Recent Progress on Lignocellulosic-Based Materials

A special issue of Polysaccharides (ISSN 2673-4176).

Deadline for manuscript submissions: closed (30 December 2025) | Viewed by 29831

Special Issue Editors


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Guest Editor
Faculty of Chemical Engineering and Environmental Protection “Cristofor Simionescu”, “Gheorghe Asachi” Technical University of Iasi, 700050 Iasi, Romania
Interests: biomass fractionation; hemicellulose extraction and characterization; pulping; papermaking; environmentally friendly materials; liquid chromatography
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Guest Editor
Faculty of Chemical Engineering and Environmental Protection, Department of Chemical Engineering, “Gheorghe Asachi” Technical University of Iasi, 700050 Iasi, Romania
Interests: bioresource processing modeling and design; transfer phenomena and unit operations of particulate solids (including applications in biomass processing)
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The concept of lignocellulosic materials refers to matter with a chemical composition that includes natural polymers such as cellulose, hemicelluloses, and lignin. Lignocellulosic materials are regarded as the most abundant category of biomass and originate in plants; they are characterized by heterogeneity, structural diversity, and chemical composition variability. This is the reason why their processing and valorization of various products may be regarded as challenging. In brief, research efforts are targeting both the finding of the particular, specific, and optimal conditions of raw material components’ separation and further value-adding all separated components. Cellulose fibers are raw materials for the production of a wide range of products: paper, bioplastics, and microfibrilated cellulose. Hemicelluloses and other carbohydrates are raw materials for sugar and fine organic chemicals and biofuels, while lignin is a candidate for the production of phenolic derivatives, adhesives, carbon nanofibers, bio-oils, biofuels, and bio-protection agents.

Today, the term lignocellulosic-based polymeric materials address both naturally occurring natural polymer-based bioresources, such as wood, straw, stalks, and other raw biomass types, as well as some of the products resulting from their processing. This Special Issue intends to cover subjects concerning the characterization of lignocellulosic materials as well as the processing and applications of the obtained products.

You may choose our Joint Special Issue in Polymers.

Dr. Adrian C. Puiţel
Dr. Mircea Teodor Nechita
Guest Editors

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Keywords

  • lignocellulosic biomass
  • biomaterials
  • fractionation
  • sugars
  • biofuels
  • hemicelluloses
  • lignin
  • fine chemicals

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Published Papers (13 papers)

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Research

Jump to: Review

9 pages, 526 KB  
Article
Absolute Molecular Weight Distribution of Cellulose in DMSO/EmimOAc (1%) with MALS Detection
by Ola Sundman
Polysaccharides 2026, 7(2), 47; https://doi.org/10.3390/polysaccharides7020047 - 16 Apr 2026
Viewed by 378
Abstract
This paper presents a method for the measurement of absolute molecular weight of cellulose using a multi-angle light scattering (MALS) detector in 99% dimethyl sulfoxide/1% 1-Ethyl-3-methylimidazolium acetate (DMSO/EmimOAc). The paper also delivers a suitable dn/dc value for cellulose in this solvent. It discusses [...] Read more.
This paper presents a method for the measurement of absolute molecular weight of cellulose using a multi-angle light scattering (MALS) detector in 99% dimethyl sulfoxide/1% 1-Ethyl-3-methylimidazolium acetate (DMSO/EmimOAc). The paper also delivers a suitable dn/dc value for cellulose in this solvent. It discusses the pros and cons of using absolute molecular weight measurements versus traditional column calibration in this solvent. The conclusion is that the dn/dc for cellulose in this solvent is 0.049 ± 0.003 mL/g. Absolute molecular weight measurements in this solvent are somewhat beneficial for celluloses with Mw > 250 kg/mol. However, for low-Mw celluloses (e.g., Avicel), it has severe limitations. Herein, it is confirmed that the DMSO/EmimOAc system can be used to replace the traditional DMAc/LiCl system for cellulose molecular weight analysis of some cellulose materials. However, the former is more costly and time-consuming than the latter. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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20 pages, 2684 KB  
Article
Influence of Powdered Lignocellulose from Alfalfa Straw and Its Carboxymethylated Derivative on the Properties of Water-Swelling Rubbers
by Abdirakym Nakyp, Elena Cherezova, Yulia Karaseva, Nurgali Akylbekov, Rakhymzhan Turmanov and Akbota Kuandykova
Polysaccharides 2026, 7(1), 16; https://doi.org/10.3390/polysaccharides7010016 - 1 Feb 2026
Viewed by 518
Abstract
The present work investigates the effect of powdered lignocellulose from alfalfa straw obtained by a chemo-extrusion method, as well as its carboxymethylated derivative, on the physicomechanical properties and swelling behavior of vulcanizates based on nitrile butadiene rubber (NBR, BNKS-28 AMN grade). Carboxymethylation of [...] Read more.
The present work investigates the effect of powdered lignocellulose from alfalfa straw obtained by a chemo-extrusion method, as well as its carboxymethylated derivative, on the physicomechanical properties and swelling behavior of vulcanizates based on nitrile butadiene rubber (NBR, BNKS-28 AMN grade). Carboxymethylation of lignocellulose was performed using microwave activation. The functional group composition of the modified lignocellulose was characterized by Fourier-transform infrared (FTIR) spectroscopy, which confirmed successful carboxymethylation and revealed a reduction in crystallinity. Thermogravimetric analysis (TGA) was used to determine the thermal stability of the swelling carboxymethylated fillers. The degree of crystallinity of the carboxymethylated swelling fillers was evaluated by X-ray diffraction (XRD). It was shown that the introduction of powdered lignocellulose and its carboxymethylated derivative into the rubber compounds lead to an increase in compound viscosity and prolong the optimum cure time, while having no effect on the scorch time, in a manner similar to that observed for the commercial product sodium carboxymethylcellulose (NaCMC). It has been shown that the introduction of powdered lignocellulose and its carboxymethylated derivative increases the tensile strength of the rubber and improves its resistance to the action of mineralized water compared with the samples containing NaCMC. It was also demonstrated that carboxymethylated lignocellulose exhibits enhanced sorption capacity comparable to that of NaCMC. Overall, carboxymethylation of lignocellulose derived from alfalfa straw significantly improves the stability and sorption characteristics of nitrile butadiene rubber composites. These findings indicate that carboxymethylated lignocellulose is a sustainable and effective alternative to industrial NaCMC for use as a functional filler in elastomeric materials. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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22 pages, 1662 KB  
Article
Comparative Assessment of Edible Oil Plant Lignocellulosic Biomass as Raw Material for a Fiber-Based Integrated Fractionation
by Adrian Cătălin Puițel, Cătălin Dumitrel Balan and Mircea Teodor Nechita
Polysaccharides 2026, 7(1), 13; https://doi.org/10.3390/polysaccharides7010013 - 31 Jan 2026
Cited by 1 | Viewed by 831
Abstract
Agricultural leftovers from oilseed crops represent an underutilized lignocellulosic resource for integrated biorefinery. In this work, rapeseed straw (RS) and sunflower stalk (SS) were evaluated as raw materials for the simultaneous recovery of hemicelluloses, lignin, and cellulose-rich fibers. Direct soda pulping (20% NaOH, [...] Read more.
Agricultural leftovers from oilseed crops represent an underutilized lignocellulosic resource for integrated biorefinery. In this work, rapeseed straw (RS) and sunflower stalk (SS) were evaluated as raw materials for the simultaneous recovery of hemicelluloses, lignin, and cellulose-rich fibers. Direct soda pulping (20% NaOH, 160 °C, 45 min) or a combination of soda pulping with water pretreatment or alkaline extraction (water or 2% NaOH, 110 °C, 40 min) were the methods used in the process. Acid precipitation was used to remove lignin from the process fluids, whereas ethanol was used to separate hemicelluloses. FTIR spectroscopy, HPLC of acidic hydrolysates, and chemical composition analysis were used to analyze solid fractions and recovered biopolymers. The combination alkaline extraction–soda pulping produced the greatest material removal: 55% for RS and 70% for SS. Xylan was the main component of the isolated hemicellulose fraction: 44.86% for RS and 40.09% for SS. Paper sheets produced from the resulting pulps exhibited tensile strength indices of 35–55 N·m/g and burst indices of 1.1–2.4 kPa·m2/g, meeting requirements for hygiene and fluting packaging papers. These results prove that RS and SS are suitable feedstocks for integrated, multi-stream biorefinery, enabling the concurrent production of paper-making fibers and value-added biopolymers. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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13 pages, 2621 KB  
Article
Elaboration and Characterization of New Polyurethane-Based Biocomposites from Jojoba Oil and Alfa Cellulose Fibers
by Ahmed Ramdani, Tarik Harit, Chakib Mokhtari and Fouad Malek
Polysaccharides 2026, 7(1), 9; https://doi.org/10.3390/polysaccharides7010009 - 13 Jan 2026
Viewed by 751
Abstract
A series of biocomposites were elaborated by incorporating cellulose fibers, obtained from raw alfa plant, into a new polyurethane (PU) matrix synthesized from jojoba oil. The cellulose content was adjusted between 0% and 50%. To examine their properties, several characterization methods were employed. [...] Read more.
A series of biocomposites were elaborated by incorporating cellulose fibers, obtained from raw alfa plant, into a new polyurethane (PU) matrix synthesized from jojoba oil. The cellulose content was adjusted between 0% and 50%. To examine their properties, several characterization methods were employed. Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analyses confirmed that the extracted cellulose and the polyurethane matrix have high interfacial adhesion. Thermal stability was assessed using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). They indicate that the composites remained thermally stable in air up to 265 °C and exhibited glass transition temperatures (Tg) in the range of −38 to −7 °C, depending on the fiber percentage inside the polyurethane-based biocomposite. The corresponding mechanical properties increased with the addition of cellulose, reaching optimal improvement at 40% fiber content. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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25 pages, 3982 KB  
Article
Acetylated Xylan as Renewable Feedstock for Biodegradable Food Packaging: Synthesis, Structural Characterization and Performance Evaluation
by Petronela Nechita, Mirela Iana-Roman and Silviu-Marian Năstac
Polysaccharides 2025, 6(3), 85; https://doi.org/10.3390/polysaccharides6030085 - 19 Sep 2025
Viewed by 1512
Abstract
This study investigates the potential of acetylated xylan as a functional component in coatings for biodegradable paper-based food packaging. Acetylated xylan was synthesized in the laboratory via the reaction of native beechwood xylan with acetic anhydride. Multilayer coatings composed of acetylated xylan, chitosan, [...] Read more.
This study investigates the potential of acetylated xylan as a functional component in coatings for biodegradable paper-based food packaging. Acetylated xylan was synthesized in the laboratory via the reaction of native beechwood xylan with acetic anhydride. Multilayer coatings composed of acetylated xylan, chitosan, and zinc oxide nanoparticles (ZnO NPs) were applied to paper substrates as single and double layers (approximately 5 g/m2) to enhance their barrier and antimicrobial properties. The coated papers were evaluated for mechanical properties, resistance to water, oil, and grease, antimicrobial activity against pathogenic bacteria, and biodegradability in soil. The combination of xylan derivatives with chitosan significantly improved surface hydrophobicity (contact angle ~87°) and achieved complete inhibition (100%) of Staphylococcus aureus and Salmonella spp., without compromising biodegradability. Incorporation of ZnO NPs further enhanced both the barrier properties and antimicrobial efficacy, particularly against S. aureus. A high biodegradation rate (~92%) was recorded after 42 days of soil burial. These results demonstrate the suitability of xylan-based multilayer coatings as sustainable alternatives for food packaging applications. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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19 pages, 4559 KB  
Article
In Situ Silanization of Ligno-Cellulosic Microfibers Derived from Industrial Waste to Enhance Mechanical Properties of Natural Rubber Compounds
by Patricia Castaño-Rivera, Alexandra Soto-Arriagada, Eduardo Troncoso Ortega, Karen Galvez-Garrido, Gustavo Cabrera-Barjas, Héctor Aguilar-Bolados, Johanna Castaño and Miguel Ángel Pereira
Polysaccharides 2025, 6(3), 70; https://doi.org/10.3390/polysaccharides6030070 - 8 Aug 2025
Cited by 1 | Viewed by 1217
Abstract
Nowadays, the use of materials from renewable resources, such as agricultural waste and forest residues, has increased. In this work, industrial waste recovered from a recycled paper/cardboard company was mechanically refined to obtain ligno-cellulosic microfibers (LCMFs). The obtained LCMFs were well characterized and [...] Read more.
Nowadays, the use of materials from renewable resources, such as agricultural waste and forest residues, has increased. In this work, industrial waste recovered from a recycled paper/cardboard company was mechanically refined to obtain ligno-cellulosic microfibers (LCMFs). The obtained LCMFs were well characterized and chemically modified in situ together with natural rubber through silanization. The effect of in situ silanizated LCMFs, by using (3-triethoxysilylpropyl) tetrasulfide (Si69) as a silane coupling agent, on natural rubber (NR) compound properties was studied. The NR compound with silanizated LCMFs at 2.5 phr of Si69 (NR MF Si2) increased NR stiffness significantly. For example, the 300% modulus of NR MF Si2 was around 9 units higher than that of NR. The physical–mechanical properties, crosslink density, curing behavior, infrared spectroscopy, and microscopy of the compounds were studied to confirm the in situ silanization of the microfibers and its reinforcement effect on the NR matrix. The storage modulus (E′) obtained from Dynamic Mechanical Analysis suggested that the silanizated samples presented an uneven crosslinking, but it was enough to stiffen the NR chains. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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10 pages, 4764 KB  
Article
A Direct Preparation of Cellulose Nanocrystals by ZnCl2-Based Deep Eutectic Solvent
by Hoai An Vu, Quang Tung Le and Van Quyen Nguyen
Polysaccharides 2025, 6(3), 61; https://doi.org/10.3390/polysaccharides6030061 - 8 Jul 2025
Cited by 3 | Viewed by 2507
Abstract
Here, we demonstrated a direct method to produce cellulose nanocrystals (CNCs) with a rod-like shape from microcrystalline cellulose by a ZnCl2-based deep eutectic solvent (DES) with a high yield (~80.1%). We obtained CNCs, crystalline index (68.9%), with a width of ~30–50 [...] Read more.
Here, we demonstrated a direct method to produce cellulose nanocrystals (CNCs) with a rod-like shape from microcrystalline cellulose by a ZnCl2-based deep eutectic solvent (DES) with a high yield (~80.1%). We obtained CNCs, crystalline index (68.9%), with a width of ~30–50 nm and a length of 200–400 nm. Importantly, we were able to functionalize the CNCs with an acetyl, -(CO)CH3, group, which could potentially modulate the hydrophobic property of the CNCs. We attributed the formation of the CNCs to the Lewis acid effect of ZnCl2, which can hydrolyze the amorphous cellulose regime. Our study opens a new path to directly isolate cellulose nanocrystals with several functional groups on the surface of CNCs. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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13 pages, 711 KB  
Article
Feruloylated Arabinoxylans from Nixtamalized Maize Bran By-Product as a Baking Ingredient: Physicochemical, Nutritional, and Functional Properties
by Daniela D. Herrera-Balandrano, Juan G. Báez-González, Elizabeth Carvajal-Millán, Vania Urías-Orona, Gerardo Méndez-Zamora and Guillermo Niño-Medina
Polysaccharides 2025, 6(3), 59; https://doi.org/10.3390/polysaccharides6030059 - 2 Jul 2025
Viewed by 1432
Abstract
In this study, feruloylated arabinoxylans (FAXs) extracted from nixtamalized maize bran were assessed as a functional ingredient in white bread. FAXs were added at percentages of 0.15% and 0.30% to bread, and a control sample without FAXs was prepared. Regarding texture profile analysis, [...] Read more.
In this study, feruloylated arabinoxylans (FAXs) extracted from nixtamalized maize bran were assessed as a functional ingredient in white bread. FAXs were added at percentages of 0.15% and 0.30% to bread, and a control sample without FAXs was prepared. Regarding texture profile analysis, hardness values in bread treated with FAXs ranged from 34.32 N (T5) to 51.03 N (T3), with all values for FAXs-added bread being lower than 64.43 N obtained for the control sample (TC). With respect to color, most of the FAX-treated samples had higher overall values than the control sample, with L* values ranging from 50.49 (T4) to 59.40 (T6). The total color difference (ΔE) values ranged from 2.07 (T2) to 6.32 (T6), indicating differences between the control sample and the FAX-treated samples. In the analysis of proximate composition, all FAX-treated bread had higher levels of crude fiber content than the control sample, and water activity (aw) values were lower in the control sample than in bread treated with FAXs. Regarding total phenols, FAX-treated bread ranged from 1.57 (T6) to 1.98 (T1) mgFAE/g, being higher than the 1.24 mgFAE/g found in the control sample (TC). The antioxidant capacity levels, namely, DPPH, ABTS, and FRAP, were 9.36–17.01, 8.86–17.64, and 3.05–5.07 µmolTE/g, respectively. Thus, it is possible to conclude that adding FAXs to bread formulations improves the hardness, crude fiber content, and functional properties of bread. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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19 pages, 2086 KB  
Article
Corn Stalks-Derived Hemicellulosic Polysaccharides: Extraction and Purification
by Adrian Cătălin Puițel, Cătălin Dumitrel Balan and Mircea Teodor Nechita
Polysaccharides 2025, 6(1), 2; https://doi.org/10.3390/polysaccharides6010002 - 5 Jan 2025
Cited by 3 | Viewed by 3040
Abstract
Nowadays, agricultural biomass is one the most valuable sources of natural polysaccharides. In addition to primary agricultural goods, agricultural waste is abundant, diverse, and renewable and can also be utilized as raw material for the production of polysaccharides and their derivatives. The extraction [...] Read more.
Nowadays, agricultural biomass is one the most valuable sources of natural polysaccharides. In addition to primary agricultural goods, agricultural waste is abundant, diverse, and renewable and can also be utilized as raw material for the production of polysaccharides and their derivatives. The extraction and purification of agri-waste-derived polysaccharides involves multiple processes that can vary depending on the type of raw material and the specific polysaccharides targeted. This study proposes a particular pathway from corn waste to hemicellulosic polysaccharides, which involves alkaline treatment and several physicochemical separation/purification phases using precipitation and ion exchange resins (Purolite A400, Purolite A100+, Purolite C100H). The ion exchange separation stage was optimized to retain most of the acid-soluble lignin derivatives from the extraction liquors. The process parameters considered for optimization included the solid (resin) liquid (black liquor pH 4.5) ratio, contact time, and temperature. These ranged from 0.05 to 0.15 g·mL−1, 30 to 180 min, and 20 to 50 °C, respectively. The chemical composition of the separated hemicelluloses varied from 44.43 to 75.28% for xylan, 2.43 to 3.93% for glucan, 1.86 to 2.44% for galactan and 8.93 to 12.68% for arabinan. The total carbohydrate content increased from 57.65 to 96.3%. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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16 pages, 5761 KB  
Article
Influence of the Purification Degree of Cellulose from Posidonia oceanica on the Properties of Cellulose-PLA Composites
by Paula Camarena-Bononad, Pedro A. V. Freitas, Chelo González-Martínez, Amparo Chiralt and Maria Vargas
Polysaccharides 2024, 5(4), 807-822; https://doi.org/10.3390/polysaccharides5040050 - 5 Dec 2024
Cited by 9 | Viewed by 2438
Abstract
PLA biocomposites, incorporating 5% wt. of lignocellulosic fibres (LF) from Posidonia oceanica waste with different degrees of cellulose purification, were obtained by melt blending and compression moulding. The LF were obtained after removing part of the non-cellulosic components by subcritical water extraction at [...] Read more.
PLA biocomposites, incorporating 5% wt. of lignocellulosic fibres (LF) from Posidonia oceanica waste with different degrees of cellulose purification, were obtained by melt blending and compression moulding. The LF were obtained after removing part of the non-cellulosic components by subcritical water extraction at 150 and 170 °C and after bleaching the extracted residues with hydrogen peroxide or sodium chlorite. The non-bleached LF provided the composites with a brown colour and opacity, while the bleached LF impacted the optical properties of composites to a lower extent, depending on their whiteness. The LF composition had a noticeable effect on the composites’ mechanical and barrier properties. All LF reduced the water vapour barrier capacity while promoting the oxygen barrier of the films. Bleached LF enhanced the film stiffness and reduced extensibility and resistance to break, whereas non-bleached LF had lower impacts on the tensile parameters. Considering the mechanical and barrier performance of the composites, the fibres obtained at 170 °C and bleached with sodium chlorite exhibited the best behaviour. Nevertheless, if transparency and colour are not limiting for the use of the films, untreated LF allowed for good preservation of the water vapour permeability of PLA films and enhanced the oxygen barrier capacity, with a similar mechanical response as the other non-bleached fractions. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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24 pages, 8975 KB  
Article
Grease, Oxygen, and Air Barrier Properties of Cellulose-Coated Copy Paper
by Ronald Sabo, Cody Schilling, Craig Clemons, Daniel Franke, Neil R. Gribbins, Michael Landry, Kimberly Hoxie and Peter Kitin
Polysaccharides 2024, 5(4), 783-806; https://doi.org/10.3390/polysaccharides5040049 - 4 Dec 2024
Cited by 5 | Viewed by 4505
Abstract
Cellulose nanomaterials have been demonstrated to be excellent barriers against grease, oxygen, and other vapors, but their implementation in packaging materials is challenging because of numerous technical and practical challenges. In this work, the oxygen, air, grease, and heptane barrier performance of copy [...] Read more.
Cellulose nanomaterials have been demonstrated to be excellent barriers against grease, oxygen, and other vapors, but their implementation in packaging materials is challenging because of numerous technical and practical challenges. In this work, the oxygen, air, grease, and heptane barrier performance of copy papers coated with cellulose nanocrystals (CNCs), oxidized cellulose nanofibrils (TOCNs), and carboxymethyl cellulose (CMC) weas examined. The effects of different materials and processing conditions were evaluated for their impacts on the resulting barrier properties. TOCN coatings demonstrated significantly better barrier properties than CNC and CMC coatings due to the long-range networked structure of TOCN suspensions eliciting enhanced film formation at the paper surface. Neat coatings of nanocellulose did not readily result in strong oxygen barriers, but the addition of CMC and/or an additional waterborne water barrier coating was found to result in oxygen barriers suitable for packaging applications (1 cm3/m2·day transmission at low humidity with a 10 g/m2 coating). Cast films and thick coatings of CMC were good barriers to oxygen, grease, and air, and its addition to cellulose nanomaterial suspensions aided the coating process and reduced coating defects. In all cases, the incorporation of additional processing aids or coatings was necessary to achieve suitable barrier properties. However, maintaining the strong barrier properties of nanocellulose coatings after creasing remains challenging. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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Review

Jump to: Research

28 pages, 6229 KB  
Review
Mechanical Pretreatment of Plant Biomass: Mechanisms, Energy Efficiency, Technologies, and Life Cycle Assessment
by Ekaterina Podgorbunskikh, Tatiana Skripkina and Aleksey Bychkov
Polysaccharides 2026, 7(2), 38; https://doi.org/10.3390/polysaccharides7020038 - 24 Mar 2026
Viewed by 1050
Abstract
Mechanical pretreatment techniques are essential for overcoming lignocellulosic biomass recalcitrance in emerging biorefineries. This review critically synthesizes advances from 2020 to 2025 across fundamental mechanisms, hybrid technologies, energy efficiency, Life Cycle Assessment, and industrial scalability. The analysis reveals that effective pretreatment targets supramolecular [...] Read more.
Mechanical pretreatment techniques are essential for overcoming lignocellulosic biomass recalcitrance in emerging biorefineries. This review critically synthesizes advances from 2020 to 2025 across fundamental mechanisms, hybrid technologies, energy efficiency, Life Cycle Assessment, and industrial scalability. The analysis reveals that effective pretreatment targets supramolecular modification—defect generation in cellulose crystallites and the creation of reactive sites—beyond simple particle size reduction. Impact–shear regimes prove most effective for fibrous materials. Hybrid approaches are examined: mechanocatalysis enables solvent-free depolymerization, while mechanoenzymatic technologies achieve hydrolysis without bulk water, though enzyme denaturation under mechanical stress remains unresolved. Energy consumption is the primary upscaling barrier, with Life Cycle Assessment identifying electricity use as the dominant environmental hotspot and emphasizing burden per unit of final product as the critical metric. Technology Readiness Level assessment provides a strategic framework: continuous extruders and mills are industrially mature for bulk applications, while high-intensity batch devices are suited for high-value coproducts. A research agenda prioritizing mechanistic understanding, hybrid process engineering, feedstock diversification, and embedded sustainability assessment is proposed. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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32 pages, 4580 KB  
Review
Crystallinity Changes in Modified Cellulose Substrates Evidenced by Spectral and X-Ray Diffraction Data
by Magdalena-Cristina Stanciu, Fulga Tanasă and Carmen-Alice Teacă
Polysaccharides 2025, 6(2), 30; https://doi.org/10.3390/polysaccharides6020030 - 4 Apr 2025
Cited by 35 | Viewed by 8072
Abstract
The crystallinity of cellulose substrates is a key factor in their processability, as well as an indication of their susceptibility to undergo sensitive reactions (such as enzymatic saccharification) with high yields. FT-IR and X-ray diffraction spectroscopy are useful, reliable, and easy-to-reach solid-state characterization [...] Read more.
The crystallinity of cellulose substrates is a key factor in their processability, as well as an indication of their susceptibility to undergo sensitive reactions (such as enzymatic saccharification) with high yields. FT-IR and X-ray diffraction spectroscopy are useful, reliable, and easy-to-reach solid-state characterization methods for assessing the crystallinity of different cellulose substrates including wood and wood-based materials. Due to their specific methodology, they can be used to analyze not only starting materials and their final products but also intermediates. Data obtained by these methods substantiated the structural changes in cellulose substrates, as well as the alterations that occurred in their supramolecular architectures. The conversion of crystalline cellulose I into amorphous cellulose II during enzymatic saccharification, with or without pre-treatment (solubilization in ILs), was evidenced beyond any reasonable doubt by FT-IR and XRD experimental results. Enzyme hydrolysis rates of the ILs-treated cellulose substrates can be significantly increased, as evidenced by reducing sugar yields. Crystallinity index values for cellulose of different origins (initial, pre-treated with ILs, and hydrolyzed with enzyme, as well as cellulose submitted to one-pot procedure with ILs and enzyme) can be determined using FTIR and X-ray diffraction data and discussed for comparison purposes. The same solid-state characterization methods can be also successfully employed for investigation of surface changes, expressed as cellulose crystallinity, in wood samples before and after impregnation with natural-based products, as well as under biodegradation conditions in soil burial tests. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Materials)
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