Alkaloid purification using rosin-based polymer-bonded silica stationary phase in HPLC.

Alkaloids are important natural products that exhibit a wide spectrum of pharmacological activities. To efficiently separate and purify them, a rosin-based polymer-bonded silica stationary phase in high-performance liquid chromatography was synthesized via the surface radical polymerization of ethylene glycol maleic rosinate acrylate and methacrylic acid onto functionalized silica. The stationary phases, columns, optimization of chromatographic conditions for alkaloids, and thermodynamic behavior of the analytes on the column were fully studied. Under the optimized conditions, the prepared column efficiently purified natural camptothecine, caffeine, and evodiamine with the corresponding purities of 92, 96, and 97%. With this work, we have developed an efficient approach to isolate alkaloids and promoted the research on rosin-based materials in biomedicine and analytical chemistry.

Lignocellulosic biomass to biofuels and biochemicals: A comprehensive review with a focus on ethanol organosolv pretreatment technology.

Lignocellulosic biomass is one of the potential feedstocks to produce second-generation cellulosic ethanol and biochemicals. To enhance the enzymatic digestibility of lignocellulosic biomass for efficient enzymatic saccharification, a variety of pretreatment methods have been studied. Among these, organosolv pretreatment using ethanol is a promising pretreatment method owing to its inherent advantages, such as low solvent cost, lack of toxicity, the ability to retain most cellulose fraction in substrates for enzymatic hydrolysis, coproduction of high-purity lignin and hemicellulosic sugars, easy solvent recovery, and reuse. In this review, the research progress regarding different types of ethanol organosolv pretreatment processes has been summarized in terms of methods, substrate properties, reaction mechanisms, delignification kinetic as well as the impact of pretreatment methods on the enzymatic digestibility. Attempts are also made to provide insights into the complete utilization of lignocellulosic biomass to achieve high potential revenues. Though some ethanol organosolv processes have been studied or are being developed towards commercialization, ethanol organosolv pretreatment is still facing some challenges. Finally, the direction for future work is given to develop a proper ethanol organosolv pretreatment for commercialization.

Enhancement of fermentable sugar yield by competitive adsorption of non-enzymatic substances from yeast and cellulase on lignin.

BACKGROUND: Enhancement of enzymatic digestibility by some supplementations could reduce enzyme loading and cost, which is still too high to realize economical production of lignocellulosic biofuels. A recent study indicates that yeast hydrolysates (YH) have improved the efficiency of cellulases on digestibility of furfural residues (FR). In the current work, the components of YH were separated by centrifugation and size exclusion chromatography and finally characterized in order to better understand this positive effect. RESULTS: A 60.8% of nitrogen of yeast cells was remained in the slurry (YHS) after hydrothermal treatment. In the supernatant of YH (YHL), substances of high molecular weight were identified as proteins and other UV-absorbing compounds, which showed close molecular weight to components of cellulases. Those substances attributed to a synergetic positive effect on enzymatic hydrolysis of FR. The fraction of YHL ranged from 1.19 to 2.19 mL (elution volume) contained over 50% of proteins in YHL and had the best performance in stimulating the release of glucose. Experiment results proved the adsorption of proteins in YHL on lignin. CONCLUSIONS: Supplementation of cellulases with YH enhances enzymatic digestibility of FR mainly by a competitive adsorption of non-enzymatic substances on lignin. The molecular weight of these substances has a significant impact on their performance. Different strategies can be used for a good utilization of yeast cells in terms of biorefinery concept.

Comparison of hydrophilic variation and bioethanol production of furfural residues after delignification pretreatment.

Furfural residue (FR) is a waste lignocellulosic material with enormous potential for bioethanol production. In this study, bioethanol production from FR after delignification was compared. Hydrophilic variation was measured by conductometric titration to detect the relationship between hydrophilicity and bioethanol production. It was found that ethanol yield increased as delignification enhanced, and it reached up to 75.6% of theoretical yield for samples with 8.7% lignin. The amount of by-products decreased as delignification increased. New inflection points appeared in conductometric titration curves of samples that were partially delignified, but they vanished in the curves of the highly delignified samples. Total charges and carboxyl levels increased after slight delignification, and they decreased upon further delignification. These phenomena suggested some new hydrophilic groups were formed during pretreated delignification, which would be beneficial to enzymatic hydrolysis. However, some newly formed groups may act as toxicant to the yeast during simultaneous saccharification and fermentation.

Structural characterization of lignin from the green pretreatments for co-producing xylo-oligosaccharides and glucose: Toward full biomass utilization.

Three green non-enzymatic catalysis pretreatments (NECPs) including autohydrolysis, subcritical CO2-assisted seawater autohydrolysis, and inorganic salt catalysis were utilized to simultaneously produce xylo-oligosaccharides (XOS), glucose, and cellulolytic enzyme lignin (CEL) from sugarcane bagasse (SCB). The yield of XOS in all three NECPs was over 50 % with a competitive glucose yield of enzymatic hydrolysis. And the effects of different pretreatments on the chemical structure and composition of CEL samples were also investigated. The pretreatments significantly increased the thermal stability, yield, and purity of the CEL samples. Moreover, the net yield of lignin was 58.3 % with lignin purity was 98.9 % in the autohydrolysis system. Furthermore, there was a decrease in the molecular weight of CEL samples as the pretreatment intensity increased. And the original lignin structural units sustained less damage during the NECPs, due to the cleavage of the ß-O-4 bonds dominating lignin degradation. Meanwhile, these pretreatments increased the phenolic-OH in CEL samples, making the lignin more reactive, and enhancing its subsequent modification and utilization. Collectively, the described techniques have demonstrated practical significance for the coproduction of XOS and glucose, and lignin, providing a promising strategy for full utilization of biomass.

Degradable, anti-swelling, high-strength cellulosic hydrogels via salting-out and ionic coordination.

Cellulosic hydrogels are widely used in various applications, as they are natural raw materials and have excellent degradability. However, their poor mechanical properties restrict their practical application. This study presents a facile approach for fabricating cellulosic hydrogels with high strength by synergistically utilizing salting-out and ionic coordination, thereby inducing the collapse and aggregation of cellulose chains to form a cross-linked network structure. Cellulosic hydrogels are prepared by soaking cellulose in an Al2(SO4)3 solution, which is both strong (compressive strength of up to 16.99 MPa) and tough (compressive toughness of up to 2.86 MJ/m3). The prepared cellulosic hydrogels exhibit resistance to swelling in different solutions and good biodegradability in soil. The cellulosic hydrogels are incorporated into strain sensors for human-motion monitoring by introducing AgNWs. Thus, the study offers a promising, simple, and scalable approach for preparing strong, degradable, and anti-swelling hydrogels using common biomass resources with considerable potential for various applications.

Integrated process of starch ethanol and cellulosic lactic acid for ethanol and lactic acid production.

The sequential production of bioethanol and lactic acid from starch materials and lignocellulosic materials was investigated as ethanol fermentation broth (EFB) can provide nutrients for lactic acid bacteria. A complete process was developed, and all major operations are discussed, including ethanol fermentation, broth treatment, lactic acid fermentation, and product separation. The effect of process parameters, including ethanol fermentation conditions, treatment methods, and the amount of EFB used in simultaneous saccharification and fermentation (SSF), is investigated. Under the selected process conditions, the integrated process without additional chemical consumption provides a 1.08 acid/alcohol ratio (the broth containing 22.4 g/L ethanol and 47.6 g/L lactic acid), which corresponds to a polysaccharide utilization ratio of 86.9 %. Starch ethanol can thus promote cellulosic lactic acid by providing important nutrients for lactic acid bacteria, and in turn, cellulosic lactic acid could promote starch ethanol by improving the profit of the ethanol production process. Two process alternatives for the integration of starch ethanol and cellulosic lactic acid are compared, and some suggestions are given regarding the reuse of yeast following the cellulosic SSF step for lactic acid production.

Structural variations of lignin and lignin-carbohydrate complexes from the fruit shells of Camellia oleifera during ripening.

Camellia oleifera fruit shell (CFS), a waste lignocellulosic biomass resulting from Camellia oleifera oil production industry, is abundantly available in Southern China. Herein, to understand the structural variations of CFS lignins and lignin-carbohydrate complexes (LCC) during ripening, the native lignin and LCC fractions from CFS (harvested every seven days from October 1 to 30, 2022) were isolated and characterized systematically. The molecular weights of both MWL and DEL fractions steadily increased during ripening. CFS lignins contained abundance of ß-O-4' linkages (maximum of 58.6 per 100Ar in DEL-2), and had low S/G ratios (S/G < 0.6). Moreover, the amounts of ß-O-4' linkages in MWL, DEL, and LCC-AcOH fractions increased first and then decreased during ripening. The main lignin-carbohydrate linkages in the LCC-AcOH fractions were benzyl-ether (7.0-9.4 per 100Ar) and phenyl-glycoside (4.5-5.2 per 100Ar) bonds. Based on the quantitative results, the potential structural diagrams of lignins from different ripening stages of CFS were proposed. Additionally, the LCC-AcOH fractions exhibited pronounced antioxidant capacity and were promising as natural antioxidants. The properties and functions of lignin in plant cell walls, as well as its further appreciation, are crucial for the design and selection of feasible pretreatment strategies for the lignocellulosic materials.

Efficient co-production of xylo-oligosaccharides and fermentable sugars from sugarcane bagasse by glutamic acid pretreatment.

In the production of xylo-oligosaccharides (XOS) by organic acid pretreatment, it is often difficult to isolate organic acids from XOS. Here, an acidic amino acid, glutamic acid (GA), was used to pretreat sugarcane bagasse (SCB) to prepare XOS and fermentable sugars. The effects of GA concentration, hydrolysis temperature, and pretreatment time on the yield and polymerization distribution of XOS were investigated. After hydrolysis by 0.2 M GA at 140 °C for 30 min, the maximum yield of X2-5 was 53.3%, and the concentrations of xylose and furfural were 1.8 g/L and 0.1 g/L, respectively. Meanwhile, GA increased the pore size and porosity of SCB as well as the number of functional groups of amino acid residues, which improved the enzymatic efficiency and the maximum yield of glucose was 95.3%. Thus, GA pretreatment provides a more economical, environmentally friendly and sustainable method for the co-production of XOS and glucose from SCB.

Coproduction of xylooligosaccharides, glucose, and less-condensed lignin from sugarcane bagasse using syringic acid pretreatment.

Current strategies for the production of xylooligosaccharides (XOS) from biomass through non-enzymatic catalysis often led to a certain degree of lignin condensation, which severely restrains subsequent enzyme hydrolysis of cellulose. Herein, syringic acid (SA) pretreatment was investigated to coproduce XOS, glucose, and less-condensed lignin from sugarcane bagasse. SA acted as a catalyst and lignin condensation inhibitor during the pretreatment. The highest XOS yield of 58.7% (27.7% xylobiose and 24.7% xylotriose) was obtained at 180 °C - 20 min - 9% SA, and the corresponding xylose/XOS ratio was only 0.42. Compared with the pretreatment at 180 °C - 20 min - 0% SA, the addition of 9% SA increased the glucose yield from 85.7% to 92.4% and decreased the degree of lignin condensation from 0.55 to 0.42. Moreover, 26.7% of SA could be easily recovered. This work presents a pretreatment strategy in which the efficient production of XOS and the suppression of lignin condensation are achieved simultaneously.

Self-healing, EMI shielding, and antibacterial properties of recyclable cellulose liquid metal hydrogel sensor.

Flexible hydrogels are promising materials for the preparation of artificial intelligence electronics and wearable devices. Introducing a rigid conductive material into the hydrogels can improve their electrical conductivities. However, it may have poor interfacial compatibility with the flexible hydrogel matrix. Therefore, we prepared a hydrogel containing flexible and highly ductile liquid metal (LM). The hydrogel can be used as a strain sensor to monitor human motion. The hydrogel showed many properties (i.e., recyclability, EMI shielding properties (33.14 dB), antibacterial (100 %), strain sensitivity (gauge factor = 2.92), and self-healing) that cannot be achieved simultaneously by a single hydrogel. Furthermore, the recycling of LM and their application to hydrogel-based EMI shielding materials have not been investigated previously. Due to its excellent properties, the prepared flexible hydrogel has great potential for applications in artificial intelligence, personal healthcare, and wearable devices.

Evaluation of cellulases produced from four fungi cultured on furfural residues and microcrystalline cellulose.

Four fungal strains-Trichoderma viride, Aspergillus niger, Trichoderma koningii, and Trichoderma reesei-were selected for cellulase production using furfural residues and microcrystalline cellulose (MCC) as the substrates. The filter paper activity (FPA) of the supernatant from each fungus was measured, and the performance of the enzymes from different fungal strains was compared. Moreover, the individual activities of the three components of the cellulase system, i.e., ß-glucosidase, endoglucanase, and exoglucanase were evaluated. T. koningii showed the highest activity (27.81 FPU/ml) on furfural residues, while T. viride showed an activity of 21.61 FPU/ml on MCC. The FPA of the crude enzyme supernatant from T. koningii was 30% higher on furfural residues than on MCC. T. koningii and T. viride exhibited high stability and productivity and were chosen for cellulases production. The crystallinity index (CrI) of the furfural residues varied after digested by the fungi. The results indicated differences in the functioning of the cellulase system from each fungus. In the case of T. koningii, T. reesei and T. viride, furfural residues supported a better environment for cellulase production than MCC. Moreover, the CrI of the furfural residues decreased, indicating that this material was largely digested by the fungi. Thus, our results suggest that it may be possible to use the cellulases produced from these fungi for the simultaneous saccharification and fermentation of lignocellulosic materials in ethanol production.

Coproduction xylo-oligosaccharides with low degree of polymerization and glucose from sugarcane bagasse by non-isothermal subcritical carbon dioxide assisted seawater autohydrolysis.

High pretreatment temperature is necessary to obtain xylo-oligosaccharides (XOS) with low degree of polymerization (DP). However, traditional isothermal pretreatment for XOS production may increase the generation of xylose and furfural with the reaction time extending (10-100 min). In this study, non-isothermal subcritical CO2-assisted seawater autohydrolysis (NSCSA) firstly used seawater and CO2 for the coproduction of XOS with low DP and glucose. 51.44% XOS was obtained at 205 °C/5 MPa, and low-DP (2-4) XOS accounted for 79.13% of the total XOS. Furthermore, the specific surface area and total pore volume of the pretreated sugarcane bagasse (SCB) were 1.96 m2/g and 0.011 cm3/g, respectively, increased by 148% and 83% than that of nature SCB. Compared with subcritical CO2 pretreatment, NSCSA is an efficient method for the coproduction of XOS with low DP and glucose through inorganic salts in seawater and H2CO3 formed from CO2.

Intelligent hydrogel with both redox and thermo-response based on cellulose nanofiber for controlled drug delivery.

The purpose of this study is to develop a hydrogel with temperature and redox response to control drug delivery. However, the strength of temperature sensitive N-isopropylacrylamide (NIPAM) hydrogel is weak. Therefore, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidized cellulose nanofiber (CNF) is introduced to improve this problem. The compressive strength of hydrogels increased by 360% after CNF addition. Meanwhile, N,N'-bis(acryloyl)cystamine (BACy) is introduced into the hydrogels as a cross-linker, imparting redox responsive properties to the hydrogels. Tumor therapeutic drugs are used as model drugs for in vitro release studies. The drug release rate of hydrogel is regulated by temperature and reducing environment. The maximum cumulative release rate of doxorubicin (DOX) is 39.56%, and the Berberine (BBR) is 99.50% after 60 h. The swelling and transparency of hydrogels showed dramatic changes in the range of 30-40 °C. Cytotoxicity experiments demonstrated that the hydrogel had almost no cytotoxicity.

Production of xylooligosaccharides from Camellia oleifera Abel fruit shell using a shell-based solid acid catalyst.

This study aimed to produce xylooligosaccharides (XOS) from Camellia oleifera Abel fruit shell (CFS) using a shell-based solid acid derived from CFS (CFS-BSA). CFS-BSA preparation was optimized by incomplete carbonization at 450 °C for 1 h, followed by sulfonation at 130 °C for 8 h to yield a -SO3H functional group concentration of 1.04 mmol/g. When CFS-BSA was used to hydrolyze CFS with a 1:5 ratio of CFS-BSA to CFS at 170 °C for 20 min, a maximum XOS yield (X2-X5) of 51.41 % was achieved, which was notably higher than when using subcritical H2O solely. CFS-BSA can be recycled and reused at least six times by sieving without a substantial loss in its catalytic activity. CFS-BSA can also be used to produce XOS from other lignocellulosic materials such as corncob (41.04 %), sugarcane bagasse (45.03 %), corn stalk (45.89 %), birchwood (46.05 %), and poplar (40.10 %).

Enzymatic degradation of steam-pretreated Lespedeza stalk (Lespedeza crytobotrya) by cellulosic-substrate induced cellulases.

The cellulase production by Trichoderma viride, cultivated on different substrates, namely steam-pretreated Lespedeza, filter paper, microcrystalline cellulose (MCC) or carboxymethyl cellulose (CMC), was studied. Different cellulase systems were secreted when cultivated on different substrates. The cellulolytic enzyme from steam-pretreated Lespedeza medium performed the highest filter paper activity, exoglucanase and endoglucanase activities, while the highest ß-glucosidase activity was obtained from the enzyme produced on filter paper medium. The hydrolytic potential of the enzymes produced from different media was evaluated on steam-pretreated Lespedeza. The cellulase from steam-pretreated Lespedeza was found to have the most efficient hydrolysis capability to this specific substrate. The molecular weights of the cellulases produced on steam-pretreated Lespedeza, filter paper and MCC media were 33, 37 and 40 kDa, respectively, and the cellulase from CMC medium had molecular weights of 20 and 43 kDa. The degree of polymerization, crystallinity index and micro structure scanned by the scanning electron microscopy of degraded steam-pretreated Lespedeza residues were also studied.

Xylo-oligosaccharides and lignin production from Camellia oleifera shell by malic acid hydrolysis at mild conditions.

Camellia oleifera shell (COS), a by-product of processing woody vegetable oil, is rich in hemicellulose and lignin. In this study, we investigated the effects of acid concentration, pretreatment temperature and reaction time on the concentration and yield of xylo-oligosaccharides (XOS) and the degree of polymerization (DP) distribution of XOS when pretreating COS with malic acid (MA). Under moderate condition (2 M MA, 120 â„ƒ, 30 min), the maximum yield of XOS with DP 2-4 was 48.78% (based on the initial xylan) with low xylose, 5-hydroxymethylfurfural (HMF) and furfural, in which xylobiose (X2), xylotriose (X3) and xylotraose (X4) concentrations were 5.22 g/L, 2.75 g/L and 2.91 g/L, respectively. In addition, acid-insoluble lignin (AIL) in the residue after MA pretreatment and milling wood lignin (MWL) were mainly composed of guaiacyl and syringyl. AIL has higher thermal stability than MWL, which can be the stabilizer for producing flame-resistant materials.

An in-situ fabrication of bamboo bacterial cellulose/sodium alginate nanocomposite hydrogels as carrier materials for controlled protein drug delivery.

Sodium alginate-bacterial cellulose (SA-BC) is a nanocomposite hydrogel with multi-layered porous surfaces fabricated using an in-situ biosynthesis modification method. The enzymatic hydrolysate (EH) of glycerol-pretreated Moso bamboo (MBEH) was the carbon source for glucose substitution to generate SA-bamboo-BC. SA, a natural biological polysaccharide, was combined with BC at dosages of 0.25%, 0.5%, 0.75% and 1% through hydrogen bonding. Compared to the native BC, the addition of 0.75% SA, termed as SA-bamboo-BC-0.75, enhanced the thermal properties. The dynamic swelling/de-swelling were pH-dependent, with an increased swelling ratio (SR) of 613% observed at pH 7.4 but a lower SR of 366% observed at pH 1.2. These differences were attributable to the electrostatic repulsion of -COO-. Two protein-based model drugs were compared to estimate their drug-release properties. Bovine serum albumin (BSA) was adsorbed on lignin from MBEH through hydrophobic interactions, resulting in poor drug release. Lysozyme (LYZ) exhibited a higher drug release rate (92.79%) over 60 h at pH 7.4 due to the static attraction between LYZ and -COO- of SA-bamboo-BC-0.75. As such, SA-bamboo-BC nanocomposite hydrogel was shown to possess sufficient swelling, drug-release and biocompatibility for substrate use.

Catalyst-Free Self-Healing Bio-Based Polymers: Robust Mechanical Properties, Shape Memory, and Recyclability.

The poor mechanical properties and disadvantages of catalysts limit the application of self-healing materials. To address these issues, catalyst-free self-healing bio-based polymers (AESO-EMPA polymers) with robust mechanical properties were prepared using epoxidized maleopimaric anhydride (EMPA) and aminated epoxidized soybean oil (AESO). The AESO-EMPA polymers are recyclable and exhibit self-healing and shape memory because of the dual-dynamic network of multiple H-bonds and dynamic ester bonds in the structure. Under the synergistic catalysis of the tertiary amines and hydroxyl groups originated from the polymers, the polymers in this study achieve network rearrangement without the need for additional catalysts. The polymers also exhibit excellent mechanical properties with a tensile strength of 29.1 ± 0.25 MPa and a Tg of 80.2 °C owing to the unique rigid backbone of rosin and the dual-dynamic network. The AESO-EMPA polymers can be used as reusable adhesives and exhibit excellent shear strength and repair rates.

Characterization of bacterial cellulose composite films incorporated with bulk chitosan and chitosan nanoparticles: A comparative study.

Ternary composite films containing bulk chitosan (CS) and chitosan nanoparticles (CSNPs) with different concentrations were prepared using bacterial cellulose/poly(vinyl alcohol) as the base film and the composites films were compared. The micromorphology and mechanical, physical, chemical, antibacterial, and optical barrier properties of the composite films were compared. CS incorporation improved the mechanical properties, as the maximum tensile strength was increased to 130.55 ± 9.42 MPa. The dense structure of CSNPs prevented water diffusion and lessened the water content of the composite membranes. The inclusion of CS and CSNPs both reduced the water solubility and water vapor permeability. CS-doped films possessed good transparency, while CSNPs had better ultraviolet-barrier properties (3.84 % of transmittance at 200-280 nm). In addition, CSNPs-embedded membranes exhibited prominent antibacterial properties against Escherichia coli and Staphylococcus aureus, which were much greater than those of CS composite membranes with a maximum bacteriostatic diameter of 10.33 ± 1.55 mm.