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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, Z

Succinylation of proteins is a commonly encountered reaction in biology and introduces negatively charged carboxylates on previously basic primary amine groups of amino acid residues. In analogy, this work investigates the succinylation of primary amines of the synthetic polyelectrolyte polyallylamine (PAA). It investigates the influence of the degree of succinylation on the cytotoxicity and antibacterial activity of the resulting polymers. Succinylation was performed in water with varying amounts of succinic anhydride and at different pH values. The PAA derivatives were analyzed in detail with respect to molecular structure using nuclear magnetic resonance and infrared absorbance spectroscopy. Polyelectrolyte and potentiometric charge titrations were used to elucidate charge ratios between primary amines and carboxylates in the polymers. The obtained materials were then evaluated with respect to their minimum inhibitory concentration againstStaphylococcus aureusandPseudomonas aeruginosa. The biocompatibility was assessed using mouse L929 fibroblasts. The degree of succinylation decreased cytotoxicity but more significantly reduced antibacterial efficacy, demonstrating the sensitivity of the fibroblast cells against this type of ampholytic polyelectrolytes. The obtained polymers were finally electrospun into microfiber webs in combination with neutral water-soluble polyvinyl alcohol. The resulting non-woven could have the potential to be used as wound dressing materials or coatings.

Dextran esters of different amino acids (glycine, $\beta $-alanine, L-ornithine, L-lysine) are investigated regarding their pK$_{a}$ values by potentiometric titration. The pK$_{a}$ values of the dextran derivatives are generally dependent on the position of the amino group in relation to the ester group, i.e. the nearer they are located in the molecule, the lower the resulting pK$_{a}$ values are, L-ornithine ester being the exception. An influence of the polymer backbone is ruled out. Stability against hydrolysis at different pH values and over longer periods at constant pH value is measured by potentiometric and polyelectrolyte titration. The $\beta $-alanine ester shows slowest hydrolysis at alkaline pH values, starting at a pH value of 8. The esters investigated are polycations at physiological pH values; thus, the charging properties are essential for using these esters as nonviral vectors in gene delivery.

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.

In this work, surfaces of casted silicone sheets and silicone tubes were functionalized with colloidal polysaccharide complexes (chitosan, carboxymethyl chitosan, and hyaluronic acid in combination with a lysine-based surfactant) in order to introduce antimicrobial and antifouling surface properties. The surface chemistry and morphology, as well as the chemical and mechanical stability of the coatings were characterized. For this purpose, different microscopic and spectroscopic methods, pH-potentiometric titrations and standard methods for evaluation of mechanical properties were used. Finally, the antimicrobial and antifouling properties of functionalized silicone materials were evaluated in vitro. The findings of the physicochemical characterization showed that a discontinuous 3-step dip-coating process can be successfully implemented to coat casted polydimethylsiloxane sheets and tubes with colloidal polysaccharide complexes. These coatings exhibit slow-release leaching in aqueous environment at pH 4.5, 7, and 8 and show very good stability against mechanical abrasion, thus displaying high stability potential during catheter insertion. The antimicrobial properties against gram-positive bacteria, gram-negative bacteria and fungi, showed inhibition of bacterial growth of up to 86%. Furthermore, the bacterial biofilm formation tests have revealed that the hyaluronic acid-surfactant coating exhibits high biofilm growth reduction.

Wet wipes are everyday products with the purpose to be flushed down the toilet after usage and dispersed into single fibres and small fragments thereby. During wet storage, these wipes can deteriorate their dispersibility over time, characterized by the slosh box disintegration test, recently named dispersibility ageing. This effect in flushable wet wipes, usually made of long man-made cellulose fibres and short wood pulp fibres, can be reduced by using unbleached softwood kraft pulp as the short fibre component. The aim of this work is to analyse mechanisms that could contribute to dispersibility ageing. Therefore, we will discuss three mechanisms that are able to explain this effect, that occurs in cellulosic fabrics when stored in water. Swelling (1) is demonstrated to be a long-term effect, but altering swelling with pH and salt addition has no effect on dispersibility ageing, making it unlikely that swelling contributes to it. With ionic shielding (2) a mechanism has been introduced that could impact dispersibility ageing by cations leaching from the wood pulp, which was demonstrated for an unbleached softwood kraft pulp by conductivity measurements over wet storage time. These cations neutralize the negatively charged pulp fibre fibrils and restrict their possibility to entangle with each other, which could contribute to decreasing dispersibility ageing. We will discuss the mechanism of interdiffusion (3) in dispersibility ageing, although we were not able to find a method that quantifies the contribution of cellulosic polymer diffusion to the time-dependent deterioration in dispersibility.

In this study, we report the isolation of cellulose nanocrystals (CNCs) from Isora plant fibers by sulfuric acid hydrolysis and their assembly on hydrophilic cellulose and silicon-di-oxide (SiO2) surfaces via a layer-by-layer (LBL) deposition method. The isolated CNCs were monodis-persed and exhibited a length of 200-300 nm and a diameter of 10-20 nm, a negative zetapotential (34-39 mV) over a wide pH range, and high stability in water at various concentrations. The multi-layered structure, adsorbed mass, conformational changes, and anticoagulant activity of sequen-tially deposited anionic (sulfated) CNCs and cationic polyethyleneimine (PEI) on the surfaces of cellulose and SiO2 by LBL deposition were investigated using a quartz crystal microbalance tech-nique. The organization and surface features (i.e., morphology, thickness, wettability) of CNCs ad-sorbed on the surfaces of PEI deposited at different ionic strengths (50-300 mM) of sodium chloride were analysed in detail by profilometry layer-thickness, atomic force microscopy and contact angle measurements. Compared to cellulose (control sample), the total coagulation time and plasma deposition were increased and decreased, respectively, for multilayers of PEI/CNCs. This study should provide new possibilities to fabricate and tailor the physicochemical properties of multilayer films from polysaccharide-based nanocrystals for various biomedical applications. Acknowledgments: The authors acknowledge Volker Ribitsch (retired) from the University of Graz/Austria for his support and valuable discussion for this manuscript. The authors also acknowledge the financial support from the Slovenian National Research Agency ARRS (Grant No. J4-1764). Scopus

Engineering functional biomaterials surfaces that resist biofilm formation triggered by unspecific protein adsorption is a key challenge, and these biosurfaces hold a huge potential in implant-associated infection. Herein, we report a water-based facile approach to install carboxylated-hyaluronic acid and sulfated-fucoidan on cationically tethered polydimethylsiloxane (PDMS) implant. We showed that these hydrophilic, charged, polysaccharide-based biosurfaces/biocoatings provide long-term stability, no adsorption of proteins (albumin and fibrinogen), similar to zwitterionic polymers, and enhanced resistance to plasma deposition and growth of Staphylococcus aureus pathogen. These findings shall pave the way in developing novel biocoatings, thereby broadening the applicability of PDMS-based implants in complex biological applications.

We report here a one-step aqueous method for the synthesis of isolated and purified polysaccharide-amino acid conjugates. Two different types of amino acid esters: glycine methyl ester and L-tryptophan methyl ester, as model compounds for peptides, were conjugated to the polysaccharide carboxymethylcellulose (CMC) in water using carbodiimide at ambient conditions. Detailed and systematic pH-dependent charge titration and spectroscopy (infrared, nuclear magnetic resonance: 1H, 13C- DEPT 135, 1H- 13C HMBC/HSQC correlation), UV–vis, elemental and ninhydrin analysis provided solid and direct evidence for the successful conjugation of the amino acid esters to the CMC backbone via an amide bond. As the concentration of amino acid esters increased, a conjugation efficiency of 20–80% was achieved. Activated charcoal aided base-catalyzed deprotection of the methyl esters improved the solubility of the conjugates in water. The approach proposed in this work should have the potential to tailor the backbone of polysaccharides containing di- or tri-peptides.

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)., The authors would like to thank Dr. Thomas Luxbacher for valuable discussions and assistance with SurPASS 3. The authors also acknowledge the financial support provided by the Slovenian Research Agency (grants no.: P2-0118, J4-1764 as well as through the Young Researcher Program) and the Spanish Ministry of Economy, Industry and Competitiveness (grant no.: CTQ2017-88948-P).

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.

Thin films of trimethylsilyl cellulose are obtained by spin coating and regenerated to cellulose. The surface is activated with N,N′-carbonyldiimidazole and aminolysis with lysine is carried out in aqueous solution to yield a cellulose lysine carbamate film. The surface is analytically characterized by ATR-IR spectroscopy, zetapotential measurements, contact angle measurements, and atomic force microscopy. The amount of functional groups is determined by pH potentiometric titration as well as the ninhydrin test and is in the range of 25 pmolcm−2. Adsorption of bovine serum albumine (BSA) and fibrinogen on the cellulose film and the cellulose lysine carbamate surface is studied at different pH values by quartz crystal microbalance with dissipation monitoring (QCM-D). The adsorption of BSA is significantly reduced by modification with lysine. At physiological pH value (7.4) the adsorption of fibrinogen is even six times lower (1.0 mgm−2) compared to the pure cellulose surface. Thus, cellulose thin films with lysine moieties are promising candidates for hemo-compatible antifouling surfaces in the field of blood contacting devices.

Nonspecific protein deposition on Lyocell fibers via a cationization step was explored by adsorption of two different N,N,N -trimethyl chitosan chlorides (TMCs). Both, the cationization and the subsequent protein deposition steps were performed and monitored in situ by evaluating the zeta potential using the streaming potential method. Both employed TMCs (degree of substitution with N + Me 3 Cl groups: 0.27 and 0.64) irreversibly adsorb on the fibers as proven by charge reversal (−12 to +7 mV for both derivatives) after the final rinsing step. Onto these cationized fibers, BSA was deposited at different pH values (4, 5, and 7). Charge titrations revealed that close to the isoelectric point of BSA (4.7), BSA deposition was particularly favored, while at lower pH values (pH 4), hardly any adsorption took place due to electrostatic repulsion of the cationic fibers and the positively charged BSA. This work sets the foundation for further investigations to use zeta potential measurements for protein adsorption studies on fibrous materials.

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&middot, m&minus, 1 K&minus, 1, which was comparable to and lower than the commercial insulators such as mineral wools (0.040 W&middot, 1) and polystyrene foams (0.035 W&middot, 1). 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.

Silicones are widely used medical materials that are also applied for tympanostomy tubes with a trending goal to functionalise the surface of the latter to enhance the healing of ear inflammations and other ear diseases, where such medical care is required. This study focuses on silicone surface treatment with various antimicrobial coatings. Polysaccharide coatings in the form of chitosan nanoparticles alone, or with an embedded drug mixture composed of amoxicillin/clavulanic acid (co-amoxiclav) were prepared and applied onto silicone material. Plasma activation was also used as a pre-treatment for activation of the material&rsquo, s surface for better adhesion of the coatings. The size of the nanoparticles was measured using the DLS method (Dynamic Light Scattering), stability of the dispersion was determined with zeta potential measurements, whilst the physicochemical properties of functionalised silicone materials were examined using the UV-Vis method (Ultraviolet-Visible Spectroscopy), SEM (Scanning Electron Microscopy), XPS (X-Ray Photoelectron Spectroscopy). Moreover, in vitro drug release testing was used to follow the desorption kinetics and antimicrobial properties were tested by a bacterial cell count reduction assay using the standard gram-positive bacteria Staphylococcus aureus. The results show silicone materials as suitable materials for tympanostomy tubes, with the coating developed in this study showing excellent antimicrobial and biofilm inhibition properties. This implies a potential for better healing of ear inflammation, making the newly developed approach for the preparation of functionalised tympanostomy tubes promising for further testing towards clinical applications.

Chitosan (CS) in different forms has already been extensively studied, as an active surface agent integrated onto different medical devices. The latest trend in applications is to design nanolayers by the specific CS nanoparticles (NPs) that should be manipulatively (reversible/irreversible) attached onto those materials. High specific area due to nanosize level, as well as manipulation of binding, could increase the bioactive properties of polymer materials, functionalized by chitosan nanoparticles (CSNPs), and in this way reduce the biggest problems of medical devices connected with infections. In this chapter, CS and its derivatives are presented for drug delivery, as well as for functionalization of the surface of different polymer materials, which are applied in several health areas, such as hygiene medical materials, i.e., wound dressings, tampons, urethral catheters, and cardiovascular grafts.

This study describes the formation of cellulose based polyelectrolyte charge complexes on the surface of biodegradable polycaprolactone (PCL) thin films. Anionic sulphated cellulose (CS) and protonated cationic amino cellulose (AC) were used to form these complexes with a layer-by-layer coating technique. Both polyelectrolytes were analyzed by charge titration methods to elucidate their pH-value dependent protonation behavior. A quartz crystal microbalance with dissipation (QCM-D) in combination with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used to follow the growth, stability and water content of up to three AC/CS bi-layers in aqueous environment. This was combined with coagulation studies on one, two and three bilayers of AC/CS, measuring the thrombin formation rate and the total coagulation time of citrated blood plasma with QCM-D. Stable mixed charged bilayers could be prepared on PCL and significantly higher masses of AC than of CS were present in these complexes. Strong hydration due to the presence of ammonium and sulphate substituents on the backbone of cellulose led to a significant BSA repellent character of three bilayers of AC/CS coatings. The total plasma coagulation time was increased in comparison to neat PCL, indicating an anticoagulative nature of the coatings. Surprisingly, a coating solely composed of an AC layer significantly prolonged the total coagulation time on the surfaces although it did not prevent fibrinogen deposition. It is suggested that these cellulose derivative-based coatings can therefore be used to prevent unwanted BSA deposition and fibrin clot formation on PCL to foster its biomedical application.

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.

Chitosan (CS) and trimethyl chitosan (TMC) solutions, as well as nanoparticles synthesized by ionic gelation method are studied. Their characterization is focused on determining the charge and antimicrobial properties against common pathogenic microorganisms and Lactobacillus spp., usually found in resident microbiota of vaginal and gastrointestinal tract. Special emphasis is given to the evaluation of antimicrobial activity in relation to the available cationic charge and the presence of nano-sized chitosan in comparison with chitosan macromolecules. In order to investigate the chitosan's antimicrobial mode of action diffusion nuclear magnetic resonance (D-NMR) is used as a novel approach. This technique enables the monitoring of chitosan nanoparticles (CSNP) effects onto healthy Lactobacillus cells. D-NMR results indicate that CSNP interact with the membrane of Lactobacillus cells, causing the perturbation of the membrane wall and lead to the death of the cells, suggesting the mechanism of Lactobacillus inhibition caused by CSNP. Lactobacillus inhibition is also reflected in low minimal inhibitory concentration (MIC).

This study presents a simple and straightforward method for the preparation of aqueous-based stable polysaccharide-metal oxide nanoparticles composites — composed of carboxymethyl cellulose (CMC) and titanium dioxide nanoparticles (TiO2 NPs), and their interaction with the cellulose surface, is presented. Using a combination of anionic polysaccharide CMC as a stabilizer agent and ultrasound probe sonication technique as an agitation tool, a highly stable dispersion of CMC/TiO2 NPs composites is prepared in water, with and without the presence of calcium chloride electrolyte, at various pH values. The results of the dynamic light scattering and the zeta-potential measurements showed that the quality, the stability of the dispersions and the hydrodynamic radius of the particles (ca, 200–300 nm) remain well-preserved for several weeks under normal storage conditions. The transmission electron microscope revealed that the morphology and size of the dry particles size (ca. 25–50 nm) remain unchanged and are not influenced by the addition of the stabilizer CMC, the electrolyte or the pH value of the solution. The presence of electrolyte and the low pH of the dispersions strongly favored an irreversible and enhanced deposition of CMC/TiO2 NPs on cellulose surface as showed by a quartz crystal microbalance with dissipation. A linear correlation between the concentration of CMC and the adsorbed mass of polymer and NPs, and the water content of the adsorbed layers is observed. X-ray photoelectron spectroscopy and atomic force microscopy are combined to prove the successful immobilization of polymer and NPs on the cellulose surface. The knowledge gained from this study can be extended not only for the stabilization of various metal oxide nanoparticles but also for the development of green polymer/NPs composites, that may have the potential to be used as functional coatings in biomedical (e.g. wound dressing) applications.

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.

A basic strategies to deal with the above described problems of CAUTI and biofilm formation is aimed toward modification of the implant’s surface-chemical properties, coating with a desired agent, and by manipulation of the surface roughness or morphology which can prevent the attachment of bacteria to the implant [1]. This chapter will be devoted predominantly to coating of silicon-based medical implants. Two strategies are common in coating of medical implants to achieve the above-mentioned goals.

Urethral catheters should satisfy variety of requirements connected to the specific application. Besides antifouling and antimicrobial properties, they should meet optimal mechanical properties, which are mostly related to the comfort during use. The comfort is extremely important since it is a direct indication of possible damage to the urethral mucosa.

Polysaccharides are the most important organic raw materials, building blocks in several fields and machineries of life [1]. Since the 1980s, naturally occurring polysaccharides, represented by cellulose, have been re-evaluated as outstanding chemicals and/or materials with various uses. Natural polysaccharides from different sources exhibit some special characteristics at the molecular and supramolecular levels, which are associated with their hydrogen-bonding ability, side-group reactivity, which can be modified covalently or by ionic bonds, enzymatic degradability, chirality, semi-rigidity, etc.

As there is a large gap in the field of fibre microbiological testing, the successful establishment of appropriate techniques is extremely appreciated. Antimicrobials prevent bacterial cell division by damaging the cell wall or affecting the permeabilities of cells’ membranes ; they denature proteins, block enzyme activity, prevent cell survival, etc. Intracellular potassium cations are released by the inhibitions of pathogenic micro-organisms. Their quantitative determination enables monitoring of the bactericidal effect regarding antimicrobials. It can be used as an alternative technique for determining the inhibition of micro-organisms in contact with antimicrobial agents. Chitosan, a biodegradable natural polymer, possesses antimicrobial characteristics that depend on a number of factors such as the protonated amino groups’ quantities, degree of acetylation, molecular weight, solvents, etc. Over recent years chitosan has become extremely attractive for fibre functionalization usage. The aim of this paper was to apply spectrophotometry and potentiometry using potassium ion-selective electrode, respectively, for the quantitative analysis of potassium efflux, resulting from the degradation of micro-organisms’ membranes in contact with chitosan itself, as well as with cellulose fibres functionalised by chitosan.

Biofilm formation triggered by uncontrolled protein adsorption, on medical devices is the leading cause of catheter-associated urinary tract infections (CAUTI) during implantation. Herein, we report a water-based, green and one-step strategy to functionalize surfaces of silicone catheters, poly(dimethylsiloxane) (PDMS), with antifouling and antimicrobial substances to avoid uncontrolled protein adsorption and microbial attachment. A novel synergetic formulation consisting of an anionic glycosaminoglycan (hyaluronic acid, HA) and a lysine-derived biocompatible cationic surfactant (Nϵ-myristoyl-lysine methyl ester, MKM) was prepared, resulting in the formation of nanoparticles (NPs, ca. 100-250 nm). Besides their high stability and long-lasting hydrophilicity in ambient and aqueous environments for 60 days, the nanometric layers (48 ± 3 nm) of HA-MKM NPs on PDMS showed no adsorption of BSA and lysozyme and substantially lower adsorption of fibrinogen as revealed by a quartz crystal microbalance with dissipation (QCM-D). In vitro antimicrobial test with S. aureus, E. coli, P. aeruginosa, P. mirabilis, C. albicans microbes under dynamic conditions revealed that the microbial growth was hampered by 85% compared with unmodified PDMS. Given the multiple functionalities, charges and diverse physiochemical properties of polysaccharide-lysine-based surfactant mixtures, this approach can be easily extended to the development of novel coatings on other silicone-based materials, thereby broadening potential applicability of PDMS-based biomaterials/devices in microfluidics, diagnostic biosensors and others. © 2017 The Royal Society of Chemistry., L. Perez acknowledges Spanish Plan national I + D + I MAT2012-38047-C02-02. The authors are grateful to Mag. D. Reishofer and Assoc. Prof. Dr Thomas Grießer from the Technical University of Graz and University of Leoben for their help in regard of AFM, profilometry and XPS measurements. The authors are grateful for the financial support provided by the research program P2-0118 Textile chemistry and Slovenian Research Agency (project no. J2-7413). T. Mohan acknowledge the European Union WoodWisdom-NET+ project PShapes.

The flavonoid rutin (RU) is a known antioxidant substance of plant origin. Its potential application in pharmaceutical and cosmetic fields is, however, limited, due to its low water solubility. This limitation can be overcome by polymerization of the phenolic RU into polyrutin (PR). In this work, an enzymatic polymerization of RU was performed in water, without the addition of organic solvents. Further, the chemical structure of PR was investigated using 1H NMR, and FTIR spectroscopy. Size-exclusion chromatography (SEC) was used to determine the molecular weight of PR, while its acid/base character was studied by potentiometric charge titrations. Additionally, this work investigated the antioxidant and free radical scavenging potential of PR with respect to its chemical structure, based on its ability to (i) scavenge non biological stable free radicals (ABTS), (ii) scavenge biologically important oxidants, such as O2&bull, NO&bull, and OH&bull, and (iii) chelate Fe2+. The influence of PR on fibroblast and HaCaT cell viability was evaluated to confirm the applicability of water soluble PR for wound healing application.

Mixtures of natural and biodegradable surfactants and ionic polysaccharides have attracted considerable research interest in recent years because they prosper as antimicrobial materials for medical applications. In the present work, interactions between the lysine-derived biocompatible cationic surfactant Nε-myristoyl-lysine methyl ester, abbreviated as MKM, and the sodium salt of hyaluronic acid (NaHA) are investigated in aqueous media by potentiometric titrations using the surfactant-sensitive electrode and pyrene-based fluorescence spectroscopy. The critical micelle concentration in pure surfactant solutions and the critical association concentration in the presence of NaHA are determined based on their dependence on the added electrolyte (NaCl) concentration. The equilibrium between the protonated (charged) and deprotonated (neutral) forms of MKM is proposed to explain the anomalous binding isotherms observed in the presence of the polyelectrolyte. The explanation is supported by theoretical model calculations of the mixed-micelle equilibrium and the competitive binding of the two MKM forms to the surface of the electrode membrane. It is suggested that the presence of even small amounts of the deprotonated form can strongly influence the measured electrode response. Such ionic-nonionic surfactant mixtures are a special case of mixed surfactant systems where the amount of the nonionic component cannot be varied independently as was the case for some of the earlier studies. © 2015 American Chemical Society., This work was partially supported by the Slovenian Research Agency, ARRS, through the Physical Chemistry program P1-0201, program P2 0118, and project L2-4060. LP generously thanks the Spanish Plan National I+D+I MAT2012-38047-C02-02.

Stable hydrophilic and protein-repellent surfaces from nontoxic polysaccharides are highly desirable in several biomedical applications such as implants and prosthetics. Herein, a water-based one-step strategy to functionalize polydimethylsiloxane (PDMS) surfaces with chitosan-based bioparticles is described to suppress the adsorption of blood plasma proteins, which causes biofilm formation and implant-associated infection. Micro- and nanosized chitosan (Chi) and carboxymethyl chitosan (CMChi) particles, featuring high stability, hydrophilicity, and zwitterionic feature, are synthesized in an ecofriendly solvent water and their interaction with PDMS surfaces is investigated in-real time over a wide range of pH (3–10) using a quartz crystal microbalance with dissipation (QCM-D). The results show that both Chi and CMChi form stable colloidal particles at pH close to their zero-point charge, and thus exhibit maximum adsorption and irreversibly bound layers on PDMS surfaces. Coating from CMChi shows high stability, improved hydrophilicity, and subsequently no adsorption of bovine serum albumin and enhanced resistance to fibrinogen, compared to Chi and native PDMS, as revealed by water contact angle and QCM-D measurements. The results demonstrate the possibility to develop novel and biobased coating materials to address unspecific protein adsorption not only on silicone-based implants but also on other biomaterials in general.