Self-Formation of Lignin Particles Through Melt-Extrusion for Active Biodegradable Food Packaging.

This study presents a method for the self-formation of lignin particles within a polylactic acid (PLA) matrix during melt-extrusion, eliminating the need for separation and drying steps typically associated with submicro-size lignin particles. This method effectively mitigates the problem of agglomeration often associated with the drying step. Softwood kraft lignin, guaiacyl lignin (GL-lignin), was dissolved in low-molecular-weight poly(ethylene glycol) (PEG) and was introduced into a twin-screw extruder using a liquid feeder. Lignin particles within a particle size range of 200-500 nm were observed in the extrudate of the PLA/PEG/GL-lignin composites. PLA/PEG/GL-lignin composite films were produced through blown film extrusion. These composite films demonstrated superior ultraviolet (UV)-barrier and antioxidant properties compared to neat PLA films, with optical and mechanical characteristics comparable to those of neat PLA. Moreover, migration values of the composite films in various food simulants were below regulatory limits, suggesting their potential for food packaging applications. This self-formation process offers a promising approach for utilizing lignin for PLA applications.

Enhanced antifungal properties of poly(butylene succinate) film with lignin nanoparticles and trans-cinnamaldehyde for mango packaging.

Sustainable poly(butylene succinate) (PBS) films incorporating lignin nanoparticles (LN) and trans-cinnamaldehyde (CN) have been developed to preserve mango freshness and provide food safety. PBS/LN, PBS/CN, and PBS/LN/CN composite films were produced by blown film melt extrusion. This study investigated the effect of CN-LN on the CN remaining content, thermal, mechanical, and barrier properties, diffusion coefficient, and antifungal activity of PBS films both in vitro and in vivo. Results showed that LN in the PBS/LN/CN composite film contained more CN than in the PBS/CN film. The compatibility of CN-LN with PBS produced homogeneous surfaces with enhanced barrier properties. PBS/LN/CN composite films demonstrated superior antifungal efficacy, inhibiting the growth of Colletotrichum gloeosporioides and preserving mango quality during storage. Results suggested that incorporating LN into PBS composite films prolonged the sustained release of antifungal agents, thereby inhibiting microbial growth and extending the shelf life of mangoes. Development of PBS/LN/CN composite films is a beneficial step toward reducing food waste and enhancing food safety.

Nanostructured N/S doped carbon dots/mesoporous silica nanoparticles and PVA composite hydrogel fabrication for anti-microbial and anti-biofilm application.

Regarding the convergence of the worldwide epidemic, the appearance of bacterial infection has occasioned in a melodramatic upsurge in bacterial pathogens with confrontation against one or numerous antibiotics. The implementation of engineered nanostructured particles as a delivery vehicle for antimicrobial agent is one promising approach that could theoretically battle the setbacks mentioned. Among all nanoparticles, silica nanoparticles have been found to provide functional features that are advantageous for combatting bacterial contagion. Apart from that, carbon dots, a zero-dimension nanomaterial, have recently exhibited their photo-responsive property to generate reactive oxygen species facilitating to enhance microorganism suppression and inactivation ability. In this study, potentials of core/shell mesoporous silica nanostructures (MSN) in conjugation with carbon dots (CDs) toward antimicrobial activity against Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli have been investigated. Nitrogen and sulfur doped CDs (NS/CDs) conjugated with MSN which were cost effective nanoparticles exhibited much superior antimicrobial activity for 4 times as much as silver nanoparticles against all bacteria tested. Among all nanoparticles tested, 0.40 M NS/CDs@MSN showed the greatest minimal biofilm inhibitory at very low concentration (< 0.125 mg mL-1), followed by 0.20 M NS/CDs@MSN (0.5 mg mL-1), CD@MSN (25 mg mL-1), and MSN (50 mg mL-1), respectively. Immobilization of NS/CDs@MSN in polyvinyl alcohol (PVA) hydrogel was performed and its effect on antimicrobial activity, biofilm controlling efficiency, and cytotoxicity toward fibroblast (NIH/3 T3 and L-929) cells was additionally studied for further biomedical applications. The results demonstrated that 0.40 M NS/CDs-MSN@PVA hydrogel exhibited the highest inhibitory effect on S. aureus > P. aeruginosa > E. coli. In addition, MTT assay revealed some degree of toxicity of 0.40 M NS/CDs-MSN@PVA hydrogel against L-929 cells by a slight reduction of cell viability from 100% to 81.6% when incubated in the extract from 0.40 M NS/CDs-MSN@PVA hydrogel, while no toxicity of the same hydrogel extract was detected toward NIH/3 T3 cells.

Unraveling the Adsorption Behavior of Thymol on Carbon and Silica Nanospheres for Prolonged Antibacterial Activity: Experimental and DFT Studies.

Functionalization of thymol (Thy) on nanocarriers is a key step in achieving prolonged antimicrobial activity. This requires nanomaterials with uniform particle diameters and suitable thymol sorption. Herein, hollow carbon (HC) and SiO2-carbon core-shell (SiO2@C) were investigated due to their diverse morphologies and ease of surface modification. HC (14 ± 1 nm size) and SiO2@C (10 ± 1.5 nm size) were synthesized by the Stöber method before thymol was loaded by incipient wetness impregnation. Nanoparticle physicochemical properties were characterized by advanced techniques, including X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). Adsorption energies of thymol on the carbon and SiO2 surfaces were elucidated by density functional theory (DFT) simulations. Moreover, the in vitro thymol release profiles and antibacterial activity were evaluated. The experimental results indicated that the oxy-carbon surface species of HC led to longer thymol release profiles than the -OH group of SiO2@C. The DFT calculations revealed that the weaker physical interaction of thymol on HC was better for drug release than that on SiO2@C. Thus, a longer thymol release profile of HC with hollow structures showed better antibacterial performance against Gram-positive bacteria Staphylococcus aureus than that of SiO2@C with core-shell structures. This work confirms the important role of carbon morphology and specific functional groups in thymol release profiles for the further development of inhibition products.

Lignin Nanoparticles for Enhancing Physicochemical and Antimicrobial Properties of Polybutylene Succinate/Thymol Composite Film for Active Packaging.

The natural abundance, polymer stability, biodegradability, and natural antimicrobial properties of lignin open a wide range of potential applications aiming for sustainability. In this work, the effects of 1% (w/w) softwood kraft lignin nanoparticles (SLNPs) on the physicochemical properties of polybutylene succinate (PBS) composite films were investigated. Incorporation of SLNPs into neat PBS enhanced Td from 354.1 °C to 364.7 °C, determined through TGA, whereas Tg increased from -39.1 °C to -35.7 °C while no significant change was observed in Tm and crystallinity, analyzed through DSC. The tensile strength of neat PBS increased, to 35.6 MPa, when SLNPs were added to it. Oxygen and water vapor permeabilities of PBS with SLNPs decreased equating to enhanced barrier properties. The good interactions among SLNPs, thymol, and PBS matrix, and the high homogeneity of the resultant PBS composite films, were determined through FTIR and FE-SEM analyses. This work revealed that, among the PBS composite films tested, PBS + 1% SLNPs + 10% thymol showed the strongest microbial growth inhibition against Colletotrichum gloeosporioides and Lasiodiplodia theobromae, both in vitro, through a diffusion method assay, and in actual testing on active packaging of mango fruit (cultivar "Nam Dok Mai Si Thong"). SLNPs could be an attractive replacement for synthetic substances for enhancing polymer properties without compromising the biodegradability of the resultant material, and for providing antimicrobial functions for active packaging applications.

Physicochemical properties of lignin nanoparticles from softwood and their potential application in sustainable pre-harvest bagging as transparent UV-shielding films.

Technical lignin can be mainly obtained as a waste by-product from pulp industry, and it exhibits unique properties including ultraviolet adsorption, biodegradable, antibacterial, and antioxidant which can be utilized for bioplastic applications. However, common limitations of technical lignin for plastic applications are compatibility mainly due to poor interfacial adhesion, relatively large particle size and impurity. In this study lignin nanoparticles from softwood (S-LNPs) were successfully produced through a continuous-green-scalable antisolvent precipitation and the suitability of S-LNPs for fabrication of bio-composite polybutylene succinate (PBS) films using conventional blown film extrusion was examined. The attained S-LNPs showed lower ash content, higher phenolic content and higher lignin content compared to pristine softwood kraft lignin (S-lignin). Rheological property including shear viscosity and melt-flow index was determined. The obtained PBS/S-LNP composite films showed improved tensile modulus, higher water vapor transmission rate and excellent UV-shielding ability compared to neat PBS and PBS/S-lignin films. Accelerated weathering testing was conducted to replicate outdoor conditions. Degradation indices including carbonyl, vinyl and hydroxyl of the weathered PBS/lignin composites were evaluated for photo-oxidative stability. The S-LNPs as multifunctional bio-additives in biodegradable composite film exhibited superior performances of transparency, UV-absorption and stiffness with high photo-oxidative stability suitable for outdoor applications.

Cryo-Induced Cellulose-Based Nanogel from Elaeis guineensis for Antibiotic Delivery Platform.

Cryo-induced hydrogel from cellulose is a new class of biomaterials for drug delivery, cell delivery, bone and skin tissue engineering for cell proliferation and regeneration applications. This research aimed to synthesize cryo-induced hydrogel from cellulose and carboxymethyl cellulose (CMC) produced from empty bunch's cell wall of Elaeis guineensis. First, the experiment was to produce cellulose-rich material using hot-compressed water extraction followed by alkaline delignification and bleaching with H2O2. The obtained bleached EFB cellulose was used as the substrate for CMC, and the optimal condition with the highest degree of carboxyl substitution (DS) of 0.75 was achieved when varying NaOH and monochloroacetic acid concentration as well as etherification temperature using fractional factorial design. For cryogelation study, hydrogels were synthesized from cellulose, CMC and beta-cyclodextrin (ß-CD) by dissolving cellulose-based matrix in a NaOH/urea system, and the cellulose (CEL) solution was frozen spontaneously at -40 °C followed by high speed mixing to loosen cellulose fibrils. Epichlorohydrin (ECH) and Polyethylene glycol diglycidyl ether (PEGDE) were used as a cross-linker. First, the ratio of cellulose and CMC with different amounts of ECH was investigated, and subsequently the proper ratio was further studied by adding different crosslinkers and matrices, i.e., CMC and ß-CD. From the result, the ECH crosslinked CMC-CEL (E-CMC-CEL) gel had the highest swelling properties of 5105% with the average pore size of lyophilized hydrogel of 300 µm. In addition, E-CMC-CEL gel had the highest loading and release capability of tetracycline in buffer solution at pH 7.4 and 3.2. At pH 7.4, tetracycline loading and release properties of E-CMC-CEL gel were 65.85 mg g-1 dry hydrogel and 46.48 mg g-1 dry hydrogel (70.6% cumulative release), respectively. However, at pH 3.2, the loading and release capabilities of Tetracycline were moderately lower at 16.25 mg g-1 dry hydrogel and 5.06 mg g-1 dry hydrogel, respectively. The findings presented that E-CMC-CEL hydrogel was a suitable material for antibiotic tetracycline drug carrying platform providing successful inhibitory effect on Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa, respectively.

Platinum/carbon dots nanocomposites from palm bunch hydrothermal synthesis as highly efficient peroxidase mimics for ultra-low H2O2 sensing platform through dual mode of colorimetric and fluorescent detection.

Detection of hydrogen peroxide and glucose in nanomolar level is crucial for point-of-care medical diagnosis. It has been reported that human's central nervous system diseases such as Alzheimer's disease, Parkinson's disease, and even amyotrophic lateral sclerosis, are presumably caused H2O2 or reactive radical species (ROS). Sensing of H2O2 released from human biofluids, tissues, organ from metabolism disorder at ultra-low concentration assists for early identification of severe diabetis mellitus related to glucose, and heart attack, as well as stroke related to cholesterol. In this work, carbon dots (CDs) having an average diameter at 6.99 nm with highly photoluminescence performance were successfully synthesized from palm empty fruit bunch (EFB) using green and environmentally friendly process via hydrothermal condition. CDs acted well on peroxidase-like activity for H2O2 detection at room temperature, however their sensitivity on ultra-low H2O2 concentration needed to be improved. To enhance their reactivity on H2O2 nanozyme activity at room temperature, synthesis of hybrid metal nanoparticles (AgNPs and PtNPs) on CDs surface was established. The findings exhibited that CDs/PtNPs was the most suitable nanozyme achieving highly efficient peroxidase mimic for dual mode of colorimetric and fluorescent H2O2 sensing platform at very low limit of detection of 0.01 mM (10 nM) H2O2.

The Role of N and S Doping on Photoluminescent Characteristics of Carbon Dots from Palm Bunches for Fluorimetric Sensing of Fe3+ Ion.

This work aims to enhance the value of palm empty fruit bunches (EFBs), an abundant residue from the palm oil industry, as a precursor for the synthesis of luminescent carbon dots (CDs). The mechanism of fIuorimetric sensing using carbon dots for either enhancing or quenching photoluminescence properties when binding with analytes is useful for the detection of ultra-low amounts of analytes. This study revealed that EFB-derived CDs via hydrothermal synthesis exceptionally exhibited luminescence properties. In addition, surface modification for specific binding to a target molecule substantially augmented their PL characteristics. Among the different nitrogen and sulfur (N and S) doping agents used, including urea (U), sulfate (S), p-phenylenediamine (P), and sodium thiosulfate (TS), the results showed that PTS-CDs from the co-doping of p-phenylenediamine and sodium thiosulfate exhibited the highest PL properties. From this study on the fluorimetric sensing of several metal ions, PTS-CDs could effectively detect Fe3+ with the highest selectivity by fluorescence quenching to 79.1% at a limit of detection (LOD) of 0.1 µmol L-1. The PL quenching of PTS-CDs was linearly correlated with the wide range of Fe3+ concentration, ranging from 5 to 400 µmol L-1 (R2 = 0.9933).

Solvothermal-Based Lignin Fractionation From Corn Stover: Process Optimization and Product Characteristics.

Fractionation of lignocellulosic is a fundamental step in the production of value-added biobased products. This work proposes an initiative to efficiently extract lignin from the corn stover using a single-step solvothermal fractionation in the presence of an acid promoter (H2SO4). The organic solvent mixture used consists of ethyl acetate, ethanol, and water at a ratio of 30: 25:45 (v/v), respectively. H2SO4 was utilized as a promoter to improve the performance and selectivity of lignin removal from the solid phase and to increase the amount of recovered lignin in the organic phase. The optimal conditions for this extraction, based on response surface methodology (RSM), are a temperature of 180°C maintained for 49.1 min at an H2SO4 concentration of 0.08 M. The optimal conditions show an efficient reaction with 98.0% cellulose yield and 75.0% lignin removal corresponding to 72.9% lignin recovery. In addition, the extracted lignin fractions, chemical composition, and structural features were investigated using Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance spectroscopy (2D-HSQC NMR). The results indicate that the recovered lignin primarily contains a ß-O-4 linking motif based on 2D-HSQC spectra. In addition, new C-C inter-unit linkages (i.e., ß-ß, and ß-5) are not formed in the recovered lignin during H2SO4-catalyzed solvothermal pretreatment. This work facilitates effective valorization of lignin into value-added chemicals and fuels.

Effects of Modified Activated Carbon on Microwave-Accelerated Organosolv Fractionation of Rice Husk.

Organosolv fractionation is a promising approach for the separation of lignocellulosic components in integrated biorefineries where each component can be fully valorized into valuable platform chemicals and biofuels. In this study, microwave-accelerated organosolv fractionation was developed for the modification of lignocellulosic fractionation of rice husk. The fractionation condition was optimized for 1 h with the microwave irradiation at 300 W using a ternary solvent mixture composed of 24%:32%:44% water/ethanol/methyl isobutyl ketone. The effects of mineral acids (HCl, H3PO4, and H2SO4) and heterogeneous acid promoters (HCl, H3PO4, and H2SO4 impregnated over activated carbon) on the efficiency and selectivity of product yields (i.e., glucan, hemicellulose-derived products, and lignin) were also investigated. It was found that the use of H3PO4-activated carbon as the promoter showed superior performance on the fractionation of rice husk components, resulting in 88.8% recovery of cellulose, with 63.8% purity in the solid phase, whereas the recovery of hemicellulose (66.4%) with the lowest formation of furan and 5-hydroxymethyl furfural and lignin (81.0%) without sugar cross-contamination was obtained in the aqueous ethanol phase and organic phase, respectively. In addition, the morphology structure of fractionated rice husk presented 2.6-fold higher surface area (5.4 m2/g) of cellulose-enriched fraction in comparison with the native rice husk (2.1 m2/g), indicating the improvement of enzyme accessibility. Besides, the chemical changes of isolated lignin were also investigated by Fourier-transform infrared spectroscopy. This work gives pieces of information into the efficiencies of the microwave strategy as a climate neighborly elective fractionation method for this serious starting material in the biotreatment facility business.

Fractionation and characterization of lignin from sugarcane bagasse using a sulfuric acid catalyzed solvothermal process.

Conversion of lignocellulosic residue to bioenergy and biofuel is a promising platform for global sustainability. Fractionation is an initial step for isolating lignocellulosic components for subsequent valorization. The aim of this research is to develop the solvothermal fractionation of sugarcane bagasse to produce high purity lignin. The physio-chemical structure of isolated lignin from this process was determined. In this study, a central composite design-based response surface methodology (RSM) was used to optimize an acid promoter for isolating lignin from sugarcane bagasse using a solvothermal fractionation process. The reaction was carried out with sulfuric acid, at a concentration of 0.01-0.02 M and a reaction temperature of 180-200 °C for 30-90 min. The optimal conditions for the experiment were obtained at the acid concentration of 0.02 M with a temperature of 200 °C for 90 min in methyl isobutyl ketone (MIBK)/methanol/water (35% : 25% : 40% v/v%). The results showed that 88% of lignin removal was done in the solid phase, while 87% of lignin recovery was conducted in the organic phase. Furthermore, the changes in the physico-chemical characteristics of solid residue and lignin recovery were analyzed using various techniques. GPC analysis of recovered lignin from the organic fraction showed a lower M w (1374 g mol-1) and polydispersity index (1.75) compared to commercial organosolv lignin. The major lignin degradation temperature of commercial organosolv lignin was estimated to be 410 °C, whereas BGL showed two main degradations at 291 °C and 437 °C, which could point to potential relationships with the degradation of ß-O-4 cross-links. The results indicated that recovered lignin was mostly cross-linked by ß-O-4 cross-links. In addition, Py-GC/MS and 2D HSQC NMR gave more information regarding the compositional and structural features of recovered lignin. The development of the sulfuric acid catalyzed solvothermal process in this study provides efficient extraction of high-value organosolv lignin from sugarcane bagasse and the production of recovered lignin in the organic phase with low contamination from other contents. The lignin characteristic data can contribute to the development of lignin valorization in value-added applications.

Efficiency of Catalytic Liquid Hot Water Pretreatment for Conversion of Corn Stover to Bioethanol.

Lignocellulose is a promising raw material for the production of second-generation biofuels. In this study, the effects of acid-catalyzed liquid hot water (LHW) on pretreatment of corn stover (CS) for subsequent hydrolysis and conversion to ethanol were studied. The effects of reaction temperature, acid concentration, and residence time on glucose yield were evaluated using a response surface methodology. The optimal condition was 162.4 °C for 29.5 min with 0.45% v/v of sulfuric acid, leading to the maximum glucose yield of 91.05% from enzymatic hydrolysis of the cellulose-enriched fraction. Conversion of the solid fraction to ethanol by simultaneous saccharification and fermentation resulted in a theoretical ethanol yield of 93.91% based on digestible glucose. Scanning electron microscopy revealed disruption on the microstructure of the pretreated CS. Increases of crystallinity index and surface area of the pretreated biomass were observed along with alteration in the functional group profiles, as demonstrated by Fourier transform infrared spectroscopy. This work provides an insight into the effects of LHW on the enzymatic susceptibility and modification of the physicochemical properties of CS for further application on bioethanol production in biorefinery.

Effect of HCOOK/Ethanol on Fe/HUSY, Ni/HUSY, and Ni-Fe/HUSY Catalysts on Lignin Depolymerization to Benzyl Alcohols and Bioaromatics.

We have investigated the production of benzyl alcohols and bioaromatics via the reductive lignin depolymerization process over Fe/H-style ultrastable Y (HUSY), Ni/HUSY, and Ni-Fe/HUSY catalysts using HCOOK/ETOH in air. Synergy effect between HCOOK and the catalysts improved the depolymerization process, resulting in a higher bio-oil recovery. HCOOK does not act solely as an in situ hydrogen source; it also interacts with lignin to enable its initial depolymerization via a base-catalyzed mechanism to low-molecular-weight fragments, and in tandem with the catalyst, the hydrogenolysis rate of the depolymerized lignin monomers was enhanced. Fe/HUSY displayed an excellent activity for the catalytic reductive step in contrast to Ni/HUSY and Ni-Fe/HUSY by facilitating methoxy group removal via hydrogenolysis, thereby contributing to the yield and stabilization of the low-molecular-weight aromatics [diethyl ether (DEE)-soluble products]. Fe/HUSY gave the highest DEE product yield of >99 wt % and a total benzyl alcohol yield of 16 wt % with a total selectivity of 47 wt % (60 wt % for aromatic alcohols). Fe/HUSY was reused for the lignin depolymerization reaction without much loss of its initial activity, giving 13 wt % yield of benzyl alcohols with a selectivity of 58 wt % (77 wt % for aromatic alcohols).

Biochemical characterization and synergism of cellulolytic enzyme system from Chaetomium globosum on rice straw saccharification.

BACKGROUND: Efficient hydrolysis of lignocellulosic materials to sugars for conversion to biofuels and chemicals is a key step in biorefinery. Designing an active saccharifying enzyme system with synergy among their components is considered a promising approach. RESULTS: In this study, a lignocellulose-degrading enzyme system of Chaetomium globosum BCC5776 (CG-Cel) was characterized for its activity and proteomic profiles, and synergism with accessory enzymes. The highest cellulase productivity of 0.40 FPU/mL was found for CG-Cel under the optimized submerged fermentation conditions on 1% (w/v) EPFB (empty palm fruit bunch), 2% microcrystalline cellulose (Avicel®) and 1% soybean meal (SBM) at 30 °C, pH 5.8 for 6 d. CG-Cel worked optimally at 50-60 °C in an acidic pH range. Proteomics analysis by LC/MS/MS revealed a complex enzyme system composed of core cellulases and accessory hydrolytic/non-hydrolytic enzymes attacking plant biopolymers. A synergistic enzyme system comprising the CG-Cel, a ß-glucosidase (Novozyme® 188) and a hemicellulase Accellerase® XY was optimized on saccharification of alkaline-pretreated rice straw by a mixture design approach. Applying a full cubic model, the optimal ratio of ternary enzyme mixture containing CG-Cel: Novozyme® 188: Accellerase® XY of 44.4:20.6:35.0 showed synergistic enhancement on reducing sugar yield with a glucose releasing efficiency of 256.4 mg/FPU, equivalent to a 2.9 times compared with that from CG-Cel alone. CONCLUSIONS: The work showed an approach for developing an active synergistic enzyme system based on the newly characterized C. globosum for lignocellulose saccharification and modification in bio-industries.