Lignin nanoparticles as a highly efficient adsorbent for the removal of methylene blue from aqueous media.

This work demonstrated enhanced adsorption capabilities of lignin nanoparticles (LNPs) synthesized via a straightforward hydrotropic method compared to pristine lignin (PL) powder for removing methylene blue dye from aqueous solutions. Kraft lignin was used as a precursor and p-toluenesulfonic acid as the hydrotrope to produce spherical LNPs with ~ 200 nm diameter. Extensive characterization by SEM, AFM, DLS, zeta potential, and BET verified successful fabrication of microporous LNPs with fourfold higher specific surface area (14.9 m2/g) compared to PL (3.4 m2/g). Significantly reduced particle agglomeration and rearranged surface chemistry (zeta potential of -13.3 mV) arising from the self-assembly of lignin fractions under hydrotropic conditions enabled the application of LNPs and superior adsorbents compared to PL. Batch adsorption experiments exhibited up to 14 times higher methylene blue removal capacity, from 20.74 for PL to 127.91 mg/g for LNPs, and ultrafast equilibrium uptake within 3 min for LNPs compared to 10 min for PL. Kinetic modeling based on pseudo-first-order and pseudo-second-order equations revealed chemisorption as the predominant mechanism, with a rate constant of 0.032825 g/mg·h for LNPs-over an order of magnitude higher than PL (0.07125 g/mg·h). Isotherm modeling indicated Langmuir monolayer adsorption behavior on relatively uniform lignin surface functional groups. The substantially augmented adsorption performance of LNPs arose from the increased surface area and abundance of surface functional groups, providing greater accessibility of chemically active binding sites for rapid dye uptake. Overall, this work demonstrates that tailoring lignin nanoparticle structure and surface chemistry via scalable hydrotropic synthesis is a simple and sustainable approach for producing highly efficient lignin-based nano-adsorbents for organic dye removal from industrial wastewater.

Comparative study on liquid versus gas phase hydrochloric acid hydrolysis for microcrystalline cellulose isolation from sugarcane bagasse.

Microcrystalline cellulose (MCC) was successfully synthesized from sugarcane bagasse using a rapid, low-temperature hydrochloric acid (HCl) gas treatment. The primary aim was to develop an energy-efficient "green" cellulose extraction process. Response surface methodology optimized the liquid-phase hydrolysis conditions to 3.3 % HCl at 117 °C for 127 min to obtain MCC with 350 degree of polymerization. An alternative gas-phase approach utilizing gaseous HCl diluted in hot 40 °C air was proposed to accelerate MCC production. The cellulose pulp was moistened to 15-18 % moisture content and then exposed to HCl gas, which was absorbed by the moisture in the cellulose fibers to generate a highly concentrated acidic solution that hydrolyzed the cellulose. The cellulose pulp was isolated from depithed bagasse through soda pulping, multistage bleaching and cold alkali purification. Hydrolysis was conducted by saturating the moist cellulose fibers with gaseous HCl mixed with hot air. Extensive analytical characterization using FT-IR, XRD, SEM, TGA, DSC, particle size, and porosity analyses verified comparable physicochemical attributes between MCC samples prepared via liquid and gas phase methods. The gas-produced MCC revealed 85% crystallinity, 71 Å crystallite dimensions, and thermally stable rod-shaped morphology with an average diameter below 200 µm. The similar material properties validate the proposed gas-based technique as an equally effective yet more energy-efficient alternative to conventional aqueous acid hydrolysis for fabricating highly pure MCC powders from lignocellulose. This sustainable approach enables the value-addition of sugarcane bagasse agro-industrial residue into cellulosic nanomaterials for wide-ranging industrial applications. In summary, the key achievements of this work are rapid MCC production under mild temperatures using HCl gas, optimization of liquid phase hydrolysis, successful demonstration of gas phase method, and extensive characterization verifying equivalence between both protocols. The gas methodology offers a greener cellulose extraction process from biomass.

Surfactants facilitated glycerol organosolv pretreatment of lignocellulosic biomass by structural modification for co-production of fermentable sugars and highly reactive lignin.

This study reported that surfactants could facilitate the organosolv pretreatment of lignocellulosic biomass (LCB) to produce fermentable sugars and highly active lignin. Under the optimized conditions, the surfactant-assisted glycerol organosolv (saGO) pretreatment achieved 80.7% delignification with a retention of 93.4% cellulose and 83.0% hemicellulose. The saGO pretreated substrate exhibited an excellent enzymatic hydrolyzability, achieving 93% of glucose yield from the enzymatic hydrolysis at 48 h. Structural analysis showed that the saGO lignin contained rich ß-O-4 bondings with less repolymerization and lower phenolic hydroxyl groups, thus forming highly reactive lignin fragments. The analysis evidenced that the surfactant graft the lignin by structural modification, which was responsible for the excellent substrate hydrolyzability. The co-production of fermentable sugars and organosolv lignin almost recovered a gross energy (87.2%) from LCB. Overall, the saGO pretreatment holds a lot of promise for launching a novel pathway towards lignocellulosic fractionation and lignin valorization.

Construction of Cu-N coordination into natural biopolymer lignin backbone for highly efficient and selective removal of cationic dyes.

Here, a Cu2+-doped lignin-based adsorbent (Cu-AL) was fabricated via the amination and Cu2+-doping of industrial alkali lignin for massive and selective adsorption of cationic dyes azure B (AB) and saffron T (ST). The Cu-N coordination structures endowed Cu-AL with stronger electronegativity and higher dispersity. Through the electrostatic attraction, π-π interaction, H-bonding, and Cu2+ coordination, the adsorption capacities of AB and ST reached up to 1168 and 1420 mg g-1, respectively. The pseudo-second-order model and Langmuir isotherm model were more relevant to the AB and ST adsorption on Cu-AL. Based on the thermodynamic study, the adsorption progresses were endothermic, spontaneous, and feasible. The Cu-AL maintained high removal efficiency to dyes after 4 reuses (>80%). Importantly, the Cu-AL could efficiently remove and separate AB and ST from dye mixtures even in real time. All the above characteristics demonstrated that Cu-AL was an excellent adsorbent for fast wastewater treatment.

High-purity cellulose production from birch wood by γ-valerolactone/water fractionation and IONCELL-P process.

This study presents an environmentally friendly process to produce high-purity cellulose (dissolving pulp) from birch wood by combining γ-valerolactone (GVL)/water fractionation and ionic liquid treatment of pulp, IONCELL-P (IP). A paper grade pulp was produced from optimal GVL cook with a similar composition to birch kraft pulp and was bleached with ECF sequence before the hemicelluloses were removed using the IONCELL-P process. The purity of the GVL-IP pulp significantly exceeded that of commercial prehydrolysis kraft (PHK) and prehydrolysis soda-anthraquinone (PH-Soda-AQ) pulps. IONCELL-P extraction removed more than 90% of the hemicelluloses, resulting in a dissolving pulp with a purity of 96% and a high molecular mass fraction, 2.3 times higher than that of a conventional PHK pulp. GVL-IP pulps are suitable not only for regenerated cellulose fibers or films, but also for high-purity, high-viscosity cellulose acetate and ethers, which cannot be produced in an environmentally friendly way by conventional processes.

Glycerol organosolv pretreatment can unlock lignocellulosic biomass for production of fermentable sugars: Present situation and challenges.

The complex structure of lignocellulosic biomass forms the recalcitrance to prevent the embedded holo-cellulosic sugars from undergoing the biodegradation. Therefore, a pretreatment is often required for an efficient enzymatic lignocellulosic hydrolysis. Recently, glycerol organosolv (GO) pretreatment is revealed potent in selective deconstruction of various lignocellulosic biomass and effective improvement of enzymatic hydrolysis. Evidently, the GO pretreatment is capable to modify the structure of dissolved components by glycerolysis, i.e., by trans-glycosylation onto glyceryl glycosides and by hydroxylation grafting onto glyceryl lignin. Such modifications tend to protect these main components against excessive degradation, which can be mainly responsible for the obviously less fermentation inhibitors arising in the GO pretreatment. This pretreatment can provide opportunities for valorization of emerging lignocellulosic biorefinery with production of value-added biochemicals. Recent advances in GO pretreatment of lignocellulosic biomass followed by enzymatic hydrolysis are reviewed, and perspectives are made for addressing remaining challenges.

Thermostable Cellulases / Xylanases From Thermophilic and Hyperthermophilic Microorganisms: Current Perspective.

The bioconversion of lignocellulose into monosaccharides is critical for ensuring the continual manufacturing of biofuels and value-added bioproducts. Enzymatic degradation, which has a high yield, low energy consumption, and enhanced selectivity, could be the most efficient and environmentally friendly technique for converting complex lignocellulose polymers to fermentable monosaccharides, and it is expected to make cellulases and xylanases the most demanded industrial enzymes. The widespread nature of thermophilic microorganisms allows them to proliferate on a variety of substrates and release substantial quantities of cellulases and xylanases, which makes them a great source of thermostable enzymes. The most significant breakthrough of lignocellulolytic enzymes lies in lignocellulose-deconstruction by enzymatic depolymerization of holocellulose into simple monosaccharides. However, commercially valuable thermostable cellulases and xylanases are challenging to produce in high enough quantities. Thus, the present review aims at giving an overview of the most recent thermostable cellulases and xylanases isolated from thermophilic and hyperthermophilic microbes. The emphasis is on recent advancements in manufacturing these enzymes in other mesophilic host and enhancement of catalytic activity as well as thermostability of thermophilic cellulases and xylanases, using genetic engineering as a promising and efficient technology for its economic production. Additionally, the biotechnological applications of thermostable cellulases and xylanases of thermophiles were also discussed.

The effects of gelatin-CMC films incorporated with chitin nanofiber and Trachyspermum ammi essential oil on the shelf life characteristics of refrigerated raw beef.

The effects of gelatin-carboxymethyl cellulose (Gel-CMC) based films containing chitin nano fiber (CHNF) and Trachyspermum ammi essential oil (Ajowan), on the shelf life extension of the raw beef at refrigerated temperature (4 °C) over a 12-day period were evaluated. Ajowan essential oil (AJEO) and CHNF were added to the films at 0.24, 0.64 and 1% v/v; and 2 and 4 wt%, respectively. The microbiological (total viable count, psychrotrophic count, Pseudomonas spp., Staphylococcus aureus, lactic acid bacteria, molds and yeasts), the chemical (pH, thiobarbituric acid and total volatile basic nitrogen), color and sensory properties of the packaged samples were evaluated periodically. Bacteria grew the most quickly in the control samples, followed by those wrapped with the Gel-CMC films; The lowest microbial counts, the least change in the chemical properties and the highest sensory scores after 12 days of storage were obtained for the samples wrapped in the films incorporated with 1% AJEO and 4 wt% CHNF.

The optimization of gelatin-CMC based active films containing chitin nanofiber and Trachyspermum ammi essential oil by response surface methodology.

The effects of carboxymethyl cellulose (CMC: 4-16 wt%), chitin nanofiber concentrations (CHNF: 2-5 wt%) and Trachyspermum ammi (Ajowan) essential oil (AJEO: 0.26-1 v/v%) on the physical and antimicrobial characteristics of the gelatin-based nanocomposite films were studied by response surface methodology (RSM). The optimization was based on maximizing contact angle, ultimate tensile strength (UTS), strain at break (SAB), lightness (L), antibacterial activity, while minimizing water vapour permeability)WVP(, solubility, swelling, yellowness index (YI), and total color difference (ΔE) values. An increase in the CMC/gelatin ratio in the film formulations caused a decrease in WVP, SAB, ΔE, and YI. In addition, the incorporation of CHNF improved their mechanical strength and barrier properties. Furthermore, the addition of AJEO clearly improved the antimicrobial activity against Staphylococcus aureus and Escherichia coli, while reducing the mechanical and light barrier properties. The optimal values of CMC, CHNF and AJEO for composition of the gelatin film were 15.83 (wt%), 3 (wt%) and 0.74 (v/v%), respectively.

Concurrent production of sodium lignosulfonate and ethanol from bagasse spent liquor.

This study was done with the aim of lignosulfonate and ethanol production from different spent liquors of bagasse pulping process. For this purpose, alkali lignin from bagasse alkali liquor was separated and was sulfomethylated to produce soda lignosulfonate (SLig). Furthermore, raw bagasse was directly treated with sodium sulfite in acidic and neutral conditions to produce BLig and NLig bagasse lignosulfonate, respectively. In addition, the pentoses and hexoses impurities in lignosulfonates were fermented to ethanol using Candida guilliermondii. Results showed that the molecular weight of NLig lignosulfonate was considerably high comparing to the SLig and BLig lignosulfonates. A high level of thermal resistance was found in case of SLig regarding to the other samples at 500 °C. Fermentation of the spent liquors with Candida guilliermondii led to a maximum ethanol yield of 7.0, 1.0 and 5.1 g L-1 in NLig, SLig and BLig, respectively.

Antimicrobial evaluation of novel poly-lactic acid based nanocomposites incorporated with bioactive compounds in-vitro and in refrigerated vacuum-packed cooked sausages.

Biodegradability and antimicrobial activity of food packaging materials are among the most attractive parameters in modern food industries. In order to develop biodegradable poly-lactic acid (PLA) film to antibacterial nanocomposites, different concentration of Zataria multiflora Bioss. essential oil (ZME), propolis ethanolic extract (PEE) and cellulose nanofiber (CNF) were incorporated to the polymer by solvent casting method. The resulting films were characterized by mechanical and physical tests and their antimicrobial application was evaluated in-vitro against four common foodborne pathogens and in vacuum-packed cooked sausages during refrigerated storage. Mechanical examination revealed that addition of ZME and PEE made films more flexible and incorporation of CNF improved almost all mechanical parameters tested. Moreover, according to physical analysis, incorporation of 0.5% v/v ZME to the composite primary solutions improved water vapor permeability of the resulting films. Almost all of the active films were effective against the tested bacteria except for PLA/PEE films, and maximum antibacterial effects recorded for the films containing both ZME and PEE. Based on the microbiological and sensory evaluation of the sausages, all of the PLA/1%ZME/PEE composites increased the shelf life to >40days. The results indicate that incorporation of natural antimicrobial substances such as ZME and PEE to packaging material could be an interesting approach in development of active packaging material without significant negative effect on polymer technical properties.

Effect of cellulosic fiber scale on linear and non-linear mechanical performance of starch-based composites.

Cellulosic nanofibers (NFs) from kenaf bast were used to reinforce glycerol plasticized thermoplastic starch (TPS) matrices with varying contents (0-10wt%). The composites were prepared by casting/evaporation method. Raw fibers (RFs) reinforced TPS films were prepared with the same contents and conditions. The aim of study was to investigate the effects of filler dimension and loading on linear and non-linear mechanical performance of fabricated materials. Obtained results clearly demonstrated that the NF-reinforced composites had significantly greater mechanical performance than the RF-reinforced counterparts. This was attributed to the high aspect ratio and nano dimension of the reinforcing agents, as well as their compatibility with the TPS matrix, resulting in strong fiber/matrix interaction. Tensile strength and Young's modulus increased by 313% and 343%, respectively, with increasing NF content from 0 to 10wt%. Dynamic mechanical analysis (DMA) revealed an elevational trend in the glass transition temperature of amylopectin-rich domains in composites. The most eminent record was +18.5°C shift in temperature position of the film reinforced with 8% NF. This finding implied efficient dispersion of nanofibers in the matrix and their ability to form a network and restrict mobility of the system.

Analysis and Testing of Bisphenol A-Free Bio-Based Tannin Epoxy-Acrylic Adhesives.

A tannin-based epoxy acrylate resin was prepared from glycidyl ether tannin (GET) and acrylic acid. The influence of the reaction condition for producing tannin epoxy acrylate was studied by FT-MIR, 13C-NMR, MALDI-TOF spectroscopy and shear strength. The best reaction conditions for producing tannin epoxy acrylate resin without bisphenol A was by reaction between GET and acrylic acid in the presence of a catalyst and hydroquinone at 95 °C for 12 h. FT-MIR, 13C-NMR and MALDI-TOF analysis have confirmed that the resin has been prepared under these conditions. The joints bonded with this resin were tested for block shear strength. The results obtained indicated that the best strength performance was obtained by the bioepoxy-acrylate adhesive resin prepared at 95 °C for a 12-h reaction.

Kenaf bast cellulosic fibers hierarchy: a comprehensive approach from micro to nano.

Cellulosic fibers from kenaf bast were isolated in three distinct stages. Initially raw kenaf bast fibers were subjected to an alkali pulping process. Then pulped fibers undergone a bleaching process and finally both pulped and bleached fibers were separated into their constituent nanoscale cellulosic fibers by mechanical shearing. The influence of each treatment on the chemical composition of fibers was investigated. Moreover morphology, functional groups, crystallinity, and thermal behavior of fiber hierarchy at different stages of purification were studied using scanning and transmission electron microscopies, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), respectively. Microscopy studies revealed that applied procedures successfully isolated nanoscale cellulosic fibers from both unbleached and bleached pulps. Chemical composition analysis and FTIR spectroscopy showed that lignin and hemicellulose were almost entirely removed by the applied treatments. XRD and TGA analyses demonstrated progressive enhancement of properties in fibers, hierarchically, in going from micro to nano scale. Interestingly no significant evolution was observed between obtained data of characterized ubnleached and bleached nanofibers.

Preparation of cellulose/polyvinyl alcohol biocomposite films using 1-n-butyl-3-methylimidazolium chloride.

This study has been focused on developing cellulose/polyvinyl alcohol (PVA), a biocomposite film, pretreated with 1-n-butyl-3-methylimidazolium chloride ([bmim]Cl). The dissolved polymers were blended and their biocomposite films including cellulose and cellulose/PVA were prepared. The effect of PVA composition with cellulose was evaluated by comparing the physical, mechanical, chemical and thermal characteristics of produced films with neat cellulosic film. The results showed that the ionic liquid had a great capability in dissolving the polymers. Furthermore, in composition of the raw cellulose some chemical bonds were incorporated between the two components. Water uptake, thickness swelling and water vapor permeability of blend films were increased comparing to cellulosic film. Mechanical strength and Young's modulus of the films made of cellulose/PVA were decreased while the strain at break was increased. The optical transparency and thermal properties of the blend films were almost the same as neat cellulosic film. This work demonstrated a promising route for the preparation of biodegradable green composites. In addition, this biocomposite film is composed of sustainable biodegradable resources, which is suitable for release to the environment. The biocomposite films showed good optical transparency, thermal stabilities properties.

Effects of dissolution of some lignocellulosic materials with ionic liquids as green solvents on mechanical and physical properties of composite films.

In this study two imidazole-based ionic liquids (ILs), namely 1-butyl-3-methyl-1-imidazolium chloride ([BMIM]Cl) and 1,3-methyl imidazolium dimethyl sulfate ([DiMIM][MeSO4]), were used to dissolve ball-milled poplar wood (PW), chemi-mechanical pulp (CMP), and cotton linter (CEL). A set of comparative experiments was carried out, and physical and mechanical properties of the composite films from three different raw materials were determined by means of optical transparency (OT), scanning electron microscopy (SEM), water absorption (WA), thickness swelling (TS), water vapor permeability (WVP), and tensile strength (σb). The overall evaluation indicates the inability of [DiMIM][MeSO4] in complete dissolution of lignocellulosic materials, and sample treatment with this solvent did not lead to water soluble degradation products. However, dissolution trials using [BMIM]Cl were able to dissolve all used lignocellulosic materials by destroying inter and intramolecular hydrogen bonds between lignocelluloses. The OT, WA, TS, and σb of regenerated CEL films were much higher than those of CMP and PW composites. In addition, CEL film showed the lowest WVP compared to WF and CMP composite films. This work demonstrated a promising route for the preparation of biodegradable green cellulose composite films.

WITHDRAWN: Elucidation of structural condensation in lignin of eastern cottonwood.

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Improving wet and dry strength properties of recycled old corrugated carton (OCC) pulp using various polymers.

In this study, the application of different dosages of low and high molecular weights (MW) of chitosan (Ch), cationic starch (CS) and poly vinyl alcohol (PVA) were systematically investigated using old corrugated carton (OCC) furnishes. Various sequences of above-mentioned polymeric additives were also examined to find out the optimal combination for improving both wet and dry tensile strength. For each treatment, 4 handsheets, each having basis weight of 100 g/m(2), were made. In general, the tensile strength of handsheets was significantly affected by the addition of polymeric agents. The enhancing effect of additives on dry tensile property was much higher than wet condition. The results also showed that the tensile strength of the samples made from OCC furnishes were improved upon the addition of high molecular weight chitosan (ChI) compared to the untreated ones (control). The low MW chitosan did not change the properties of handsheets dramatically. Application of polymeric agents moderately decreased the stretch to rupture, however with increasing dosage the stretch was improved. Sequential addition of used polymers showed that triple application of polymers was beneficial to both dry and wet tensile strength, although the effect was larger for dry. The best results in wet and dry tensile strengths were achieved using sequential of PVA-ChI-CS. Sequential addition of oppositely charged polymers forms a macromolecular layered structure of polyelectrolytes.

Removal of Acid Orange 7 and Remazol Black 5 reactive dyes from aqueous solutions using a novel biosorbent.

This study utilizes canola stalks (CS), an agro-residue, as a biosorbent to remove two different dyes, namely Acid Orange 7 (AO7) and Remozol Black 5 (RB5) from aqueous solutions. The effects of operational parameters on the efficiency of dye removal including pH, adsorbent mass, initial dye concentration and contact time have been investigated. For both tested dyes, the maximum absorption capacity was reached at initial pH 2.5 and 120 min contact time. The results showed that the absorption of both dyes depended on the pH of milieu, temperature, dye and CS concentrations. Freundlich and Langmuir models were used to analyze the obtained experimental data. The isotherms are found to be linear over the entire concentration range for both dyes. The highest value of linear correlation coefficients for AO7 (0.9926) and RB5 (0.9882) showed that the Langmuir is the best model to fit the experimental data. Kinetic study of absorption was done applying the pseudo first-order and the pseudo second-order equations. Absorption of both dyes could be well predicted by the pseudo second-order equation. The obtained results are very promising since: (i) high levels of dye removal (>90%) were achieved with low contact times biosorbent/dye (less than 20 min contact); and (ii) the whole CS can be successfully used as biosorbent of AO7 and RB5 dyes in aqueous solution without needing any chemical modifications.

The effect of combination enzymatic and advanced oxidation process treatments on the colour of pulp and paper mill effluent.

The efficiency of advanced oxidation processes (AOPs), enzymatic treatment and combined enzymatic/AOP sequences for the colour remediation of soda and chemimechanical pulp and paper mill effluent was investigated. The results indicated that under all circumstances, the AOP using ultraviolet irradiation (photo-Fenton) was more efficient in the degradation of effluent components in comparison with the dark reaction. It was found that both versatile peroxidase (VP) from Bjerkandera adusta and laccase from Trametes versicolor, as pure enzymes, decolorize the deep brown effluent to a clear light-yellow solution. In addition, it was found that in the laccase treatment, the decolorization rates of both effluents were enhanced in the presence of 2, 2'-azinobis (3-ethylbenzthiazoline-6-sulfonate), while in the case of VP, Mn(+2) decreased the efficiency of the decolorization treatment. The concomitant use of enzymes and AOPs imposes a considerable effect on the colour remediation of effluent samples.