Corn-cob cellulose supported poly(hydroxamic acid) Cu(II) complex was prepared by the surface modification of waste corn-cob cellulose through graft copolymerization and subsequent hydroximation. The complex was characterized by IR, UV, FESEM, TEM, XPS, EDX and ICP-AES analyses. The complex has been found to be an efficient catalyst for 1,3-dipolar Huisgen cycloaddition (CuAAC) of aryl/alkyl azides with a variety of alkynes as well as one-pot three-components reaction in the presence of sodium ascorbate to give the corresponding cycloaddition products in up to 96% yield and high turn over number (TON 18,600) and turn over frequency (TOF 930h-1) were achieved. The complex was easy to recover from the reaction mixture and reused six times without significant loss of its catalytic activity.
Chitin-encapsulated cadmium sulfide quantum dots (CdS@CTN QDs) were successfully synthesized from chitin and Cd(NO3)2 precursor using the colloidal chemistry method, toward the development of biocompatible and biodegradable QDs for biomedical applications. CdS@CTN QDs exhibited the nanocrystalline cubic CdS encapsulated by α-chitin. The average particle size of CdS@CTN QDs was estimated using empirical Henglein model to be 3.9 nm, while their crystallite size was predicted using Scherrer equation to be 4.3 nm, slightly larger compared to 3-mercaptopropionic acid-capped CdS QDs (3.2 and 3.6 nm, respectively). The mechanism of formation was interpreted based on the spectroscopic data and X-ray crystal structures of CdS@CTN QDs fabricated at different pH values and mass ratios of chitin to Cd(NO3)2 precursor. As an important step to explore potential biomolecular and biological applications of CdS@CTN QDs, their antibacterial activities were tested against four different bacterial strains; i.e. Escherichia coli, Bacillus subtillus, Staphylococcus aureus and Pseudomonas aeruginosa.
This review outlines new developments in the biomedical applications of environmentally friendly ('green') chitosan and chitosan-blend electrospun nanofibers. In recent years, research in functionalized nanofibers has contributed to the development of new drug delivery systems and improved scaffolds for regenerative medicine, which is currently one of the most rapidly growing fields in all of the life sciences. Chitosan is a biopolymer with non-toxic, antibacterial, biodegradable and biocompatible properties. Due to these properties, they are widely applied for biomedical applications such as drug delivery, tissue engineering scaffolds, wound dressings, and antibacterial coatings. Electrospinning is a novel technique for chitosan nanofiber fabrication. These nanofibers can be used in unique applications in biomedical fields due to their high surface area and porosity. The present work reviews recent reports on the biomedical applications of chitosan-based nanofibers in detail.
Naturally derived antimicrobial peptides (AMPs) are an attractive source of new antimicrobial agents. However, clinical application of AMPs is associated with poor bioavailability and toxicity. In this study, we address these limitations by designing a new series of chitosan derivatives to mimic the amphiphilic topology of AMPs. The synthesized chitosan derivatives were found to self-assemble into nanoparticles in the aqueous environment. Among the compounds, a chitosan derivative grafted with arginine and oleic acid (CH-Arg-OA) exhibited the most potent antimicrobial activity, especially against Gram-negative bacteria. It also caused minimal cell death when tested in HEK293 and HepG2 cell lines, thus confirming the role of cationicity and lipophilicity for selective bacteria targeting. CH-Arg-OA exhibited its antimicrobial activity by disrupting bacterial membranes and causing the leakage of cytoplasmic contents. Thus, amphiphilic chitosan nanoparticles offer a great promise as a new class of AMPs mimics that is effective against Gram-negative bacteria.
Bionanocomposite films based on regenerated cellulose (RC) and incorporated with zeolite at different concentrations were fabricated by dissolving cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid using a simple green method. The interactions between the zeolite and the cellulose matrix were confirmed by Fourier transform infrared spectra. Mechanical properties of the nanocomposite films significantly improved as compared with the pure regenerated cellulose film, without the loss of extensibility. Zeolite incorporation enhanced the thermal stability and char yield of the nanocomposites. The scanning electron microscopy and transmission electron microscopy showed that zeolite was uniformly dispersed in the regenerated cellulose matrix. In vitro cytotoxicity test demonstrated that both RC and RC/zeolite nanocomposite films are cytocompatible. These results indicate that the prepared nanocomposites have potential applications in biodegradable packaging, membranes and biomedical areas.
Agar is a jelly-like biopolymer synthesized by many red seaweeds as their major cell wall component. Due to its excellent rheological properties, it has been exploited commercially for applications in food, cosmetic, pharmaceutical, biomedical and biotechnology industries. Despite its multiple uses, the biosynthesis of this phycocolloid is not fully understood. The current knowledge on agar biosynthesis is inferred from plant biochemistry and putative pathways for ulvan and alginate biosynthesis in green and brown seaweeds, respectively. In this review, the gaps in our current knowledge on agar biosynthetic pathway are discussed, focusing on the biosynthesis of agar precursors, elongation of agar polysaccharide chain and side chain modification. The development of molecular markers for the screening of desired seaweeds for industrial exploitation is also discussed.
Infection control and wound healing profiles of sodium carboxymethylcellulose (SCMC) films were investigated as a function of their anti-bacterial action, physical structures, polymer molecular weights and carboxymethyl substitution degrees. The films were prepared with in vitro polymer/film and in vivo microbe-colonized wound healing/systemic infection profiles examined. Adhesive high carboxymethyl substituted SCMC films aided healing via attaching to microbes and removing them from wound. Pseudomonas aeruginosa was removed via encapsulating in gelling low molecular weight SCMC film, whereas Staphylococcus aureus was trapped in tight folds of high molecular weight SCMC film. Incomplete microbe removal from wound did not necessary translate to inability to heal as microbe remnant at wound induced fibroblast migration and aided tissue reconstruction. Using no film nonetheless will cause systemic blood infection. SCMC films negate infection and promote wound healing via specific polymer-microbe adhesion, and removal of S. aureus and P. aeruginosa requires films of different polymer characteristics.
Acetone soluble oil palm empty fruit bunch cellulose acetate (OPEFB-CA) of DS 2.52 has been successfully synthesized in a one-step heterogeneous acetylation of OPEFB cellulose without necessitating the hydrolysis stage. This has only been made possible by the mathematical modeling of the acetylation process by manipulating the variables of reaction time and acetic anhydride/cellulose ratio (RR). The obtained model was verified by experimental data with an error of less than 2.5%. NMR analysis showed that the distribution of the acetyl moiety among the three OH groups of cellulose indicates a preference at the C6 position, followed by C3 and C2. XRD revealed that OPEFB-CA is highly amorphous with a degree of crystallinity estimated to be ca. 6.41% as determined from DSC. The OPEFB-CA films exhibited good mechanical properties being their tensile strength and Young's modulus higher than those of the commercial CA.
In this study cellulose nanocrystals were isolated from oil palm trunk (Elaeis guineensis) using acid hydrolysis method. The morphology and size of the nanocrystals were characterized using scanning electron microscopy and transmission electron microscopy. The results showed that the nanocrystals isolated from raw oil palm trunk (OPT) fibers and hot water treated OPT fibers had an average diameter of 7.67 nm and 7.97 nm and length of 397.03 nm and 361.70 nm, respectively. Fourier Transform Infrared spectroscopy indicated that lignin and hemicellulose contents decreased. It seems that lignin was completely removed from the samples during chemical treatment. Thermogravimetric analysis demonstrated that cellulose nanocrystals after acid hydrolysis had higher thermal stability compared to the raw and hot water treated OPT fibers. The X-ray diffraction analysis increased crystallinity of the samples due to chemical treatment. The crystalline nature of the isolated nanocrystals from raw and hot water treated OPT ranged from 68 to 70%.
Cellulose and its forms are widely used in biomedical applications due to their biocompatibility, biodegradability and lack of cytotoxicity. It provides ample opportunities for the functionalization of supported magnetic nanohybrids (CSMNs). Because of the abundance of surface hydroxyl groups, they are surface tunable in either homogeneous or heterogeneous solvents and thus act as a substrate or template for the CSMNs' development. The present review emphasizes on the synthesis of various CSMNs, their physicomagnetic properties, and potential applications such as stimuli-responsive drug delivery systems, MRI, enzyme encapsulation, nucleic acid extraction, wound healing and tissue engineering. The impact of CSMNs on cytotoxicity, magnetic hyperthermia, and folate-conjugates is highlighted in particular, based on their structures, cell viability, and stability. Finally, the review also discussed the challenges and prospects of CSMNs' development. This review is expected to provide CSMNs' development roadmap in the context of 21st-century demands for biomedical therapeutics.
Cellulose with ample hydroxyl groups is considered as a promising supportive biopolymer for fabricating cellulose supported promising magnetic sorbents (CMS) for magnetic solid-phase extraction (MSPE). The easy recovery via external magnetic field, and recyclability of CMS, associated with different types and surface modifications of cellulose has made them a promising sorbent in the field of solid-phase extraction. CMS based sorbent can offer improved adsorption and absorption capabilities due to its high specific surface area, porous structure, and magnetic attraction feature. This review mainly focuses on the fabrication strategies of CMS using magnetic nanoparticles (MNPs) and various forms of cellulose as a heterogeneous and homogeneous solution either in alkaline mediated urea or Ionic liquids (ILs). Moreover, CMS will be elaborated based on their structures, synthesis, physical performance, and chemical attraction of MNPs and their MSPE in details. The advantages, challenges, and prospects of CMS in future applications are also presented.
Low bioavailability and poor water solubility have limited the utilization of curcumin in conventional dosing methods. As an alternative, microemulsions as drug carrier can improve curcumin delivery. A cetyltrimethylammonium bromide-nanocrystalline cellulose (CTAB-NCC)-based microemulsion was developed and its potential use as a topical delivery method for curcumin was investigated. The effect of microemulsion's particle size and its microstructure as well as the presence of the CTAB-NCC nanoparticle on the topical delivery of curcumin was studied. In vitro permeation studies showed higher penetration rate of curcumin from the oil-in-water type-microemulsions. The skin permeation profile of curcumin followed Higuchi release kinetics. Furthermore, use of the (CTAB-NCC)-based microemulsion enhanced curcumin accumulation in the skin and these system showed non cytotoxicity effect on L929 cell line. These results showed the potential of (CTAB-NCC)-based microemulsions as controlled-release topical systems for the delivery of curcumin and potentially other lipophilic drugs.
Microcrystalline cellulose (MCC) extracted from empty fruit bunches (EFB), stalk and spikelet were characterised through physicochemical and microstructure analyses. Raw stalk fibres yielded the highest cellulose content (42.43%), followed by EFB (32.33%) and spikelet (18.83%). Likewise, lowest lignin and residual oil content was reported in raw stalk fibres compared to EFB and spikelet. SEM revealed significant changes on fibres' surface morphology throughout the extraction process. FTIR analysis showed that main characteristic peaks of hemicellulose and lignin was absent on the extracted MCC. The crystallinity index for MCC extracted from EFB (82.5%), stalk (82.2%) and spikelet (86.5%) was comparable to commercial MCC (81.9%). Results suggested stalk fibres is more preferable for the production of MCC compared to EFB and spikelet. Further rheological studies showed viscoelastic behaviour with no significant differences between commercial and stalk-based MCC, while modelling work showed ability to simulate complex deformation of the MCC-hydrogel/food mixture during processing/handling stage.
Acetylated, propionylated and butyrylated rice and quinoa starches at different levels of modification and starch concentrations, were used to stabilize oil-in-water starch Pickering emulsions at 10% oil fraction. Short-chain fatty acid modified starch Pickering emulsions (SPEs) were characterized after emulsification and after 50 days of storage. The particle size distribution, microstructure, emulsion index, and stability were evaluated. An increase in starch concentration led to a decrease of emulsion droplet sizes. Quinoa starch has shown the capability of stabilizing Pickering emulsions in both the native and modified forms. The emulsifying capacity of SPEs was improved by increasing the chain length of SCFA. Modified quinoa starch with higher chain lengths (i.e. propionylated and butyrylated), at higher levels of modification, showed higher emulsion index (>71%) and stability over the entire 50 days storage. At optimized formulation, SCFA-starch particles have the potential in stabilizing emulsions for functional foods, pharmaceutical formulations, or industrial food applications.
Polymer electrolytes were developed by solution casting technique utilizing the materials of cellulose acetate (CA), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and deep eutectic solvent (DES). The DES is synthesized from the mixture of choline chloride and urea of 1:2 ratios. The increasing DES content well plasticizes the CA:LiTFSI:DES matrix and gradually improves the ionic conductivity and chemical integrity. The highest conducting sample was identified for the composition of CA:LiTFSI:DES (28 wt.%:12 wt.%:60 wt.%), which has the greatest ability to retain the room temperature ionic conductivity over the entire 30 days of storage time. The changes in FTIR cage peaks upon varying the DES content in CA:LiTFSI:DES prove the complexation. This complexation results in the collapse of CA matrix crystallinity, observed from the reduced intensity of XRD diffraction peaks. The DES-plasticized sample is found to be more heat-stable compared to pure CA. Nevertheless, the addition of DES diminishes the CA:LiTFSI matrix's heat-resistivity but at the minimum addition the thermal stability is enhanced.
Two solid biopolymer electrolytes (SBEs) systems of carboxymethyl cellulose doped ammonium chloride (CMC-AC) and propylene carbonate plasticized (CMC-AC-PC) were prepared via solution casting technique. The ionic conductivity of SBEs were analyzed using electrical impedance spectroscopy (EIS) in the frequency range of 50 Hz-1 MHz at ambient temperature (303K). The highest ionic conductivity of CMC-AC SBE is 1.43 × 10(-3)S/cm for 16 wt.% of AC while the highest conductivity of plasticized SBE system is 1.01 × 10(-2)S/cm when added with 8 wt.% of PC. TGA/DSC showed that the addition of PC had increased the decomposition temperature compared of CMC-AC SBE. Fourier transform infrared (FTIR) spectra showed the occurrence of complexation between the SBE components and it is proved successfully executed by Gaussian software. X-ray diffraction (XRD) indicated that amorphous nature of SBEs. It is believed that the PC is one of the most promising plasticizer to enhance the ionic conductivity and performance for SBE system.
In this study, the interactions of α-tocopherol (α-TOH) in PVOH-starch blends were investigated. α-TOH is an interacting agent possesses a unique molecule of polar chroman "head" and non-polar phytyl "tail" which can improve surface interaction of PVOH and starch. It showed favorable results when blending PVOH-starch with α-TOH, where the highest tensile strengths were achieved at 60 wt.% PVOH-starch blend for 1 phr α-TOH and 50 wt.% for 3 phr α-TOH, respectively. This due to the formation of miscible PVOH-starch as resulted by the compatibilizing effect of α-TOH. Moreover, the enthalpy of melting (ΔHm) of 60 wt.% PVOH-starch and 50 wt.% PVOH-starch added with 1 and 3 phr α-TOH respectively were higher than ΔHm of the neat PVOH-starch blends. The thermogravimetry analysis also showed that α-TOH can be used as thermal stabilizer to reduce weight losses at elevated temperature. The surface morphologies of the compatible blends formed large portion of continuous phase where the starch granules interacted well with α-TOH by acting as compatilizer to reduce surface energy of starch for embedment into PVOH matrix.
Chitin was successfully grafted with polystyrene by free radical mechanism using ammonium persulfate (APS) initiator. The reaction was carried out in aqueous medium. The effect of pH, chitin:monomer weight ratio, APS, reaction time and reaction temperature were investigated. The results showed that the optimum conditions for grafting of polystyrene were found as follows: pH 7, chitin:monomer weight ratio of 1:3, 0.4 g of APS, reaction temperature of 60 °C and reaction time 2 h. The graft copolymer was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA) and differential scanning electron microscopy (DSC). Gel permeation chromatography (GPC) analysis carried out on the hydrolyzed graft copolymer showed that the Mn and Mw were 6.3395×10(4) g/mol and 1.69283×10(5) g/mol, respectively, with polydispersity index of 2.7.
Chitin biopolymer has received significant attention recently by many industries as a green technology. Nanotechnology has been used to make chitin nanocrystals (ChiNCs) that are rod-shaped natural nanomaterials with nanoscale size. Owing to the unique features such as biodegradability, biocompatibility, renewability, rod-shape, and excellent surface and interfacial, physiochemical, and thermo-mechanical properties; ChiNCs have been green and attractive products with wide applications specifically in medical and pharmaceutical, food and packaging, cosmetic, electrical, and electronic, and also in the oil and gas industry. This review aims to give a comprehensive and applied insight into ChiNCs technology. It starts with reviewing different sources of chitin and their extraction methods followed by the characterization of ChiNCs. Furthermore, a detailed investigation into various complex fluids (dispersions, emulsions, foams, and gels) stabilized by ChiNCs and their characterisation have been thoroughly deliberated. Finally, the current status including ground-breaking applications, untapped investigations, and future prospective have been presented.
The coronavirus pandemic, COVID-19 has a global impact on the lives and livelihoods of people. It is characterized by a widespread infection by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), where infected patients may develop serious medical complications or even face death. Development of therapeutic is essential to reduce the morbidity and mortality of infected patients. Chitosan is a versatile biomaterial in nanomedicine and exhibits anti-microbial, anti-cancer and immunomodulatory properties. This review highlights the progress in chitosan design and application pertaining to the anti-viral effects of chitosan and chitosan derivatives (hydroxypropyl trimethylammonium, sulfate, carboxymethyl, bromine, sialylglycopolymer, peptide and phosphonium conjugates) as a function of molecular weight, degree of deacetylation, type of substituents and their degree and site of substitution. The physicochemical attributes of these polymeric therapeutics are identified against the possibility of processing them into nanomedicine which can confer a higher level of anti-viral efficacy. The designs of chitosan for the purpose of targeting SARS-CoV-2, as well as the ever-evolving strains of viruses with a broad spectrum anti-viral activity to meet pandemic preparedness at the early stages of outbreak are discussed.