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Special Issue "Advances in Functionalization of Lignocellulosic Materials"

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Biomaterials".

Deadline for manuscript submissions: closed (30 April 2016)

Special Issue Editors

Guest Editor
Dr. Jalel Labidi

Chemical and EnvironmChemical and Environmental Engineering Department, University of the Basque Country, Plaza Europa 1 20018 Donostia-San Sebastián, Spain
Website | E-Mail
Interests: biomaterials; nanomaterials; polysaccharide; biorefinery; green chemistry
Guest Editor
Dr. Susana C. M. Fernandes

Division of Glycoscience, School of Biotechnology, Royal Institute of Technology (KTH), AlbaNova University Centre, Roslagstullsbacken 21, 106 91 Stockholm, Sweden
Website | E-Mail
Interests: bioinspitration; biopolymers; bionanocomposites; (bio)materials; functionalization

Special Issue Information

Dear Colleagues,

The applications of lignocelulosic materials for the elaboration of materials have been widely studied during the last few decades. Lignocelulosic materials, e.g., cellulose, hemicelluloses and lignin, have been functionalized in order to improve their compatibility with other (bio)polymers to fabricate (nano)composite materials, or to add new functionalities, namely antimicrobial and antioxidant activities. The high hydrophilic nature of the lignocelulosic materials adversely affects their compatibility with hydrophobic matrices and it may cause a loss of bond strength, even with hydrophilic polymers. Surface modification of the fibers reduces their hydrophilicity and improves the fiber-matrix adhesion in composites. On the other hand, the functionalization of the lignocelulosic materials with (bio)active molecules or nanoparticles introduce new original properties to the final materials. The development of advanced fuctionalization of lignocellulosic materials to tailor the surface properties of the materials open the door to the development of new applications in different fields (bionancomposites, membranes, medical aplications, etc.) and meet the market requirements.

It is our pleasure to invite you to submit a manuscript for this Special Issue. Full papers, short communications, and reviews are all welcome.

Dr. Jalel Labidi
Dr. Susana C. M. Fernandes
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1500 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.


Keywords

  • lignocellulosic materials
  • functionalization
  • composites
  • surface properties

Published Papers (9 papers)

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Research

Jump to: Review

Open AccessArticle Preparation and Characterization of Polyvinyl Alcohol-Chitosan Composite Films Reinforced with Cellulose Nanofiber
Materials 2016, 9(8), 644; doi:10.3390/ma9080644
Received: 28 June 2016 / Revised: 21 July 2016 / Accepted: 26 July 2016 / Published: 29 July 2016
Cited by 11 | PDF Full-text (7870 KB) | HTML Full-text | XML Full-text
Abstract
In this study microcrystalline cellulose (MCC) was oxidized by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation. The treated cellulose slurry was mechanically homogenized to form a transparent dispersion which consisted of individual cellulose nanofibers with uniform widths of 3–4 nm. Bio-nanocomposite films were then prepared from
[...] Read more.
In this study microcrystalline cellulose (MCC) was oxidized by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation. The treated cellulose slurry was mechanically homogenized to form a transparent dispersion which consisted of individual cellulose nanofibers with uniform widths of 3–4 nm. Bio-nanocomposite films were then prepared from a polyvinyl alcohol (PVA)-chitosan (CS) polymeric blend with different TEMPO-oxidized cellulose nanofiber (TOCN) contents (0, 0.5, 1.0 and 1.5 wt %) via the solution casting method. The characterizations of pure PVA/CS and PVA/CS/TOCN films were performed in terms of field emission scanning electron microscopy (FESEM), tensile tests, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The results from FESEM analysis justified that low loading levels of TOCNs were dispersed uniformly and homogeneously in the PVA-CS blend matrix. The tensile strength and thermal stability of the films were increased with the increased loading levels of TOCNs to a maximum level. The thermal study indicated a slight improvement of the thermal stability upon the reinforcement of TOCNs. As evidenced by the FTIR and XRD, PVA and CS were considered miscible and compatible owing to hydrogen bonding interaction. These analyses also revealed the good dispersion of TOCNs within the PVA/CS polymer matrix. The improved properties due to the reinforcement of TOCNs can be highly beneficial in numerous applications. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
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Open AccessFeature PaperArticle Rapeseed and Raspberry Seed Cakes as Inexpensive Raw Materials in the Production of Activated Carbon by Physical Activation: Effect of Activation Conditions on Textural and Phenol Adsorption Characteristics
Materials 2016, 9(7), 565; doi:10.3390/ma9070565
Received: 7 April 2016 / Revised: 13 June 2016 / Accepted: 4 July 2016 / Published: 12 July 2016
Cited by 1 | PDF Full-text (4772 KB) | HTML Full-text | XML Full-text
Abstract
The production of activated carbons (ACs) from rapeseed cake and raspberry seed cake using slow pyrolysis followed by physical activation of the obtained solid residues is the topic of this study. The effect of activation temperature (850, 900 and 950 °C), activation time
[...] Read more.
The production of activated carbons (ACs) from rapeseed cake and raspberry seed cake using slow pyrolysis followed by physical activation of the obtained solid residues is the topic of this study. The effect of activation temperature (850, 900 and 950 °C), activation time (30, 60, 90 and 120 min) and agent (steam and CO2) on the textural characteristics of the ACs is investigated by N2 adsorption. In general, higher activation temperatures and longer activation times increase the BET specific surface area and the porosity of the ACs, regardless of the activation agent or raw material. Steam is more reactive than CO2 in terms of pore development, especially in the case of raspberry seed cake. The performance of the ACs in liquid adsorption is evaluated by batch phenol adsorption tests. Experimental data are best fitted by the Freundlich isotherm model. Based on total yield, textural characteristics and phenol adsorption, steam activation at 900 °C for 90 min and CO2 activation at 900 °C for 120 min are found as the best activation conditions. Raspberry seed cake turns out to be a better raw material than rapeseed cake. Moreover, AC from raspberry seed cake produced by steam activation at 900 °C for 90 min performs as well as commercial AC (Norit GAC 1240) in phenol adsorption. The adsorption kinetics of the selected ACs are best fitted by the pseudo-second-order model. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
Open AccessArticle LCA of 1,4-Butanediol Produced via Direct Fermentation of Sugars from Wheat Straw Feedstock within a Territorial Biorefinery
Materials 2016, 9(7), 563; doi:10.3390/ma9070563
Received: 19 May 2016 / Revised: 30 June 2016 / Accepted: 4 July 2016 / Published: 12 July 2016
Cited by 3 | PDF Full-text (1383 KB) | HTML Full-text | XML Full-text
Abstract
The bio-based industrial sector has been recognized by the European Union as a priority area toward sustainability, however, the environmental profile of bio-based products needs to be further addressed. This study investigated, through the Life Cycle Assessment (LCA) approach, the environmental performance of
[...] Read more.
The bio-based industrial sector has been recognized by the European Union as a priority area toward sustainability, however, the environmental profile of bio-based products needs to be further addressed. This study investigated, through the Life Cycle Assessment (LCA) approach, the environmental performance of bio-based 1,4-butanediol (BDO) produced via direct fermentation of sugars from wheat straw, within a hypothetical regional biorefinery (Campania Region, Southern Italy). The aim was: (i) to identify the hotspots along the production chain; and (ii) to assess the potential environmental benefits of this bio-based polymer versus the reference conventional product (fossil-based BDO). Results identified the prevailing contribution to the total environmental load of bio-based BDO in the feedstock production and in the heat requirement at the biorefinery plant. The modeled industrial bio-based BDO supply chain, showed a general reduction of the environmental impacts compared to the fossil-based BDO. The lowest benefits were gained in terms of acidification and eutrophication, due to the environmental load of the crop phase for feedstock cultivation. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
Open AccessArticle Enrichment of Cellulosic Waste Hemp (Cannabis sativa) Hurd into Non-Toxic Microfibres
Materials 2016, 9(7), 562; doi:10.3390/ma9070562
Received: 5 May 2016 / Revised: 1 July 2016 / Accepted: 5 July 2016 / Published: 11 July 2016
Cited by 2 | PDF Full-text (3863 KB) | HTML Full-text | XML Full-text
Abstract
In this study a largely available lignocellulose feedstock hemp (Cannabis sativa), obtained as an industrial waste, was used for cellulose extraction. The extraction of cellulose microfibres from hemp biomass was conducted by alkaline treatment and an acidification process. The extracted cellulose
[...] Read more.
In this study a largely available lignocellulose feedstock hemp (Cannabis sativa), obtained as an industrial waste, was used for cellulose extraction. The extraction of cellulose microfibres from hemp biomass was conducted by alkaline treatment and an acidification process. The extracted cellulose microfibres were characterised using Fourier-transformed infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The viability of the study was determined by growing human fibroblasts on the preparation which resulted in being non-toxic; indicating its potential in preparing biological scaffolds. Upon enzymatic hydrolysis of the cellulose microfibre using cellulase from Trichoderma reesei, a maximum of 909 mg/g of reducing sugars were obtained, which endorses its suitability for biofuel production. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
Open AccessArticle Physicochemical Characterization of Functional Lignin–Silica Hybrid Fillers for Potential Application in Abrasive Tools
Materials 2016, 9(7), 517; doi:10.3390/ma9070517
Received: 28 April 2016 / Revised: 30 May 2016 / Accepted: 20 June 2016 / Published: 25 June 2016
Cited by 4 | PDF Full-text (2174 KB) | HTML Full-text | XML Full-text
Abstract
Functional lignin–SiO2 hybrid fillers were prepared for potential application in binders for phenolic resins, and their chemical structure was characterized. The properties of these fillers and of composites obtained from them with phenolic resin were compared with those of systems with lignin
[...] Read more.
Functional lignin–SiO2 hybrid fillers were prepared for potential application in binders for phenolic resins, and their chemical structure was characterized. The properties of these fillers and of composites obtained from them with phenolic resin were compared with those of systems with lignin or silica alone. The chemical structure of the materials was investigated by Fourier transform infrared spectroscopy (FT-IR) and carbon-13 nuclear magnetic resonance spectroscopy (13C CP MAS NMR). The thermal stability of the new functional fillers was examined by thermogravimetric analysis–mass spectrometry (TG-MS). Thermo-mechanical properties of the lignin–silica hybrids and resin systems were investigated by dynamic mechanical thermal analysis (DMTA). The DMTA results showed that abrasive composites with lignin–SiO2 fillers have better thermo-mechanical properties than systems with silica alone. Thus, fillers based on lignin might provide new, promising properties for the abrasive industry, combining the good properties of lignin as a plasticizer and of silica as a filler improving mechanical properties. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
Open AccessArticle Functionalization of Cellulose Nanocrystals in Choline Lactate Ionic Liquid
Materials 2016, 9(7), 499; doi:10.3390/ma9070499
Received: 29 April 2016 / Revised: 15 June 2016 / Accepted: 20 June 2016 / Published: 23 June 2016
Cited by 2 | PDF Full-text (3789 KB) | HTML Full-text | XML Full-text
Abstract
Cellulose nanocrystals (CNCs) are valuable nanomaterials obtained from renewable resources. Their properties make them suitable for a wide range of applications, including polymer reinforcement. However, due to their highly hydrophilic character, it is necessary to modify their surface with non-polar functional groups before
[...] Read more.
Cellulose nanocrystals (CNCs) are valuable nanomaterials obtained from renewable resources. Their properties make them suitable for a wide range of applications, including polymer reinforcement. However, due to their highly hydrophilic character, it is necessary to modify their surface with non-polar functional groups before their incorporation into a hydrophobic polymer matrix. In this work, cellulose nanocrystals were modified using a silane coupling agent and choline lactate, an ionic liquid derived from renewable resources, as a reaction medium. Modified cellulose nanocrystals were characterized by infrared spectroscopy, showing new peaks associated to the modification performed. X-ray diffraction was used to analyze the crystalline structure of functionalized cellulose nanocrystals and to optimize the amount of silane for functionalization. Poly(lactic acid) (PLA) nanocomposites containing 1 wt % of functionalized cellulose nanocrystals were prepared. They were characterized by field-emission scanning electron microscopy (FE-SEM) and mechanical tests. The use of choline lactate as reaction media has been shown to be an alternative method for the dispersion and silanization of the cellulose nanocrystals without the addition of an external catalyst. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
Open AccessArticle Water Uptake Behavior and Young Modulus Prediction of Composites Based on Treated Sisal Fibers and Poly(Lactic Acid)
Materials 2016, 9(5), 400; doi:10.3390/ma9050400
Received: 19 February 2016 / Revised: 11 May 2016 / Accepted: 17 May 2016 / Published: 21 May 2016
PDF Full-text (2219 KB) | HTML Full-text | XML Full-text
Abstract
The main aim of this work was to study the effect of sisal fiber surface treatments on water uptake behavior of composites based on untreated and treated fibers. For this purpose, sisal fibers were treated with different chemical treatments. All surface treatments delayed
[...] Read more.
The main aim of this work was to study the effect of sisal fiber surface treatments on water uptake behavior of composites based on untreated and treated fibers. For this purpose, sisal fibers were treated with different chemical treatments. All surface treatments delayed the water absorption of fibers only for a short time of period. No significant differences were observed in water uptake profiles of composites based on fibers with different surface treatments. After water uptake period, tensile strength and Young modulus values of sisal fiber/poly(lactic acid) (PLA) composites were decreased. On the other hand, composites based on NaOH + silane treated fibers showed the lowest diffusion coefficient values, suggesting that this treatment seemed to be the most effective treatment to reduce water diffusion rate into the composites. Finally, Young modulus values of composites, before water uptake period, were predicted using different micromechanical models and were compared with experimental data. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
Open AccessArticle Immobilization of Trypsin in Lignocellulosic Waste Material to Produce Peptides with Bioactive Potential from Whey Protein
Materials 2016, 9(5), 357; doi:10.3390/ma9050357
Received: 30 March 2016 / Revised: 3 May 2016 / Accepted: 4 May 2016 / Published: 12 May 2016
Cited by 3 | PDF Full-text (6830 KB) | HTML Full-text | XML Full-text
Abstract
In this study, trypsin (Enzyme Comission 3.4.21.4) was immobilized in a low cost, lignocellulosic support (corn cob powder—CCP) with the goal of obtaining peptides with bioactive potential from cheese whey. The pretreated support was activated with glyoxyl groups, glutaraldehyde and IDA-glyoxyl. The immobilization
[...] Read more.
In this study, trypsin (Enzyme Comission 3.4.21.4) was immobilized in a low cost, lignocellulosic support (corn cob powder—CCP) with the goal of obtaining peptides with bioactive potential from cheese whey. The pretreated support was activated with glyoxyl groups, glutaraldehyde and IDA-glyoxyl. The immobilization yields of the derivatives were higher than 83%, and the retention of catalytic activity was higher than 74%. The trypsin-glyoxyl-CCP derivative was thermally stable at 65 °C, a value that was 1090-fold higher than that obtained with the free enzyme. The trypsin-IDA-glyoxyl-CCP and trypsin-glutaraldehyde-CCP derivatives had thermal stabilities that were 883- and five-fold higher, respectively, then those obtained with the free enzyme. In the batch experiments, trypsin-IDA-glyoxyl-CCP retained 91% of its activity and had a degree of hydrolysis of 12.49%, while the values for trypsin-glyoxyl-CCP were 87% and 15.46%, respectively. The stabilized derivative trypsin-glyoxyl-CCP was also tested in an upflow packed-bed reactor. The hydrodynamic characterization of this reactor was a plug flow pattern, and the kinetics of this system provided a relative activity of 3.04 ± 0.01 U·g−1 and an average degree of hydrolysis of 23%, which were suitable for the production of potentially bioactive peptides. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
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Review

Jump to: Research

Open AccessReview Plant Fibre: Molecular Structure and Biomechanical Properties, of a Complex Living Material, Influencing Its Deconstruction towards a Biobased Composite
Materials 2016, 9(8), 618; doi:10.3390/ma9080618
Received: 14 June 2016 / Revised: 14 July 2016 / Accepted: 15 July 2016 / Published: 26 July 2016
PDF Full-text (4776 KB) | HTML Full-text | XML Full-text
Abstract
Plant cell walls form an organic complex composite material that fulfils various functions. The hierarchical structure of this material is generated from the integration of its elementary components. This review provides an overview of wood as a composite material followed by its deconstruction
[...] Read more.
Plant cell walls form an organic complex composite material that fulfils various functions. The hierarchical structure of this material is generated from the integration of its elementary components. This review provides an overview of wood as a composite material followed by its deconstruction into fibres that can then be incorporated into biobased composites. Firstly, the fibres are defined, and their various origins are discussed. Then, the organisation of cell walls and their components are described. The emphasis is on the molecular interactions of the cellulose microfibrils, lignin and hemicelluloses in planta. Hemicelluloses of diverse species and cell walls are described. Details of their organisation in the primary cell wall are provided, as understanding of the role of hemicellulose has recently evolved and is likely to affect our perception and future study of their secondary cell wall homologs. The importance of the presence of water on wood mechanical properties is also discussed. These sections provide the basis for understanding the molecular arrangements and interactions of the components and how they influence changes in fibre properties once isolated. A range of pulping processes can be used to individualise wood fibres, but these can cause damage to the fibres. Therefore, issues relating to fibre production are discussed along with the dispersion of wood fibres during extrusion. The final section explores various ways to improve fibres obtained from wood. Full article
(This article belongs to the Special Issue Advances in Functionalization of Lignocellulosic Materials)
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