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Nanocelluloses: Synthesis, Modification and Applications

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A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (31 August 2019) | Viewed by 59885

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Prof. Dr. Elena Vismara

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Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Via Mancinelli 7, 20131 Milan, Italy
Interests: nanocellulose and its application; preparation of hybrid organic–inorganic nanoparticles for biomedical applications; synthesis of carbohydrate derivatives with antimetastatic properties; polymeric materials from natural and synthetic fibers for sanitary and environmental applications; recovery of cellulose from natural and industrial waste for the synthesis of artificial fibers
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Dear Colleagues,

Nanocelluloses (NCs), namely cellulose-based materials with peculiar physicochemical properties, appear as a new research, offering a wide range of specific applications, quite different from those of cellulose. NC structure, properties, and nanocomposites and NCs have been defined as a new family of nature-based materials. The approach to provide NCs is intimately correlated to the NC source. NC recovery from waste materials is a concrete opportunity to take advantage of cellulose-containing wastes and to enhance them.

Another nanocellulose that has been studied in recent years, and that is prepared by biotechnology, is bacterial nanocellulose (BNC), a nanofibrilar polymer produced by strains such as Gluconacetobacter xylinus. BNC cannot be ignored by researchers interested in nanocellulose due to its unique properties, such as chemical purity, biocompatibility, inertness and non-toxicity, biofunctionality and hypoalergenicity, good mechanical strength, high absorbency, and the possibility of forming any shape and size.

We look forward to receiving your valuable contributions in the forms of reviews, communications, and academic articles.

Prof. Dr. Elena Vismara
Guest Editor

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Keywords

nanocellulose
waste recovery
nanocellulose composites
bacterial nanocellulose
industrial applications of nanocellulose
biomedical applications of bacterial nanocellulose

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Published Papers (9 papers)

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18 pages, 4092 KiB

Open AccessArticle

Blending Gelatin and Cellulose Nanofibrils: Biocomposites with Tunable Degradability and Mechanical Behavior

by Elisabetta Campodoni, Margherita Montanari, Samuele M. Dozio, Ellinor B. Heggset, Silvia Panseri, Monica Montesi, Anna Tampieri, Kristin Syverud and Monica Sandri

Nanomaterials 2020, 10(6), 1219; https://doi.org/10.3390/nano10061219 - 22 Jun 2020

Cited by 17 | Viewed by 3840

Abstract

Many studies show how biomaterial properties like stiffness, mechanical stimulation and surface topography can influence cellular functions and direct stem cell differentiation. In this work, two different natural materials, gelatin (Gel) and cellulose nanofibrils (CNFs), were combined to design suitable 3D porous biocomposites for soft-tissue engineering. Gel was selected for its well-assessed high biomimicry that it shares with collagen, from which it derives, while the CNFs were chosen as structural reinforcement because of their exceptional mechanical properties and biocompatibility. Three different compositions of Gel and CNFs, i.e., with weight ratios of 75:25, 50:50 and 25:75, were studied. The biocomposites were morphologically characterized and their total- and macro- porosity assessed, proving their suitability for cell colonization. In general, the pores were larger and more isotropic in the biocomposites compared to the pure materials. The influence of freeze-casting and dehydrothermal treatment (DHT) on mechanical properties, the absorption ability and the shape retention were evaluated. Higher content of CNFs gave higher swelling, and this was attributed to the pore structure. Cross-linking between CNFs and Gel using DHT was confirmed. The Young’s modulus increased significantly by adding the CNFs to Gel with a linear relationship with respect to the CNF amounts. Finally, the biocomposites were characterized in vitro by testing cell colonization and growth through a quantitative cell viability analysis performed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Additionally, the cell viability analysis was performed by the means of a Live/Dead test with Human mesenchymal stem cells (hMSCs). All the biocomposites had higher cytocompatibility compared to the pure materials, Gel and CNFs. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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22 pages, 6677 KiB

Open AccessArticle

Bacterial Nanocellulose and Its Surface Modification by Glycidyl Methacrylate and Ethylene Glycol Dimethacrylate. Incorporation of Vancomycin and Ciprofloxacin

by Elena Vismara, Andrea Bernardi, Chiara Bongio, Silvia Farè, Salvatore Pappalardo, Andrea Serafini, Loredano Pollegioni, Elena Rosini and Giangiacomo Torri

Nanomaterials 2019, 9(12), 1668; https://doi.org/10.3390/nano9121668 - 22 Nov 2019

Cited by 26 | Viewed by 4017

Abstract

Among nanocelluloses, bacterial nanocellulose (BNC) has proven to be a promising candidate in a range of biomedical applications, from topical wound dressings to tissue-engineering scaffolds. Chemical modifications and incorporation of bioactive molecules have been obtained, further increasing the potential of BNC. This study describes the incorporation of vancomycin and ciprofloxacin in BNC and in modified BNC to afford bioactive BNCs suitable for topical wound dressings and tissue-engineering scaffolds. BNC was modified by grafting glycidylmethacrylate (GMA) and further cross-linking with ethylene glycol dimethacrylate (EGDMA) with the formation of stable C–C bonds through a radical Fenton-type process that involves generation of cellulose carbon centred radicals scavenged by methacrylate structures. The average molar substitution degree MS (MS = methacrylate residue per glucose unit, measured by Fourier transform infrared (FT–IR) analysis) can be modulated in a large range from 0.1 up to 3. BNC-GMA, BNC-EGDMA and BNC-GMA-EGDMA maintain the hydrogel status until MS reaches the value of 1. The mechanical stress resistance increase of BNC-GMA and BNC-GMA-EGDMA of MS around 0.8 with respect to BNC suggests that they can be preferred to BNC for tissue-engineering scaffolds in cases where the resistance plays a crucial role. BNC, BNC-GMA, BNC-EGDMA and BNC-GMA-EGDMA were loaded with vancomycin (VC) and ciprofloxacin (CP) and submitted to release experiments. BNC-GMA-EGDMA of high substitution degree (0.7–1) hold up to 50 percentage of the loaded vancomycin and ciprofloxacin amount, suggesting that they can be further investigated for long-term antimicrobial activity. Furthermore, they were not colonized by Staphylococcus aureus (S.A.) and Klebsiella pneumonia (K.P.). Grafting and cross-linking BNC modification emerges from our results as a good choice to improve the BNC potential in biomedical applications like topical wound dressings and tissue-engineering scaffolds. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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10 pages, 3519 KiB

Open AccessArticle

A Highly Efficient and Durable Fluorescent Paper Produced from Bacterial Cellulose/Eu Complex and Cellulosic Fibers

by Mingquan Zhang, Xiao Wu, Zhenhua Hu, Zhouyang Xiang, Tao Song and Fachuang Lu

Nanomaterials 2019, 9(9), 1322; https://doi.org/10.3390/nano9091322 - 15 Sep 2019

Cited by 13 | Viewed by 4062

Abstract

The general method of producing fluorescent paper by coating fluorescent substances onto paper base faces the problems of low efficiency and poor durability. Bacterial cellulose (BC) with its nanoporous structure can be used to stabilize fluorescent particles. In this study, we used a novel method to produce fluorescent paper by first making Eu/BC complex and then processing the complex and cellulosic fibers into composite paper sheets. For this composting method, BC can form very stable BC/Eu complex due to its nanoporous structure, while the plant-based cellulosic fibers reduce the cost and provide stiffness to the materials. The fluorescent paper demonstrated a great fluorescent property and efficiency. The ultraviolet absorbance or the fluorescent intensity of the Eu-BC fluorescent paper increased with the increase of Eu-BC content but remained little changed after Eu-BC content was higher than 5%. After folding 200 times, the fluorescence intensity of fluorescent paper decreased by only 0.7%, which suggested that the Eu-BC fluorescent paper has great stability and durability. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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17 pages, 4489 KiB

Open AccessArticle

Arginine/Nanocellulose Membranes for Carbon Capture Applications

by Davide Venturi, Alexander Chrysanthou, Benjamin Dhuiège, Karim Missoum and Marco Giacinti Baschetti

Nanomaterials 2019, 9(6), 877; https://doi.org/10.3390/nano9060877 - 10 Jun 2019

Cited by 24 | Viewed by 4597

Abstract

The present study investigates the influence of the addition of l-arginine to a matrix of carboxymethylated nanofibrillated cellulose (CMC-NFC), with the aim of fabricating a mobile carrier facilitated transport membrane for the separation of CO₂. Self-standing films were prepared by casting an aqueous suspension containing different amounts of amino acid (15–30–45 wt.%) and CMC-NFC. The permeation properties were assessed in humid conditions (70–98% relative humidity (RH)) at 35 °C for CO₂ and N₂ separately and compared with that of the non-loaded nanocellulose films. Both permeability and ideal selectivity appeared to be improved by the addition of l-arginine, especially when high amino-acid loadings were considered. A seven-fold increment in carbon dioxide permeability was observed between pure CMC-NFC and the 45 wt.% blend (from 29 to 220 Barrer at 94% RH), also paired to a significant increase of ideal selectivity (from 56 to 185). Interestingly, while improving the separation performance, water sorption was not substantially affected by the addition of amino acid, thus confirming that the increased permeability was not related simply to membrane swelling. Overall, the addition of aminated mobile carriers appeared to provide enhanced performances, advancing the state of the art for nanocellulose-based gas separation membranes. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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17 pages, 6340 KiB

Open AccessArticle

Composite Membranes Derived from Cellulose and Lignin Sulfonate for Selective Separations and Antifouling Aspects

by Andrew Colburn, Ronald J. Vogler, Aum Patel, Mariah Bezold, John Craven, Chunqing Liu and Dibakar Bhattacharyya

Nanomaterials 2019, 9(6), 867; https://doi.org/10.3390/nano9060867 - 7 Jun 2019

Cited by 24 | Viewed by 5900

Abstract

Cellulose-based membrane materials allow for separations in both aqueous solutions and organic solvents. The addition of nanocomposites into cellulose structure is facilitated through steric interaction and strong hydrogen bonding with the hydroxy groups present within cellulose. An ionic liquid, 1-ethyl-3-methylimidazolium acetate, was used as a solvent for microcrystalline cellulose to incorporate graphene oxide quantum dots into cellulose membranes. In this work, other composite materials such as, iron oxide nanoparticles, polyacrylic acid, and lignin sulfonate have all been uniformly incorporated into cellulose membranes utilizing ionic liquid cosolvents. Integration of iron into cellulose membranes resulted in high selectivity (>99%) of neutral red and methylene blue model dyes separation over salts with a high permeability of 17 LMH/bar. With non-aqueous (alcohol) solvent, iron–cellulose composite membranes become less selective and more permeable, suggesting the interaction of iron ions cellulose OH groups plays a major role in pore structure. Polyacrylic acid was integrated into cellulose membranes to add pH responsive behavior and capacity for metal ion capture. Calcium capture of 55 mg Ca²⁺/g membrane was observed for PAA-cellulose membranes. Lignin sulfonate was also incorporated into cellulose membranes to add strong negative charge and a steric barrier to enhance antifouling behavior. Lignin sulfonate was also functionalized on the commercial DOW NF270 nanofiltration membranes via esterification of hydroxy groups with carboxyl group present on the membrane surface. Antifouling behavior was observed for both lignin-cellulose composite and commercial membranes functionalized with lignin. Up to 90% recovery of water flux after repeated cycles of fouling was observed for both types of lignin functionalized membranes while flux recovery of up to 60% was observed for unmodified membranes. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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16 pages, 2408 KiB

Open AccessArticle

Electrospinning of Cellulose Nanocrystal-Filled Poly (Vinyl Alcohol) Solutions: Material Property Assessment

by J. Elliott Sanders, Yousoo Han, Todd S. Rushing and Douglas J. Gardner

Nanomaterials 2019, 9(5), 805; https://doi.org/10.3390/nano9050805 - 27 May 2019

Cited by 29 | Viewed by 5666

Abstract

Poly (vinyl alcohol) (PVA) and cellulose nanocrystals (CNC) random composite mats were prepared using the electrospinning method. PVA/CNC mats were reinforced with weight concentrations of 0, 20 and 50% CNC (w/w) relative to PVA. Scanning electron microscopy was used to measure the fiber diameter, which ranged from 377 to 416 nm. Thermogravimetric analysis (TGA) confirmed the presence of CNC fibers in the mat fibers which were not visible by scanning electron microscope (SEM). Mechanical testing was conducted using ASTM D 638 on each sample group at 10 mm min⁻¹. Neat PVA and PVA/CNC mats were heat treated at 170 °C for 2h hours, and the morphological structure was maintained with some fiber diameter reduction. Mechanical property results after heat treatment showed a decrease in tensile strength, an increase in tensile stiffness and a decrease in strain to yield (%). This effect was attributable to enhanced diffusion bonding of the mat fiber intersections. The CNC fibers also increased mat stiffness, and reduced strain to yield in non-treated mats. The use of CNCs show potential for compounding into bulk polymer composites as a reinforcement filler, and also show promise for chemical crosslinking attributable to the –OH groups on both the PVA, in addition to esterification of the vinyl group, and CNC. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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13 pages, 4618 KiB

Open AccessArticle

Improved Dispersion of Bacterial Cellulose Fibers for the Reinforcement of Paper Made from Recycled Fibers

by Zhouyang Xiang, Jie Zhang, Qingguo Liu, Yong Chen, Jun Li and Fachuang Lu

Nanomaterials 2019, 9(1), 58; https://doi.org/10.3390/nano9010058 - 4 Jan 2019

Cited by 6 | Viewed by 4138

Abstract

Bacterial cellulose (BC) can be used to improve the physical properties of paper. However, previous studies have showed that the effectiveness of this improvement is impaired by the agglomeration of the disintegrated BC fibers. Effective dispersion of BC fibers is important to their reinforcing effects to paper products, especially those made of recycled fibers. In this study, carboxymethyl cellulose, xylan, glucomannan, cationized starch, and polyethylene oxide were used to improve the dispersion of BC fibers. With dispersed BC fibers, the paper made of recycled fiber showed improved dry tensile strength. The best improvement in dry tensile index was 4.2 N·m/g or 12.7% up, which was obtained by adding BC fibers dispersed with glucomannan. Glucomannan had the highest adsorption onto BC fibers, i.e., 750 mg/g at 1000 mg/L concentration, leading to the best colloidal stability of BC fiber suspension that had no aggregation in 50 min at 0.1 weight ratio of glucomannan to BC. TEMPO-mediated oxidation of BC was effective in improving its colloidal stability, but not effective in improving the ability of BC fiber to enhance paper dry tensile index while the wet tensile index was improved from 0.89 N·m/g to 1.59 N·m/g, i.e., ~80% improvement. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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11 pages, 1588 KiB

Open AccessArticle

Synthesis of Nanofibrillated Cellulose by Combined Ammonium Persulphate Treatment with Ultrasound and Mechanical Processing

by Inese Filipova, Velta Fridrihsone, Ugis Cabulis and Agris Berzins

Nanomaterials 2018, 8(9), 640; https://doi.org/10.3390/nano8090640 - 21 Aug 2018

Cited by 59 | Viewed by 5687

Abstract

Ammonium persulfate has been known as an agent for obtaining nanocellulose in recent years, however most research has focused on producing cellulose nanocrystals. A lack of research about combined ammonium persulfate oxidation and common mechanical treatment in order to obtain cellulose nanofibrils has been identified. The objective of this research was to obtain and investigate carboxylated cellulose nanofibrils produced by ammonium persulfate oxidation combined with ultrasonic and mechanical treatment. Light microscopy, atomic force microscopy (AFM), powder X-Ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Zeta potential measurements were applied during this research. The carboxylated cellulose suspension of different fractions including nanofibrils, microfibrils and bundles were produced from bleached birch Kraft pulp fibers using chemical pretreatment with ammonium persulfate solution and further defibrillation using consequent mechanical treatment in a high shear laboratory mixer and ultrasonication. The characteristics of the obtained nanofibrils were: diameter 20–300 nm, crystallinity index 74.3%, Zeta potential −26.9 ± 1.8 mV, clear FTIR peak at 1740 cm⁻¹ indicating the C=O stretching vibrations, and lower thermostability in comparison to the Kraft pulp was observed. The proposed method can be used to produce cellulose nanofibrils with defined crystallinity. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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Review

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20 pages, 4448 KiB

Open AccessReview

Bacterial Cellulose: Production, Modification and Perspectives in Biomedical Applications

by Selestina Gorgieva and Janja Trček

Nanomaterials 2019, 9(10), 1352; https://doi.org/10.3390/nano9101352 - 20 Sep 2019

Cited by 339 | Viewed by 20895

Abstract

Bacterial cellulose (BC) is ultrafine, nanofibrillar material with an exclusive combination of properties such as high crystallinity (84%–89%) and polymerization degree, high surface area (high aspect ratio of fibers with diameter 20–100 nm), high flexibility and tensile strength (Young modulus of 15–18 GPa), high water-holding capacity (over 100 times of its own weight), etc. Due to high purity, i.e., absence of lignin and hemicellulose, BC is considered as a non-cytotoxic, non-genotoxic and highly biocompatible material, attracting interest in diverse areas with hallmarks in medicine. The presented review summarizes the microbial aspects of BC production (bacterial strains, carbon sources and media) and versatile in situ and ex situ methods applied in BC modification, especially towards bionic design for applications in regenerative medicine, from wound healing and artificial skin, blood vessels, coverings in nerve surgery, dura mater prosthesis, arterial stent coating, cartilage and bone repair implants, etc. The paper concludes with challenges and perspectives in light of further translation in highly valuable medical products. Full article

(This article belongs to the Special Issue Nanocelluloses: Synthesis, Modification and Applications)

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