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Special Issue "Cellulose Chemical Modifications—Towards Sustainable Materials"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Green Chemistry".

Deadline for manuscript submissions: closed (31 March 2018)

Special Issue Editor

Guest Editor
Dr. Janet L. Scott

Centre for Sustainable Chemical Technologies, Department of Chemistry, University of Bath, Bath, BA2 7AY, UK
Website | E-Mail
Interests: sustainable chemical technologies; functional materials; renewable sources; green chemistry

Special Issue Information

Dear Colleagues,

Cellulose is an abundant and renewable biopolymer, relied upon by nature to provide structure and strength to many organisms. The exquisite secondary structures, resulting from intermolecular interactions amongst polymer chains, provide fibrils and fibres of a range of dimensions, morphologies and stiffness and these can be exploited in many materials applications, from polymer fillers to tuneable hydrogels. Solution processing has been enhanced by the discovery that ionic liquids assist dissolution, leading to further opportunities in blending, compounding and forming of cellulose. Chemical modification of cellulose may be employed to confer specific properties to materials (surfaces and bulk), to render cellulose compatible with other polymers, or provide anchoring points for ligands or active agents, greatly widening opportunities for use cellulose based materials.

This Special Issue is devoted to providing an overview of recent developments in the chemical modification of cellulose to enhance materials properties, particularly with a view to developing more sustainable materials, i.e., where the chemistry used is ‘green’ and the product ‘environmentally friendly’.

Dr. Janet L. Scott
Guest Editor

Manuscript Submission Information

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Keywords

  • Cellulose
  • Chemical modification
  • Green chemistry
  • Sustainable materials

Published Papers (9 papers)

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Research

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Open AccessArticle Potential of Cellulose Functionalized with Carboxylic Acid as Biosorbent for the Removal of Cationic Dyes in Aqueous Solution
Molecules 2018, 23(4), 743; https://doi.org/10.3390/molecules23040743
Received: 27 February 2018 / Revised: 16 March 2018 / Accepted: 21 March 2018 / Published: 23 March 2018
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Abstract
In the last decade, adsorption has been used to minimize the pollution caused by dyes, which represents a serious environmental problem. In this context, this work reports the preparation of phthalic anhydride-modified cellulose (PhCel), through the reaction of cellulose (Cel) with phthalic anhydride
[...] Read more.
In the last decade, adsorption has been used to minimize the pollution caused by dyes, which represents a serious environmental problem. In this context, this work reports the preparation of phthalic anhydride-modified cellulose (PhCel), through the reaction of cellulose (Cel) with phthalic anhydride (Ph). The efficiency of the reaction was observed by elemental analysis, Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and thermogravimetry/derivative thermogravimetry (TG/DTG). The adsorbent matrix (Cel and PhCel) was used in the removal of crystal violet (CV) and methylene blue (MB) dyes in aqueous medium. In the kinetic study, the experimental data obtained had the best fit to the pseudo-first-order model. In general, the isotherms obtained at different temperatures had a best fit to the model proposed by Langmuir, and the CV and MB adsorption process in adsorbent matrixes can be favored strictly by hydrogen bonds and/or electrostatic interactions for Cel and electrostatic interactions for PhCel. Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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Open AccessArticle Amine-Functionalized Sugarcane Bagasse: A Renewable Catalyst for Efficient Continuous Flow Knoevenagel Condensation Reaction at Room Temperature
Received: 29 November 2017 / Revised: 20 December 2017 / Accepted: 22 December 2017 / Published: 24 December 2017
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Abstract
A biomass-based catalyst with amine groups (–NH2), viz., amine-functionalized sugarcane bagasse (SCB-NH2), was prepared through the amination of sugarcane bagasse (SCB) in a two-step process. The physicochemical properties of the catalyst were characterized through FT-IR, elemental analysis, XRD, TG,
[...] Read more.
A biomass-based catalyst with amine groups (–NH2), viz., amine-functionalized sugarcane bagasse (SCB-NH2), was prepared through the amination of sugarcane bagasse (SCB) in a two-step process. The physicochemical properties of the catalyst were characterized through FT-IR, elemental analysis, XRD, TG, and SEM-EDX techniques, which confirmed the –NH2 group was grafted onto SCB successfully. The catalytic performance of SCB-NH2 in Knoevenagel condensation reaction was tested in the batch and continuous flow reactions. Significantly, it was found that the catalytic performance of SCB-NH2 is better in flow system than that in batch system. Moreover, the SCB-NH2 presented an excellent catalytic activity and stability at the high flow rate. When the flow rate is at the 1.5 mL/min, no obvious deactivation was observed and the product yield and selectivity are more than 97% and 99% after 80 h of continuous reaction time, respectively. After the recovery of solvent from the resulting solution, a white solid was obtained as a target product. As a result, the SCB-NH2 is a promising catalyst for the synthesis of fine chemicals by Knoevenagel condensation reaction in large scale, and the modification of the renewable SCB with –NH2 group is a potential avenue for the preparation of amine-functionalized catalytic materials in industry. Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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Open AccessArticle Combinative Scouring, Bleaching, and Cationization Pretreatment of Greige Knitted Cotton Fabrics for Facilely Achieving Salt-Free Reactive Dyeing
Molecules 2017, 22(12), 2235; https://doi.org/10.3390/molecules22122235
Received: 31 October 2017 / Revised: 7 December 2017 / Accepted: 12 December 2017 / Published: 18 December 2017
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Abstract
In order to facilely achieve pretreatment and salt-free dyeing of greige knitted cotton fabrics, a combinative scouring, bleaching, and cationization pretreatment of the fabrics is designed in this study. The fabrics are first treated in a bath containing commercial scouring and bleaching agents,
[...] Read more.
In order to facilely achieve pretreatment and salt-free dyeing of greige knitted cotton fabrics, a combinative scouring, bleaching, and cationization pretreatment of the fabrics is designed in this study. The fabrics are first treated in a bath containing commercial scouring and bleaching agents, and then glycidyltrimethylammonium chloride (GTA) is directly added into the bath to achieve cationization of the fabrics. Utilization of the alkaline and high-temperature conditions in scouring and bleaching process, cationization can facilely proceed in a short time. Optimal pretreatment conditions are as follows: greige knitted cotton fabrics are treated in a bath containing 4 g/L scouring agent and 6 g/L 30% hydrogen peroxide at 90 °C for 60 min, and then 30 g/L GTA and 3 g/L sodium hydroxide are added in the bath for another 15 min treatment. Fiber performances, including whiteness, water absorptivity, diffusion time, and capillary effect, are tested and evaluated. X-ray diffraction analysis, surface morphology, and thermal analysis of the pretreated cotton are also investigated and compared with that treated only with scouring and bleaching agents. Much higher dye fixation and color yield could be realized on the pretreated cotton in salt-free reactive dyeing. Colorimetric properties of the dyes are studied and good colorfastness of the dyes on the cationic fabrics are obtained. All of the above results show promising prospects of this combinative pretreatment in real application. Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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Open AccessArticle Cellulose Nanofibers Prepared via Pretreatment Based on Oxone® Oxidation
Molecules 2017, 22(12), 2177; https://doi.org/10.3390/molecules22122177
Received: 27 October 2017 / Revised: 4 December 2017 / Accepted: 5 December 2017 / Published: 8 December 2017
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Abstract
Softwood sulfite bleached cellulose pulp was oxidized with Oxone® and cellulose nanofibers (CNF) were produced after mechanical treatment with a high-shear homogenizer. UV-vis transmittance of dispersions of oxidized cellulose with different degrees of mechanical treatment was recorded. Scanning electron microscopy (SEM) micrographs
[...] Read more.
Softwood sulfite bleached cellulose pulp was oxidized with Oxone® and cellulose nanofibers (CNF) were produced after mechanical treatment with a high-shear homogenizer. UV-vis transmittance of dispersions of oxidized cellulose with different degrees of mechanical treatment was recorded. Scanning electron microscopy (SEM) micrographs and atomic force microscopy (AFM) images of samples prepared from the translucent dispersions showed individualized cellulose nanofibers with a width of about 10 nm and lengths of a few hundred nm. All results demonstrated that more translucent CNF dispersions could be obtained after the pretreatment of cellulose pulp by Oxone® oxidation compared with the samples produced without pretreatment. The intrinsic viscosity of the cellulose decreased after oxidation and was further reduced after mechanical treatment. Almost translucent cellulose films were prepared from the dispersions of individualized cellulose nanofibers. The procedure described herein constitutes a green, novel, and efficient route to access CNF. Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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Open AccessArticle Direct Modification of Microcrystalline Cellulose with Ethylenediamine for Use as Adsorbent for Removal Amitriptyline Drug from Environment
Molecules 2017, 22(11), 2039; https://doi.org/10.3390/molecules22112039
Received: 4 October 2017 / Revised: 2 November 2017 / Accepted: 17 November 2017 / Published: 22 November 2017
Cited by 1 | PDF Full-text (4556 KB) | HTML Full-text | XML Full-text
Abstract
Cellulose derivatives have been widely used as adsorbents for the removal of micropollutants such as drugs, dyes, and metals, due to their abundance, low cost and non-contaminating nature. In this context, several studies have been performed searching for new adsorbents (cellulose derivatives) efficient
[...] Read more.
Cellulose derivatives have been widely used as adsorbents for the removal of micropollutants such as drugs, dyes, and metals, due to their abundance, low cost and non-contaminating nature. In this context, several studies have been performed searching for new adsorbents (cellulose derivatives) efficient at contaminant removal from aqueous solutions. Thus, a new adsorbent was synthesized by chemical modification of cellulose with ethylenediamine in the absence of solvent and applied to the adsorption of amitriptyline (AMI) in aqueous solution. The modification reaction was confirmed by X-ray Diffraction (XRD), elemental analysis, Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetry/Differential Scanning Calorimeter (TG/DSC), solid state Nuclear Magnetic Resonance of 1H and 13C (1H-NMR and 13C-NMR). Moreover, the effectiveness of reaction was confirmed by computational calculations using Density Functional Theory (DFT) at level B3LYP/6-31G(d). This adsorption process was influenced by pH, time, concentration, temperature and did not show significant changes due to the ionic strength variation. Through these experiments, it was observed that the maximum adsorption capacity of AMI by CN polymer at 298 K, 300 min, and pH 7 was 87.66 ± 0.60 mg·g−1. Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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Open AccessArticle One-Bath Pretreatment for Enhanced Color Yield of Ink-Jet Prints Using Reactive Inks
Molecules 2017, 22(11), 1959; https://doi.org/10.3390/molecules22111959
Received: 30 September 2017 / Revised: 4 November 2017 / Accepted: 9 November 2017 / Published: 13 November 2017
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Abstract
In order to facilely increase the color yield of ink-jet prints using reactive inks, one-bath pretreatment of cotton fabrics with pretreatment formulation containing sodium alginate, glycidyltrimethylammonium chloride (GTA), sodium hydroxide, and urea is designed for realizing sizing and cationization at the same time.
[...] Read more.
In order to facilely increase the color yield of ink-jet prints using reactive inks, one-bath pretreatment of cotton fabrics with pretreatment formulation containing sodium alginate, glycidyltrimethylammonium chloride (GTA), sodium hydroxide, and urea is designed for realizing sizing and cationization at the same time. The pretreatment conditions, including the concentrations of GTA and alkali, baking temperature, and time are optimized based on the result of thecolor yield on cationic cotton for magenta ink. The mechanism for color yield enhancement on GTA-modified fabrics is discussed and the stability of GTA in the print paste is investigated. Scanning electron microscopey, tear strength, and thermogravimetric analysis of the modified and unmodified cotton are studied and compared. Using the optimal pretreatment conditions, color yield on the cationic cotton for magenta, cyan, yellow, and black reactive inks are increased by 128.7%, 142.5%, 71.0%, and 38.1%, respectively, compared with the corresponding color yield on the uncationized cotton. Much less wastewater is produced using this one-bath pretreatment method. Colorfastness of the reactive dyes on the modified and unmodified cotton is compared and boundary clarity between different colors is evaluated by ink-jet printing of colorful patterns. Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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Open AccessArticle Acetylation of Microcrystalline Cellulose by Transesterification in AmimCl/DMSO Cosolvent System
Molecules 2017, 22(9), 1419; https://doi.org/10.3390/molecules22091419
Received: 3 July 2017 / Revised: 21 August 2017 / Accepted: 24 August 2017 / Published: 27 August 2017
Cited by 1 | PDF Full-text (1765 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Recently, IL/cosolvent systems have generated a lot of interest as cellulose-dissolving solvents and reaction media for various kinds of cellulose modification. In the present study, both 1-allyl-3-methylimidazolium chloride (AmimCl)/dimethyl sulfoxide (DMSO) and AmimCl/N,N-dimethylformamide (DMF) systems were employed to synthesize
[...] Read more.
Recently, IL/cosolvent systems have generated a lot of interest as cellulose-dissolving solvents and reaction media for various kinds of cellulose modification. In the present study, both 1-allyl-3-methylimidazolium chloride (AmimCl)/dimethyl sulfoxide (DMSO) and AmimCl/N,N-dimethylformamide (DMF) systems were employed to synthesize cellulose acetate by transesterification. Microcrystalline cellulose, 1,8-diazabicyclo[5.4.0]undec-7-ene and isopropenyl acetate were chosen as the raw material, catalyst and acetylation reagent, respectively. The results revealed that DMSO was a suitable cosolvent for the transesterification in the homogeneous solution. Moreover, DMSO had a positive effect on the reaction as the cosolvent under the given conditions and the degree of the substitution of cellulose acetate could be significantly enhanced through increasing the molar ratio of DMSO. The synthesized products were characterized by Fourier transform infrared (FT-IR) spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy (1H-NMR and 13C-NMR), correlation spectroscopy (COSY), heteronuclear single quantum correlation (HSQC) spectroscopy, and X-ray diffraction (XRD) to confirm the chemical and physical structure of the cellulose acetate generated. The thermal properties were also evaluated using thermogravimetric analysis (TGA)/derivative thermogravimetry (DTG). Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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Review

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Open AccessFeature PaperReview Recent Advances in Modified Cellulose for Tissue Culture Applications
Molecules 2018, 23(3), 654; https://doi.org/10.3390/molecules23030654
Received: 29 January 2018 / Revised: 9 March 2018 / Accepted: 12 March 2018 / Published: 14 March 2018
Cited by 1 | PDF Full-text (3761 KB) | HTML Full-text | XML Full-text
Abstract
Tissue engineering is a rapidly advancing field in regenerative medicine, with much research directed towards the production of new biomaterial scaffolds with tailored properties to generate functional tissue for specific applications. Recently, principles of sustainability, eco-efficiency and green chemistry have begun to guide
[...] Read more.
Tissue engineering is a rapidly advancing field in regenerative medicine, with much research directed towards the production of new biomaterial scaffolds with tailored properties to generate functional tissue for specific applications. Recently, principles of sustainability, eco-efficiency and green chemistry have begun to guide the development of a new generation of materials, such as cellulose, as an alternative to conventional polymers based on conversion of fossil carbon (e.g., oil) and finding technologies to reduce the use of animal and human derived biomolecules (e.g., foetal bovine serum). Much of this focus on cellulose is due to it possessing the necessary properties for tissue engineering scaffolds, including biocompatibility, and the relative ease with which its characteristics can be tuned through chemical modification to adjust mechanical properties and to introduce various surface modifications. In addition, the sustainability of producing and manufacturing materials from cellulose, as well as its modest cost, makes cellulose an economically viable feedstock. This review focusses specifically on the use of modified cellulose materials for tissue culturing applications. We will investigate recent techniques used to promote scaffold function through physical, biochemical and chemical scaffold modifications, and describe how these have been utilised to reduce reliance on the addition of matrix ligands such as foetal bovine serum. Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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Open AccessReview Recent Advances in Solvents for the Dissolution, Shaping and Derivatization of Cellulose: Quaternary Ammonium Electrolytes and their Solutions in Water and Molecular Solvents
Molecules 2018, 23(3), 511; https://doi.org/10.3390/molecules23030511
Received: 15 December 2017 / Revised: 6 February 2018 / Accepted: 14 February 2018 / Published: 25 February 2018
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Abstract
There is a sustained interest in developing solvents for physically dissolving cellulose, i.e., without covalent bond formation. The use of ionic liquids, ILs, has generated much interest because of their structural versatility that results in efficiency as cellulose solvents. Despite some limitations, imidazole-based
[...] Read more.
There is a sustained interest in developing solvents for physically dissolving cellulose, i.e., without covalent bond formation. The use of ionic liquids, ILs, has generated much interest because of their structural versatility that results in efficiency as cellulose solvents. Despite some limitations, imidazole-based ILs have received most of the scientific community’s attention. The objective of the present review is to show the advantages of using quaternary ammonium electrolytes, QAEs, including salts of super bases, as solvents for cellulose dissolution, shaping, and derivatization, and as a result, increase the interest in further investigation of these important solvents. QAEs share with ILs structural versatility; many are liquids at room temperature or are soluble in water and molecular solvents (MSs), in particular dimethyl sulfoxide. In this review we first give a historical background on the use of QAEs in cellulose chemistry, and then discuss the common, relatively simple strategies for their synthesis. We discuss the mechanism of cellulose dissolution by QAEs, neat or as solutions in MSs and water, with emphasis on the relevance to cellulose dissolution efficiency of the charge and structure of the cation and. We then discuss the use of cellulose solutions in these solvents for its derivatization under homogeneous and heterogeneous conditions. The products of interest are cellulose esters and ethers; our emphasis is on the role of solvent and possible side reactions. The final part is concerned with the use of cellulose dopes in these solvents for its shaping as fibers, a field with potential commercial application. Full article
(This article belongs to the Special Issue Cellulose Chemical Modifications—Towards Sustainable Materials)
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