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1.
Carbohydr Polym ; 345: 122565, 2024 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-39227120

RESUMO

A green protocol to extract chitin from crab shells using water soluble ionic liquids (ILs) is here reported. Compared to conventional multistep acid-base extraction methods, this one-pot procedure achieves pulping of recalcitrant crustacean waste shells by employing ammonium acetate, ammonium formate and hydroxylammonium acetate as water-soluble, low-cost and easy to prepare ILs. An extensive parametric analysis of the pulping process has been carried out with different ILs, different ratios, temperature and time. The optimized protocol provides a high-quality chitin comparable, if not better, to commercial chitin. The best results were obtained at 150 °C with ammonium formate prepared in-situ from aqueous ammonia and formic acid: chitin was isolated in a 17 wt% yield (based on dried crab shells as starting biowaste), a degree of acetylation (DA) > 94 %, a crystallinity index of 39-46 %, a molecular weight up to 6.6 × 105 g/mol and a polydispersity of ca 2.0.


Assuntos
Exoesqueleto , Braquiúros , Quitina , Animais , Quitina/química , Quitina/isolamento & purificação , Exoesqueleto/química , Braquiúros/química , Líquidos Iônicos/química , Química Verde/métodos , Acetilação , Temperatura , Formiatos/química , Aranhas/química
2.
Bioresour Technol ; 413: 131535, 2024 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-39326536

RESUMO

The recovery of furfural from hemicellulosic biowastes is important for developing sustainable and renewable energy alternatives to fossil fuels. However, current methods are inefficient and environmentally questionable. To address this issue, this study introduces neoteric hydrophobic solvents, specifically deep eutectic solvents (DESs) and ionic liquids (ILs). Of the 32 solvents tested, thymol:decanoic acid 1:1 (Thy:DecA) DES and trihexyltetradecyl phosphonium bis(trifluoro methylsulfonyl) imide [P14,6,6,6][NTf2] IL were the most effective, with extraction efficiencies of 94.1% and 97.1%, respectively. These solvents outperformed the reference solvent toluene, with an efficiency of 81.2%, while also showing favorable characteristics in multiple investigated criterions. For the first time, excellent performance stability was demonstrated under various operational conditions and reusability over multiple extraction and regeneration cycles. Furthermore, to provide insights into the molecular mechanisms of extraction, computational quantum chemistry modeling was employed, which showed a strong agreement with the experimental results. The development of these new neoteric solvents for furfural recovery from biowaste offers a highly effective, sustainable, and eco-friendly alternative to traditional solvents, representing a significant breakthrough in the field of renewable bioenergy production and sustainable materials recovery.

3.
Angew Chem Int Ed Engl ; : e202410229, 2024 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-39231298

RESUMO

Homogeneous metal salt catalysts play a pivotal role in industrial production of 5-hydroxymethylfurfural (HMF). Herein, we first proposed the anion effect on steerable production of HMF using metal salts with different anions as catalyst in a biphasic system of tetrahydrofuran (THF)/NaCl aqueous solution (NaCl aq). Notably, the anions affected the catalytic activity of the metal salts, leading to an order of magnitude difference in the HMF yields, i.e., AlBr3(74.0 mol%)> AlCl3 (60.8 mol%) > Al2(SO4)3 (35.2 mol%) > Al(NO3)3 (14.9 mol%). The anion effect on steerable production of HMF could be attributed to the proximity effect and electron tension. Anions form close-range interactions with glucose molecules by proximity effect to promote electron transfer, facilitating the isomerization of glucose to fructose. Besides, anions induce a reduction of the electron cloud density of glucose carbon atoms, generating electron tension that rapidly transforms glucose from the ground state to the transition state, thereby increasing the HMF yield. Based on the revelation of anions effect and evaluation of techno-economic process, we expect to provides theoretical guidance for high-throughput screening of metal salt catalysts in industrial biorefinery.

4.
ChemSusChem ; : e202401489, 2024 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-39223088

RESUMO

Lignin valorization through heterogeneous photocatalysis is a promising pathway for obtaining value-added products, including chemical building blocks, biofuels, etc. However, several challenges still demand attention and resolution in this field. One of the key parameters in the heterogeneous photocatalytic process is the synthesis of efficient photocatalysts that can accomplish efficient and selective reactions. Selective conversion of lignin can be achieved by using heterojunction photocatalysts which can efficiently separate charge carriers' and promote selective reactions by band structure modulation. This work details a straightforward approach for synthesizing heterojunction photocatalysts based on Bi4Ti3O12 and BiOI involving the hydrothermal and co-precipitation methods. Additionally, the synthesized composites were employed in the selective oxidation of veratryl alcohol, a lignin-derived model compound, to produce high-value-added veratraldehyde. The experimental results showed that the BiOI/Bi4Ti3O12 heterojunction (12.5 mol % BiOI) showed superior activity with a veratraldehyde yield of 5.4 and 27.2 times higher than those of Bi4Ti3O12 and BiOI, respectively. The mechanistic studies revealed that the improved activity and selectivity were due to the enhanced charge carriers' separation and the suppression of reactive oxygen species formation through modulation of band structure. This study allows a green approach to lignin-derived biomass valorization to obtain high-value chemicals.

5.
Heliyon ; 10(14): e34791, 2024 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-39148987

RESUMO

In this study, double dehydration of sorbitol into isosorbide using commercial sulfonic acid resin as a catalyst was carried out under vacuum conditions generated by water ejection. To improve the efficiency and selectivity of the process, optimum reaction conditions prescribed by temperature, catalyst loading, and reaction time were investigated using the Box-Behnken design (BBD) together with Response Surface Methodology (RSM). The results showed that using the water ejection system could increase reaction activity. Statistically, all the reaction parameters were found to significantly affect the double dehydration reaction response, including sorbitol conversion, 1,4-sorbitant yield, and isosorbide yield. Furthermore, accurate predictive equations for all the reaction responses displayed R2 > 95 %, with no significant errors observed. The optimized conditions resulted in the complete conversion of sorbitol with 6.42 % 1,4-sorbitant yield and 67.55 % isosorbide yield. The equations yielded predicted values of the responses with minor variances being lower than 1 % when compared with the experimental values. However, the efficiency of the catalyst decreased steadily over recycling cycle due to reduced active sites and textural properties, likely caused by structural collapse and by-product accumulation. This work contributes to biomass valorization by optimizing the effective process for the production of isosorbide via commercial catalysts under vacuum conditions.

6.
ChemSusChem ; : e202401190, 2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-39213475

RESUMO

Replacing fossil fuels with renewable, bio-based alternatives is inevitable for the modern chemical industry, in line with the 12 principles of green chemistry. 2,5-Furandicarboxylic acid (FDCA) is a promising platform molecule that can be derived from 5-hydroxymethyl furfural (HMF) via sustainable electrochemical oxidation. Herein, we demonstrate TEMPO-mediated electrooxidation of HMF to FDCA in ElectraSyn 2.0 using inexpensive commercially available electrodes: graphite anode and stainless-steel cathode, thereby avoiding the often cumbersome electrode preparation. Key parameters such as concentration of HMF, KOH, and catalyst loading were optimized by experimental design. Under the optimized conditions, using only a low amount of TEMPO (5 mol%), high yield and Faradaic efficiency of 96% were achieved within 2.5 hours. Moreover, since FDCA is a monomer of the bio-based poly(ethylene furanoate), PEF, we aimed to investigate its recovery by depolymerization, which could be of paramount importance in the circular economy of the FDCA. For this, a new polar aprotic solvent, methyl sesamol (MeSesamol), was used, allowing the facile depolymerization of PEF at room temperature with high monomer yields (up to 85%), while the cosolvent MeSesamol was recycled with high efficiency (95-100%) over five reaction cycles.

7.
ChemSusChem ; : e202401405, 2024 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-39138129

RESUMO

Sustainable production of valuable biochemicals and biofuels from lignocellulosic biomass necessitates the development of durable and high-performance catalysts. To assist the next stage catalyst design for hydrothermal treatment of biosugars, this paper provides a critical review of (1) recent advances in biosugar hydrothermal valorization using heterogeneous catalysts, (2) the deactivation process of catalysts based on recycling tests of representative biosugar hydrothermal treatments, (3) state-of-the-art understandings of the deactivation mechanisms of heterogeneous catalysts, and (4) strategies of preparing durable catalysts and the regeneration of deactivated catalysts. Based on the review, challenges and perspectives are proposed. Some remarkable achievements in heterogeneous catalysis of biosugars are highlighted. The understanding of catalyst durability needs to be further increased based on full examination of the catalytic performance based on the conversion of substrates, the yield and selectivity of products. Further, a full examination of the physiochemical changes based on multiple characterization techniques is required to illuminate the relationships between treatment variables and catalyst durability. Collectively, a clear understanding of the relationships between chemical reaction pathways, treatment variables and the physiochemistry of catalysts is encouraged to be gained to advise the development of heterogeneous catalysts for long-term and efficient hydrothermal upgrading of biosugars.

8.
Food Chem ; 459: 140415, 2024 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-39032363

RESUMO

Brown macroalgae represent a sustainable and abundant source of lipids with acknowledged functional and health benefits. Nonetheless, macroalgae lipidome has been poorly unraveled due to lipids complex structural and chemical diversity. In this study, a comprehensive lipidomic analysis was performed in four macroalgae: Saccharina latissima, Fucus vesiculosus, Fucus serratus and the invasive Sargassum muticum, using HILIC-C30RP-HRMS. Neutral lipids (tri-, di-glycerides) comprised 72-82% of total lipids (TL) with a highly unsaturation profile (27-49% depending on species). The polar lipidome comprised glycolipids, phospholipids, betaine lipids and sphingolipids with varied content among macroalgae. S. latissima displayed the greatest level of glycolipids (23% of TL), by contrast with the dominance of long-chain polyunsaturated betaine lipids (10-18% of TL) in the other species, particularly in S. muticum. Phospholipids and sphingolipids were detected in low abundance (<1.7% of TL). This study elevated the potential of brown macroalgae as an emerging reservoir of bioactive lipids with nutritional relevance.


Assuntos
Lipidômica , Lipídeos , Phaeophyceae , Alga Marinha , Alga Marinha/química , Alga Marinha/metabolismo , Lipídeos/química , Lipídeos/análise , Phaeophyceae/química , Phaeophyceae/metabolismo , Glicolipídeos/química , Glicolipídeos/metabolismo , Glicolipídeos/análise
9.
Int J Biol Macromol ; 275(Pt 2): 133685, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38971283

RESUMO

The urgent need for a simple and cost-effective thermochemical process to produce biochar has prompted this study. The aim was to develop a straightforward thermochemical process under O2-limited conditions for the production of coconut-based biochar (CBB) and to assess its ability to remove methylene blue (MB) through adsorption, comparing it with CBB produced by slow pyrolysis. CBBs were obtained under different atmospheric conditions (O2-limited, muffle furnace biochar (MFB); and inert, pyrolytic reactor biochar (PRB)), at 350, 500, and 700 °C, and for 30 and 90'. MFB and PRB were characterized using FTIR, RAMAN, SEM, EDS, and XRD analyses. Adsorption tests were conducted using 1.0 g L-1 of MFB and PRB, 10 mg L-1 of MB at 25 °C for 48 h. Characterization revealed that atmospheric conditions significantly influenced the yield and structural features of the materials. PRB exhibited higher yields and larger cavities than MFB, but quite similar spectral features. Adsorption tests indicated that MFB and PRB had qt values of 33.1 and 9.2 mg g-1, respectively, which were obtained at 700 °C and 90', and 700 °C and 30', respectively. This alternative method produced an innovative and promising lignocellulose-based material with great potential to be used as a biosorbent.


Assuntos
Carvão Vegetal , Cocos , Lignina , Cocos/química , Carvão Vegetal/química , Lignina/química , Adsorção , Azul de Metileno/química , Temperatura
10.
Heliyon ; 10(13): e33641, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-39040382

RESUMO

The present surge in environmental consciousness has pushed for the use of biodegradable plasticizers, which are sustainable and abundant in plant resources. As a result of their biocompatibility and biodegradability, Calotropis gigantiea leaf plasticizers (CLP) serve as viable alternatives to chemical plasticizers. First time, the natural plasticizers from the Calotropis leaves were extracted for this study using a suitable chemical approach that was also environmentally friendly. The XRD results showed a reduced crystallinity index of 20.2 % and a crystalline size of 5.3 nm, respectively. TGA study revealed that the CLP has good thermal stability (244 °C). Through FT-IR study, the existence of organic compounds in CLP can be investigated by key functional groups such as alcohol, amine, amide, hydrocarbon, alkene, aromatic, etc. Further the presence of alcoholic, amino, and carboxyl constituents was confirmed by UV investigation. SEM, EDAX analysis, and AFM are used to examine the surface morphology of the isolated plasticizer. SEM pictures reveal rough surfaces on the CLP surface pores, which makes them suitable for plasticizing new bioplastics with improved mechanical properties. Poly (butylene adipate-co-terephthalate) (PBAT), a biodegradable polymer matrix, was used to investigate the plasticization impact after the macromolecules were characterised. The biofilm PBAT/CLP had a thickness of 0.8 mm. In addition, the reinforcement interface was examined using scanning electron microscopy. When CLP is loaded differently in PBAT, the tensile strength and young modulus change from 15.30 to 24.60 MPa and from 137 to 168 MPa, respectively. CLP-reinforced films demonstrated better surface compatibility and enhanced flexibility at a loading of 2 % when compared to pure PBAT films. Considering several documented characteristics, CLP may prove to be an excellent plasticizer for resolving environmental issues in the future.

11.
Polymers (Basel) ; 16(13)2024 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-39000767

RESUMO

Catalytic biomass pyrolysis is one of the most promising routes for obtaining bio-sustainable products that replace petroleum derivatives. This study evaluates the production of aromatic compounds (benzene, toluene, and xylene (BTX)) from the catalytic pyrolysis of lignocellulosic biomass (Pinus radiata (PR) and Eucalyptus globulus (EG)). Chilean natural zeolite (NZ) was used as a catalyst for pyrolysis reactions, which was modified by double ion exchange (H2NZ) and transition metals impregnation (Cu5H2NZ and Ni5H2NZ). The catalysts were characterized by nitrogen adsorption, X-ray diffraction (XRD), ammonium programmed desorption (TPD-NH3), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). Analytical pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) allowed us to study the influence of natural and modified zeolite catalysts on BTX production. XRD analysis confirmed the presence of metal oxides (CuO and NiO) in the zeolite framework, and SEM-EDS confirmed successful metal impregnation (6.20% for Cu5H2NZ and 6.97% for Ni5H2NZ). Py-GC/MS revealed a reduction in oxygenated compounds such as esters, ketones, and phenols, along with an increase in aromatic compounds in PR from 2.92% w/w (without catalyst) to 20.89% w/w with Ni5H2NZ at a biomass/catalyst ratio of 1/5, and in EG from 2.69% w/w (without catalyst) to 30.53% w/w with Ni5H2NZ at a biomass/catalyst ratio of 1/2.5. These increases can be attributed to acidic sites within the catalyst pores or on their surface, facilitating deoxygenation reactions such as dehydration, decarboxylation, decarbonylation, aldol condensation, and aromatization. Overall, this study demonstrated that the catalytic biomass pyrolysis process using Chilean natural zeolite modified with double ion exchange and impregnated with transition metals (Cu and Ni) could be highly advantageous for achieving significant conversion of oxygenated compounds into hydrocarbons and, consequently, improving the quality of the condensed pyrolysis vapors.

12.
Artigo em Inglês | MEDLINE | ID: mdl-38926307

RESUMO

Diversifying energy sources and managing waste biomass are two pressing contemporary issues. The new technology proposed in this study aims to address both by converting waste biomass into energy and fertilizer through the use of a biofuel cell (BFC). The purpose of this study is to assess the environmental impacts associated with this innovative technology through a Life Cycle Assessment (LCA). To achieve the goal, the production and use of the cell were modelled, considering both laboratory-scale operations and industrial-scale approximations. The study explored alternative scenarios, such as sensitivity analyses involving different acids and bases, renewable energy sources, and heat recovery. Comparisons with conventional biomass waste treatments (anaerobic digestion and composting) demonstrated that the BFC technology remains competitive. To further improve the BFC's environmental footprint, efforts should focus on reducing energy requirements and enhancing nutrient recovery during scale-up. These insights are crucial for advancing sustainable waste treatment technologies and maximizing the potential of discarded biomass in an environmentally friendly manner.

13.
Int J Biol Macromol ; 273(Pt 2): 132897, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38848826

RESUMO

Lignin-derived carbon nanodots (LCNs) are nanometer-scale carbon spheres fabricated from naturally abundant lignin. Owing to rich and highly heritable graphene like π-π conjugated structure of lignin, to fabricate LCNs from it not only endows LCNs with on-demand tunable size and optical features, but also further broadens the green and chemical engineering of carbon nanodots. Recently, they have become increasingly popular in sensing, bioimaging, catalysis, anti-counterfeiting, energy storage/conversion, and others. Despite the enormous research efforts put into the ongoing development of lignin value-added utilization, few commercial LCNs are available. To have a deeper understanding of this issue, critical impacts on the preparation, properties, and applications of state-of-the-art LCNs are carefully reviewed and discussed. A concise analysis of their unique advantages, limitations for specific applications, and current challenges and outlook is conducted. We hope that this review will stimulate further advances in the functional material-oriented production of lignin.


Assuntos
Carbono , Lignina , Lignina/química , Carbono/química , Nanopartículas/química , Catálise , Nanoestruturas/química
14.
Int J Biol Macromol ; 274(Pt 2): 133349, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38925179

RESUMO

New routes for biomass valorization have been developing by the scientific community. The aim of this work was developing a novel OrganoCat-based protocol and deeply understand the structure of the obtained lignins. Microwave-assisted OrganoCat-based process was performed using a biphasic system (ethyl acetate and oxalic acid or HCl) at mild conditions. OrganoCat-based lignins (OCLs) were characterized by compositional analysis, FTIR, 1H, 13C, 1H13C HSQC, 31P NMR, TGA and GPC. The solubility of OCLs in different organic solvents and their antioxidant capacity against DPPH were investigated. The spectroscopic analyses showed that OCLs have high residual extractives and the lignin motifs were preserved. OCLs have presented lower thermal stability than MWL, but showed great antioxidant activities and high solubility in a wide range of organic solvents. A novel biorefinery protocol yielded coconut shell lignins with peculiar structural and compositional features and several technological applications through an eco-friendly, sustainable and relatively low-cost biphasic pulping process.


Assuntos
Antioxidantes , Cocos , Lignina , Micro-Ondas , Solubilidade , Lignina/química , Antioxidantes/química , Antioxidantes/farmacologia , Cocos/química , Solventes/química , Química Verde
15.
Environ Sci Pollut Res Int ; 31(31): 44272-44288, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38941052

RESUMO

One of the hottest research topics over the last decades was the valorization or/and recycling of agro-industrial wastes into different valuable liquid or solid products, which is considered a sustainable and low-cost approach. In this study, we developed zero-valent iron nanoparticles from Palm Petiole Extract (P-NZVI) using a green and straightforward approach. The as-synthesized P-NZVI was used to adsorb Cr(VI) in water. The physico-chemical characterizations of P-NZVI, including the particle size, crystalline structure, surface area, morphology, and functional groups, were investigated via several techniques such as UV-vis spectroscopy, SEM, TEM, XRD, FTIR, AFM, DLS, pHZPC measurement, and BET analysis. The adsorption performance of P-NZVI was studied under different operational parameters, including pollutant concentration, pH, temperature, and adsorbent mass. The adsorption rate was found to be 89.3% within 40 min, corresponding to the adsorption capacity of 44.47 mg/g under the following conditions: initial Cr(VI) concentration of 40 mg/L, pH 5, and a P-NZVI dosage of 1 g/L. It was found that the adsorption pattern follows the Langmuir and the pseudo-second-order kinetic models, indicating a combination of monolayer adsorption and chemisorption mechanisms. The thermodynamic study shows that the adsorption process is endothermic and spontaneous. The reusability of P-NZVI was carried out four times, showing a slight decrease from 89.3 to 87%. These findings highlight that P-NZVI's could be an effective green adsorbent for removing Cr(VI) or other types of toxic pollutants from water.


Assuntos
Cromo , Ferro , Nanopartículas Metálicas , Poluentes Químicos da Água , Poluentes Químicos da Água/química , Ferro/química , Adsorção , Cromo/química , Nanopartículas Metálicas/química , Purificação da Água/métodos , Arecaceae/química , Cinética , Química Verde , Extratos Vegetais/química
16.
ChemSusChem ; : e202400472, 2024 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-38705869

RESUMO

Hydrogen peroxide (H2O2) has been considered an energy carrier (fuel) and oxidizer for various chemical synthesis and environmental remediation processes. Biomass valorization can generate high-value-added products in a green and pollution-free way to solve the energy and environmental crisis. The biomass valorization coupled with H2O2 generation via photo-, electro-, and photoelectrocatalysis plays a positive role in sustainable targets, which can maximize energy utilization and realize the production of value-added products and fuel synthesis. Recently, catalyst design and mechanism studies in H2O2 generation coupled with biomass valorization are in the infancy stage. Herein, this review begins with a background on photo-, electro-, and photoelectrocatalytic techniques for H2O2 generation, biomass valorization, and the H2O2 generation couples with biomass valorization. Meanwhile, the progress and reaction mechanism are reviewed. Finally, the prospects and challenges of a synergistic coupled system of H2O2 synthesis and value-added biomass in achieving high conversion, selectivity, and reaction efficiency are envisioned.

17.
Int J Biol Macromol ; 270(Pt 1): 132298, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38750863

RESUMO

Microcrystalline cellulose (MCC) is one of the essential functional excipients in the formulation of tablets. The need for cheaper MCC sources has drawn significant attention to exploring renewable sources. In this study, MCC was produced from soybean hull (SBH), the primary by-product of the soy industry, using a novel, simplified, and cost-effective approach. Various characterization techniques were used to study the physicochemical properties and micromeritics of the SBH-based MCC powders and compare them to those of the commercial Avicel PH-101. SBH MCCs had a larger particle size, a broader particle size distribution, a higher degree of polymerization, a higher degree of crystallinity, better thermal stability, and slightly superior flowability and compressibility than Avicel PH-101. The tableting blends (containing 60 % MCC) were prepared, and the post-compression out-of-die Heckel analysis showed that formulations with aggregated SBH MCCs were less ductile than those made with Avicel PH-101, resulting in a lower porosity (better compressibility) of the latter at higher compression pressures. The hardness values for all formulations were above 6 kg, with higher values for those made with Avicel PH-101. The lubricant sensitivity was lower for SBH MCCs. All tablets made using developed formulations showed very low friability (<0.1 %) and short disintegration times (<90 s), making them well-suited candidates for manufacturing orally disintegrating tablets (ODTs).


Assuntos
Celulose , Excipientes , Glycine max , Pós , Comprimidos , Celulose/química , Glycine max/química , Excipientes/química , Tamanho da Partícula , Composição de Medicamentos/métodos
18.
Angew Chem Int Ed Engl ; 63(26): e202402241, 2024 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-38567831

RESUMO

Herein we present a new strategy for the oxidative synthesis of formamides from various types of amines and bioderived formyl sources (DHA, GLA and GLCA) and molecular oxygen (O2) as oxidant on g-C3N4 supported Cu catalysts. Combined characterization data from EPR, XAFS, XRD and XPS revealed the formation of single CuN4 sites on supported Cuphen/C3N4 catalysts. EPR spin trapping experiments disclosed ⋅OOH radicals as reactive oxygen species and ⋅NR1R2 radicals being responsible for the initial C-C bond cleavage. Control experiments and DFT calculations showed that the successive C-C bond cleavage in DHA proceeds via a reaction mechanism co-mediated by ⋅NR1R2 and ⋅OOH radicals based on the well-equilibrated CuII and CuI cycle. Our catalyst has much higher activity (TOF) than those based on noble metals.

19.
Angew Chem Int Ed Engl ; 63(22): e202403547, 2024 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-38485666

RESUMO

Chiral carboxylic acid production from renewable biomass by chemocatalysis is vitally important for reducing our carbon footprint, but remains underdeveloped. We herein establish a strategy that make use of a stereogenic center of biomass to achieve a rare example of D-glyceric acid production with the highest yield (86.8 %) reported to date as well as an excellent ee value (>99 %). Unlike traditional asymmetric catalysis, chiral catalysts/additives are not required. Ample experiments combined with quantum chemical calculations established the origins of the stereogenic center and catalyst performance. The chirality at C4 in D-xylose was proved to be retained and successfully delivered to C2 in D-glyceric acid during C-C cleavage. The remarkable cooperative-roles of Ag+ and Ag0 in the constructed Ag/γ-Al2O3 catalyst are disclosed as the crucial contributors. Ag+ was responsible for low-temperature activation of D-xylose, while Ag0 facilitated the generation of active O* from O2. Ag+ and active O* cooperatively promoted the precise cleavage of the C2-C3 bond, and more importantly O* allowed the immediate fast oxidization of the D-glyceraldehyde intermediate to stabilize D-glyceric acid, thereby inhibiting the side reaction that induced racemization. This strategy makes a significant breakthrough in overcoming the limitation of poor enantioselectivity in current chemocatalytic conversion of biomass.

20.
Molecules ; 29(5)2024 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-38474449

RESUMO

In this work, a novel sustainable approach was proposed for the integral valorisation of Arctium lappa (burdock) seeds and roots. Firstly, a preliminary recovery of bioactive compounds, including unsaturated fatty acids, was performed. Then, simple sugars (i.e., fructose and sucrose) and phenolic compounds were extracted by using compressed fluids (supercritical CO2 and propane). Consequently, a complete characterisation of raw biomass and extraction residues was carried out to determine the starting chemical composition in terms of residual lipids, proteins, hemicellulose, cellulose, lignin, and ash content. Subsequently, three alternative ways to utilise extraction residues were proposed and successfully tested: (i) enzymatic hydrolysis operated by Cellulases (Thricoderma resei) of raw and residual biomass to glucose, (ii) direct ethanolysis to produce ethyl levulinate; and (iii) pyrolysis to obtain biochar to be used as supports for the synthesis of sulfonated magnetic iron-carbon catalysts (Fe-SMCC) to be applied in the dehydration of fructose for the synthesis of 5-hydroxymethylfurfural (5-HMF). The development of these advanced approaches enabled the full utilisation of this resource through the production of fine chemicals and value-added compounds in line with the principles of the circular economy.


Assuntos
Arctium , Arctium/química , Lignina/química , Extratos Vegetais/química , Celulose , Frutose
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