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1.
Int J Biol Macromol ; 264(Pt 1): 130378, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38428774

RESUMO

Polyethylene is the most commonly used plastic product, and its biodegradation is a worldwide problem. Latex clearing protein derived from Streptomyces sp. strain K30 (LcpK30) has been reported to be able to break the carbon-carbon double bond inside oxidized polyethylene and is an effective biodegradation enzyme for polyethylene. However, the binding of the substrate to the enzyme was difficult due to the hydrophobic nature of polyethylene. Therefore, to further improve the efficiency of LcpK30, the effect of different anchor peptides on the binding capacity of LcpK30 to the substrate was screened in this study. The results of fluorescence confocal microscopy showed that the anchoring peptide LCI had the most significant improvement in effect and was finally selected for further application in a UV-irradiated PE degradation system. The degradation results showed that LCI was able to improve the degradation efficiency of LcpK30 by approximately 1.15 times in the presence of equimolar amounts of protein compared with wild-type. This study further improves the application of LcpK30 in the field of polyethylene degradation by modification.


Assuntos
Látex , Streptomyces , Látex/química , Polietileno , Proteínas de Bactérias/química , Peptídeos/metabolismo , Carbono/metabolismo , Biodegradação Ambiental
2.
ChemSusChem ; : e202301497, 2024 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-38446050

RESUMO

Interface modification and bulk doping are two major strategies to improve the photovoltaic performance of perovskite solar cells (PSCs). Dipolar molecules are highly favored due to their unique dipolarity. This review discusses the basic concepts and characteristics of dipoles. In addition, the role of dipoles in PSCs and the corresponding conventional characterization methods for dipoles are introduced. Then, we systematically summarize the latest progress in achieving efficient and stable PSCs in dipole materials at several key interfaces. Finally, we look forward to the future application directions of dipole molecules in PSCs, aiming at providing deep insight and inspiration for developing efficient and stable PSCs.

3.
Int J Biol Macromol ; 260(Pt 1): 129473, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38242405

RESUMO

A guanidine-based Deep Eutectic Solvent (DES) consisting of 1,3-diaminoguanidine monohydrochloride and glycerol was utilized to prepare C-CNC from dissolving pulp. The pulp fibers were oxidized to dialdehyde cellulose by periodate, then fibrillated through the hydrogen bonds shear of DES and aminocationized through Schiff base effect of the amino groups in the DES solvent to obtain C-CNC. The results revealed that the characterization of the DES (such as viscosity, polarity, and pH) was related to the molar ratio of glycerol/guanidine-salts. The hydrogen bond network structure of DES solvent with optimal system was simulated by DFT and its damage to fiber hydrogen bond network was predicted. The C-CNC produced under the optimal reaction conditions (molar ratio of 1:2, 90 °C for 2 h) was highly dispersible with an average length and diameter of 85 ± 35 nm and 5.0 ± 1.2 nm, a charge density of 2.916 mol/g. C-CNC exhibited excellent flocculation when added to fine fiber suspensions of chemomechanical slurries, achieving rapid flocculation and settling onto fibers in <1 min. The DES solvent maintained its reactivity after 5 cycles. This study lays the foundation for the batch preparation of nanocellulose in an environmentally friendly manner and its application as a green additive in paper industry.


Assuntos
Solventes Eutéticos Profundos , Glicerol , Guanidina , Guanidinas , Bioensaio , Solventes
4.
Sci Rep ; 14(1): 99, 2024 01 02.
Artigo em Inglês | MEDLINE | ID: mdl-38167939

RESUMO

Identifying potential prognostic factors of CSM patients could improve doctors' clinical decision-making ability. The study retrospectively collected the baseline data of population characteristics, clinical symptoms, physical examination, neurological function and quality of life scores of patients with CSM based on the clinical big data research platform. The modified Japanese Orthopedic Association (mJOA) score and SF-36 score from the short-term follow-up data were entered into the cluster analysis to characterize postoperative residual symptoms and quality of life. Four clusters were yielded representing different patterns of residual symptoms and quality of patients' life. Patients in cluster 2 (mJOA RR 55.8%) and cluster 4 (mJOA RR 55.8%) were substantially improved and had better quality of life. The influencing factors for the better prognosis of patients in cluster 2 were young age (50.1 ± 11.8), low incidence of disabling claudication (5.0%) and pathological signs (63.0%), and good preoperative SF36-physiological function score (73.1 ± 24.0) and mJOA socre (13.7 ± 2.8); and in cluster 4 the main influencing factor was low incidence of neck and shoulder pain (11.7%). We preliminarily verified the reliability of the clustering results with the long-term follow-up data and identified the preoperative features that were helpful to predict the prognosis of the patients. This study provided reference and research basis for further study with a larger sample data, extracting more patient features, selecting more follow-up nodes, and improving clustering algorithm.


Assuntos
Doenças da Medula Espinal , Espondilose , Humanos , Prognóstico , Qualidade de Vida , Estudos Retrospectivos , Reprodutibilidade dos Testes , Resultado do Tratamento , Estudos Prospectivos , Análise por Conglomerados , Vértebras Cervicais/patologia , Espondilose/diagnóstico
5.
Int J Biol Macromol ; 254(Pt 3): 127958, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37951428

RESUMO

Flexible wearable devices are garnering significant interest, with conductive hydrogels emerging as a particularly notable category. While many of these hydrogels offer impressive conductivity, they often lack the innate ability to adhere autonomously to human skin. The ideal hydrogel should possess both superior adhesion properties and a wide responsive range. This study introduces a novel double-network conductive hydrogel, synthesized from lignosulfonate sodium and ionic liquid using a one-pot method. The gel's mechanical robustness (fracture elongation of ∼3500 % and tensile strength of ∼130 kPa) and exceptional conductivity sensing performance arise from the synergistic effects of electrostatic interactions, dynamic hydrogen bonding, and a three-dimensional network structure. Additionally, the phenolic hydroxyl and sulfonic groups from lignosulfonate sodium imbue the hydrogel with adhesive qualities, allowing it to easily bond with varied material surfaces. This hydrogel excels in human physiological signal detection and wireless monitoring, demonstrating a rapid response time (149 ms) and high sensitivity (a maximum gauge factor of 10.9 for strains between 400 and 600 %). Given these properties, the flexible, self-adhesive, and conductive hydrogel showcases immense promise for future applications in wearable devices and wireless transmission sensing.


Assuntos
Líquidos Iônicos , Humanos , Confiabilidade dos Dados , Condutividade Elétrica , Hidrogéis
6.
J Hazard Mater ; 465: 133074, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38029591

RESUMO

Public health depends on indoor air quality (IAQ), hence soft measurement techniques must be implemented in the subway environment for more precise and reliable monitoring of indoor particulate matter concentration levels. Adaptive boosting (AdaBoost), an ensemble learning technique, is simple to code and less prone to overfitting. Compared to a single model, it is better able to take into consideration the intricate elements included in air quality data. It is suggested to use an adaptive boosting of long short-term memory (AdaBoost-LSTM) model and kernel principal component analysis (KPCA) for ensemble learning. The kernel function and PCA are first coupled to create KPCA, which is a nonlinear dimensionality reduction method for IAQ. This removes the negative impacts of noise interference. The learning performance of LSTM is then enhanced using AdaBoost as an ensemble learning technique. The KPCA-AdaBoost-LSTM model can deliver higher modeling performance, according to the results. The R2 reached 0.9007 and 0.8995 when predicting PM2.5 in the hall and platform. SHapley Additive exPlanations (SHAP) analysis was used to interpret the input contributions of the model, enhancing the interpretability and transparency of the proposed soft sensor.

7.
Int J Biol Macromol ; 254(Pt 3): 127995, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37949282

RESUMO

Latex clearing protein from Streptomyces sp. strain K30 (LcpK30) is a natural oxidoreductase that can catalyse the cleavage of rubber through dioxygenation. It has significant potential applications in polymer degradation. However, its limited expression in engineered strains restricts its utility. This study aimed to enhance the soluble expression and enzyme activity of LcpK30 in E. coli BL21 (DE3) by optimizing fermentation conditions and making molecular modifications. The enzyme activity reached 5.05 U·mL-1 by optimizing the induction conditions, adding cofactors, and using chemical chaperones, which was 237.1 % of the initial case. Further enhancements in soluble expression were achieved through site mutations guided by the PROSS server, resulting in 8 out of 13 mutants with increased protein expression, a high positive mutation rate of 61.5 %. Subsequently, combined mutants were created by merging single mutants with enhanced protein expression and enzyme activity. The top three double mutants, G91D/S149A, G91D/A210H, and G91D/H296P, displayed expression levels at 173.3 %, 173.3 %, and 153.3 % of the wild-type LcpK30, respectively. These mutants also exhibited enhanced fermentation enzyme activity, reaching 149.5 %, 250.0 %, and 420.2 % compared to the wild-type, along with improved specific activities. This study provides insights for the efficient production of LcpK30 and a practical foundation for its application.


Assuntos
Látex , Streptomyces , Látex/química , Escherichia coli/genética , Escherichia coli/metabolismo , Fermentação , Proteínas de Bactérias/química
8.
Carbohydr Polym ; 326: 121621, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38142077

RESUMO

Conductive hydrogels have received increasing attention in the field of wearable electronics, but they also face many challenges such as temperature tolerance, biocompatibility, and stability of mechanical properties. In this paper, a double network hydrogel of MXene/TEMPO bacterial cellulose (TOBC) system is proposed. Through solvent replacement, the hydrogel exhibits wide temperature tolerance (-20-60 °C) and stable mechanical properties. A large number of hydrogen bonds, MXene/TOBC dynamic three-dimensional network system, and micellar interactions endow the hydrogel with excellent mechanical properties (elongation at break ~2800 %, strength at break ~420 kPa) and self-healing ability. The introduction of tannic acid prevents the oxidation of MXene and the loss of electrical properties of the hydrogel. In addition, the sensor can also quickly (74 ms) and sensitive (gauge factor = 15.65) wirelessly monitor human motion, and the biocompatibility can well avoid the stimulation when it comes into contact with the human body. This series of research work reveals the fabrication of MXene-like flexible wearable electronic devices based on self-healing, good cell compatibility, high sensitivity, wide temperature tolerance and durability, which can be used in smart wearable, wireless monitoring, human-machine Interaction and other aspects show great application potential.


Assuntos
Celulose , Hidrogéis , Humanos , Condutividade Elétrica
9.
Int J Biol Macromol ; 257(Pt 2): 128800, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38101658

RESUMO

Electro-conductive hydrogels emerge as a stretchable conductive materials with diverse applications in the synthesis of flexible strain sensors. However, the high-water content and low cross-links density cause them to be mechanically destroyed and freeze at subzero temperatures, limiting their practical applications. Herein, we report a one-pot strategy by co-incorporating cellulose nanofiber (CNF), Poly pyrrole (PPy) and glycerol with polyvinyl alcohol (PVA) to prepare hydrogel. The addition of PPy endowed the hydrogel with good conductivity (∼0.034 S/m) compared to the no PPy@CNF group (∼0.0095 S/m), the conductivity was increased by 257.9 %. The hydrogel exhibits comparable ionic conductivity at -18 °C as it does at room temperature. It's attributed to the glycerol as a cryoprotectant and the formation of hydrated [Zn(H2O)n]2+ ions via strong interaction between Zn2+ and water molecules. Moreover, the cellulose nanofiber intrinsically assembled into unique hierarchical structures allow for strong hydrogen bonds between adjacent cellulose and PPy polymer chains, greatly improve the mechanical strength (stress∼0.65 MPa, strain∼301 %) and excellent viscoelasticity (G'max âˆ¼ 82.7 KPa). This novel PPy@CNF-PVA hydrogel exhibits extremely high Gauge factor (GF) of 2.84 and shows excellent sensitivity, repeatability and stability. Therefore, the hydrogel can serve as reliable and stable strain sensor which shows excellent responsiveness in human activities monitoration.


Assuntos
Nanofibras , Polímeros , Humanos , Álcool de Polivinil , Celulose , Pirróis , Glicerol , Condutividade Elétrica , Hidrogéis , Poli A , Água
10.
Int J Biol Macromol ; 259(Pt 1): 128891, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38143065

RESUMO

The toxic volatile organic compounds (VOCs), especially formaldehyde (FA), released from decoration materials pose a great threat to human health. In this study, formaldehyde adsorption performance of the specially formulated nanocellulose/chitosan aerogel (CNFCA) was investigated in simulated atmosphere. The physicochemical property of the composite aerogel was characterized, which had a large specific surface area (153.67 m2/g), a rough surface and an ultra-thin and porous structure. The composite aerogel showed excellent adsorption capacity for the formaldehyde, its theoretical maximum adsorption capacity was as high as 83.89 mg/g, and the adsorption process was more in accordance with the pseudo-second-order kinetics. The chromogenic reaction between the 4-amino-3-benzo-5-mercapto-1,2,4-triazolium (AHMT) and CNFCA was found that the color of the composite aerogel was depended on the free formaldehyde concentration. Based on this phenomenon, a colorimetric card was proposed and built to detection the formaldehyde in the atmosphere. Moreover, the adsorption mechanism research was found that the CNFCA with a multilayer structure belonged to physicochemical complex adsorption.


Assuntos
Quitosana , Humanos , Adsorção , Atmosfera , Celulose , Formaldeído
11.
J Sci Food Agric ; 2023 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-37997286

RESUMO

BACKGROUND: Cherry tomatoes are nutritious and favored by consumers. Processing them into dried cherry tomatoes can prolong their storage life and improve their flavor. The pretreatment of tomato pericarp is crucial for the subsequent processing. However, the traditional physical and chemical treatments of tomato pericarp generally cause nutrient loss and environmental pollution. RESULTS: In this study, a novel enzymatic method for cherry tomatoes was performed using mixed enzymes containing cutinase, cellulase and pectinase. Results showed that the pericarp permeability of cherry tomatoes was effectively improved due to enzymatic treatment. Changes in the microscopic structure and composition of the cuticle were revealed. After treatment with different concentrations of enzymes, cherry tomatoes exhibited higher pericarp permeability and sensory quality to varying degrees. The lycopene content and total polyphenol content significantly increased 2.4- and 1.45-fold, respectively. In addition, the satisfactory effect of the six-time reuse of enzymes on cherry tomatoes could still reach the same level as the initial effect, which effectively reduced the cost of production. CONCLUSIONS: This study revealed for the first time that a mixed enzymatic treatment consisting of cutinase, pectinase and cellulase could effectively degrade the cuticle, enhance the pericarp permeability and improve the quality of cherry tomatoes, with the advantages of being mildly controllable and environmentally friendly, providing a new strategy for the processing of dried cherry tomatoes. © 2023 Society of Chemical Industry.

12.
J Agric Food Chem ; 71(43): 16212-16220, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37851455

RESUMO

Lacto-N-neotetraose (LNnT), an abundant human milk oligosaccharide (HMO), has been approved as a novel functional additive for infant formulas. Therefore, LNnT biosynthesis has attracted extensive attention. Here, a high LNnT-producing, low lacto-N-triose II (LNT II)-residue Escherichia coli strain was constructed. First, an initial LNnT-producing chassis strain was constructed by blocking lactose, UDP-N-acetylglucosamine, and UDP-galactose competitive consumption pathways and introducing ß-1,3-N-acetylglucosaminyltransferase LgtA and ß-1,4-galactosyltransferase LgtB. Subsequently, the supply of LNnT precursors was increased by enhancing UDP-N-acetylglucosamine and UDP-galactose synthesis, inactivating LNT II extracellular transporter SetA, and improving UTP synthesis. Then, modular engineering strategy was used to optimize LNnT biosynthetic pathway fluxes. Moreover, pathway fluxes were fine-tuned by modulating translation initiation strength of essential genes lgtB, prs, and lacY. Finally, LNnT production reached 6.70 g/L in a shake flask and 19.40 g/L in a 3 L bioreactor with 0.47 g/(L h) productivity, with 1.79 g/L LNT II residue, highest productivity level, and lowest LNT II residue thus far.


Assuntos
Vias Biossintéticas , Galactose , Lactente , Humanos , Galactose/metabolismo , Escherichia coli/genética , Escherichia coli/metabolismo , Acetilglucosamina/metabolismo , Oligossacarídeos/química , Leite Humano/química , Difosfato de Uridina/metabolismo
13.
Polymers (Basel) ; 15(19)2023 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-37836025

RESUMO

N-doping is a very useful method to improve the electrochemical performance of porous carbon (PC) materials. In this study, the potential of furfural residue (FR), a solid waste in furfural production, as a precursor to producing PC materials for supercapacitors was highlighted. To obtain an N-doped PC with a high specific surface area (SSA) and hierarchical porous structure, the urea-KOH synergistic activation method was proposed. The obtained FRPCK-Urea showed a high SSA of 1850 m2 g-1, large pore volume of 0.9973 cm3 g-1, and interconnected micro/mesoporous structure. Besides, urea can also serve as a nitrogen source, resulting in a high N content of 5.31% in FRPCK-Urea. These properties endow FRPCK-Urea with an excellent capacitance of 222.7 F g-1 at 0.5 A g-1 in 6 mol L-1 KOH aqueous electrolyte in a three-electrode system. The prepared FRPCK-Urea possessed a well capacitance retention at current densities from 0.5 to 20 A g-1 (81.90%) and cycle durability (96.43% after 5000 cycles), leading to FRPCK-Urea to be a potential electrode material for supercapacitors. Therefore, this work develops an effective way for the high-valued utilization of FR.

14.
Orthop Surg ; 15(10): 2709-2715, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37675762

RESUMO

STUDY DESIGN: Single-center, retrospective study. OBJECTIVE: Hemivertebra resection is the only treatment option for congenital cervical scoliosis (CCS). However, this procedure is complex and technically demanding. It often requires a considerably long operation, and there is substantial intraoperative bleeding. Therefore, we have attempted to treat CCS with a concave side distraction comprising a three-dimensional (3D) printed titanium cage. The purpose of this study is to evaluate the safety and efficacy of this technique for the treatment of patients with CCS. METHODS: A series of 22 patients with CCS who underwent a concave side distraction technique between 2019 and 2021 were retrospectively reviewed and analyzed. Radiological measurements included the Cobb angle of the distraction segments, the kyphosis angle, the range of movement, and the distraction correction angle. Student's t-test and Spearman correlation analysis were used for statistical analysis. p < 0.05 was considered statistically significant. RESULTS: The study included 12 males and 10 females whose ages ranged from 6 to 14 years old (9.8 ± 2.1 years old). Follow-up times ranged from 15 to 30 months (25.8 ± 3.6 months). Among 22 patients, two patients developed a postoperative C5 nerve root palsy and recovered after being treated with conservative treatment for 6 months. The duration of surgery ranged from 229 to 756 min (389 ± 112 min), and the estimated volume of blood loss ranged from 100 to 600mL (235 ± 121 mL). The coronal Cobb angle (p < 0.001), kyphosis angle (p < 0.05), and range of movement (p < 0.001) between the last follow-up and preoperative period were significantly different. A total of 28 segments were distracted, and the Cobb angle of the distraction segment ranged from 2.4 to 14.1° (8.5 ± 3.0°). There were six upper cervical spines (8.9 ± 1.9°) and 22 lower cervical spines (8.4 ± 3.2°) with no significant difference between them (p = 0.130). In addition, there was no correlation between the angle of the concave side distraction and patients' age (r = 0.018, p = 0.315). The fusion was solid between the bone and the customized 3D-printed pore metal cage at the final follow-up. CONCLUSION: The concave side distraction comprising a customized 3D-printed titanium cage implantation can provide satisfactory correction results and is a safe and reliable procedure for treating CCS.

15.
Phys Chem Chem Phys ; 25(36): 24377-24385, 2023 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-37681280

RESUMO

Cu/SiO2 is one of the most promising catalysts for the furfural (FF) hydrogenation reaction but suffers from the difficulty of tailoring the microstructure and surface properties. Herein, we developed a MOF-derived Cu/SiO2 catalyst (Cu/SiO2-MOF) for FF hydrogenation to 2-methyl furan (2-MF). In comparison with Cu/SiO2 catalysts prepared from ammonia evaporation (Cu/SiO2-AE) and traditional impregnation (Cu/SiO2-TI), the copper species in Cu/SiO2-MOF could not only be anchored on the silica surface via forming Cu-O-Si bonds but also exposed many more active sites. In this way, a higher ratio of Cu+/(Cu+ + Cu0) and richer oxygen defects were constructed via strong metal-support interactions, which were responsible for the superior catalytic performance. In addition, it was found that the solvent effect on product distribution played an important role in adjusting the selectivity to 2-MF and cyclopentanone (CPO). The present work not only provides a deep insight into the catalytic mechanism of Cu/SiO2-MOF for the FF hydrogenation reaction but also sheds light on the design and synthesis of highly efficient catalysts for other heterogeneous catalysis fields.

16.
Global Spine J ; : 21925682231200136, 2023 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-37684040

RESUMO

STUDY DESIGN: Prospective observational study. OBJECTIVE: To evaluate the predictive value of the preoperative Short Form-36 survey (SF-36) scale for postoperative axial neck pain (ANP) in patients with degenerative cervical myelopathy (DCM) who underwent anterior cervical decompression and fusion (ACDF) surgery. METHODS: This study enrolled patients with DCM who underwent ACDF surgery at author's Hospital between May 2010 and June 2016. RESULTS: Out of 126 eligible patients, 122 completed the 3-month follow-up and 117 completed the 1-year follow-up. The results showed that the preoperative social functioning (SF) subscale score of the SF-36 scale was significantly lower in patients with moderate-to-severe postoperative ANP than in those with no or mild postoperative ANP at both follow-up timepoints (P < .05). ACDF at C4-5 level resulted in a higher ANP rate than ACDF at C5-6 or C6-7 level, both at 3-month (P = .019) and 1-year (P = .004) follow-up. Multivariate logistic regression analysis confirmed that the preoperative social functioning subscale score was an independent risk factor for moderate-to-severe postoperative ANP at 3 months and 1 year after surgery, and preoperative NRS was an independent risk factor at 1-year follow-up. No other demographic, clinical, or radiographic factors were found to be associated with postoperative ANP severity (P < .05). CONCLUSIONS: Preoperative social functioning subscale score of SF-36 scale might be a favorable predictive tool for postoperative ANP in DCM patients who underwent ACDF surgery.

17.
Angew Chem Int Ed Engl ; 62(45): e202313133, 2023 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-37735100

RESUMO

Introducing fluorine (F) groups into a passivator plays an important role in enhancing the defect passivation effect for the perovskite film, which is usually attributed to the direct interaction of F and defect states. However, the interaction between electronegative F and electron-rich passivation groups in the same molecule, which may influence the passivation effect, is ignored. We herein report that such interactions can vary the electron cloud distribution around the passivation groups and thus changing their coordination with defect sites. By comparing two fluorinated molecules, heptafluorobutylamine (HFBM) and heptafluorobutyric acid (HFBA), we find that the F/-NH2 interaction in HFBM is stronger than the F/-COOH one in HFBA, inducing weaker passivation ability of HFBM than HFBA. Accordingly, HFBA-based perovskite solar cells (PSCs) provide an efficiency of 24.70 % with excellent long-term stability. Moreover, the efficiency of a large-area perovskite module (14.0 cm2 ) based on HFBA reaches 21.13 %. Our work offers an insight into understanding an unaware role of the F group in impacting the passivation effect for the perovskite film.

18.
Phys Chem Chem Phys ; 25(27): 18215-18223, 2023 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-37394949

RESUMO

The efficient production of γ-valerolactone (GVL) from renewable lignocellulose that is synthesized in plants by photosynthesis to replace the declining fossil resources conforms to the principles of circular economy. Compared to direct hydrogenation by H2 molecules, catalytic transfer hydrogenation (CTH) of levulinic acid (LA) and/or its esters to GVL with organic alcohols as a hydrogen source is a much milder route. The synergistic catalysis between Lewis and Brønsted acids is indispensable in the CTH process. Considering that unsaturated coordinated Zr species could act as Lewis acid sites and phosphotungstic acid (PTA) could dissociate protons as Brønsted acid sites, UiO-66 (Zr) was thus "acidified" by encapsulating PTA in its channels to tune the ratio of Brønsted to Lewis acid sites as a bifunctional catalyst so as to better understand the catalytic structure-performance relationship in the CTH process. To address the dilemma of encapsulated PTA that is prone to leach, a rapid surface sealing strategy was adopted to establish a polyimide (PI) coating over the surface of UiO-66 introducing a space confinement effect via an anhydride-amine coupling reaction. The as-synthesized PTA/UiO-66@PI catalyst exhibited 100% of LA conversion, a 93.2% of GVL yield and high recyclability for at least five consecutive cycles. Moreover, a reaction pathway followed by esterification, hydrogenation and dealcoholization as well as a catalytic hydrogenation mechanism based on intermolecular hydride ß-H transfer were proposed. Current work not only provides a high-performance and high-stability catalytic system to selectively produce GVL from LA or its esters, but also sheds light on the catalytic mechanism of the CTH process at the molecular level.

19.
Macromol Rapid Commun ; 44(17): e2300175, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37222244

RESUMO

Cellulose is a promising feedstock for the production of sustainable materials. To fully utilize its potential, exploring efficient cellulose solvents is a paramount prerequisite. In this study, ten superbase amino acid ionic liquids (SAAILs) are synthesized using 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with different amino acid anions via a simple neutralization method. The properties of these SAAILs, such as viscosity and glass transition temperature, varied with their cation and anion structures. The ability of the SAAILs to dissolve cellulose is related to their Kamlet-Taft parameters, particularly hydrogen bond basicity (ß). The main driving force for cellulose dissolution in SAAILs is thought to be hydrogen bonding interactions between SAAILs and cellulose hydroxyl groups. Four SAAILs composed of DBN or DBU cations and proline, or aspartic acid anions are identified as promising solvents for preparing regenerated cellulose films (RCFs). The RCF prepared from [DBN]Proline(Pro) showed a favorable combination of high tensile strength (76.9 MPa), high Young's modulus (5201.2 MPa), good transparency (≈70% at 550 nm), and smooth surface morphology. These halogen- and metal-free SAAILs show the potential to provide a new avenue for cellulose processing.


Assuntos
Líquidos Iônicos , Líquidos Iônicos/química , Aminoácidos , Solubilidade , Solventes , Celulose/química , Prolina , Ânions
20.
Bioresour Technol ; 376: 128937, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36948430

RESUMO

Deep eutectic solvents (DESs) with different acidity and alkalinity were applied for biomass pretreatment, and the conditions were optimized by response surface methodology. The results showed that lactic acid/betaine hydrochloride had the optimal pretreatment efficiency, where the removal rates of hemicellulose and lignin came up to 89% and 73%, and the enzymolysis efficiency was as high as 92%. Furthermore, eight types of chloride salts with different valence states were introduced into the DESs as the third component. The chloride salts could improve the pretreatment efficiency and positively correlated with the metal valence state. Specifically, AlCl3 was significantly superior in improving the pretreatment efficiency, where the enzymolysis efficiency reached 96% due to the destruction of crystalline region and the esterification of partial cellulose. Therefore, it is proposed that adding highly valent metal salts to acidic DESs has higher pretreatment and enzymatic efficiency.


Assuntos
Solventes Eutéticos Profundos , Lignina , Lignina/química , Cloretos , Sais , Solventes/química , Hidrólise , Biomassa
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