption and interfiber strength of cellulosic fibers as well as on the properties of high-density fiberboard (HDF) panels. The results obtained for HDF prepared using renewable formulations were compared to the results for HDF obtained using conventional synthetic paraffin wax (hydrowax), which is the hydrophobic agent currently utilized by the industry. Four tall oil distillation products (TODPs) with different levels of fatty and rosin acids were used for preparing the hydrophobic formulations with Furfuryl alcohol as an organic solvent. According to determinations with an automated vapor sorption apparatus, the formulations had a similar effect with hydrowax on the sorption behavior of natural fibers. Unlike to hydrowax treatment, the ultimate tensile strength of cellulosic paper-sheets treated with the formulations remained unchanged or significantly increased. At the standard addition load of 1% (wt/wt dry fibers) of the formulations, HDF panels showed comparable and only in one case, e.g., TODP3-based formulation, slightly higher thickness swelling (24 h) than those with hydrowax. The best performing formulation (TODP2-based) in terms of tensile strength of paper sheets did not significantly change the mechanical properties of HDF panels in both standard climate and high humid conditions. Promising results at the standard and humid climate conditions were obtained for HDF panels manufactured with higher TODP2-based formulation amounts (3-5%) and reduced melamine-urea-formaldehyde resin content (10-12% instead of 14%, wt dry resin/wt dry fibers).

Furfuryl alcohol is a precursor for furfurylthiol in coffee.[Pubmed:32920267]

Food Chem. 2021 Feb 1;337:128008.

This study investigated the role of Furfuryl alcohol (FFA) in the formation of furfurylthiol (FFT), the most important odorant in roasted coffee, using in-bean and spiking experiments. Green beans were spiked with FFA, and after roasting FFT was quantified by stable isotope dilution analysis. The FFT level in the roasted beans increased dose-dependently with addition of FFA. Additionally, beans were spiked with isotopically labelled d2-FFA which generated isotopically labelled d2-FFT after roasting. However, no labelled furfural was observed. The results unambiguously show that FFA serves as a precursor of FFT in coffee. On the other hand, the data indicate that furfural stems not from oxidation of FFA and plays no major role as precursor for FFT formation during coffee roasting. The suggested formation pathway leads from FFA to the furfuryl cation, then protein-bound S-furfuryl-l-cysteine and by subsequent elimination to FFT.