Physicochemical Characterization of Packaging Foils Coated by Chitosan and Polyphenols Colloidal Formulations.

In this research, antimicrobial polysaccharide chitosan was used as a surface coating for packaging material. The aim of our research was to establish an additive formulation of chitosan and antioxidative plant extracts as dispersion of nanoparticles. Chitosan nanoparticles with embedded thyme, rosemary and cinnamon extracts were synthesized, and characterized for this purpose. Two representative, commercially used foils, polypropylene (PP) and polyethylene (PE), previously activated by UV/ozone to improve coating adhesion, were functionalized using chitosan-extracts nanoparticle dispersions. The foils were coated by two layers. A solution of macromolecular chitosan was applied onto foils as a first layer, followed by the deposition of various extracts embedded into chitosan nanoparticles that were attached as an upper layer. Since active packaging must assure bioactive efficiency at the interface with food, it is extremely important to understand the surface characteristics and phenomena of functionalized foils. The physico-chemical analyses of functionalized foils were thus comprised of surface elemental composition, surface charge, wettability, as well as surface morphology. It has been shown that coatings were applied successfully with an elemental composition, surface charge and morphology that should enable coating stability, homogeneity and consequently provide an active concept of the packaging surface in contact with food. Moreover, the wettability of foils was improved in order to minimize the anti-fogging behavior.

Electrokinetic behaviour of porous TiO2-coated implants.

It is known that the "race for the surface" determining the in vivo response is strictly connected to the physico-chemical properties of the material, especially at its surface. Accordingly, the study of surface roughness, charge and wettability is fundamental to predict the bio-response to the implant. In this work, streaming potential was chosen as a reliable method to quantify the solid surface charge of hydrothermally treated (HT) TiO2-anatase nano-crystalline coatings, grown on titanium substrates. The influence of metal and ionic conductance on the zeta potential values was taken into account, allowing for the correlation of the surface charge with the coating porosity, the semiconductor character of the TiO2 nano-crystals and the metallic nature of the bulk titanium.

Solution blow co-spinning of cellulose acetate with poly(ethylene oxide). Structure, morphology, and properties of nanofibers.

Cellulose acetate (CA) nanofibers are prepared using solution blow co-spinning (SBS) with poly(ethylene oxide) (PEO). The pure CA membranes are obtained by washing water-soluble PEO from the fibrous CA-PEO blend. Nanofibrous membranes are characterized using optical and scanning electron microscopy (SEM), differential scanning calorimetry (DSC), infrared spectroscopy (ATR-FTIR), and surface zeta potential measurements. Thermal transitions from DSC and ATR-FTIR spectra analysis were used to confirm the removal of the PEO. Although the characteristic signals of PEO are not observed by FTIR, an additional thermal step transition in CA nanofibers indicates the embedding of a small amount of PEO (up to 6 wt%). SEM analysis shows that CA-PEO blends are constituted by fibers with mean diameters from 671 to 857 nm (depending on the SBS parameters), while after PEO removal, diameters range from 567 to 605 nm. We propose a new method for staining CA-PEO membranes with iodine solution in absolute ethanol that allows the differentiation of CA and PEO components with an optical microscope. The microscopy results suggest that PEO assists in the spinning by enveloping CA nanofibers, allowing uninterrupted processing. The successful deacetylation to cellulose using an aqueous KOH solution is confirmed with zeta potential measurements and ATR-FTIR.

Proteins at polysaccharide-based biointerfaces: A comparative study of QCM-D and electrokinetic measurements.

Controlling protein adsorption on biomaterial surfaces requires a thorough understanding of interfacial phenomena. Proteins adhering after implantation influence successful biointegration. Deciphering adsorption mechanisms at biointerfaces is crucial and of high interest. Here, a combination of time-resolved in situ electrokinetic measurements and quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to understand the adsorption phenomena of blood proteins at thin layers of polysaccharide-based biointerfaces. Adsorption kinetics of bovine serum albumin (BSA), fibrinogen (Fg), and γ-globulin (γG) was studied on polydimethylsiloxane (PDMS) coatings functionalised with chitosan-surfactant complex and hyaluronic acid. The functionalised surfaces show a suppressed protein affinity compared to hydrophobic PDMS. Fg exhibits peculiar adsorption behaviour on PDMS, stemming from the highly oriented end-on adsorption with freely moving α chains. BSA demonstrates arbitrary surface orientation, while γG shows preferential surface orientation on PDMS, exposing a higher density of cationic moieties. The combination of the mentioned techniques proved beneficial for the investigation of interactions, orientations, and changes at biointerfaces in real-time. The approach is versatile and promising where research on surfaces and interfaces is in high demand.

In Vitro Bioelectrochemical Properties of Second-Generation Oxide Nanotubes on Ti-13Zr-13Nb Biomedical Alloy.

Surface charge and in vitro corrosion resistance are some of the key parameters characterizing biomaterials in the interaction of the implant with the biological environment. Hence, this work investigates the in vitro bioelectrochemical behavior of newly developed oxide nanotubes (ONTs) layers of second-generation (2G) on a Ti-13Zr-13Nb alloy. The 2G ONTs were produced by anodization in 1 M (NH4)2SO4 solution with 2 wt.% of NH4F. The physical and chemical properties of the obtained bamboo-inspired 2G ONTs were characterized using scanning electron microscopy with field emission and energy dispersive spectroscopy. Zeta potential measurements for the examined materials were carried out using an electrokinetic analyzer in aqueous electrolytes of potassium chloride, phosphate-buffered saline and artificial blood. It was found that the electrolyte type and the ionic strength affect the bioelectrochemical properties of 2G ONTs layers. Open circuit potential and anodic polarization curve results proved the influence of anodizing on the improvement of in vitro corrosion resistance of the Ti-13Zr-13Nb alloy in PBS solution. The anodizing conditions used can be proposed for the production of long-term implants, which are not susceptible to pitting corrosion up to 9.4 V.

Active Cellulose Acetate/Chitosan Composite Films Prepared Using Solution Blow Spinning: Structure and Electrokinetic Properties.

Cellulose acetate (CA), a very promising derivative of cellulose, has come into the focus of research due to its highly desired good film-forming ability for food packaging applications. Frequently, this derivative is used in combination with other compounds (polymers, nanoparticles) in order to obtain active materials. Here, we report the preparation of thin films made of cellulose acetate loaded with chitosan (CS) using the solution blow spinning (SBS) method. Films are prepared by SBS processing of the polymers mixture solution, considering the following variables: (i) the concentration of cellulose acetate and chitosan in the solution and (ii) the solvent system consisting of acetic or formic acid. The prepared materials are characterized in terms of physical properties, roughness (optical profilometer), porosity, wettability (contact angle measurements), chemical structure (Fourier transform infrared spectrometry), and electrokinetic properties (zeta potential). SBS enables the preparation of CA/CS films with high water vapor permeability, high porosity, and also higher water contact angle compared with pure CA films. The electrokinetic properties of composites are influenced by the inclusion of chitosan, which causes a shift of the isoelectric point (IEP) towards higher pH values, but the magnitude of the shift is not in correlation with chitosan concentration. Adsorption kinetic studies using bovine serum albumin (BSA) as a model protein reveal that chitosan modified cellulose acetate films manifest low affinity towards proteins that suggests prevention of biofilm formation on its surface.

Chromium (III) and chromium (VI) removal and organic matter interaction with nanofiltration.

Chromium (Cr) is a toxic inorganic contaminant for drinking water, in which the concentration has to be controlled for human health and safety. Cr retention was investigated with stirred cell experiments using sulphonated polyethersulfone nanofiltration (NF) membranes of different molecular weight cut-off (MWCO). Cr(III) and Cr(VI) retention follow the order of the MWCO of the studied NF membranes; HY70-720 Da > HY50-1000 Da > HY10-3000 Da with a pH dependency, especially for Cr(III). The importance of the charge exclusion was highlighted when Cr(OH)4- (for Cr(III)) and CrO42- (for Cr(VI)) was the predominant species in the feed solution. In presence of organic matter, namely humic acid (HA), Cr(III) retention increased by 60 %, while no influence of HA was observed for Cr(VI). HA did not induce major modifications on the membrane surface charge for these membranes. Solute-solute interaction, in particular Cr(III)-HA complexation, was the responsible mechanism for the increase in Cr(III) retention. This was confirmed by asymmetric flow field-flow fractionation, coupled with inductively coupled plasma mass spectrometry (FFFF-ICP-MS) analysis. Cr(III)-HA complexation was significant at HA concentrations as low as 1 mgC/L. The chosen NF membranes were able to achieve the EU guideline (25 µg/L) for Cr in drinking water for a feed concentration of 250 µg/L.

Assessment of the Capability of Magnetic Nanoparticles to Recover Neodymium Ions from Aqueous Solution.

Magnetic nanoparticles (MNPs) have received increasing attention for various applications due to their fast synthesis, versatile functionalization, and recyclability by the application of a magnetic field. The high surface-to-volume ratio of MNP dispersions has suggested their use as an adsorbent for the removal of heavy metal ions. We investigated the applicability of MNPs composed of a maghemite core surrounded by a silica shell functionalized with aminopropylsilane, γ-Fe2O3-NH4OH@SiO2(APTMS), for the removal of neodymium ions (Nd3+) from aqueous solution. The MNPs were characterized for their size, composition, surface functionality and charge. Despite of the promising properties of MNPs, their removal from the aqueous dispersion with an external magnet was not sufficient to reliably quantify the adsorption of Nd3+ by UV-Vis spectroscopy.

Catching Speedy Gonzales: Driving forces for Protein Film Formation on Silicone Rubber Tubing During Pumping.

Interfacial adsorption is a major concern in the processing of biopharmaceutics as it not only leads to a loss of protein, but also to particle formation. Protein particle formation during peristaltic pumping is linked to interfacial adsorption to the tubing and subsequent tearing of the formed protein film. In the current study, driving forces and rate of the adsorption of a monoclonal antibody to the silicone rubber surface during pumping, as well as particle formation, were studied in different formulations. Particle concentration and size distribution were influenced by the formulation parameters; specifically high ionic strength led to more particles and the build-up of particles larger than 25 µm. Formulation pH and ionic strength had an effect on the total amount of adsorbed protein. Adsorbed protein amounts increased when the Debye length of the protein was decreased, leading to a higher packing density. Atomic force microscopy and streaming potential determination revealed that the irreversible protein film formation on the hydrophobic tubing surface occurs in less than a second. Electrostatic interactions are the dominating factor for the initial adsorption speed. In intimate contact to the silicone rubber surface, hydrophobic interactions govern the protein adsorption. PS20 quickly coats the tubing surface which leads to an increase in hydrophilicity and shielding of electrostatic interactions, thereby efficiently inhibiting protein adsorption. Overall, atomic force microscopy and streaming potential determination possess great potential for the characterization of adsorbed protein films and the adsorption kinetic evaluation in high-speed mode. Protein adsorption to silicone tubing is driven by a combination of electrostatic and hydrophobic interactions which is effectively shielded by PS20.

Effective Removal of Acid Dye in Synthetic and Silk Dyeing Effluent: Isotherm and Kinetic Studies.

Here, we propose a low-cost, sustainable, and viable adsorbent (pine tree-derived biochar) to remove acid dyes such as acid violet 17 (AV), which is used in the silk dyeing industry. As a case study, the AV removal process was demonstrated using synthetic effluent and further as a proof of concept using real dye effluent produced from the Sirumugai textile unit in India. The pine tree-derived biochar was selected for removal of aqueous AV dye in batch and fixed-bed column studies. The adsorbent material was characterized for crystallinity (XRD), surface area (BET), surface morphology and elemental compositions (SEM-EDX), thermal stability (TGA), weight loss (DGA), and functional groups (FTIR). Batch sorption studies were performed to evaluate (i) adsorption at various pH values (at pH 2 to 7), (ii) isotherms (at 10, 25, and 35 °C) to assess the temperature effect on the sorption efficiency, and (iii) kinetics to reveal the effect of time, adsorbent dose, and initial concentration on the reaction rate. After systematic evaluation, 2 g/L biochar, 25 mg/L AV, pH 3, 40 °C, and 40 and 360 min in a completely mixed batch study resulted in 50 and 90% dye removal, respectively. The isoelectric point at pH 3.7 ± 0.2 results in maximum dye removal, therefore suggesting that monitoring the ratio of different effluent (acid/wash/dye) can improve the colorant removal efficiency. The Langmuir isotherm best fits with the sorption of AV to biochar, provided a maximal dye uptake of 29 mg/g at 40 °C, showing that adsorption was endothermic. Fixed-bed studies were conducted at room temperature with an initial dye concentration of 25 and 50 mg/L. The glass columns were packed with biochar (bed depth 20 cm, pore volume = 14 mL) at an initial pH of 5.0 and a 10 mL/min flow rate for 120 min. Finally, the regeneration of the adsorbent was achieved using desorption studies conducted under the proposed experimental conditions resulted in 90-93% removal of AV even after five cycles of regeneration.

Insight into the Surface Properties of Wood Fiber-Polymer Composites.

The surface properties of wood fiber (WF) filled polymer composites depend on the filler loading and are closely related to the distribution and orientation in the polymer matrix. In this study, wood fibers (WF) were incorporated into thermoplastic composites based on non-recycled polypropylene (PP) and recycled (R-PP) composites by melt compounding and injection moulding. ATR-FTIR (attenuated total reflection Fourier transform infrared spectroscopy) measurements clearly showed the propagation of WF functional groups at the surface layer of WF-PP/WF-R-PP composites preferentially with WF loading up to 30%. Optical microscopy and nanoindentation method confirmed the alignment of thinner skin layer of WF-PP/WF-R-PP composites with increasing WF addition. The thickness of the skin layer was mainly influenced by the WF loading. The effect of the addition of WF on modulus and hardness, at least at 30 and 40 wt.%, varies for PP and R-PP matrix. On the other hand, surface zeta potential measurements show increased hydrophilicity with increasing amounts of WF. Moreover, WF in PP/R-PP matrix is also responsible for the antioxidant properties of these composites as measured by DPPH (2,2'-diphenyl-1-picrylhydrazyl) assay.

Polysaccharide-Based Bilayer Coatings for Biofilm-Inhibiting Surfaces of Medical Devices.

Chitosan (Chi) and 77KS, a lysine-derived surfactant, form polyelectrolyte complexes that reverse their charge from positive to negative at higher 77KS concentrations, forming aggregates that have been embedded with amoxicillin (AMOX). Dispersion of this complex was used to coat polydimethylsiloxane (PDMS) films, with an additional layer of anionic and hydrophilic hyaluronic acid (HA) as an outer adsorbate layer to enhance protein repulsion in addition to antimicrobial activity by forming a highly hydrated layer in combination with steric hindrance. The formed polysaccharide-based bilayer on PDMS was analyzed by water contact angle measurements, X-ray photoelectron spectroscopy (XPS), and surface zeta (ζ)-potential. All measurements show the existence and adhesion of the two layers on the PDMS surface. Part of this study was devoted to understanding the underlying protein adsorption phenomena and identifying the mechanisms associated with biofouling. Thus, the adsorption of a mixed-protein solution (bovine serum albumin, fibrinogen, γ-globulin) on PDMS surfaces was studied to test the antifouling properties. The adsorption experiments were performed using a quartz crystal microbalance with dissipation monitoring (QCM-D) and showed improved antifouling properties by these polysaccharide-based bilayer coatings compared to a reference or for only one layer, i.e., the complex. This proves the benefit of a second hyaluronic acid layer. Microbiological and biocompatibility tests were also performed on real samples, i.e., silicone discs, showing the perspective of the prepared bilayer coating for medical devices such as prostheses, catheters (balloon angioplasty, intravascular), delivery systems (sheaths, implants), and stents.

Interpretation of electrokinetic measurements with porous films: role of electric conductance and streaming current within porous structure.

It is shown that in tangential electrokinetic measurements with porous films the porous structure makes contribution not only to the cell electric conductance (as demonstrated previously) but also to the observed streaming current. Both of these contributions give rise to dependences of streaming-potential and streaming-current coefficients on the channel height. However, due to the combined contribution of two phenomena, the dependence of streaming-potential coefficient on the channel height may be rather complicated and not allow for simple extrapolation. At the same time, the dependences of streaming-current coefficient and cell electric conductance on the channel height turn out linear and can be easily extrapolated to zero channel heights. This enables one to determine separately the contributions of external surface of porous film and of its porous structure to the streaming current and of the channel and porous structure to the cell electric conductance. This procedure is illustrated by the measurements of tangential electrokinetic phenomena and electric conductance with Millipore mixed-cellulose membrane filters of various average pore sizes (from 0.025 to 5 mum) in the so-called adjustable-gap cell of SurPASS electrokinetic instrument (Anton Paar GmbH). The design of this cell allows for easy and quasi-continuous variation of channel height as well as accurate determination of cell electric conductance, streaming-current coefficient, and channel height (from the cell hydraulic permeability). The quality of linear fits of experimental data has been found to be very good, and thus, the extrapolation procedures were quite reliable and accurate. Zeta-potentials could be determined of both external film and internal pore surfaces. It is demonstrated that the porous structures make considerable contributions to both streaming-current coefficient and cell electric conductance especially in the case of filters with larger pores. It is also found that, rather surprisingly, in filters with smaller pores the reduction in the filter electric conductivity turns out essentially stronger than could be expected proceeding from the filter porosity.

Zeta potential determination of polymeric materials using two differently designed measuring cells of an electrokinetic analyzer.

The so-called zeta potential can be determined through electrokinetic measurements and indicates the status regarding surface charges along the interface between solids and liquids. Surface charge gives us information about the condition, quality, and characteristics of a macroscopic surface in the polar medium. In our study the zeta potential was determined using a "SurPASS" electrokinetic analyzer based on the streaming current and streaming potential measurements. The aim of the research was to compare the results of two differently designed measuring cells ("Adjustable Gap Cell" and "Clamping Cell") but operating on the same principle. In order to investigate this problem, the zeta potential was determined for the three polymeric materials: poly(ethylene terephthalate) foil, thin-film polyamide composite membranes for nanofiltration and reverse osmosis. The results obtained with "Clamping Cell" versus "Adjustable Gap Cell" showed differences in zeta potential, where the "Adjustable Gap Cell" gave more reproducible results. One reason for this behaviour could be the different geometries of the streaming channels. A more likely reason is the design of the "Clamping Cell", that requires a sample size larger than necessary for zeta potential determination.

Applicability of electro-osmotic flow for the analysis of the surface zeta potential.

The analysis of the surface zeta potential (SZP) opens up new possibilities in the characterization of various materials used for scientific or industrial applications. It provides at the same time insight into the material surface chemistry and elucidates the interactions with charged species in the aqueous test solution. For this purpose, an accurate, reliable and repeatable analysis of the SZP is the key factor. This work focuses on a detailed and systematic comparison of two electrokinetic techniques, i.e. the mapping of the electro-osmotic flow (EOF) and the measurement of the streaming potential (SP), for the surface zeta potential (SZP) determination of several materials with varying properties. Both techniques have advantages as well as drawbacks. The applicability of latex polymer material and inorganic tracer particles at varying ionic strength, the interaction between oppositely charged tracer particles and solid surfaces, the assessment of the pH dependence of the SZP and the isoelectric point (IEP), and the effects of sample porosity and conductance have been investigated. Although in some cases the EOF method gives a SZP similar to the streaming potential measurement, especially when the tracer particle exhibits the same charge as the solid surface, it was revealed that reliable results were only obtained with the streaming potential and streaming current method. Several obstacles such as elevated conductivity at higher ionic strength, the applied voltage for the EM measurement, and the nature of tracer particles lower the accuracy and reliability of the SZP determined by the EOF method. It was shown that the EOF method is not applicable to oppositely charged surface and tracer particles and also limited to low salinity conditions especially when using polymeric tracer particles. Although the EOF method does not require the formation of a capillary flow channel, it disables a non-destructive SZP of fragile or valuable samples, such as QCM-D sensors, in comparison to the SP approach.

Nanocellulose production from recycled paper mill sludge using ozonation pretreatment followed by recyclable maleic acid hydrolysis.

Nanocellulose (NC) have garnered much interest worldwide due to its physical and chemical properties. Nanocellulose is produced from biomass materials by bleaching pretreatment, followed by acid hydrolysis. This work demonstrated the production of NC from recycled paper sludge (RPS), a crystalline cellulose rich waste, by ozonation pretreatment, followed by maleic acid hydrolysis. Ozonation resulted in removal of lignin (as evident by TGA analysis), negative zeta potential of RPS and enhanced NC production, from 60 mg/L to over 80 mg/L after 60-120 min of ozone treatment. Maleic acid was successfully recovered, although longer ozonation times reduced the amount of acid available for recovery. These results demonstrate that ozonation can be used as an effective pretreatment for NC production.

Effect of Chitin Nanofibrils on Biocompatibility and Bioactivity of the Chitosan-Based Composite Film Matrix Intended for Tissue Engineering.

This paper discusses the mechanical and physicochemical properties of film matrices based on chitosan, as well as the possibility of optimizing these properties by adding chitin nanofibrils. It is shown that with the introduction of chitin nanofibrils as a filler, the mechanical stability of the composite materials increases. By varying the concentration of chitin nanofibrils, it is possible to obtain a spectrum of samples with different bioactive properties for the growth of human dermal fibroblasts. Film matrices based on the nanocomposite of chitosan and 5 wt % chitin nanofibrils have an optimal balance of mechanical and physicochemical properties and bioactivity in relation to the culture of human dermal fibroblasts.

Chitosan/glycosaminoglycan scaffolds for skin reparation.

Burns and chronic wounds, often related to chronic diseases (as diabetes and cancer), are challenging lesions, difficult to heal. The prompt and full reconstitution of a functional skin is at the basis of the development of biopolymer-based scaffolds, representing a 3D substrate mimicking the dermal extracellular matrix. Aim of the work was to develop scaffolds intended for skin regeneration, according to: fabrication by electrospinning from aqueous polysaccharide solutions; prompt and easy treatment to obtain scaffolds insoluble in aqueous fluids; best performance in supporting wound healing. Three formulations were tested, based on chitosan (CH) and pullulan (P), associated with glycosaminoglycans (chondroitin sulfate - CS or hyaluronic acid - HA). A multidisciplinary approach has been used: chemico-physical characterization and preclinical evaluation allowed to obtain integrated information. This supports that CS gives distinctive properties and optimal features to the scaffold structure for promoting cell proliferation leading tissue reparation towards a complete skin restore.

Modification of ceramic microfilters with colloidal zirconia to promote the adsorption of viruses from water.

The purpose of this study was to test the feasibility of modifying commercial microporous ceramic bacteria filters to promote adsorption of viruses. The internal surface of the filter medium was coated with ZrO(2) nanopowder via dip-coating and heat-treatment in order to impart a filter surface charge opposite to that of the target viruses. Streaming potential measurements revealed a shift in the isoelectric point from pH <3 to between pH 5.5 and 9, respectively. While the base filter elements generally exhibited only 75% retention with respect to MS2 bacteriophages, the modified elements achieved a 7log removal (99.99999%) of these virus-like particles. The coating process also increased the specific surface area of the filters from approximately 2m(2)/g to between 12.5 and 25.5m(2)/g, thereby also potentially increasing their adsorption capacity. The results demonstrate that, given more development effort, the chosen manufacturing process has the potential to yield effective virus filters with throughputs superior to those of current virus filtration techniques.

Investigating the time-dependent zeta potential of wood surfaces.

This work reports on streaming potential measurements through natural capillaries in wood and investigates the cause of a time-dependent zeta potential measured during the equilibration of wood cell-walls with an electrolyte solution. For the biomaterial, this equilibration phase takes several hours, which is much longer than for many other materials that have been characterized by electrokinetic measurements. During this equilibration phase the zeta potential magnitude is decaying due to two parallel mechanisms: (i) the swelling of the cell-wall which causes a dimensional change reducing the charge density at the capillary interface; (ii) the transport of ions from the electrolyte solution into the permeable cell-wall which alters the electrical potential at the interface by internal charge compensation. The obtained results demonstrate the importance of equilibration kinetics for an accurate determination of the zeta potential, especially for materials that interact strongly with the measurement electrolyte. Moreover, the change in zeta potential with time can be correlated with the bulk swelling of wood if the effect of electrolyte ion diffusion is excluded. This study shows the potential of streaming potential measurements of wood, and possibly of other hygroscopic and nanoporous materials, to reveal kinetic information about their interaction with liquids, such as swelling and ion uptake.