The adsorption of carboxymethyl cellulose (CMC), one of the most important cellulose derivatives, is crucial for many scientific investigations and industrial applications. Especially for surface ...modifications and functionalization of materials, the polymer is of interest. The adsorption properties of CMC are dependent not only on the solutions state, which can be influenced by the pH, temperature, and electrolyte concentration, but also on the chemical composition of the adsorbents. We therefore performed basic investigation studies on the interaction of CMC with a variety of polymer films. Thin films of cellulose, cellulose acetate, deacetylated cellulose acetate, polyethylene terephthalate, and cyclo olefin polymer were therefore prepared on sensors of a QCM-D (quartz crystal microbalance) and on silicon substrates. The films were characterized with respect to the thickness, wettability, and chemical composition. Subsequently, the interaction and deposition of CMC in a range of pH values without additional electrolyte were measured with the QCM-D method. A comparison of the QCM-D results showed that CMC is favorably deposited on pure cellulose films and deacetylated cellulose acetate at low pH values. Other hydrophilic surfaces such as silicon dioxide or polyvinyl alcohol coated surfaces did not adsorb CMC to a significant extent. Atomic force microcopy confirmed that the morphology of the adsorbed CMC layers differed depending on the substrate. On hydrophobic polymer films, CMC was deposited in the form of larger particles in lower amounts whereas hydrophilic cellulose substrates were to a high extent uniformly covered by adsorbed CMC. The chemical similarity of the CMC backbone seems to favor the irreversible adsorption of CMC when the molecule is almost uncharged at low pH values. A selectivity of the cellulose CMC interaction can therefore be assumed. All CMC treated polymer films exhibited an increased hydrophilicity, which confirmed their modification with the functional molecule.
Herein, colloidal dispersions of alkaline nanoparticles (NPs: CaCO3 and Mg(OH)2) are stabilized by trimethylsilyl cellulose (TMSC) in hexamethyldisiloxane and employed to treat historical wood pulp ...paper by an effortless dip-coating technique. Both alkaline NPs exhibit high stability and no size and shape changes upon stabilization with the polymer, as shown by UV–vis spectroscopy and transmission electron microscopy. The long-term effect of NP/TMSC coatings is investigated in detail using accelerated aging. The results from the pH-test and back-titration of coated papers show a complete acid neutralization (pH ∼ 7.4) and introduction of adequate alkaline reserve even after prolonged accelerated aging. Scanning electron microscopy–energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and infrared and water contact angle measurements showed the introduction of a thin and smooth hydrophobic NP/TMSC coating on the paper fibers. Acid-catalyzed desilylation of TMSC was observed by declining C-Si infrared absorbance peaks upon aging. The CaCO3 coatings are superior to Mg(OH)2 with respect to a reduced yellowing and lower cellulose degradation upon aging as shown by colorimetric measurements and degree of polymerization analysis. The tensile strength and folding endurance of coated and aged papers are improved to 200–300 and 50–70% as illustrated by tensile strength and double folding endurance measurements.
The fabrication of superadsorbent for dye adsorption is a hot research area at present. However, the development of low-cost and highly efficient superadsorbents against toxic textile dyes is still a ...big challenge. Here, we fabricated hydrophobic cellulose nanofiber aerogels from cellulose nanofibers through an eco-friendly silanization reaction in liquid phase, which is an extremely efficient, rapid, cheap, and environmentally friendly procedure. Moreover, the demonstrated eco-friendly silanization technique is easy to commercialize at the industrial level. Most of the works that have reported on the hydrophobic cellulose nanofiber aerogels explored their use for the elimination of oil from water. The key novelty of the present work is that the demonstrated hydrophobic cellulose nanofibers aerogels could serve as superadsorbents against toxic textile dyes such as crystal violet dye from water and insulating materials for building applications. Here, we make use of the possible hydrophobic interactions between silane-modified cellulose nanofiber aerogel and crystal violet dye for the removal of the crystal violet dye from water. With a 10 mg/L of crystal violet (CV) aqueous solution, the silane-modified cellulose nanofiber aerogel showed a high adsorption capacity value of 150 mg/g of the aerogel. The reason for this adsorption value was due to the short-range hydrophobic interaction between the silane-modified cellulose nanofiber aerogel and the hydrophobic domains in crystal violet dye molecules. Additionally, the fabricated silane-modified cellulose nanofiber hydrophobic aerogels exhibited a lower thermal conductivity value of 0.037 W·m
K
, which was comparable to and lower than the commercial insulators such as mineral wools (0.040 W·m
K
) and polystyrene foams (0.035 W·m
K
). We firmly believe that the demonstrated silane-modified cellulose nanofiber aerogel could yield an eco-friendly adsorbent that is agreeable to adsorbing toxic crystal violet dyes from water as well as active building thermal insulators.
Biocatalysis is increasingly becoming an alternative method for the synthesis of industrially relevant complex molecules. This can be realized by using enzyme immobilized polysaccharide-based 3D ...scaffolds as compatible carriers, with defined properties. Especially, immobilization of either single or multiple enzymes on a 3D printed polysaccharide scaffold, exhibiting well-organized interconnected porous structure and morphology, is a versatile approach to access the performance of industrially important enzymes. Here, we demonstrated the use of nanocellulose-based 3D porous scaffolds for the immobilization of glycosyltransferases, responsible for glycosylation in natural biosynthesis. The scaffolds were produced using an ink containing nanofibrillated cellulose (NFC), carboxymethyl cellulose (CMC), and citric acid. Direct-ink-writing 3D printing followed by freeze-drying and dehydrothermal treatment at elevated temperature resulted in chemically cross-linked scaffolds, featuring tunable negative charges (2.2–5.0 mmol/g), pore sizes (10–800 μm), fluid uptake capacity, and exceptional dimensional and mechanical stability in the wet state. The negatively charged scaffolds were applied to immobilize two sugar nucleotide-dependent glycosyltransferases (C-glycosyltransferase, Zbasic2-CGT; sucrose synthase, Zbasic2-SuSy), each harboring a cationic binding module (Zbasic2) to promote charge-based enzyme adsorption. Both enzymes were immobilized at ∼30 mg of protein/g of dry carrier (∼20% yield), independent of the scaffold used. Their specific activities were 0.50 U/mg (Zbasic2-CGT) and 0.19 U/mg (Zbasic2-SuSy), corresponding to an efficacy of 37 and 18%, respectively, compared to the soluble enzymes. The glycosyltransferases were coimmobilized and shown to be active in a cascade reaction to give the natural C-glycoside nothofagin from phloretin (1.0 mM; ∼95% conversion). All enzyme bound scaffolds showed reusability of a maximum of 5 consecutive reactions. These results suggest that the 3D printed and cross-linked NFC/CMC-based scaffolds could present a class of solid carriers for enzyme (co)-immobilization, with promising applications in glycosyltransferase-catalyzed synthesis and other fields of biocatalysis.
The application of hydrogels coupled with 3-dimensional (3D) printing technologies represents a modern concept in scaffold development in cartilage tissue engineering (CTE). Hydrogels based on ...natural biomaterials are extensively used for this purpose. This is mainly due to their excellent biocompatibility, inherent bioactivity, and special microstructure that supports tissue regeneration. The use of natural biomaterials, especially polysaccharides and proteins, represents an attractive strategy towards scaffold formation as they mimic the structure of extracellular matrix (ECM) and guide cell growth, proliferation, and phenotype preservation. Polysaccharide-based hydrogels, such as alginate, agarose, chitosan, cellulose, hyaluronan, and dextran, are distinctive scaffold materials with advantageous properties, low cytotoxicity, and tunable functionality. These superior properties can be further complemented with various proteins (e.g., collagen, gelatin, fibroin), forming novel base formulations termed "proteo-saccharides" to improve the scaffold's physiological signaling and mechanical strength. This review highlights the significance of 3D bioprinted scaffolds of natural-based hydrogels used in CTE. Further, the printability and bioink formation of the proteo-saccharides-based hydrogels have also been discussed, including the possible clinical translation of such materials.
•Paper impregnation with 10 % ATP for an effective protection of historical paper against mould development.•3D surface topography showed no adverse effects of ATP on paper support.•Portable “on the ...spot” non-invasive FTIR spectroscopy in reflection mode is an effective method for a rapid and highly sensitive detection of mould biofilms.
Even though contamination of historical paper by moulds causes aesthetic, physical, and biochemical biodeterioration, dissolving cellulose fibers and inks, the currently applied physical and chemical disinfection methods are either extremely dangerous to human health (ethylene oxide), may harm the underlying support material, or their efficiency is dependent on fungal species, many of which may resist. Therefore, our aim was to test a new paper impregnation agent, aminopropyl-terminated polydimethylsiloxane (ATP), in regards to its biological potency, ease of handling and support material safety. According to the Gelest Inc. (Morrisville, PA 19067) safety data sheet DMS-A31, ATP in solution causes eye irritation, but in dry from is relatively safe. Our biofouling experiments with four cellulase-active fungal strains, originally isolated from historical books, were conducted directly on impregnated and aged paper at verifying concentrations of ATP and at a relative humidity of 95 %. Fungal biofilm development was quantified using micro-invasive fluorescence microscopy and after incubation non-invasive FTIR spectroscopy was also employed. 3D surface topography scan results showed that ATP impregnation at a concentration of 30 % does not harm the visible structural characteristics of the tested paper and no alterations in surface roughness parameters were observed and is therefore safe for the supporting material. At least a 10 % paper impregnation was needed for an effective suppression of fungal biofilm development and tolerance to lower concentrations was species dependent, with Penicillium canescens ZIM-9717 tolerating 1 % of ATP and Aspergillus niger ZIM-9721 tolerating 1 % and 5 % of ATP. Lastly, we have shown that portable “on the spot” non-invasive FTIR spectroscopy in reflection mode can be effectively used for a rapid but highly sensitive detection and monitoring of mould biofilms on paper support materials. This is important, because sampling and fluorescence dye staining in fluorescence microscopy, will harm the integrity of cultural heritage books and documents. Therefore, non-invasive FTIR spectroscopy can provide for an initial overview or insight into the microbiological condition of library and paper materials.
Medical implant-associated infections resulting from biofilm formation triggered by unspecific protein adsorption are the prevailing cause of implant failure. However, implant surfaces rendered with ...multifunctional bioactive nanocoatings offer a promising alternative to prevent the initial attachment of bacteria and effectively interrupt biofilm formation. The need to research and develop novel and stable bioactive nanocoatings for medical implants and a comprehensive understanding of their properties in contact with the complex biological environment are crucial. In this study, we developed an aqueous stable and crosslinker-free polyelectrolyte–surfactant complex (PESC) composed of a renewable cationic polysaccharide, chitosan, a lysine-based anionic surfactant (77KS), and an amphoteric antibiotic, amoxicillin, which is widely used to treat a number of infections caused by bacteria. We successfully introduced the PESC as bioactive functional nanolayers on the “model” and “real” polydimethylsiloxane (PDMS) surfaces under dynamic and ambient conditions. Besides their high stability and improved wettability, these uniformly deposited nanolayers (thickness: 44–61 nm) with mixed charges exhibited strong repulsion toward three model blood proteins (serum albumin, fibrinogen, and γ-globulin) and their competitive interactions in the mixture in real-time, as demonstrated using a quartz crystal microbalance with dissipation (QCM-D). The functional nanolayers with a maximum negative zeta potential (ζ: −19 to −30 mV at pH 7.4), water content (1628–1810 ng cm–2), and hydration (low viscosity and elastic shear modulus) correlated with the mass, conformation, and interaction nature of proteins. In vitro antimicrobial activity testing under dynamic conditions showed that the charged nanolayers actively inhibited the growth of both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria compared to unmodified PDMS. Given the ease of fabrication of multifunctional and charged biobased coatings with simultaneous protein-repellent and antimicrobial activities, the limitations of individual approaches could be overcome leading to a better and advanced design of various medical devices (e.g., catheters, prosthetics, and stents).
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•Zeolites included in the nanofibers increased the adsorption capacity of model VOC.•Silicalite type of zeolite adsorbed 60 % higher amount of model VOC.•Up-scaling of the process ...with a 150 fold increase of formed CA/UHSZ nanofibers.•Diffusion of ammonia vapours is not influenced by the structure of the material.
The optimized preparation of novel electrospun nanofibrous composites from cellulose acetate (CA) and ultra-high silica zeolites (UHSZ) are reported as a promising material for the adsorption of Volatile Organic Compound (VOCs). Two types of UHSZs, i.e. silicalite and USY were prepared by hydrothermal crystallization while the fabrication of composites was performed using single needle and needle-less electrospinning systems, demonstrating the scalability of the composite fibres’ manufactured. Herein, factors such as properties of spinning solutions and electrospinning process parameters were studied, as well as interactions between the CA and UHSZs. In addition, Quartz Crystal Microbalance - Dissipation technique (QCM-D) was employed with an aim to study the adsorption behaviour of newly developed composites using ammonia as a model pollutant. The QCM-D data revealed that the presence of UHSZs in the CA materials increased adsorption capacity, designating CA/UHSZ composites as potential materials suitable for a large-scale removal of VOCs from polluted air.
This work describes the interaction of the human blood plasma proteins albumin, fibrinogen, and γ-globulins with micro- and nanopatterned polymer interfaces. Protein adsorption studies were ...correlated with the fibrin clotting time of human blood plasma and with the growth of primary human pulmonary artery endothelial cells (hECs) on these patterns. It was observed that blends of polycaprolactone (PCL) and trimethylsilyl-protected cellulose form various thin-film patterns during spin coating, depending on the mass ratio of the polymers in the spinning solutions. Vapor-phase acid-catalyzed deprotection preserves these patterns but yields interfaces that are composed of hydrophilic cellulose domains enclosed by hydrophobic PCL. The blood plasma proteins are repelled by the cellulose domains, allowing for a suggested selective protein deposition on the PCL domains. An inverse proportional correlation is observed between the amount of cellulose present in the films and the mass of irreversibly adsorbed proteins. This results in significantly increased fibrin clotting times and lower masses of deposited clots on cellulose-containing films as revealed by quartz crystal microbalance with dissipation measurements. Cell viability of hECs grown on these surfaces was directly correlated with higher protein adsorption and faster clot formation. The results show that presented patterned polymer composite surfaces allow for a controllable blood plasma protein coagulation and a significant biological response from hECs. It is proposed that this knowledge can be utilized in regenerative medicine, cell cultures, and artificial vascular grafts by a careful choice of polymers and patterns.
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•CNF/LS/CaCl2 composite membranes are formed by a dispersion casting procedure.•The addition of CaCl2 reduces the ζ potential and promotes the aggregation of CNF.•The addition of ...CaCl2 promotes LS deposition on CNFs already in dispersion phase.•Composite membranes provide excellent passive flame retardancy.•LS component contribute for up to 100 % UVA/UVB shielding capacity.
The use of biomass to produce value-adding materials is a core objective of the circular economy, which has attracted great research interest in recent decades. In this context, we present here a simple dispersion-casting process for consolidation of cellulose nanofibrils (CNF), lignosulphonate (LS)-rich bio-waste and CaCl2 in composite membranes. The addition of CaCl2 to CNF and LS dispersions reduces the ζ potential, due to an electrostatic screening, which promotes the aggregation of CNF, increases its moisture content and promotes LS deposition on CNFs already in the dispersion phase. Addition of both the LS and CaCl2 to CNF dispersion has an adverse effect on the mechanical properties of the final membranes. The effectiveness of the new composite membranes has been described in terms of their passive (charring) flame retardancy and 100 % UVA/UVB shielding capacity, both identified for membranes with the highest LS content, as well as high electronic resistance.
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