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1.
ChemSusChem ; : e202400638, 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39248204

RESUMEN

The transformation from fossil resources, crude oil and natural gas to biomass-derived feedstocks is an urgent and major challenge for the chemical industry. The valorization of lignocellulose as renewable resource is a promising pathway offering access to a wide range of platform chemicals, such as vanillin, furfural and 5-HMF. The subsequent conversion of such platform chemicals is one crucial step in the value-added chain. The electrochemical hydrodimerization (EHD) is a sustainable tool for C-C coupling of these chemicals to their corresponding hydrodimers hydrovanilloin, hydrofuroin and 5,5´-bis(hydroxymethyl)hydrofuroin (BHH). This review covers the current state of art concerning the mechanism of the electrochemical reduction of biobased aldehydes and studies targeting the electrochemical production of these hydrodimers in aqueous media. Moreover, the subsequent conversion of these hydrodimers to valuable additives, polymers and long carbon chain synfuels will be summarized offering a broad scope for their application in the chemical industry.

2.
Heliyon ; 10(16): e36100, 2024 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-39224380

RESUMEN

Static infusion of oak chips in wine is a common practice during wine ageing, aimed at improving sensory properties and stability of wines. The wine/chips contact required to reach the desired effect can last several weeks or months. A low-pressure continuous dynamic (LPCD) extractor in which a closed-circle, low-pressure continuous flow of wine passes through an extraction cell filled with chips, was evaluated as a tool to tune red wine properties in few hours. The aim of this work was to evaluate the effect of the use of a LPCD extractor the effect on color, volatile compounds and sensory properties of a Primitivo wine, as well as to assess the combined effect of LPCD extractor, passive microxygenation through polyethylenetereftalate (PET) containers and exogenous tannins. Their combined effect caused a significant increase of stabilized pigments was observed, without compromising the aroma profile. LPCD extraction, passive micro-oxygenation through plastic materials and enological tannins can be considered as a low-cost, and potentially low-impact, integrated technological platform suitable to tune wine sensory properties and stability, when either traditional approaches (such as barrel aging) or other assisted extraction technologies are not applicable or preferred, even in small wineries.

3.
Talanta ; 281: 126854, 2024 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-39260253

RESUMEN

Assessing the levels of furfural in insulating oils is a crucial technical method for evaluating the degree of aging and mechanical deterioration of oil-paper insulation. The surface-enhanced Raman spectroscopy (SERS) technique provides an effective method for enhancing the sensitivity of in-situ detection of furfural. In this study, a homogeneous three-dimensional (3D) urchin-like Au@W18O49 heterostructure was synthesized as a SERS substrate using a straightforward hydrothermal method. The origin of the superior Raman enhancement properties of the 3D urchin-like heterostructures formed by the noble metal Au and the plasmonic semiconductor W18O49, which is rich in oxygen vacancies, is analyzed experimentally in conjunction with density-functional theory (DFT) calculations. The Raman enhancement is further amplified by the remarkable dual localized surface plasmon resonance (LSPR) effect, which generates a strong local electric field and creates numerous "hot spots," in addition to the interfacial charge transport (CT). The synergistic effect of these factors results in the 3D urchin-like Au@W18O49 heterostructure exhibiting exceptionally high SERS activity. Testing the rhodamine 6G (R6G) probe resulted in a Raman enhancement factor of 3.41 × 10-8, and the substrate demonstrated excellent homogeneity and stability. Furthermore, the substrate was effectively utilized to achieve highly sensitive in-situ surface-enhanced Raman scattering (SERS) detection of dissolved furfural in complex plant insulating oils. The development of the 3D urchin-like Au@W18O49 heterostructure and the exploration of its enhancement mechanism provide theoretical insights for the advancement of high-performance SERS substrates.

4.
ChemSusChem ; : e202401390, 2024 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-39261279

RESUMEN

2,5-furandicarboxylic acid (FDCA) is an important organic platform compound that has been widely used in the fields of medicine, pesticides, dyes, plastics and resins due to its unique structure and properties. In recent years, with the emphasis on sustainable development and green chemistry, the synthesis of FDCA from biomass has attracted extensive attention. The catalytic conversion of furfural (FF) to FDCA has the advantages of easy availability of the raw material, environmental friendliness, economic feasibility and so on, which is an important direction for FDCA synthesis in the future. This paper mainly reviews the prepare pathways of furoic acid (FA) and FDCA using FF as a starting material, including the selective conversion of FF and FA to target products under different types of catalysts. First, the research progress in the synthesis of FA from FF was summarized, and then the advances in the catalytic conversion of FA to FDCA was reviewed. In addition, the development of efficient and green catalysts and the optimization of existing synthesis protocols are emphasized as key factors to improve the yield and purity of FDCA while reducing production costs. Finally, the opportunities and challenges were discussed.

5.
Carbohydr Res ; 545: 109258, 2024 Sep 12.
Artículo en Inglés | MEDLINE | ID: mdl-39278155

RESUMEN

Although the xylose mutarotation and transformation have been investigated largely separately, their relationship has been rarely systematically elaborated. The effect of several factors such as xylose concentration, temperature, and salt concentration, affecting the mutarotation of xylose are discussed. Nine alkali halides (LiCl, NaCl, KCl, LiBr, NaBr, KBr, LiI, NaI, and KI) are used to test salt effects. The relationship between xylose rotation rate constant (kM), specific optical rotation at equilibrium ([α]eqm), α/ß ratio, H chemical shift difference (ΔΔδ), Gibbs free energy difference (ΔG), hydrogen ion or hydroxide ion concentration ([H+] or [OH-]), and xylose conversion is discussed. Different salts dissolved in water result in different pH of the solutions, which affect the mutarotation of xylose, with the nature of both cation and anion. Shortly, the smaller the cation radius is and the larger the anion radius is, the greater the mutarotation rate is. In the dehydration of xylose to furfural in salty solutions, xylose conversion is positively correlated to mutarotation rate, H+ or OH- concentration, and the energy difference between α-xylopyranose and ß-xylopyranose. Although the [α]eqm of xylose is positively correlated with α/ß configuration ratio, there is no obvious correlation with xylose dehydration. The conversion to furfural in chlorides is superior to that in bromines and iodides, which is due to the fact that the pH of chloride salts is smaller than that of the corresponding bromide and iodized salts. Higher H+ concentration prefers to accelerate the formation of furfural. In basic salt solutions, the xylulose selectivity is higher than that of furfural at the initial stage of reaction. The furfural selectivity and carbon balance are better in acidic condition rather than in basic condition. In H2O-MTHF (2-Methyltetrahydrofuran) biphasic system, the optimal furfural selectivity of 81.0 % is achieved at 190 °C in 1 h with the assistance of LiI and a little HCl (0.2 mmol, 8 mmol/L in aqueous phase). A high mutarotation rate represents rapid xylose conversion, but a high furfural selectivity prefers in acidic solutions, which would be perfect if organic solvents were available to form biphasic systems.

6.
Food Chem X ; 23: 101777, 2024 Oct 30.
Artículo en Inglés | MEDLINE | ID: mdl-39295964

RESUMEN

Aging is an important process for improving wine and brandy quality. In this study, the chemical characterization and sensory properties of spine grape brandies were compared after aging with various species of wood chips, including French oak (FO), American oak (AO), Mongolian oak (MO), Japanese blue oak (JO), chestnut, catalpa, and cherry. The results showed that high color intensity and significant concentrations of tannins and polyphenols were observed in the brandies aged with FO, AO, and chestnut chips. The volatile compounds, such as ethyl decanoate, ethyl 2-methylbutanoate, ethyl octanoate, methyl salicylate, (Z)-2-hexenol, and furfural, contributed to the floral, fruity, and roasted/smoky attributes of the brandies aged with FO, AO, and chestnut chips. The 1-butanol, 1-propanol, phenylethanol, phenylethyl acetate, isoamyl acetate, and linalool contributed to the fruity, honey, and floral attributes of the brandies aged with JO and cherry chips. These findings are extremely useful for the production of differentiated and high-quality spine grape brandies.

7.
Heliyon ; 10(17): e37550, 2024 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-39296078

RESUMEN

Iran, a leading honey-producing country, faces challenges in honey exports. This study aimed to evaluate the melissopalynological and physicochemical characteristics of local honeys belonging to Iranian flora, and compare them with Iranian commercial honeys. For this purpose, seven local honey samples were collected from Iran's renowned floristic regions, alongside seven commercial multi-floral honeys from a supermarket. Moisture content (MC), total solids (TS), pH, free acidity (FA), ash, electrical conductivity (EC), sugar profile, hydroxymethyl furfural (HMF), diastase number (DN), and proline were assessed. The sugar profile was analyzed by high-performance liquid chromatography with a refractive index detector (HPLC-RID). Pollen analysis classified local honeys as multi-floral. The results revealed that MC, TS, pH, FA, ash, and EC values in both local and commercial samples conformed to approved standards (Codex Alimentarius and European Union). Two local and one commercial sample exclusively satisfied the sucrose standard level. Of the local honeys, two samples complied with HMF standard, while five fulfilled DN criterion, and four had proline values within acceptable ranges. Conversely, HMF (56.32-228.11 mg/kg), DN (3.13-7.22 Schade units/g), and proline (109.84-173.86 mg/kg) levels in all commercial samples failed to meet the standard. A significant correlation was found between ash and EC (r = 0.915, p < 0.01) in local honeys, whereas no strong correlation (r = 0.299) existed in commercial samples. Hierarchical cluster analysis confirmed that Iranian honeys lacked clustering by botanical origin, possibly due to extensive sugar adulteration or thermal treatment. Overall, study findings confirmed the significantly inferior quality of Iranian commercial honeys compared to local varieties, albeit some local samples also exhibited quality concerns. Accordingly, it is recommended that regulatory bodies provide periodic training for beekeepers and establish monitoring programs to enhance honey quality, thereby boosting Iran's share in the global honey export market.

8.
Chemphyschem ; : e202400628, 2024 Sep 18.
Artículo en Inglés | MEDLINE | ID: mdl-39292518

RESUMEN

The burgeoning field of frustrated Lewis pair (FLP) heterogeneous catalysts has garnered significant interest in recent years, primarily due to their inherent ability to activate H-source molecules, such as H2, thereby facilitating hydrogenation reactions. However, the application of single metal atom catalysts incorporating FLP sites has been relatively under-explored. In this study, non-precious transition metal atoms were anchored onto a C2N framework with an intrinsic cavity and a defective N-C sheet. Theoretical calculations substantiated energy barriers as low as 0.10 eV for isopropanol activation, thereby positioning these catalysts as highly promising candidates for catalytic transfer hydrogenation of furfural. Electronic structure analyses revealed that the H-O bond breakage in isopropanol molecules was significantly facilitated by the presence of FLP sites within the catalysts. Notably, both Ni-C2N and Ni-N6-C demonstrated exceptional potential as selective catalysts for the hydrogenation of furfural into furfuryl alcohol, exhibiting remarkably low barriers of only 0.65-0.72 eV for the rate-determining steps, which are notably lower than those observed in many traditional catalysts. Theoretical investigations strongly imply that the construction of single atom catalysts with FLP sites could significantly enhance the activity and selectivity for hydrogenation reactions, thus stimulating the experimental synthesis of such catalysts.

9.
Chempluschem ; : e202400343, 2024 Sep 04.
Artículo en Inglés | MEDLINE | ID: mdl-39231200

RESUMEN

The development of platform chemicals derived from biomass, in particular, 5-hydroxymethylfurfural (5-HMF) and furfural (FUR), is of crucial importance in biorefinery. Over the past decades, metal-supported nanostructured zeolites, in particular, metal-supported hierarchically porous zeolites or metal-encapsulated zeolites, have been extensively elaborated because of their multiple functionalities and superior properties, for example, shape-selectivity, (hydro)thermal stability, tunable acidity and basicity, redox properties, improved diffusion, and intimacy of multiple active sites. In this review, the effects of such properties of metal-supported nanostructured zeolites on the enhanced catalytic performances in furanic compound upgrading are discussed. In addition, the recent rational design of metal-supported nanostructured zeolites is exemplified. Consequently, the ongoing challenges for further developing metal-supported nanostructured zeolites-based catalysts and their applications in HMF and FUR upgrading are identified.

10.
Heliyon ; 10(15): e35077, 2024 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-39157344

RESUMEN

This comprehensive review explores furfural production from agricultural residues, focusing on its significance as a low-volume, high-value asset crucial for environmental sustainability. It covers diverse production technologies, recent advancements, and applications in agriculture, evaluating furfural's potential to enhance crop resilience and yield. Showing its role in a circular economy, the review discusses how furfural can replace conventional petrochemical processes, thereby reducing environmental impact. Case studies, such as successful implementations with cotton biomass byproducts, illustrate furfural's practical applications and environmental benefits. The study underscores the need for ongoing research, supportive policies, and furfural's growing role in sustainable agriculture and industry. It is focused on furfural's essential contribution to promoting environmental stewardship and sustainable practices. By examining furfural's role as a value-added product from agricultural residues, this review provides insights into its economic viability and potential challenges.

11.
Talanta ; 279: 126660, 2024 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-39116733

RESUMEN

Detecting the furfural concentration in Baijiu can be used to assess the quality of Baijiu, allowing for the optimization of processing techniques and the enhancement of overall quality. In this paper, a fluorescence-enhanced method based on carbon dots (o-CDs) is developed for the furfural determination in Chinese Baijiu. In an environment full-filled with ·SO4- and ·OH, furfural undergone a direct surface reaction with the ortho-diamino groups at o-CDs. The created furan-based imidazole increased the surface electron density, leading an emission enhancement and color changes from orange to green. Thereby, a linear fluorescence response of o-CDs-TA to furfural is established in water with a detection limit of 30.5 nM. Finally, after ethanol correction it is used to determine furfural in Chinese Baijiu with high precision and reproducibility, providing a new strategy with low-cost and high sensitivity. In particular, the idea of covalently connecting target molecule to the CDs surface via the assistance of free radical opens a new avenue to merge the nanoscale and molecular realms through implementing chemical role into carbon nanostructures.

12.
Carbohydr Polym ; 343: 122420, 2024 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-39174113

RESUMEN

A novel biphasic system containing water-soluble deep eutectic solvent (DES) and cyclopentyl methyl ether (CPME) was developed to treat Eucalyptus for furfural production, extracting lignin and enhancing cellulose enzymatic hydrolysis. Herein effect of DES type, water content in DES, temperature and time on furfural yield in water-soluble DES/CPME pretreatment process was firstly evaluated. A maximum furfural yield of 80.6 % was attained in 10 min at 150 °C with choline chloride (ChCl)/citric acid monohydrate (CAM)/CPME system containing 30 wt% water and 2.5 wt% SnCl4·5H2O, which was higher than that obtained from ChCl/CAM/CPME system without water (55.5 %) and H2O/CPME system (49.7 %). These results demonstrated that the water-soluble DES/CPME system was a powerful method enhancing the furfural production. Under the optimal pretreatment conditions, the delignification and glucose yield were reached to 72.7 % and 94.3 %, respectively. The extracted lignin showed low molecular weight and ß-aryl-ether was obviously cleaved. Additionally, water-soluble DES/CPME pretreatment led to a significant removal of hemicelluloses (100.0 %) and lignin (72.7 %) and introduced morphological changes on cell walls, especially from the cell corner (CC) and secondary wall (SW) layers. Overall, this work proposed a practical one-step fractionation strategy for co-producing furfural, lignin and fermentable sugar, providing a way to biorefinery.

13.
J Biosci Bioeng ; 138(4): 314-323, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39098474

RESUMEN

Economically feasible ethanol production requires efficient hydrolysis of lignocellulosic biomass and high-temperature processing to enable simultaneous saccharification and fermentation. During the lignocellulolysic hydrolysate, the yeast must encounter with a multiple of inhibitors such as heat and furfural. To solve this problem, a potential fermentative yeast strain that tolerated simultaneous multistress and enhance ethanol concentration was investigated. Twenty yeast isolates were classified into two major yeast species, namely Pichia kudriavzevii (twelve isolates) and Candida tropicalis (eight isolates). All P. kudriavzevii isolates were able to grow at high temperature (45 °C) and exhibited stress tolerance toward furfural. Among P. kudriavzevii isolates, NUCG-S3 presented the highest specific growth rate under each stress condition of heat and furfural, and multistress. Morphological changes in P. kudriavzevii isolates (NUCG-S2, NUCG-S3, NUKL-P1, NUKL-P3, and NUOR-J1) showed alteration in mean cell length and width compared to the non-stress condition. Ethanol production by glucose was also determined. The yeast strain, NUCG-S3, gave the highest ethanol concentrations at 99.46 ± 0.82, 62.23 ± 0.96, and 65.80 ± 0.62 g/l (P < 0.05) under temperature of 30 °C, 40 °C, and 42 °C, respectively. The tolerant isolated yeast NUCG-S3 achieved ethanol production of 53.58 ± 3.36 and 48.06 ± 3.31 g/l (P < 0.05) in the presence of 15 mM furfural and multistress (42 °C with 15 mM furfural), respectively. Based on the results of the present study, the novel thermos and furfural-tolerant yeast strain P. kudriavzevii NUCG-S3 showed promise as a highly proficient yeast for high-temperature ethanol fermentation.


Asunto(s)
Etanol , Fermentación , Furaldehído , Pichia , Pichia/metabolismo , Pichia/crecimiento & desarrollo , Pichia/fisiología , Etanol/metabolismo , Furaldehído/metabolismo , Furaldehído/análogos & derivados , Estrés Fisiológico , Candida tropicalis/metabolismo , Candida tropicalis/crecimiento & desarrollo , Calor , Glucosa/metabolismo , Hidrólisis , Biomasa , Lignina/metabolismo
14.
J Adv Res ; 2024 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-39128701

RESUMEN

INTRODUCTION: The efficiency of zinc oxide (ZnO) nanoparticles for environmental decontamination is limited by their reliance on ultraviolet (UV) light and rapid charge carrier recombination. Carbon doping has been proposed to address these challenges by potentially enhancing visible light absorption and charge separation. OBJECTIVES: This study aims to introduce a novel, single-step synthesis method for carbon-doped ZnO (C-Z) nanoparticles, leveraging the decomposition of zinc nitrate hexahydrate and furfural under a nitrogen atmosphere to improve photocatalytic activity under visible light. METHODS: A series of C-Z variants (C-Z-1 to C-Z-5) and an undoped sample (ZnO-0) were synthesized. The influence of furfural on the synthesis process and doping mechanism was analyzed by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and UV-visible diffuse reflectance spectroscopy (DRS). RESULTS: XPS confirmed the integration of carbon within the ZnO matrix, and XRD indicated increased lattice dimensions owing to doping. DRS revealed bandgap narrowing, suggesting enhanced charge separation. Among the variants, C-Z-3 significantly outperformed the others, showing a 12-fold increase in the photocatalytic degradation rate of Rhodamine B compared to undoped ZnO. CONCLUSION: The developed single-step synthesis method for C-Z nanoparticles represents a major advancement in materials engineering for ecological applications. The enhanced photocatalytic activity under visible light, as demonstrated by C-Z-3, underscores the potential of these nanoparticles for environmental decontamination.

15.
Food Chem X ; 23: 101667, 2024 Oct 30.
Artículo en Inglés | MEDLINE | ID: mdl-39139493

RESUMEN

By examining and analyzing bran-free fermented Baijiu (BFB) with varying storage periods (0-20 years), it was observed that the overall concentration of volatile compounds initially increases and subsequently decreases over time. Furthermore, BFB exhibited more kinds of long chain esters, higher concentration of acetals, and reduced furfural content. The process of cellaring can enhance the aged, sweet, and fruity aroma of BFB. 16 flavor compounds, including 1,1-diethoxyethane, ethyl dodecanoate, and ethyl hexadecanoate, can be used as markers for vintage BFB, and electronic sensory technology was capable of discerning BFB in different years. The results of redundancy analysis (RDA) showed a positive correlation between metals and aldehydes, esters, and ketones, while indicating a negative correlation with acids and alcohols. Al, Fe, and Ca underwent the most significant changes during storage period, and they were positively correlated with differential substances, such as benzaldehyde, vanillin, ethyl isovalerate, and ethyl palmitate (P < 0.01).

16.
ChemSusChem ; : e202401277, 2024 Aug 08.
Artículo en Inglés | MEDLINE | ID: mdl-39115033

RESUMEN

Catalyst development for upgrading bio-based chemicals towards primary amines has increasingly attracted owing to their applications in the pharmaceutical and polymer industries. The surface acidic sites in metal oxide-based catalysts play a key role in the reductive amination of aldehydes/ketones involving H2 and NH3; however, the crucial role of the type of surface acidic species and their strength remains unclear. Herein, this study exhibits the catalytic reductive amination of furfural (FUR) to furfurylamine (FUA) with Ru supported on tetragonal (Ru/T-ZrO2) and monoclinic (Ru/M-ZrO2) ZrO2. Ru/T-ZrO2 exhibited an 11.8-fold higher rate of reductive amination than Ru/M-ZrO2, giving a quantitative yield of FUA (99%) at 80 °C in 2.5 h and is recyclable up to four runs. Catalyst surface investigation using spectroscopic techniques, like X-ray photoelectron, electron paramagnetic resonance, and Raman, confirm higher oxygen vacancy sites (1.6 times) on the surface of Ru/T-ZrO2 compared to Ru/M-ZrO2. Moreover, in-situ NH3-diffuse reflectance infrared Fourier transform spectroscopy studies display that Ru/T-ZrO2 has more moderate Bronsted acidic sites (surface H-bonded hydroxyl groups) than Ru/M-ZrO2. Further, the controlled experiments and poisoning studies with KSCN and 2,6-lutidine suggest the crucial role of Ov sites (Lewis acidic sites) and surface hydroxyl groups (Bronsted acidic sites) for selective FUA formation.

17.
Biotechnol Biofuels Bioprod ; 17(1): 117, 2024 Aug 22.
Artículo en Inglés | MEDLINE | ID: mdl-39175057

RESUMEN

BACKGROUND: Lignocellulose is a renewable and sustainable resource used to produce second-generation biofuel ethanol to cope with the resource and energy crisis. Furfural is the most toxic inhibitor of Saccharomyces cerevisiae cells produced during lignocellulose treatment, and can reduce the ability of S. cerevisiae to utilize lignocellulose, resulting in low bioethanol yield. In this study, multiple rounds of progressive ionizing radiation was combined with adaptive laboratory evolution to improve the furfural tolerance of S. cerevisiae and increase the yield of ethanol. RESULTS: In this study, the strategy of multiple rounds of progressive X-ray radiation combined with adaptive laboratory evolution significantly improved the furfural tolerance of brewing yeast. After four rounds of experiments, four mutant strains resistant to high concentrations of furfural were obtained (SCF-R1, SCF-R2, SCF-R3, and SCF-R4), with furfural tolerance concentrations of 4.0, 4.2, 4.4, and 4.5 g/L, respectively. Among them, the mutant strain SCF-R4 obtained in the fourth round of radiation had a cellular malondialdehyde content of 49.11 nmol/mg after 3 h of furfural stress, a weakening trend in mitochondrial membrane potential collapse, a decrease in accumulated reactive oxygen species, and a cell death rate of 12.60%, showing better cell membrane integrity, stable mitochondrial function, and an improved ability to limit reactive oxygen species production compared to the other mutant strains and the wild-type strain. In a fermentation medium containing 3.5 g/L furfural, the growth lag phase of the SCF-R4 mutant strain was shortened, and its growth ability significantly improved. After 96 h of fermentation, the ethanol production of the mutant strain SCF-R4 was 1.86 times that of the wild-type, indicating that with an increase in the number of irradiation rounds, the furfural tolerance of the mutant strain SCF-R4 was effectively enhanced. In addition, through genome-transcriptome analysis, potential sites related to furfural detoxification were identified, including GAL7, MAE1, PDC6, HXT1, AUS1, and TPK3. CONCLUSIONS: These results indicate that multiple rounds of progressive X-ray radiation combined with adaptive laboratory evolution is an effective mutagenic strategy for obtaining furfural-tolerant mutants and that it has the potential to tap genes related to the furfural detoxification mechanism.

18.
J Mol Model ; 30(9): 312, 2024 Aug 20.
Artículo en Inglés | MEDLINE | ID: mdl-39162849

RESUMEN

CONTEXT: Milk has nutrient-rich but thermal sensitive matrix that undergoes varying degrees of Maillard reaction (MR) at heating conditions. The MR mainly occurs between lysine residues (Lys) and lactose composed of glucose (Glc) and galactose (Gal), which are abundantly sourced from dairy products. In the present study, the MRs of Glc and Gal with Lys at the initial and intermediate stages have been investigated theoretically using density functional theory (DFT) to simulate the gaseous and aqueous phases. Reaction mechanisms have been proposed, and relative energy changes of different steps were calculated according to the total mass balance. The calculations reveal that both Nα- and Nε-amine groups of Lys can react with the carbonyl functional group of Glc and Gal with the similar potential energy profiles, and Gal is more reactive than Glc. However, the barrier in Nε-channel is lower than in Nα-channel, indicating a faster reaction rate through the former channel compared with the latter. The 5-hydroxymethyl-2-furfural (HMF) and derivative are formed under 3-deoxysone route in the intermediate stage. The calculation results are helpful for proposing a reasonable MR mechanism and suggesting possible control methods of the MRs. METHODS: In this study, different levels of DFT calculations have been conducted to investigate the mechanisms and favorability of generating MR products in Glc-Lys and Gal-Lys models at initial and intermediate stages in the gaseous and aqueous conditions. In order to elucidate the molecular models from the perspectives of chemistry and geometry, DFT calculations were performed by the mean of B3LYP functional at basis sets of 6-311 + + G (d, p) and 6-311 + + G (2df, 2p) with optional solvation settings. To examine the solvation effect, the study further constructed models with solvent H2O and calculated in wB97XD functional with 6-31 + G (d) basis set. All computations were carried out Gaussian 09 suite of quantum chemistry software.


Asunto(s)
Galactosa , Glucosa , Lisina , Reacción de Maillard , Galactosa/química , Lisina/química , Glucosa/química , Teoría Funcional de la Densidad , Modelos Moleculares , Termodinámica
19.
Chembiochem ; : e202400278, 2024 Jul 02.
Artículo en Inglés | MEDLINE | ID: mdl-38953596

RESUMEN

Bio-processes based on enzymatic catalysis play a major role in the development of green, sustainable processes, and the discovery of new enzymes is key to this approach. In this work, we analysed ten metagenomes and retrieved 48 genes coding for deoxyribose-5-phosphate aldolases (DERAs, EC 4.1.2.4) using a sequence-based approach. These sequences were recombinantly expressed in Escherichia coli and screened for activity towards a range of aldol additions. Among these, one enzyme, DERA-61, proved to be particularly interesting and catalysed the aldol addition of furfural or benzaldehyde with acetone, butanone and cyclobutanone with unprecedented activity. The product of these reactions, aldols, can find applications as building blocks in the synthesis of biologically active compounds. Screening was carried out to identify optimized reaction conditions targeting temperature, pH, and salt concentrations. Lastly, the kinetics and the stereochemistry of the products were investigated, revealing that DERA-61 and other metagenomic DERAs have superior activity and stereoselectivity when they are provided with non-natural substrates, compared to well-known DERAs.

20.
Chem Biodivers ; : e202400951, 2024 Jul 22.
Artículo en Inglés | MEDLINE | ID: mdl-39034926

RESUMEN

Terminalia arjuna is an evergreen medicinal plant that belongs to the Combretaceae family of flowering plants. The bark of the plant exhibits antiviral, anticancer, hypocholesterolemic, antioxidant and antimicrobial properties. In this study, composition antibacterial activity, antioxidant activity and cytotoxicity of bark oil of Terminalia Arjuna (Roxb.) were reported. Oils were extracted by microwave assisted hydrodistillation where an oil yield of 0.18% was obtained followed by the identification of 35 compounds by gas chromatography mass spectrometry. The most abundant volatiles were furfural (11.11%), isoeugenol (9.99%), p-ethylguaiacol (9.97%), α-cadinol (9.57%), and estragole (9.47%). The oil was further evaluated against ten different drug resistant strains where oil showed significant activity against all pathogens and the highest activity was found against Acinetobacter baumannii (22mm), Klebsiella pneumoniae (22mm) and Staphylococcus aureus (22mm) in a concentration-dependent manner. Antioxidant activity evaluation demonstrated 68% radical scavenging activity by the volatile oil as compared to 81% of the standard, ascorbic acid at a concentration of 1000 µg. Cytotoxicity studies were conducted to see the effect of sample on the expression level of a housekeeping gene, Glyceraldehyde 3-phosphate dehydrogenase where it did not affect the normal transcription of the gene.

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