In recent years, visualization and characterization of lignocellulose at different scales elucidate the modifications of its ultrastructural and chemical features during hydrothermal pretreatment which include degradation and dissolving of hemicelluloses, swelling and partial hydrolysis of cellulose, melting and redepositing a part of lignin in the surface. As a result, cell walls are swollen, deformed and de-laminated from the adjacent layer, lead to a range of revealed droplets that appear on and within cell walls. Moreover, the certain extent morphological changes significantly promote the downstream processing steps, especially for enzymatic hydrolysis and anaerobic fermentation to bioethanol by increasing the contact area with enzymes. However, the formation of pseudo-lignin hinders the accessibility of cellulase to cellulose, which decreases the efficiency of enzymatic hydrolysis. This review is intended to bridge the gap between the microstructure studies and value-added applications of lignocellulose while inspiring more research prospects to enhance the hydrothermal pretreatment process.
Since the introduction of deep eutectic solvent (DES) in biomass processing field, the efficiency of DES in lignocellulosic biopolymer model compounds' (cellulose, hemicellulose and lignin) solubilisation and conversion was widely recognized. Nevertheless, DES's potential for biorefinery application can be reflected more accurately through their performance in raw lignocellulosic biomass processing rather than model compound conversion. Therefore, this review examines the studies on raw lignocellulosic biomass fractionation using DES and the subsequent conversion of DES-fractionated products into bio-based products. The review stresses on three key parts: performance of varying types of DESs and pretreatment schemes for biopolymer fractionation, properties and conversion of fractionated saccharides as well as DES-extracted lignin. The prospects and challenges of DES implementation in biomass processing will also be discussed. This review provides a front-to-end view on the DES's performance, starting from pretreatment to DES-fractionated products conversion, which would be helpful in devising a comprehensive biomass utilization process.
Nanocellulose based gas barrier materials have become an increasingly important subject, since it is a widespread environmentally friendly natural polymer. Previous studies have shown that super-high gas barrier can be achieved with pure and hierarchical nanocellulose films fabricated through simple suspension or layer-by-layer technique either by itself or incorporating with other polymers or nanoparticles. Improved gas barrier properties were observed for nanocellulose-reinforced composites, where nanocellulose partially impermeable nanoparticles decreased gas permeability effectively. However, for nanocellulose-based materials, the higher gas barrier performance is jeopardized by water absorption and shape deformation under high humidity conditions which is a challenge for maintaining properties in material applications. Thus, numerous investigations have been done to solve the problem of water absorption in nanocellulose-based materials. In this literature review, gas barrier properties of pure, layer-by-layer and composite nanocellulose films are investigated. The possible theoretical gas barrier mechanisms are described, and the prospects for nanocellulose-based materials are discussed.
The development of hybrid polysaccharide-protein complexes as Pickering emulsion stabilizers has attracted increasing research interest in recent years. This work presents an eco-friendly surface modification strategy to functionalize hydrophilic cellulose nanocrystals (CNC) using hydrophobic soy protein isolate (SPI) via mussel adhesive-inspired poly (l-dopa) (PLD) to develop improved nanoconjugates as stabilizers for oil-in-water Pickering emulsion. The physicochemical properties of the CNC-PLD-SPI nanoconjugate were evaluated by solid-state 13C NMR, FT-IR, TGA, XRD, contact angle analysis, and TEM. The modified CNC (conjugation content of 38.22 ± 1.21%) had lowered crystallinity index, higher thermal stability, and more hydrophobic than unmodified CNC, with an average particle size of 309.9 ± 8.0 nm. Use of amphiphilic CNC-PLD-SPI nanoconjugate with greater conformational flexibility as Pickering stabilizer produced oil-in-water emulsions with greater physical stability.
In the present work, the synthesis of cellulose nanowhiskers (CNW)/chitosan nanocomposite films via deep eutectic solvents (DES) changing the chemical structures were carried out. It was observed that a pure chitosan film has broadband at 3180-3400 cm-1, indicating amide and hydroxyl groups. Upon CNW incorporation, the peak gets sharper and stronger and shifts to a greater wavelength. Further, the addition of DES infuses more elements of amide into the nanocomposite films. Moreover, the mechanical properties incorporating CNW filler into a chitosan matrix show an enhancement in tensile strength (TS), Young's modulus (YM), and elongation at break. The TS and YM increase while the elongation decrease as the CNW concentration increases. The YM of biocomposite films is increased to 723 MPa at 25% CNW into chitosan films. Besides, the TS has enhanced to 11.48 MPa at 15% CNW concentration in the biocomposite films. The elongation at break has decreased to 11.7% at 25% CNW concentration. Hence, incorporating CNW into the chitosan matrix via DES can still improve the mechanical properties of the nanocomposite films. Therefore, the application of DES results in a lower YM and TS as the films are hygroscopic. In conclusion, DES can be considered the new green solvent media for synthesizing materials. It has the potential to replace ionic liquids due to its biodegradability and non-toxic properties while preserving the character of low-vapour pressure. Besides that, chitosan can be used as potential material for applications in process industries, such as the biomedical and pharmaceutical industries. Thus, DES can be used as a green solvent and aim to reduce the toxic effect of chemicals on the environment during chemical production.
Hahella is a genus that has not been well-studied, with only two identified species. The potential of this genus to produce cellulases is yet to be fully explored. The present study isolated Hahella sp. CR1 from mangrove soil in Tanjung Piai National Park, Malaysia, and performed whole genome sequencing (WGS) using NovaSeq 6000. The final assembled genome consists of 62 contigs, 7,106,771 bp, a GC ratio of 53.5%, and encoded for 6,397 genes. The CR1 strain exhibited the highest similarity with Hahella sp. HN01 compared to other available genomes, where the ANI, dDDH, AAI, and POCP were 97.04%, 75.2%, 97.95%, and 91.0%, respectively. In addition, the CAZymes analysis identified 88 GTs, 54 GHs, 11 CEs, 7 AAs, 2 PLs, and 48 CBMs in the genome of strain CR1. Among these proteins, 11 are related to cellulose degradation. The cellulases produced from strain CR1 were characterized and demonstrated optimal activity at 60 ℃, pH 7.0, and 15% (w/v) sodium chloride. The enzyme was activated by K+, Fe2+, Mg2+, Co2+, and Tween 40. Furthermore, cellulases from strain CR1 improved the saccharification efficiency of a commercial cellulase blend on the tested agricultural wastes, including empty fruit bunch, coconut husk, and sugarcane bagasse. This study provides new insights into the cellulases produced by strain CR1 and their potential to be used in lignocellulosic biomass pre-treatment.
Considering its widespread usage in various fields, such as food, pharmaceutical, medical, cosmetic and polymer composites industries, microcrystalline cellulose (MCC) is becoming impellent due to increasing demand of alternatives to non-renewable and scarce fossil materials. Although it still suffers from some drawbacks, MCC has recently gained more interest owing to its renewability, non-toxicity, economic value, biodegradability, high mechanical properties, high surface area and biocompatibility. New sources, new isolation processes, and new treatments are currently under development to satisfy the increasing demand of producing new types of MCC-based materials on an industrial scale. Therefore, this review assembles the current knowledge on the isolation of MCC from different sources using various procedures, its characterization, and its application in bio-composites. Challenges and future opportunities of MCC-based composites are discussed as well as obstacles remaining for their extensive uses.
Microalgae cultivation using open cultivation systems requires large area and it is susceptible to contamination as well as weather changes. Meanwhile, the closed systems require large capital investment, and they are susceptible to the build-up of dissolved oxygen. Air-liquid interface culture systems with low water-footprint, but high packing density can be used for microalgae cultivation if low-cost culture scaffolds are available. In this study, cellulose-based scaffolds were synthesized using NaOH/urea aqueous solution as the solvent. Titanium dioxide (TiO2), silica gel and polyethylene glycol 1000 (PEG 1000) nanoparticles were added into the membrane scaffolds to increase the hydrophilicity of nutrient absorbing to support the growth of microalgae. The membrane scaffolds were characterized by FTIR, SEM, contact angle, porosity and porometry. All three nanoparticles additives showed their ability in reducing the contact angle of membrane scaffolds from 63.4 ± 2.3° to a range of 52.6 ± 1.2° to 38.8 ± 1.5° due to the hydrophilic properties of the nanoparticles. The decreasing in pore size when nanoparticles were added did not affect the porosity of membrane scaffolds. Cellulose membrane scaffold with TiO2 showed the highest percentage of microalgae Navicula incerta growth rate of 22.1% because of the antibacterial properties of TiO2 in lowering the risk of cell contamination and enhancing the growth of N. incerta. The results exhibited that cellulose-based scaffold with TiO2 added could be an effective support in plant cell culture field.
Cellulose constitutes most of a plant's cell wall, and it is the most abundant renewable polymer source on our planet. Given the hierarchical structure of cellulose, nanocellulose has gained considerable attention as a nano-reinforcement for polymer matrices in various industries (medical and healthcare, oil and gas, packaging, paper and board, composites, printed and flexible electronics, textiles, filtration, rheology modifiers, 3D printing, aerogels and coating films). Herein, nanocellulose is considered as a sustainable nanomaterial due to its substantial strength, low density, excellent mechanical performance and biocompatibility. Indeed, nanocellulose exists in several forms, including bacterial cellulose, nanocrystalline cellulose and nanofibrillated cellulose, which results in biodegradable and environmentally friendly bionanocomposites with remarkably improved material properties. This paper reviews the recent advances in production, physicochemical properties, and structural characterization of nanocelluloses. It also summarises recent developments in several multifunctional applications of nanocellulose with an emphasis on bionanocomposite properties. Besides, various challenges associated with commercialisation and economic aspects of nanocellulose for current and future markets are also discussed inclusively.
Biomass is considered as the largest renewable energy source in the world. However, some of its inherent properties such as hygroscopicity, lower energy content, low mass density and bio-degradation on storage hinder its extensive application in energy generation processes. Torrefaction, a thermochemical process carried out at 200-300°C in a non-oxidative environment, can address these inherent problems of the biomass. In this work, torrefaction of bagasse was performed in a bench-scale tubular reactor at 250°C and 275°C with residence times of 30, 60 and 90 mins. The effects of torrefaction conditions on the elemental composition, mass yield, energy yield, oxygen/carbon (O/C) and hydrogen/carbon (H/C) ratios, higher heating values and structural composition were investigated and compared with the commercially available 'Thar 6' and 'Tunnel C' coal. Based on the targeted mass and energy yields of 80% and 90% respectively, the optimal process conditions turned out to be 250°C and 30 mins. Torrefaction of the bagasse conducted at 275°C and 90 min raised the carbon content in bagasse to 58.14% and resulted in a high heating value of 23.84 MJ/kg. The structural and thermal analysis of the torrefied bagasse indicates that the moisture, non-structural carbohydrates and hemicellulose were reduced, which induced the hydrophobicity in the bagasse and enhanced its energy value. These findings showed that torrefaction can be a sustainable pre-treatment process to improve the fuel and structural properties of biomass as a feedstock for energy generation processes.
The groundbreaking innovation and industrialization are ushering in a new era where technology development is integrated with the sustainability of materials. Over the decade, nanocrystalline cellulose (NCC) obtained from lignocellulosic biomass had created a great value in various aspects. The abundantly available empty fruit bunch (EFB) in the palm oil industry has motivated us to utilize it as a sustainable alternative for the isolation of NCC, which is a worthwhile opportunity to the waste management of EFB. Taking advantage of the shape anisotropy and amphiphilic character, NCC has been demonstrated as a natural stabilizer for oil-in-water emulsion. In this work, preparation of highly stable Pickering nanoemulsion using black cumin seed oil and NCC was attempted. Black cumin seed oil is a class of plant oil with various nutritional and pharmaceutical benefits. However, its poor solubility could substantially lower the therapeutic effect, and thus, requires a delivery system to overcome this limitation. The role of NCC in the formation of stable Pickering nanoemulsion was investigated. The emulsification process was found crucial to the resulting droplet size, whereas NCC contributed critically to its stabilization. The droplet size obtained from ultrasonication and microfluidization was approximately 400 nm, as examined using transmission electron microscopy. The droplet (oil-to-water = 2:8) has long-term stability against creaming and coalescence for more than six months. The nanoemulsion stabilized by NCC could allow a better absorption by the human body, thereby maximizing the potential of black cumin seed oil in the personal care and food industries.
As one of the potential bionanomaterials, nanocellulose has appeared as a favorable candidate for photoremediation of the environment because of its abundance in nature, inexpensive, eco-friendly, decomposable, high surface area, and outstanding mechanical properties. The current review carefully summarized the diverse type of nanocellulose, their preparation approaches, and several previous works on the use of nanocellulose for photoremediation. These include the role of nanocellulose for the increased surface active site of the hybrid photocatalysts by providing a large surface area for enhanced adsorption of photons and pollutant molecules, as a dispersing agent to increase distribution of metal/non-metal dopants photocatalysts, as well as for controlled size and morphology of the dopants photocatalysts. Furthermore, the recommendations for upcoming research provided in this review are anticipated to ignite an idea for the development of other nanocellulose-based photocatalysts. Other than delivering beneficial information on the present growth of the nanocellulose biomaterials photocatalysts, this review is expected will attract more interest to the utilization of nanocellulose photocatalyst and distribute additional knowledge in this exciting area of environmental photoremediation. This could be attained by considering that a review on nanocellulose biomaterials for environmental health photoremediation has not been described elsewhere, notwithstanding intensive research works have been dedicated to this topic.
This study focuses on the biochar formation and torrefaction performance of sugarcane bagasse, and they are predicted using the bilinear interpolation (BLI), inverse distance weighting (IDW) interpolation, and regression analysis. It is found that the biomass torrefied at 275°C for 60min or at 300°C for 30min or longer is appropriate to produce biochar as alternative fuel to coal with low carbon footprint, but the energy yield from the torrefaction at 300°C is too low. From the biochar yield, enhancement factor of HHV, and energy yield, the results suggest that the three methods are all feasible for predicting the performance, especially for the enhancement factor. The power parameter of unity in the IDW method provides the best predictions and the error is below 5%. The second order in regression analysis gives a more reasonable approach than the first order, and is recommended for the predictions.
Nanocrystalline cellulose (NCC) was isolated from oil palm empty fruit bunch pulp (EFBP) using ultrasound assisted acid hydrolysis. The obtained NCC was analysed using FESEM, XRD, FTIR, and TGA, and compared with raw empty fruit bunch fibre (REFB), empty fruit bunch pulp (EFBP), and treated empty fruit bunch pulp (TEFBP). Based on FESEM analysis, it was found that NCC has a spherical shaped after acid hydrolysis with the assistance of ultrasound. This situation was different compared to previous studies that obtained rod-like shaped of NCC. Furthermore, the crystallinity of NCC is higher compared to REFB and EFBP. According to thermal stability, the NCC obtained shows remarkable sign of high thermal stability compared to REFB and EFBP.
Roselle fiber is a renewable and sustainable agricultural waste enriched with cellulose polysaccharides. The isolation of Nanocrystalline cellulose (NCC) from roselle-derived microcrystalline cellulose (MCC) is an alternative approach to recover the agricultural roselle plant residue. In the present study, acid hydrolysis with different reaction time was carried out to degrade the roselle-derived MCC to form NCC. The characterizations of isolated NCC were conducted through Fourier Transform Infrared Ray (FTIR), Transmission Electron Microscopy (TEM), Field Emission Scanning Electron Microscopy (FESEM), Atomic Force Microscopy (AFM), Dynamic Light Scattering (DLS), Energy Dispersive Spectroscopy (EDS), X-ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). As evaluated from the performed morphological investigations, the needle-like shape NCC nanostructures were observed under TEM and AFM microscopy studies, while irregular rod-like shape of NCC was observed under FESEM analysis. With 60min hydrolysis time, XRD analysis demonstrated the highest NCC crystallinity degree with 79.5%. In thermal analysis by TGA and DSC, the shorter hydrolysis time tended to produce NCC with higher thermal stability. Thus, the isolated NCC from roselle-derived MCC has high potential to be used in application of pharmaceutical and biomedical fields for nanocomposite fabrication.
This study aimed to evaluate the bioactivities and biocompatibilities of porous polylactic acid (PLA) reinforced with cellulose nanofiber (CNF) scaffolds. The in vitro degradation behaviors of the porous PLA/CNF scaffolds were systematically measured for up to 8 weeks in a phosphate-buffered saline medium at 37 °C. The reinforcement of CNF resisted the biodegradation of the scaffolds. The in vitro cytotoxicity and biocompatibility of the scaffolds were determined using the Beas2B American Type Culture Collection cells. The 3-(4,5-cimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide cytotoxicity and proliferation tests showed that the scaffolds were non-toxic, and epithelial cells grew well on the scaffold after 7 days of culture, whereas the percentage of cell proliferation on the PLA/CNF15 scaffold was the largest, 130 %. A scratch wound-healing assay was performed to evaluate the suitability of the scaffolds for cell migration. The results demonstrated that the scaffolds exhibited good cell migration towards nearly complete wound closure.
The need to overcome the secondary surgery to remove implanted metal fixation plate leads to the idea of replacing the material with degradable bionanocomposite. In this research, polylactic acid/polypropylene (PLA/PPC) blends incorporated with halloysite nanotubes (HNT) (0-6 wt %) were considered as the candidate material for mandibular fixation plate. A single-factor design using Design Expert software was used to determine 20 different compositions of PLA/PPC/HNT nanocomposites and their mechanical properties were then measured. The optimization of the PLA/PPC/HNT nanocomposite composition was performed based on the nanocomposite's response to Young's modulus, tensile strength, and elongation at break. Further analysis suggested an optimum composition of 92.5/7.5 PLA/PPC with 6 wt % of HNT. The statistical results predicted that there was a 71.7% possibility that the proposed nanocomposite would have the following mechanical properties: Young's modulus of 2.18 GPa, a tensile strength of 64.16 MPa, and an elongation at break of 106.53%.
Biowaste, produced from nature, is preferred to be a good source of carbon and ligninolytic machinery for many microorganisms. They are complex biopolymers composed of lignin, cellulose, and hemicellulose traces. This biomass can be depolymerized to its nano-dimensions to gain exceptional properties useful in the field of cosmetics, pharmaceuticals, high-strength materials, etc. Nano-sized biomass derivatives overcome the inherent drawbacks of the parent material and offer promises as a potential material for a wide range of applications with their unique traits such as low-toxicity, biocompatibility, biodegradability and environmentally friendly nature with versatility. This review focuses on the production of value-added products feasible from nanocellulose, nano lignin, and xylan nanoparticles which is quite a novel study of its kind. Dawn of nanotechnology has converted bio waste by-products (hemicellulose and lignin) into useful precursors for many commercial products. Nano-cellulose has been employed in the fields of electronics, cosmetics, drug delivery, scaffolds, fillers, packaging, and engineering structures. Xylan nanoparticles and nano lignin have numerous applications as stabilizers, additives, textiles, adhesives, emulsifiers, and prodrugs for many polyphenols with an encapsulation efficiency of 50%. This study will support the potential development of composites for emerging applications in all aspects of interest and open up novel paths for multifunctional biomaterials in nano-dimensions for cosmetic, drug carrier, and clinical applications.
We analyzed the problematic textile fiber waste as potential precursor material to produce multilayer cotton fiber biocomposite. The properties of the products were better than the current dry bearing type particleboards and ordinary dry medium-density fiberboard in terms of the static bending strength (67.86 MPa), internal bonding strength (1.52 MPa) and water expansion rate (9.57%). The three-layer, four-layer and five-layer waste cotton fiber composite (WCFC) were tried in the experiment, the mechanical properties of the three-layer WCFC are insufficient, the five-layer WCFC is too thick and the four-layer WCFC had the best comprehensive performance. The cross-section morphology of the four-layer WCFC shows a dense structure with a high number of adhesives attached to the fiber. The hardness and stiffness of the four-layer cotton fiber composite enhanced by the high crystallinity of cellulose content, and several chemical bondings were presence in the composites. Minimum mass loss (30%) and thermal weight loss rate (0.70%/°C) was found for the four-layer WCFC. Overall, our findings suggested that the use of waste cotton fiber (WCF) to prepare biocomposite with desirable physical and chemical properties is feasible, and which can potentially be used as building material, furniture and automotive applications.
Pretreatment with pure, mixed, and diluted deep eutectic solvents (DESs) was evaluated for its effect on Napier grass through compositional and characterization studies. The morphological changes of biomass caused by pretreatment were analyzed by FTIR and XRD. The cellulose and hemicellulose content after pretreatment using mixed DES increased and decreased 1.29- and 4.25-fold, respectively, when compared to untreated Napier grass. The crystallinity index (CrI. %) of mixed DES sample increased due to the maximum removal of hemicellulose (76 %) and delignification of 62 %. The material costs of ChCl/FA and ChCl/LA for a single run are ≈2.16 USD and ≈1.65 USD, respectively. Pure DES showed that ChCl/LA pretreatment enhanced delignification efficiency and that ChCl/FA increased hemicellulose removal. It was estimated that a single run using ChCl/LA:ChCl/FA to achieve maximum hemicellulose and lignin removal would cost approximately ≈1.89 USD. Future work will evaluate the effect of DES mixture on enzyme digestibility and ethanol production from Napier grass. HYPOTHESES: Deep eutectic solvent (DES) pretreatment studies on the fractionation of lignocellulosic biomass have grown exponentially. The use of pure and diluted DES has been reported to improve saccharification efficiency, delignification, and cellulose retention (Gundupalli et al., 2022). These studies have reported maximum lignin removal but also a lower effect on hemicellulose removal from lignocellulosic biomass. It was hypothesized that mixing two pure DESs could result in maximum removal of hemicellulose and lignin after pretreatment. To our knowledge, no studies have been performed to investigate the efficiency of pretreatment using a DES mixture and compared the outcome with pure and diluted DESs. Furthermore, it was hypothesized that using two pure DESs in a mixed form could lower the material cost for each experimental run. Process efficiency was determined by compositional, XRD, and FTIR analysis. Avenues for future research include determining glucose and ethanol yields during the enzymatic saccharification and fermentation processes.