Cellulose Acetate-g-Polycaprolactone Copolymerization Using Diisocyanate Intermediates and the Effect of Polymer Chain Length on Surface, Thermal, and Antibacterial Properties.

The need for biodegradable and biocompatible polymers is growing quickly, particularly in the biomedical and environmental industries. Cellulose acetate, a natural polysaccharide, can be taken from plants and modified with polycaprolactone to improve its characteristics for a number of uses, including biomedical applications and food packaging. Cellulose acetate-g-polycaprolactone was prepared by a three-step reaction: First, polymerization of ε-caprolactone via ring-opening polymerization (ROP) reaction using 2-hydroxyethyl methacrylate (HEMA) and functionalization of polycaprolactone(PCL) by introducing NCO on the hydroxyl end of the HEMA-PCL using hexamethyl lenediisocyanate(HDI) were carried out. Then, the NCO-HEMA-PCL was grafted onto cellulose acetate (using the "grafting to" method). The polycaprolactone grafted cellulose acetate was confirmed by FTIR, the thermal characteristics of the copolymers were investigated by DSC and TGA, and the hydrophobicity was analyzed via water CA measurement. Introducing NCO-PCL to cellulose acetate increased the thermal stability. The contact angle of the unreacted PCL was higher than that of cellulose acetate-g-PCL, and it increased when the chain length increased. The CA-g-PCL50, CA-g-PCL100, and CA-g-PCL200 showed very high inhibition zones for all three bacteria tested (E. coli, S. aureus, and P. aeruginosa).

Synthesis and Characterization of Cellulose Triacetate Obtained from Date Palm (Phoenix dactylifera L.) Trunk Mesh-Derived Cellulose.

Cellulosic polysaccharides have increasingly been recognized as a viable substitute for the depleting petro-based feedstock due to numerous modification options for obtaining a plethora of bio-based materials. In this study, cellulose triacetate was synthesized from pure cellulose obtained from the waste lignocellulosic part of date palm (Phoenix dactylifera L.). To achieve a degree of substitution (DS) of the hydroxyl group of 2.9, a heterogeneous acetylation reaction was carried out with acetic anhydride as an acetyl donor. The obtained cellulose ester was compared with a commercially available derivative and characterized using various analytical methods. This cellulose triacetate contains approximately 43.9% acetyl and has a molecular weight of 205,102 g·mol-1. The maximum thermal decomposition temperature of acetate was found to be 380 °C, similar to that of a reference sample. Thus, the synthesized ester derivate can be suitable for fabricating biodegradable and "all cellulose" biocomposite systems.

Room temperature preparation of cellulose nanocrystals with high yield via a new ZnCl2 solvent system.

Here, a facile method to fabricate cellulose nanocrystals (CNCs) with high yield from microcrystalline cellulose (MCC) at room temperature (RT) is achieved by using a new solvent system of zinc chloride (ZnCl2) and a little amount of hydrochloric acid (HCl). Compared with sulphuric acid hydrolysis process, about one-fifth mole of acid is used for per gram of CNCs in our protocol. CNCs with rod-like morphology are regenerated with a maximum yield of 35.2% and high crystallinity of 73.8%. Moreover, with an additional 2 h of ball-milling, the yield of CNCs could significantly increase to 66.9% at RT. The possible formation mechanism for CNCs prepared by the solvent system of ZnCl2/HCl is proposed. As the first example of isolation of CNCs with high yield at RT using ZnCl2, this work provides a facile, energy-saving, and practical strategy for the preparation of cellulose nanomaterials.

Green synthesized nano-cellulose polyethylene imine-based biological membrane.

In hemodialysis process, membrane serves as a barrier between blood and the dialysate. The barrier when contacted by blood accompanied activation of coagulation, immunity, and cellular passageways. In the recent years, hemodialysis membrane's biocompatibility has become a issue which leads to reduce the performance during the separation process. In previous work, we developed and evaluated a cellulose-based membrane blended with polyaziridine or polyetyleneimine in formic acid for hydrophilicity, pure water flux, surface morphology, and permeation efficiency. Biocompatibility was accessed, by conducting cellular viability and cellular attachments tests. In this study, the membrane compared to a non-treated control, and cell viability revealed active and growing cell cultures after 14 days. During the cellular attachment experiment, cell cultures attached to the fabricated membrane simulated the formation of cell junctions, proving that the membrane is non-toxic and biocompatible. CA + PEI + FA membrane tested with a blood mimic fluid having density identical to renal patient's blood. The BSA concentration in the feed solution was the same as that in the blood of the renal patient. The results revealed that the CA + PEI + FA membrane was able to reject 99% bovine serum albumin (BSA) and 69.6% urea. Therefore, from biocompatibility and blood mimic fluid testing, it is confirmed that the CA + PEI + FA membrane is the finest implant for dialysis applications.

One-pot freezing-thawing preparation of cellulose nanofibrils reinforced polyvinyl alcohol based ionic hydrogel strain sensor for human motion monitoring.

Ionic conductive hydrogels have been widely applied in sensors, energy storage and soft electronics recently. However, most of the polyvinyl alcohol (PVA) based ionic hydrogels are mainly fabricated by soaking the hydrogels in high concentration electrolyte solution which can induce the waste of electrolyte and solvent. Herein, we have designed cellulose nanofibrils (CNF) and ZnSO4 reinforced PVA based hydrogels through a one-pot simple freezing-thawing method at low ZnSO4 concentration without any soaking process. Furthermore, the hydrogel with 0.4% CNF exhibited stress up to 0.79 MPa (242% strain) and high ionic conductivity of 0.32 S m-1 (0.07 M ZnSO4). Moreover, hydrogel sensor displayed high linear gauge factor 1.70 (0-200% strain), excellent stability, durability and reliability. The integrated hydrogel sensor also showed excellent sensor performance for human motion monitoring. This work provides a new prospect for the design of cellulose reinforced conductive hydrogels via a facile method.

Decorated traditional cellulose with nanoscale chiral metal-organic frameworks for enhanced enantioselective capture.

Herein, a rapid approach toward the size/morphology-controlled synthesis of [Cu(L-mal)(bipy)·2H2O] (CuLBH) was developed by adjusting the concentrations of 2-methylimidazole (2-MI) and copper ions. The chiral separation efficiency test indicated that the nano-diameter CuLBH exhibited better selective potential towards (±)-1-(1-naphthyl)ethanol (NE) by providing more fully exposed recognition sites. In order to further improve the selectivity for NE enantiomers and avoid the aggregation of MOF nanoparticles, the nanosized CuLBH-decorated carboxylated cellulose (CC) composite CC-CuLBH was designed by controlling the ratio of the solvent and Cu2+, which exhibited much higher enantioselectivity than those of pristine CC and even nano CuLBH.

Synthesis and characterization of bacterial cellulose-based composites for drug delivery.

Bacterial cellulose (BC) was produced via the static fermentation process using G. xylinus. Cellulose and diethylaminoethyl cellulose (DEAEC) were converted to carboxymethyl cellulose (CMC) and carboxymethylated diethylaminoethyl cellulose (CMDEAEC) while to prepare the composites, two different methods were used: by either direct addition of the materials to the fermentation medium or addition of the materials after the fermentation process. Structural characteristics of composites were determined using instrumental techniques. Potential application of BC, BC/CMC, and BC/CMDEAEC in drug delivery system was examined using methylene blue (MB) as a model drug where the loading capacity and swelling ratio for the samples were as follows: BC/CMC > BC/CMDEAEC > BC. The result of the in-vitro study was in favor of the release behavior of BC/CMDEAEC composite. The MB loading data were fitted using Langmuir and Freundlich equations and kinetic behavior of the release was described by Higuchi and Korsmeyer-Peppas models.

Waterproof-breathable films from multi-branched fluorinated cellulose esters.

Cellulose ester films were prepared by esterification of cellulose with a multibranched fluorinated carboxylic acid, "BRFA" (BRanched Fluorinated Acid), at different anhydroglucose unit:BRFA molar ratios (i.e., 1:0, 10:1, 5:1, and 1:1). Morphological and optical analyses showed that cellulose-BRFA materials at molar ratios 10:1 and 5:1 formed flat and transparent films, while the one at 1:1 M ratio formed rough and translucent films. Degrees of substitution (DS) of 0.06, 0.09, and 0.23 were calculated by NMR for the samples at molar ratios 10:1, 5:1, and 1:1, respectively. ATR-FTIR spectroscopy confirmed the esterification. DSC thermograms showed a single glass transition, typical of amorphous polymers, at -11 °C. The presence of BRFA groups shifted the mechanical behavior from rigid to ductile and soft with increasing DS. Wettability was similar to standard fluoropolymers such as PTFE and PVDF. Finally, breathability and water uptake were characterized and found comparable to materials typically used in textiles.

Production of nanocellulose gels and films from invasive tree species.

Wood from invasive tree species Acacia dealbata and Ailanthus altissima was used to produce high value-added nanocellulose. Firstly, bleached pulps were produced from the wood of these tree species after kraft cooking. Afterwards, the resultant pulps were pre-treated by TEMPO-mediated oxidation (Acacia dealbata) or enzymatic hydrolysis (Ailanthus altissima) followed by high-pressure homogenization. Hydrogels were obtained and characterized for their main physical and chemical properties, including rheology measurements. After freeze-drying, the surface properties of the materials were evaluated by inverse gas chromatography. Results showed that nano/micro fibrils could be obtained from the wood of these invasive species. Rheometry studies showed that Acacia-TEMPO cellulose nanofibrils form strong gels with high yield stress point and viscosities (reaching ca. 100,000 Pa·s). Additionally, the surfaces of the obtained nanocelluloses showed a dispersive component of the surface energy near 40 mJ/m2 and a prevalence of the Lewis acidic character over the basic one, as typical for cellulose-based materials. Finally, films with good mechanical and optical properties could be obtained from the cellulose hydrogels. Acacia-TEMPO film (produced by filtration/hot pressing) showed a tensile strength of 79 MPa, Young's modulus of 7.9 GPa, and a transparency of 88%. The water vapor barrier, however, was modest (permeability of 4.9 × 10-6 g/(Pa·day·m)).

Novel Ag/cellulose-doped CeO2 quantum dots for efficient dye degradation and bactericidal activity with molecular docking study.

In the present study, the novel Ag/cellulose nanocrystal (CNC)-doped CeO2 quantum dots (QDs) with highly efficient catalytic performance were synthesized using one pot co-precipitation technique, which were then applied in the degradation of methylene blue and ciprofloxacin (MBCF) in wastewater. Catalytic activity against MBCF dye was significantly reduced (99.3%) for (4%) Ag dopant concentration in acidic medium. For Ag/CNC-doped CeO2 vast inhibition domain of G-ve was significantly confirmed as (5.25-11.70 mm) and (7.15-13.60 mm), while medium- to high-concentration of CNC levels were calculated for G + ve (0.95 nm, 1.65 mm), respectively. Overall, (4%) Ag/CNC-doped CeO2 revealed significant antimicrobial activity against G-ve relative to G + ve at both concentrations, respectively. Furthermore, in silico molecular docking studies were performed against selected enzyme targets dihydrofolate reductase (DHFR), dihydropteroate synthase (DHPS), and DNA gyrase belonging to folate and nucleic acid biosynthetic pathway, respectively to rationalize possible mechanism behind bactericidal potential of CNC-CeO2 and Ag/CNC-CeO2.

3D bioprinting of dual-crosslinked nanocellulose hydrogels for tissue engineering applications.

Hydrogels based on cellulose nanofibrils (CNFs) have been widely used as scaffolds for biomedical applications, however, the poor mechanical properties of CNF hydrogels limit their use as ink for 3D bioprinting in order to generate scaffolds for tissue engineering applications. In this study, a dual crosslinkable hydrogel ink composed of a poly(ethylene glycol) (PEG) star polymer and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-oxidized nanocellulose fibers (CNFs) is presented. As the resulting hydrogel had low structural integrity, at first crosslinking of CNFs was introduced by Ca2+. Strong physical interactions between CNFs and Ca2+ cations allowed easy regulation of the viscosity of the inks for extrusion printing raising the solution viscosity by more than 1.5 times depending on the amount of Ca2+ added. The resulting hydrogel had high structural integrity and was further stabilized in a second step by photo crosslinking of PEG under visible light. In only a few seconds, hydrogels with Young's modulus between ∼10 and 30 kPa were obtained just by altering the CNF and Ca2+ content. 3D printed hydrogels supported fibroblasts with excellent cell viability and proliferation. The dual crosslinkable hydrogel ink herein developed is versatile, easy to prepare, and suitable for 3D printing of bioscaffolds with highly tailored viscoelastic and mechanical properties applicable in a wide range of regenerative medicines.

Synthesis of a pH-responsive nano-cellulose/sodium alginate/MOFs hydrogel and its application in the regulation of water and N-fertilizer.

In order to circumvent the water eutrophication caused by nitrogen loss in agriculture, slow-release and high-water containing fertilizers have captured much attention. Considering the unstable release of traditional slow-released fertilizers, novel strategies need to be designed to meet the steady release of fertilizers. Herein, by integrating cellulose-based hydrogel with MIL-100(Fe), a pH-sensitive Cellulose/MOFs hydrogel (CAM) with a high surface area (45.25 m2/g) was devised. The volume changes and the water adsorption of the hydrogels were uncovered from pH 3 to pH 11, where the highest water adsorption (100 g/g) was achieved at pH 11. Besides, a pH-sensitive urea slow release fertilizer (U-CAM) was also designed. The urea release of the U-CAM at pH 11 was much slower than that of the U-CAM at pH 3, which indicated its potential application in arid regions. In parallel with a favorable water-holding capacity, the totally loss of the soil moisture loaded with U-CAM was slowed down by 18 days as compared with the pure soil. The positive effect of the U-CAM on the growth of wheat was indexed with the germination rate, number of tillers, photosynthetic rate and chlorophyll content of the crop, which verified their further application in irrigating farming.

A new biodegradable nano cellulose-based drug delivery system for pH-controlled delivery of curcumin.

Targeted delivery and controlled release of drugs are attractive methods for avoiding the drug's leakage during blood circulation and burst release of the drug. We prepared a nano cellulose-based drug delivery system (DDS) for the effective delivery of curcumin (CUR). In the present scenario, the role of nanoparticles in fabricating the DDS is an important one and was characterized using various techniques. The drug loading capacity was high as 89.2% at pH = 8.0, and also the maximum drug release takes place at pH = 5.5. In vitro cell viability studies of DDS on MDA MB-231; breast cancer cells demonstrated its cytotoxicity towards cancer cells. The prepared DDS was also examined for apoptosis, hemocompatibility, and Chorioallantoic membrane (CAM) studies to assess its pharmaceutical field application and the investigation results recommended that it may serve as a potential device for targeted delivery and controlled release of CUR for cancer treatment.

Thiomers of Chitosan and Cellulose: Effective Biosorbents for Detection, Removal and Recovery of Metal Ions from Aqueous Medium.

Removal of toxic metal ions using adsorbents is a well-known strategy for water treatment. While chitosan and cellulose can adsorb weakly some types of metals, incorporating thiols as metal chelating agents can improve their sorption behaviors significantly. Presented in this review are the various chemical modification strategies applicable for thiolation of chitosan and cellulose in the forms of mercaptans, xanthates and dithiocarbamates. Moreover, much attention has been paid to the specific strategies for controlling the thiolation degree and characterization approaches for establishing the structure-property relationship. Also, the kinetics and isotherm models that elucidate the adsorption processes and mechanisms induced by the thiomers have been explained. These thiomers have found great potentials in the applications associated with metal removal, metal recovery and metal detection.

Association of antioxidant monophenolic compounds with ß-cyclodextrin-functionalized cellulose and starch substrates.

Polysaccharide substrates loaded with antioxidant and antimicrobial compounds, effectively protected by cyclodextrin moieties, can be a long-lasting solution to confer certain properties to fabrics, paper and other materials. ß-Cyclodextrin was attached to α-cellulose, bleached pulp and starch by a two-step esterification with a tetracarboxylic acid. The resulting derivatives were characterized by spectroscopy, thermal degradation analysis and capability of phenolphthalein inclusion. The carriers, containing between 89 and 171 µmol of ß-cyclodextrin per gram, were loaded with carvacrol, cuminaldehyde, cinnamaldehyde and hydroxytyrosol. From a stoichiometric addition, the percentage of compound retained ranged from 49% (hydroxytyrosol in pulp-cyclodextrin) to 92% (carvacrol in starch-cyclodextrin). Finally, the release rate to aqueous ethanol was measured over eight days and fitted to kinetic models. From the analysis of the mean dissolution time, it can be concluded that inserting ß-cyclodextrin units enhanced the long-term holding of phenolic active compounds in carbohydrate matrices.

Synthesis of Recyclable Magnetic Cellulose Nanofibers from Ionic Liquids for Practical Applications in Separation Science.

The present study focused on coupling cellulose nanofibers (alternative materials for plastics and metals) with a magnetic ionic liquid (synthesized by a microwave-assisted method) through mixing to yield magnetic cellulose nanofibers (MCNFs) that can be recycled by attracting them to a magnet. Accordingly, two types of ionic liquids were synthesized: (a) 1-butyl-3-methylimidazolium tetrachloroferrate(III) {[bmim] FeCl4} and (b) 1-glycidyl-3-methylimidazolium tetrachloroferrate {[glmi]FeCl4}, which were characterized by the fast atom bombardment mass spectrometry (FAB-MS) technique. Impregnation of the cellulose nanofibers with the {[bmim]FeCl4} ionic liquid caused the latter to be physically adsorbed onto the nanofibers to produce {MCNF@{[bmim]FeCl4}, whereas the corresponding {[glmi]FeCl4} ionic liquid was chemically bonded to the cellulose nanofibers to yield magnetic {MCNF@[glmi]FeCl4} nanofibers. Under the experimental conditions used, the corresponding magnetic moments were 0.222 A m2 kg-1 for {MCNF@ {[bmim]FeCl4} and 0.095 A m2 kg-1 for {MCNF@[glmi]FeCl4}.

Carboxylcellulose hydrogel confined-Fe3O4 nanoparticles catalyst for Fenton-like degradation of Rhodamine B.

Facile preparation of functional hydrogel materials for environmental catalysis is a hot research topic of soft materials science and green catalysis. In this study, a carboxylcellulose hydrogel confined Fe3O4 nanoparticles composite catalyst (Fe3O4@CHC) with magnetic recyclability has been synthesized by taking the advantages of the newly developed cellulose solution in tetramethyl guanidine/DMSO/CO2 through in situ acylation using mixed cyclic anhydrides and ion exchange reaction. The achieved Fe3O4@CHC hydrogel catalyst was shown to be an more efficient and better Fenton-like catalyst for decomposition of the organic dye rhodamine B (RhB) in the presence of hydrogen peroxide, with almost complete decomposition occurring within 180 min, in comparison with Fe3O4@cellulose hydrogel (CH) with excellent recyclability. This work provided a facile strategy for the preparation of hydrogel-based functional composite green catalytic materials, which has potential applications in green catalysis.

Development of a cellulose-based scaffold for sustained delivery of curcumin.

Due to the unique properties of cellulose-based materials, they are attractive to be developed in industrial pharmaceutics and biomedical fields. Carboxymethyl-diethyl amino ethyl cellulose scaffold (CM-DEAEC) has been synthesized in the current work as a smart novel derivative of cellulose with a great functionality in drug delivery systems. The scaffolds were well cross-linked with 2% (v/v) epichlorohydrin (ECH), loaded with curcumin (Cur), and then were analyzed by FT-IR, XRD, SEM, and mechanical strength. While developing the ideal delivery platform, curcumin (an important chemotherapeutic agent) was chosen due to its hydrophobicity and poor bioavailability. Thus, we developed a novel scaffold for efficient loading and controlled releasing of curcumin. The swelling ratio of 136%, high curcumin entrapment efficiency (up to 83.7%), sustained in vitro drug release profile, and appropriate degradability in three weeks confirmed significant properties of the CM-DEAEC scaffold. More than 99% antibacterial activity has been observed by the cross-linked curcumin loaded CM-DEAEC scaffolds. Cytotoxicity studies using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and 4',6-diamidino-2-phenylindole (DAPI) staining showed that cross-inked curcumin loaded CM-DEAEC scaffolds did not show any toxicity using L929 cells. All experiments were compared with CMC scaffolds and better characteristics of the novel scaffold for drug delivery have been confirmed.

Highly transparent, writable and photoluminescent foldable polymer film: When fluorescent dyes or pigments join cellulose-based microgel.

We prepared a self-dispersed cellulose-based microgel via chemically bonding hydrophilic gelatin peptide chain onto cellulose glucose chain. Following, a variety of highly transparent, foldable, and writable photoluminescent polymer films was obtained through loading organic dyes and inorganic pigments onto cellulose-based microgel matrix, respectively. Benefiting from the coupling sites and network effect of microgel as well as the abundant hydroxyl, amino, and imino groups in its structure, the microgel containing organic dyes and inorganic pigments exhibit good dispersion and stability, and the resultant photoluminescent films emit bright yellow, orange, yellow-green, and blue-green fluorescence under UV light, respectively, especially the cellulose-based microgel stabilized inorganic alkaline earth aluminate hybrids exhibit continuous luminescence for a long time in the dark. Compared with the existing regenerated cellulose or CNCs-based fluorescent films, the cellulose-based microgel fluorescent films present higher transmittance and good biodegradability. This study can bring new ideas for the development of flexible luminescent devices.

Research Progress on Synthesis and Application of Cyclodextrin Polymers.

Cyclodextrins (CDs) are a series of cyclic oligosaccharides formed by amylose under the action of CD glucosyltransferase that is produced by Bacillus. After being modified by polymerization, substitution and grafting, high molecular weight cyclodextrin polymers (pCDs) containing multiple CD units can be obtained. pCDs retain the internal hydrophobic-external hydrophilic cavity structure characteristic of CDs, while also possessing the stability of polymer. They are a class of functional polymer materials with strong development potential and have been applied in many fields. This review introduces the research progress of pCDs, including the synthesis of pCDs and their applications in analytical separation science, materials science, and biomedicine.