RESUMEN

Lignin is a green aromatic polymer constructed from repeating phenylpropane units, incorporating features such as phenolic hydroxyl groups, carbonyl groups, and conjugated double bonds that serve as chromophores. These structural attributes enable it to absorb a wide spectrum of ultraviolet radiation within the 250-400 nm range. The resulting properties make lignin a material of considerable interest for its potential applications in polymers, packaging, architectural decoration, and beyond. By examining the structure of lignin, this research delves into the structural influence on its UV-shielding capabilities. Through a comparative analysis of lignin's use in various UV-shielding applications, the study explores the interplay between lignin's structure and its interactions with other materials. This investigation aims to elucidate the UV-shielding mechanism, thereby offering insights that could inform the development of high-value applications for lignin in UV-shielding composite materials.

RESUMEN

Due to the diversity of industrial lignin sources and the complexity of its structure, its application as a high-value material is limited. Lignin nanoparticles (LNPs) have emerged as a hotspot for research due to their advantages of high specific surface area and high dispersion and the solvent transfer method is commonly used for the preparation of LNPs. In this paper, LNPs were prepared by solvent transfer method using DES based on sulfamic acid and urea (S/U DES) as solvent and water as anti-solvent. To explore the internal mechanism of the self-assembly of nanoparticles, a theoretical model of the solvent system and model lignin compound was constructed with the assistance of quantum chemistry and molecular dynamics theories. Through classical molecular dynamics (MD) simulations, the interaction energy, radius of gyration (ROG), solvent accessible surface area (SASS), radial and spatial distribution function (RDFs/SDFs), hydrogen bonding, and the morphology changes were analyzed to reveal the internal mechanism of self-assembly of model lignin compounds in S/U DES. This study is useful in revealing the mechanism of interaction between lignin and DES, as well as providing a benchmark for the green and efficient preparation of lignin nanoparticles.

Asunto(s)

RESUMEN

As a common flexible sensing device, gels are widely used in electronic skin, personalized health monitoring, and smart manufacturing. However, gel suffers from temperature sensitivity, long polymerization times or thickness limitations. Deep eutectic solvents (DESs) have abundant hydrogen bond networks and low saturated vapor pressure, which can accelerate the frontal polymerization of ionic gels, and overcome the temperature sensitivity problem. Here, we showed how choline chloride (ChCl)-glycerol (Gly) DES can be used to create ionic gels with different properties and functions by combining them with different monomers (acrylamide (AM), acrylic acid (AA) and itaconic acid (IA)). Subsequently, we revealed the rapid gelation mechanism of PAM-ChCl-Gly ionic gel from multiple perspectives by density functional theory and molecular dynamics simulation, which was then applied to flexible sensing. The experimental results showed that the PAM-ChCl-Gly ionic gel had excellent tensile properties, high transparency, self-adhesion and stability. In addition, its gelation time was only 90 s without heating. ChCl-Gly DES offered a plentiful and stable hydrogen bonding network. PAM-ChCl-Gly ionic gels can detect tiny pressure and strain changes, making them suitable for flexible sensing. This greatly enriched the theoretical research foundation of DES-based ionic gels and broadened their application areas.

RESUMEN

Lignin, as the aromatic polymer in the world, has attracted more attention because of rich functional groups. In this study, lignin/ZnO composites was prepared by a simple one-pot method rely on urea and ZnCl2-deep eutectic solvent (U/ZnCl2-DES) as solvent and raw material. Through molecular dynamics simulation, the interaction mechanism between lignin functional groups and DES was clarified, and it was blended with waterborne polyurethane (WPU) to form a film, while the feasibility of its application in ultraviolet shielding was evaluated. The results showed that lignin /ZnO composites with excellent ultraviolet shielding properties were successfully prepared. Compared with lignosulfonate (SL), enzymatic hydrolysis lignin (EHL) was easier to combine with ZnO, which was benefit to prepare lignin/ZnO composites. When the addition of EHL/ZnO-N12.5 complex was 1.5 %, the WPU film prepared has good mechanical properties (elongation at break was 25.53 %, tensile strength was 1422 kPa), good light transmission and ultraviolet shielding.

Asunto(s)

RESUMEN

Nano-SiO2 is a typical modifier used for urea-formaldehyde (UF) resins to balance the reduced formaldehyde content and maintain bond strength. However, the microstructure of UF resin and the interaction between UF resin and nano-SiO2 are microscopic phenomena; it is difficult to observe and study its intrinsic mechanism in traditional experimental tests. In this work, the enhancement mechanism was explored by molecular dynamics simulations combined with an experiment of the effect of nano-SiO2 additions on UF resin. The results showed that the best performance enhancement of UF resin was achieved when the addition of nano-SiO2 was 3 wt%. The effects caused by different additions of nano-SiO2 were compared and analyzed by molecular dynamics simulations in terms of free volume fraction, the radius of gyration, and mechanical properties, and the results were in agreement with the experimental values. Meanwhile, the changes in hydrogen bonding and radial distribution functions in these systems were counted to explore the interaction between nano-SiO2 and UF resin. The properties of the UF resin were enhanced mainly through the large number of different forms of hydrogen bonds with nano-SiO2, with the strongest hydrogen bond occurring between H(SiO2)… O = (PHMU).

RESUMEN

Formaldehyde emission is an intrinsic property derived from aldehyde-based resin that is used in wood-based composites. To reduce formaldehyde emission from plywood, the composite catalyst of tourmaline-titanium dioxide (T-TiO2) was fabricated by the sol-gel method. Furthermore, the impregnated paper loaded with the T-TiO2 composite catalyst was used to decorate the surface of 5-layer poplar plywood. The physicochemical structure, photocatalytic activity of T-TiO2 composite catalyst and its mechanism of degrading gaseous formaldehyde and generating air negative ions were assessed. The results discovered that the synergistic influence of the tourmaline and TiO2 anatase nanocrystals achieved good photodegradation of the gaseous formaldehyde. The neat T(20%)-TiO2 catalyst offered a higher formaldehyde removal efficiency (92.2%) than other catalysts, possessing 800 ions/cm3 of air negative ions concentration after 10-h visible light irradiation. The poplar plywood with a load of 3% T(20%)-TiO2 catalyst can stably induce the degradation formaldehyde into air negative ions with a concentration of 1200 ions/cm3 in visible light. The impregnation process of paper was feasible to be industrialized and the decorated wood-based composites can be widely applied in the furniture industry.

Asunto(s)

RESUMEN

Most phenolic resins are synthesized with non-renewable petroleum-based phenol and formaldehyde, which have adverse effects on the environment and human health. To achieve green and sustainable production of phenolic resins, it is important to replace non-renewable toxic phenol and formaldehyde. Herein, a new strategy was proposed to completely replace phenol and formaldehyde, using lignin-derived monomers to synthesize renewable phenolic resins. Lithium aluminum hydride was utilized to reduce lignin-derived monomers, including vanillin, methyl vanillate, and syringaldehyde, to generate the corresponding vanillyl and syringic alcohol. With oxalic acid as the catalyst, vanillyl and syringic alcohol could be polymerized to phenolic resins without using formaldehyde. The structure of the phenolic resins based on lignin-derived monomers was analyzed by Fourier transform infrared spectroscopy and 13C and 31P nuclear magnetic resonance spectroscopy. Differential scanning calorimetry and thermogravimetric analysis were performed to characterize the thermal properties of the phenolic resins. The phenolic resins based on lignin-derived monomers exhibited excellent adhesion strength (6.14 MPa), glass transition temperature (Tg) (107-115 °C), and thermal stability, and its performance was similar to that of the commercial Novolak phenolic resin. This study presents a promising green and sustainable approach to synthesize renewable phenolic resins based on lignin-derived monomers without using formaldehyde.

Asunto(s)

RESUMEN

Super-hydrophobic phenomena generally exist in nature, and wood can also obtain hydrophobicity by specific processing on the surface, being like the construction of microscale rough surface or decoration with low surface energy materials. In this research, the formation of hydrophobic layers on wood surface was investigated without breaking the wood's original structure. The core-shell structure particles were prepared by penetrating orthosilicate and polystyrene into the hollow mesoporous microsphere structure with tetrahydrofuran. A wood sample was coated with polydimethylsiloxane (PDMS) resin layer to enhance the adhesion of nano and micron hollow mesoporous microsphere on its surface. According to the surface structure of super-hydrophobic subjects in nature, the nano and micron hollow mesoporous microsphere were sprayed with different ratios several times to form a hydrophobic surface. The water contact angle could reach 150°, revealing that the hydrophobic behavior of the nano and micron hollow mesoporous microsphere coating was achieved. The microstructures of wood samples were examined by the scanning electron microscopy, and the chemical functional groups were investigated by the Fourier transform infrared; both verified that the hydrophobic surface was successfully coated. The thermogravimetric examination revealed the improved thermal stability of the hydrophobic wood. The scratch test was used to measure the abrasion resistance of the nano and micron hollow mesoporous microsphere coatings on wood surface. It was suggested that the nano and micron hollow mesoporous microsphere coating was an effective method to fabricate extremely hydrophobic wood products.

RESUMEN

A deep eutectic solvent (DES) derived from ferric chloride hexahydrate and betaine chloride (molar ratio of 1:1) was used as hydrolytic media for production of chitin nanocrystals (ChNCs) with a high yield (up to 88.5%). The synergistic effect of Lewis acid and released Brønsted acid from betaine hydrochloride enabled the efficient hydrolysis of chitin for production of ChNCs coupled with ultrasonication with low energy consumption. The obtained ChNCs were with an average diameter of 10 nm and length of 268 nm, and a crystallinity of 89.2% with optimal synthesis conditions (at 100 °C for 1 h with chitin-to-DES mass ratio of 1:20). The ChNCs were further investigated as efficient emulsion stabilizers, and they resulted in stable o/w emulsions even at a high oil content of 50% with a low ChNC dosage of 1 mg/g. Therefore, a potential approach based on a DES on the production of chitin-based nanoparticles as emulsifiers is introduced.

RESUMEN

Five different acidic deep eutectic solvents (DESs) composed of choline chloride and organic acids were applied to fabricate chitin nanocrystals (ChNCs). All DESs resulted in high transmittance and stable ChNCs suspensions with very high mass yield ranging from 78 % to 87.5 % under proper reaction conditions. The acidic DESs had a dual role in ChNCs fabrication, i.e. they promoted hydrolysis of chitin and acted as an acylation reagent. Physicochemical characterization of chitin revealed that the removal of amorphous area during DES treatments led to increased crystallinity of ChNCs and a dimension diversity correlated the DES used. The average diameter and length of individual ChNCs ranged from 42 nm to 49 nm and from 257 nm to 670 nm, respectively. The thermal stability of ChNCs was comparable to that of pristine chitin. Thus, acidic DESs showed to be non-toxic and environmentally benign solvents for production of functionalized chitin nanocrystals.

RESUMEN

The present work reports a rapid, tunable synthesis of resorcinol-formaldehyde (RF) carbon xerogels and their potential application as anode materials for lithium-ion battery. An iron-containing deep eutectic solvent (DES) is applied as both reaction medium and catalyst for the polymerization and graphitization. Water at different levels is employed as a co-solvent to mediate the polymerization and phase separation processes to produce a more-developed porous structure. The established binary-solvent synthesis strategy greatly simplifies the RF carbon xerogel preparation processes with a very short sol-gel time and a more acceptable ambient pressure drying. A duplex carbon configuration of rich microporosity (SBET = 566 m2 g-1) and expanded nanographite is achieved in the binary-solvent system with a DES mass fraction of 70%. The integrated structural merit is highly favorable for lithium storage, showing a reversible capacity of 633 mA h g-1 at 0.1 A g-1 and an excellent rate performance (205 mA h g-1 at 5 A g-1) as well as superior cycling stability.

RESUMEN

An efficient and one step production of acetylated and esterified chitin nanocrystals (CNCs) was successfully achieved using choline chloride-zinc chloride deep-eutectic solvent (ChCl-ZnCl2 DES). In this method, ChCl-ZnCl2 DES with a mole ratio of 1:2, was used for the esterification and O-acetylation of chitin at 90 °C for 3 h and 6 h. This strategy consisted in using ChCl-ZnCl2 DES as a green and non-volatile solvent for chitin under heterogeneous condition that, upon addition of acetic anhydride or acetic acid, simultaneous acetylation or esterification and hydrolysis occurred. The DES act as an efficient catalysis of the functional reaction. The acetylation and hydrolysis proceeded efficiently and the yield of partial acetylated CNCs was ca. 61.6% with DS (degree of substitution) of 0.23 under the optimized conditions. Acetic acid was used to substituted acid anhydride to produce CNCs. The yield of acetic acid induced CNCs was ca. 62.0% with higher DS of 0.34. A thorough investigation of the physicochemical characteristics changes of chitin pointed out that the main skeletal structure of obtained CNCs was intact. The thermal stability of CNCs decreased after treated by ChCl/ZnCl2. In addition, thermal stability of CNCs functionalized with acetic acid is lower than the ones functionalized with acetic anhydride. DES showed low expenditure and toxicity. This approach provides a novel method for production of functional chitin nanocrystals.

RESUMEN

The co-solvent prepared from glycerol and hydrochloric acid (HCl) was used for producing low molecular weight chitin from lobster shell. Different reaction temperature, time and acid concentration were studied. The results suggested that the effect of reaction temperature and acid concentration on molecular weight of chitin is most remarkable. The physicochemical properties of chitins were intact during co-solvent treatment. At least 5% HCl was necessary for demineralization and deproteinization. Low molecular weight chitin could be obtained by increasing reaction temperature, acid concentration and prolonging time. The optimized condition for production low molecular weight chitin was at 120 °C for 2 h with acid concentration of 7% (55 kDa) or at 150 °C for 2 h with acid concentration of 5% (57 kDa). This method provides a fast strategy to obtain low molecular weight chitin with high purity from lobster shell.

RESUMEN

Deep eutectic solvent (DES) prepared from choline chloride and four organic acid were evaluated for the extraction of chitin from lobster shell. It was found that the purity of chitins extracted with DESs was related to acid used. Purity of chitin extracted with choline chloride-malonic acid was the highest. Chitins extracted through DES treatment results in various molecular weight, which is associated with type of acid and temperature used during the treatment. For instance, chitin produced by malonic acid at 50 °C and 100 °C results in molecular weight of 312 KDa and 199 KDa respectively, whereas it extracted with malic acid at 100 °C results in 91 KDa. The physicochemical properties of chitins were characterized by FTIR, XRD, TG and SEM. Moreover, the CaCO3 was successfully converted into levulinic acid calcium salt which could be used as calcium supplement.

Asunto(s)

RESUMEN

For the first time in this study, chitin was solely extracted from lobster shells through a fast, easy and eco-friendly method using deep eutectic solvents (DESs), consisting of mixtures of choline chloride-thiourea (CCT), choline chloride-urea (CCU), choline chloride-glycerol (CCG) and choline chloride-malonic acid (CCMA). The physiochemical properties of the isolated chitins were compared with those of the chemically prepared one and commercial one from shrimp shells. Results showed that CCT, CCU and CCG DESs had no important effect on the elimination of proteins and minerals, while chitin obtained by CCMA DES showed a high purity. The yield (20.63±3.30%) of chitin isolated by CCMA DES was higher than that (16.53±2.35%) of the chemically prepared chitin. The chitin obtained by CCMA DES could be divided into two parts with different crystallinity (67.2% and 80.6%), which also had different thermal stability. Chitin from lobster shells showed porous structure, which is expected to be used for adsorption materials and tissue engineering.

Asunto(s)

RESUMEN

This study focused on the pretreatment with deep eutectic solvent of choline chloride (ChCl)/urea mixtures on rice straw and its chemical fractions of holocellulose, α-cellulose, and acid-insoluble-lignin (AIL). The pretreatment of ChCl/urea was significantly affected by the treated temperature prior to the treated time, and 130°C and 4h was an optimum condition for ChCl/urea pretreatment. The separation capacity of ChCl/urea on the chemical fractions was in an order of AIL (22.87%)> hemicellulose and amorphous cellulose (16.71%)>α-cellulose (9.60%). ChCl/urea had a higher selective solubility on lignin. The solubility of the whole fractionation of rice straw affected by ChCl/urea was a combination of solubilization on cellulose, hemicellulose and lignin. ChCl/urea pretreatment increased crystallinity index (CrI) of rice straw residue and α-cellulose, while had no obvious influence on CrI of holocellulose. The effect of structural properties of rice straw residue on enzymatic hydrolysis was also explored.