Cellulosic Materials Research Articles

Functionalization of cellulose nanocrystals with a potent antimalarial compound: Synthesis, characterization, and biological studies

Cellulosic materials, such as cellulose nanocrystals (CNCs), are biocompatible, biodegradable and have unique and fascinating biomedical applications. Calxinin (CXN), a potent multistage antimalarial compound was functionalised with CNCs to improve biocompatibility and enhance the bioactivity of the resulting CNC-CXN nano-conjugate. Elemental analysis, powder X-ray, SEM, AFM, Infrared, and solid-state NMR spectroscopic techniques confirmed the composition of novel CNC-CXN nano-conjugate. Next, CNC-CXN nano-conjugate did not exhibit apparent cytotoxic effects on the sensitive Vero E6 cell line up to a concentration of 4.66 μg/μl. The CNC-CXN nano-conjugate was also evaluated for its preliminary efficacy on Plasmodium falciparum (3D7) malaria parasite and showed a 50 % inhibitory concentration value of 0.02 μg/μl. Overall, the selectivity index (SI) of the CNC-CXN nano-conjugate significantly improved to 233, indicating its suitability for further validation studies in animal models.

One pot gamma radiation mediated interfacial engineering of P-N synergistic flame retardant and antibacterial cellulose fabric: novel fabrics for future applications

AbstractThe work describes an ionizing radiation mediated, toxic solvent free interfacial engineering of a novel Phosphorus-Nitrogen functionalized bifunctional cotton cellulose fabric (BCF) endowed with flame retardant (FR) and antibacterial properties. Monomers bis[2-(methacryloyloxy)ethyl] phosphate (B2MEP) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAETC) in different proportions were co-grafted onto cellulose fabric via 60Co radiation mediated Simultaneous Irradiation Grafting Process (SIGP) to incorporate Phosphorus and Nitrogen functionalities. Effects of radiation dose, monomer concentration on the grafting yield (GY) were investigated and samples were characterized using TGA, ATR-FTIR, XRD, SEM–EDX, EDXRF, CHN Elemental Analysis and XPS analytical techniques. Limiting oxygen index (IS:13501/ASTM D 2863) and vertical flammability tests (IS11871-1986) were conducted to establish the halogen free, P-N synergistic FR properties of the fabric. All the co-grafted samples were observed to possess LOI values in excess of 30%, while BCF (1:2) (GY = ~ 44%) demonstrated LOI of 32% with the least char length of 74 mm in the vertical flammability tests. Tear strength studies were carried out as per ASTMD 1424-09. Antibacterial assay revealed that the fabric possessed activity against both gram positive (S. aureus) and gram negative (E. coli) organisms, with BCF (1:4) (GY = ~ 48%) demonstrating complete killing of ~ 5 log cycles for both microorganisms in 24 h. BCF retained its FR and antibacterial properties even after multiple washing cycles. With its bonafide green credentials, durability and unique properties, multifunctional BCF fabric prepared under optimized conditions of P/N ratio > 1.7 and GY ~ 45% can be a potential candidate for future applications.

Controlling the rheology of cellulose dissolved in 4–methylmorpholine N–oxide and tensile properties of precipitated cellulose films via mixture design

AbstractProperties which control the mechanical performance of regenerated or precipitated cellulose films are currently not well-known and a mechanistic understanding of the underlying phenomena should be established. Solution rheology is a crucial property for casting films and spinning fibres in terms of process runnability, and it can have a considerable effect on the mechanical properties of the prepared cellulose products. We hypothesized that the viscosity of cellulose dissolved in 4-methylmorpholine N-oxide (NMMO) and the mechanical properties of precipitated cellulose films could potentially be improved by controlling the molecular weight distribution of cellulose pulp, taking inspiration from traditional plastic industry. We evaluated the effects of pulp blends on the viscoelastic properties of dissolved cellulose-NMMO dopes and used the dopes to prepare cellulose films and determined their mechanical properties. Lastly, we employed the determined dope and film characteristics to build linear regression models for predicting dope rheology and mechanical performance of films. Mixture films with 2:1 and 1:2 ratios of pulps with both medium and high degree of polymerization showed in average 36% and 46% higher toughness than their unimodal versions. The model results demonstrated that film performance could be tailored by changing the pulp composition. These findings play an important role in optimizing the future processability of dissolved cellulose dopes for producing bio-based cellulose materials and could bring us a step closer to traditional plastic polymer disciplines by tailoring their performance based on pulp properties. Graphic abstract

Synthesis of bioplastics and the effects of additives on the mechanical, thermal and biodegradable properties

The mounting global concern over the environmental consequences of petroleum-based plastics has prompted significant research into sustainable alternatives, with bioplastics emerging as a forerunning solution. This systematic review elucidates the multifaceted synthesis processes of bioplastics, which are derived from renewable sources such as plant starches, cellulose, and waste materials. The synthesis encompasses stages from raw material selection, pre-treatment, to the incorporation of various additives, with the aim to achieve specific properties in the resultant bioplastics. A substantial focus of this review lies in comprehensively understanding the role of additives, which serve as the pivotal agents in tailoring the mechanical and thermal characteristics of bioplastics. Additives, including cross-linking agents, plasticizers, fillers, compatibilizers, and reinforcement agents, are critically examined for their influence on attributes such as tensile strength, flexibility, thermal stability, and biodegradability. Factors such as intermolecular interactions, hydrogen bonding, and moisture content, play a determining role towards the resultant properties. The prospects for bioplastics are rapidly expanding, signalling a transformative shift in various applications ranging from eco-friendly packaging to advanced biomedical devices. This article serves as a comprehensive guide to both researchers and industry stakeholders, providing deep insights into the synthesis of bioplastics and the transformative role additives play in their functional properties.

Applying Subcritical Water Extraction to Obtain Bioactive Compounds and Cellulose Fibers from Brewer Spent Grains

Of the three types of waste generated in beer processing, brewer’s spent grain (BSG) is the most abundant and has a high potential for valorization. In this work, defatted BSG (DB) was subjected to an extraction process with subcritical water at different temperatures to obtain extracts rich in phenols and the cellulosic fractions, which were also purified by using hydrogen peroxide (H2O2). The results showed that the dry extracts obtained at 170 °C were richer in phenolics (24 mg Gallic Acid Equivalent (GAE) g−1 DB), but with lower antioxidant capacity (71 mg DB·mg−1 2,2-diphenyl-1-pikryl-hydrazyl). This extract also showed the highest antibacterial potential against L. innocua (80 mg·mL−1) and E. coli (140 mg·mL−1) than those obtained at lower temperatures. The purification of cellulose from the treated residues, using hydrogen peroxide, revealed that DB is a limited source of cellulose material since the bleached fractions showed low yields (20–25%) and low cellulose purity (42–71%), even after four bleaching cycles (1 h) at pH 12 and 8% H2O2. Despite this, the subcritical water extraction method highlights the potential of a simple process as a technological option to convert underutilized side streams like beer bagasse into added-value, potential ingredients for innovative food and pharmaceutical applications.

Isolation and Characterization of Nanocellulose from Polypodiophyta Fern Using Chemo-Mechanical Method.

Nanocellulose is considered a promising and sustainable biomaterial, with excellent properties of biorenewability with improved mechanical properties. As a unique natural biopolymer, it has been applied to many different industries, where efficient and environmentally friendly productions are in demand. For the first time, ferns from the class Polypodiopsida were used for the isolation of cellulose fibers, which was performed using a chemo-mechanical method. As chemical treatment plays a crucial role in the isolation of nanocellulose, it affects the efficiency of the extraction process, as well as the properties of the resulting nanocellulose. Therefore, mechanical fibrillation was performed via grinding, while the chemical process consisted of three different treatments: alkali treatment, bleaching, and acid hydrolysis. In three different experiments, each treatment was separately prolonged to investigate the differing properties of isolated nanocellulose. Structural analysis and morphological analysis were investigated by SEM, EDS, FT-IR, and DLS. The thermal stability of cellulose fibers was investigated by TGA/DSC. The morphology of obtained nanocellulose was confirmed via SEM analysis for all samples, with particles ranging from 20 nm up to 600 nm, while the most consistent sizes were observed for NC3, ranging from 20 to 60 nm. FT-IR spectra showed prominent absorption peaks corresponding to cellulose, as well as the absence of absorption peaks, corresponding to lignin and hemicellulose. The EDS confirmed the elemental purity of nanocellulose, while TGA/DSC indicated higher thermal stability of nanocellulose, compared to untreated fern, which started to degrade earlier than nanocellulose. Such characteristics with unique properties make nanocellulose a versatile biomaterial for the industrial production of cellulosic materials.

Progress in Biopolymer Coatings for Achieving Sustainable Paper and Paperboard Packaging for Food Applications: A Brief Review

ABSTRACTPaper and paperboard are cellulosic materials used to manufacture food packaging. However, their low resistance to water and fat, as well as their poor barrier properties have limited their packaging applications as food contact materials. The current review analyses the use of biopolymeric coatings as an alternative to improve surface and barrier properties in paper and paperboard with focus in food sector application. Advances in coated paper (board) can be classified into three groups: (1) coatings manufactured with a single biopolymer; (2) coatings manufactured with composite biopolymers; and (3) biopolymeric coatings incorporated with bioactive molecules or nanoparticles. The use of a single or composite biopolymer coating improved the mechanical, barrier properties, and grease resistance. In contrast, the use of chemical compounds and nanoparticles has imparted active properties (antibacterial and ethylene scavengers) in the resulting coating paper (board). The water vapour transmission rate has been reduced with the use of biopolymeric coatings. Future studies should focus on applying coated paper (board) in foods with a special interest in food self‐life, migration, and toxicity.

Graphenic materials prepared from magnesium ions doping cellulose and its application in electrochemical detection of adenine and guanine

Graphenic materials of high quality are in high-demand. In this study, a method is proposed for the synthesis of graphenic materials by the pyrolysis of cellulose materials. Cellulose materials were oxidized and doped with magnesium prior to pyrolysis, which improved the graphitization efficiency significantly. The obtained graphenic materials, exhibiting a well-developed porous structure, high specific surface area, were employed for the fabrication of a composite electrode. The composite electrode was employed for the simultaneously detection of adenine (AE) and guanine (GA) with excellent performance in the electrocatalytic oxidation response. Various electrochemical tests were carried out to optimized the detection of AE and GA. Under the optimized conditions, the simultaneous quantification of GA and AE is achieved from 1 – 100 μM with detection limits from 0.4 – 0.6 μM. This study offers a promising alternative for the synthesis of graphenic materials of high quality.

Characteristics of bast fibers derived from the bark of three paper-mulberry cultivars in Korea

Bast fiber from paper-mulberry (Broussonetia papyrifera) has long been utilized for handmade paper in Asia, serving as a prominent non-wood cellulose material. When restoring paper cultural assets, selecting a similar paper to the original ensures longevity and prevents deterioration issues like warping or tearing. The production of handmade paper involves several processes, including refining, steaming, and bleaching of raw materials. Once formed into sheets, the physical properties of the paper are dictated by these materials and remain unchanged unless the paper is newly made. Handmade paper production is labor-intensive and time-consuming, emphasizing the need for careful raw material selection to match desired characteristics. This study evaluated the dendrological, morphological, anatomical, and chemical compositions of three paper-mulberry wood types cultivated in Korea and inferred their suitability as pulp for papermaking or repair of archival paper specimens. Paper-mulberry wood showed differences in fiber length according to molecular phylogenetic characteristics, but there were no differences in anatomical characteristics owing to the immaturity of the wood. This study investigated the characteristics of the bast fibers from the bark of paper-mulberry trees with different genetic traits to identify favorable factors likely to affect the pulp and papermaking process and paper quality.

Ultrafast surface esterification of cellulosic materials in aqueous media at room temperature

Ultrafast surface esterification of cellulosic materials in aqueous media at room temperature

Comparative In Vivo Biocompatibility of Cellulose-Derived and Synthetic Meshes in Subcutaneous Transplantation Models.

Despite the increasing interest in cellulose-derived materials in biomedical research, there remains a significant gap in comprehensive in vivo analyses of cellulosic materials obtained from various sources and processing methods. To explore durable alternatives to synthetic medical meshes, we evaluated the in vivo biocompatibility of bacterial nanocellulose, regenerated cellulose, and cellulose nanofibrils in a subcutaneous transplantation model, alongside incumbent polypropylene and polydioxanone. Notably, this study demonstrates the in vivo biocompatibility of regenerated cellulose obtained through alkali dissolution and subsequent regeneration. All cellulose-derived implants triggered the expected foreign body response in the host tissue, characterized predominantly by macrophages and foreign body giant cells. Porous materials promoted cell ingrowth and biointegration. Our results highlight the potential of bacterial nanocellulose and regenerated cellulose as safe alternatives to commercial polypropylene meshes. However, the in vivo fragmentation observed for cellulose nanofibril meshes suggests the need for measures to optimize their processing and preparation.

Design of experiments investigation into the production of all cellulose composites using regenerated cellulosic textiles

All cellulose composites (ACCs) can be produced from native and man-made cellulosic fibres; use of the latter provides an additional application for waste-derived regenerated fibers. ACCs were prepared using an ionic liquid dissolution method, utilizing a regenerated cellulose (Tencel) textile, with and without an interleaf cellulosic film. A design of experiments methodology was applied to explore process-property relationships; concentration of the ionic liquid and the processing time and temperature were investigated. It was found that the film remained in-between the textile layers, rather than penetrating the fiber assembly, in contrast to our previous work on cotton-based ACCs. This is due to the structural differences between Tencel and cotton fabric. A multi-response optimization was conducted through a central composite face centered strategy, which captured the film system more strongly. Optimized processing conditions were identified, yielding a Young’s modulus and strain-to-failure of 5.3 GPa and 3.5% respectively, validated through in-lab samples.

Enhancing the Mechanical Properties of Regenerated Cellulose through High-Temperature Pre-Gelation

This paper investigates the effects of pre-gelation on cellulose dissolved in LiCl/DMAc solutions to enhance the properties of regenerated cellulose materials. This study focuses on characterizing the crystallinity, molecular orientation, and mechanical performance of cellulose fibers and hydrogels prepared with and without pre-gelation treatment. X-ray diffraction (XRD) analysis reveals that crystallinity improvement from 55% in untreated fibers to 59% in fibers pre-gelled for 3 and 7 days, indicating a more ordered arrangement of cellulose chains post-regeneration. Additionally, XRD patterns show improved chain alignment in pre-gelled fibers, as indicated by reduced full width at half the maximum of Azimuthal scans. Mechanical testing demonstrates a 30% increase in tensile strength and a doubling of the compression modulus for pre-gelled fibers compared to untreated fibers. These findings underscore the role of pre-gelation in optimizing cellulose material properties for applications ranging from advanced textiles to biomaterials and sustainable packaging. Future research directions include further exploration of the structural and functional benefits of pre-gelation in cellulose processing and its broader implications in material science and engineering.

From Cellulose Solutions to Aerogels and Xerogels: Controlling Properties for Drug Delivery.

A cheap and easy-to-recycle solvent, namely, aqueous NaOH with no additives, was used to dissolve cellulose and make cross-linker-free materials with varying porosity, testing them as drug delivery devices. Cellulose solutions were gelled, coagulated in a nonsolvent (water, ethanol), and dried either using supercritical CO2 (aerogels) or low-vacuum evaporation (named "xerogels"). Aerogels had densities of around 0.1 g/cm3 and specific surface areas (SSAs) of 200-400 m2/g. A significant influence of the first nonsolvent and drying mode on material properties was recorded: when the first nonsolvent was ethanol and low-vacuum drying was performed from ethanol, aerogel-like xerogels were obtained with densities of around 0.2 g/cm3 and SSAs of 200-260 m2/g. Other conditions (under evaporative drying) resulted in cellulose with much lower porosity and SSA. All materials were evaluated as drug delivery devices in simulated gastrointestinal fluids; theophylline was used as a model drug. Materials of high porosity exhibited shrinking and rapid drug release, whereas denser materials swelled and showed slower release. Two release mechanisms were suggested: diffusion through aqueous media in pores and diffusion through swollen pore walls. The results demonstrate a large spectrum of options for tuning the properties of porous cellulose materials for drug release applications.

Cotton Fabric Coating by Cationic Starches to Aim for Salt‐Free Reactive Dyeing

AbstractCationic starch (CatS) coating of cellulose fabrics enables salt‐free reactive dyeing. However, the relation of the degree of substitution and CatS concentration in the dyeing procedure are open issues. Accordingly, three cationic starches of increasing degree of substitution were used at different concentrations for the coating of cotton fabrics. Fabrics were evaluated for stiffness, dye uptake, dye exhaustion, wash fastness and nitrogen content.With an increasing degree of substitution coating solutions become more viscous, resulting in increased wet pick‐up and less stiff coated fabrics. These fabrics show increasing dye absorption and color generation. Due to the molecular size of the cationic starch, yarn/fiber ring dyeing is supposed present. Specifically, color generation can be adjusted by initial cationic starch coating concentration. Above 5 % CatS concentration ceases to have an increasing coloration effect. Pre‐treating a cellulose fabric with approximately 2.2 % CatS (Ds=0.7) enables similar coloration to a standard reactive dyeing protocol. Light fastness is reduced by 1–1.5 compared to salt‐based reactive dyeing. Rub fastness decreases by 1–2 only for higher substituted cationic starches (Ds=0.7). Nitrogen analysis reveals that a share of the CatS elutes off the fabrics into the dye bath.

Hydrothermal extraction of microcrystalline cellulose from post-consumer indigo denim fabrics and evaluation of its UV blocking property

Abstract Waste cotton clothes, including post-consumer denim fabrics, are abundant biopolymer sources due to their high cellulose content. These waste materials commonly end up in landfills, posing health and environmental concerns and losing valuable cellulosic materials. To address these, this study aims to extract and characterize microcrystalline cellulose (MCC) from post-consumer indigo denim fabrics using a one-step hydrothermal method and evaluate its UV-blocking properties. FTIR and TGA analysis of raw and bleached denim confirmed the presence and purity of cotton cellulose and the indigo dye. Extracted MCC yielded 70-84%, with a degree of polymerization (DP) of 281-299. XRD analysis of the MCC showed a cellulose Type I structure. FTIR suggests the removal of amorphous phases of cellulose, leaving the crystalline structure. SEM meanwhile revealed rod-shaped and rough-surfaced MCC particles with diameters of 10-20 μm and lengths of 45-60 μm. Both FTIR and SEM indicated the retention of indigo dye on MCC surface. Increased acid hydrolysis time led to smaller particle sizes and higher degree of crystallinity (CrI). Indigo PVA-MCC films showed good transparency and effective UV blocking. These results indicate the successful conversion of denim to MCC via the hydrothermal method and the stability of indigo dye in the cellulose matrix.

Cellulose, cellulose nanofibers, and cellulose acetate from Butia fruits (Butia odorata): Chemical, morphological, structural, and thermal properties

Cellulose possesses numerous advantageous properties and is a precursor to compounds and derivatives. The objective of this study was to isolate and characterize cellulose from Butia fruits and simultaneously produce cellulose nanofibers and cellulose acetate from the isolated cellulose. Cellulose extraction was performed using a combination of alkaline and bleaching treatments, while the production of cellulose nanofibers and cellulose acetate was achieved through acid hydrolysis and acetylation, respectively. The materials were characterized by their chemical composition, size distribution, zeta potential, morphology, relative crystallinity (XRD), functional groups (FTIR), molecular structure (NMR), and thermal stability (TGA). The Butia crude fibers presented 49.4 % cellulose, 4.5 % hemicellulose, 25.4 % lignin, and 1.3 % ash. The cellulose nanofibers presented an average diameter ranging from 13.7 to 93.1 nm and exhibited a high degree of crystallinity (63.3 %). FTIR, XRD, 13C, and 1H NMR analyses confirmed that the isolation processes effectively removed amorphous regions from the cellulose nanofibers and confirmed the cellulose acetylation process. As demonstrated, cellulosic materials derived from Butia fruit exhibit promise for various applications, including their potential use as reinforcing agents in polymer matrices, due to their high extraction yield, thermal properties, and crystallinity.

MULTIFUNCTIONAL MODIFICATION OF COTTON FABRIC FOR ANTIMICROBIAL, FLAME-RETARDANT AND OLEOPHOBIC PROPERTIES

In recent times, the investigation and development of multifunctional textiles have become a necessity for the textile and apparel industries. Therefore, this paper explores an innovative approach to enhancing the functional properties of cotton (cellulosic) fabric by integrating advanced technologies to impart oleophobic/hydrophobic, flame-retardant, and antibacterial characteristics. The methodology involves systematically applying chemical treatments utilizing a layer-by-layer finishing technique to achieve the desired multifunctionality in cotton fabric. Silver nanoparticles and a phosphorus-nitrogen-based synergistic flame-retarding agent were employed to finish the fabric. Performance testing encompasses evaluating bacterial reduction, contact angle measurements, water absorption properties, flame-retardant capabilities, and Limiting Oxygen Index (LOI). Characterization techniques such as FTIR, SEM, and EDX analysis, were carried out to assess structural and chemical modifications of the material. The results illustrate a notable transformation of the cellulosic fabric, showcasing enhanced resistance to bacterial attack, improved stain resistance, and heightened flame-retardant performance, without compromising its color indices and air permeability. The fabric retains these multifunctional attributes even after 20 cycles of laundering, which confers durability. The implications of this research extend the application of conventional cotton fabric in diverse sectors, including apparel, home furnishings, and industrial textiles.

Fabrication of clickable bamboo-sourced cellulose nanofibrils for diverse surface modifications: Hydrophobicity and fluorescence functionalities

Surface functionalization of cellulose nanofibrils (CNF) is crucial for expanding their practical application. However, most functionalization processes are complicated and laborious. Herein, this work presents a facile surface engineering strategy to create a range of functionalized CNF via thiol-ene click reaction. Initially, clickable CNF was produced by grafting a compound with both carboxylate- and norbornene groups onto bamboo cellulose via norbornene-dicarboxylic anhydride esterification followed by homogenization. The introduction of negatively charged carboxylates facilitated nanofibrillation, resulting in CNF with a diameter of 3 nm and an aspect ratio of up to 600. The introduction of norbornenes enabled diverse functionalization of CNF through click reaction. Subsequently, hexadecanethiol successfully clicked with norbornene-grafting CNF, enhancing its hydrophobicity and dispersion in organic solvents. 7-mercapto-4-methyl coumarin was also able to click with norbornene-grafting CNF, yielding fluorescence-labeled CNF while maintaining excellent aqueous dispersibility. The fluorescence-labeled CNF was demonstrated to be utilized as an eco-friendly sensor for the detection of Fe3+ ions. Additionally, it could be converted into fluorescent films or intelligent inks suitable for anti-counterfeiting purposes. This study demonstrates that the proposed surface engineering strategy provides an effective approach for producing clickable CNF and fabricating cellulosic materials with diverse functionalities that meet the demands of various applications.

Removal of Arsenic from Contaminated Water by Polypyrrole-Based Adsorbents

Worldwide, there is growing concern over the toxicity of arsenic in drinking water. The US Environmental Protection Agency and Central Pollution Control Board (India) have set a safe limit of 50 parts per billion for arsenic in drinking water. Millions of people are at immediate risk due to high concentrations of arsenic in drinking water, particularly in developing nations where arsenic poisoning symptoms have been observed. One of the essential techniques described in this article is the absorption of arsenic from contaminated water by sustainable cellulosic materials like jute and wood sawdust after suitable modification. Jute and sawdust are cheap and abundantly available in South Asia. They are functionalized with polypyrrole coating by in situ chemical polymerization of pyrrole in aqueous medium in the presence of ferric chloride. Polypyrrole-coated jute fabric (with 11.28% polypyrrole add-on) and polypyrrole-coated sawdust (with 5.28% polypyrrole add-on) are found to be excellent adsorbers of arsenic ion (As3+) from water. The effect of dosage of polypyrrole-coated adsorbents, treatment time and pyrrole concentration on the As removal efficiency have been investigated in this work. The arsenic concentration in water is determined using a microwave plasma atomic emission spectrometer with the highest level of accuracy. Maximum As removal efficiency by the polypyrrole-coated sawdust and polypyrrole-coated jute fabric is found to be 80.90% and 97.3%, respectively, from a 50 mL, 7.5 parts per million As solution with a dosage of 1 g at neutral pH. The polypyrrole-coated jute and sawdust are characterized by Fourier-transform infrared spectroscopy to understand the chemical interaction between cellulose and polypyrrole molecules. The scanning electron microscope studies reveal a uniform coating of polypyrrole around the surface of jute fibre and sawdust particles. Thermo-gravimetric analysis shows good thermal stability of jute and sawdust after polypyrrole coating.