Hybrid Materials Obtained by Immobilization of Biosynthesized Ag Nanoparticles with Antioxidant and Antimicrobial Activity.

Ag nanoparticles (AgNPs) were biosynthesized using sage (Salvia officinalis L.) extract. The obtained nanoparticles were supported on SBA-15 mesoporous silica (S), before and after immobilization of 10% TiO2 (Degussa-P25, STp; commercial rutile, STr; and silica synthesized from Ti butoxide, STb). The formation of AgNPs was confirmed by X-ray diffraction. The plasmon resonance effect, evidenced by UV-Vis spectra, was preserved after immobilization only for the sample supported on STb. The immobilization and dispersion properties of AgNPs on supports were evidenced by TEM microscopy, energy-dispersive X-rays, dynamic light scattering, photoluminescence and FT-IR spectroscopy. The antioxidant activity of the supported samples significantly exceeded that of the sage extract or AgNPs. Antimicrobial tests were carried out, in conditions of darkness and white light, on Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli and Candida albicans. Higher antimicrobial activity was evident for SAg and STbAg samples. White light increased antibacterial activity in the case of Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa). In the first case, antibacterial activity increased for both supported and unsupported AgNPs, while in the second one, the activity increased only for SAg and STbAg samples. The proposed antibacterial mechanism shows the effect of AgNPs and Ag+ ions on bacteria in dark and light conditions.

Green Approach for Synthesis of Silver Nanoparticles with Antimicrobial and Antioxidant Properties from Grapevine Waste Extracts.

The present work aims to study the possibilities of developing silver nanoparticles using natural extracts of grape pomace wastes originating from the native variety of Feteasca Neagra 6 Șt. This study focused on investigating the influence of grape pomace extract obtained by two different extraction methods (classical temperature extraction and microwave-assisted extraction) in the phytosynthesis process of metal nanoparticles. The total phenolic content of the extracts was assessed using the spectrophotometric method with the Folin-Ciocâlteu reagent, while the identification and quantification of specific components were conducted through high-performance liquid chromatography with a diode array detector (HPLC-DAD). The obtained nanoparticles were characterized by UV-Vis absorption spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM), along with assessing their antioxidant and antimicrobial properties against Gram-positive bacteria. The data collected from the experiments indicated that the nanoparticles were formed in a relatively short period of time (96 h) and, for the experimental variant involving the use of a 1:1 ratio (v/v, grape pomace extract: silver nitrate) for the nanoparticle phytosynthesis, the smallest crystallite sizes (from X-ray diffraction-4.58 nm and 5.14 nm) as well as spherical or semispherical nanoparticles with the lowest average diameters were obtained (19.99-23 nm, from TEM analysis). The phytosynthesis process was shown to enhance the antioxidant properties (determined using the DPPH assay) and the antimicrobial potential (tested against Gram-positive strains) of the nanoparticles, as evidenced by comparing their properties with those of the parent extracts; at the same time, the nanoparticles exhibited a selectivity in action, being active against the Staphylococcus aureus strain while presenting no antimicrobial potential against the Enterococcus faecalis strain.

In Vivo Assessment of Hepatic and Kidney Toxicity Induced by Silicon Quantum Dots in Mice.

In the last decade, silicon-based quantum dots (SiQDs) have attracted the attention of researchers due to their unique properties for which they are used in medical applications and in vivo imaging. Detection of cytotoxic effects in vivo is essential for understanding the mechanisms of toxicity, a mandatory step before their administration to human subjects. In this context, we aimed to evaluate the in vivo hepatic and renal acute toxicity of SiQDs obtained by laser ablation. The nanoparticles were administrated at different doses (0, 1, 10, and 100 mg of QDs/kg of body weight) by intravenous injection into the caudal vein of Swiss mice. After 1, 6, 24, and 72 h, the animals were euthanatized, and liver and kidney tissues were used in further toxicity tests. The time- and dose-dependent effects of SiQDs on the antioxidant defense system of mice liver and kidney were investigated by quantifying the activity of antioxidant enzymes (catalase, superoxide dismutase, glutathione peroxidase, glutathione reductase, and glutathione S-transferase) in correlation with the morphological changes and inflammatory status in the liver and kidneys. The results showed a decrease in the activities of antioxidant enzymes and histopathological changes, except for superoxide dismutase, in which no significant changes were registered compared with the control. Furthermore, the immunohistochemical expression of TNF-α was significant at doses over 10 mg of QDs/kg of body weight and were still evident at 72 h after administration. Our results showed that doses under 10 mg of SiQDs/kg of b.w. did not induce hepatic and renal toxicity, providing useful information for further clinical trials.

Bioactive-Loaded Hydrogels Based on Bacterial Nanocellulose, Chitosan, and Poloxamer for Rebalancing Vaginal Microbiota.

Biocompatible drug-delivery systems for soft tissue applications are of high interest for the medical and pharmaceutical fields. The subject of this research is the development of hydrogels loaded with bioactive compounds (inulin, thyme essential oil, hydro-glycero-alcoholic extract of Vitis vinifera, Opuntia ficus-indica powder, lactic acid, citric acid) in order to support the vaginal microbiota homeostasis. The nanofibrillar phyto-hydrogel systems developed using the biocompatible polymers chitosan (CS), never-dried bacterial nanocellulose (NDBNC), and Poloxamer 407 (PX) incorporated the water-soluble bioactive components in the NDBNC hydrophilic fraction and the hydrophobic components in the hydrophobic core of the PX fraction. Two NDBNC-PX hydrogels and one NDBNC-PX-CS hydrogel were structurally and physical-chemically characterized using Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), and rheology. The hydrogels were also evaluated in terms of thermo-responsive properties, mucoadhesion, biocompatibility, and prebiotic and antimicrobial effects. The mucin binding efficiency of hydrogel base systems was determined by the periodic acid/Schiff base (PAS) assay. Biocompatibility of hydrogel systems was determined by the MTT test using mouse fibroblasts. The prebiotic activity was determined using the probiotic strains Limosilactobacillus reuteri and Lactiplantibacillus plantarum subsp. plantarum. Antimicrobial activity was also assessed using relevant microbial strains, respectively, E. coli and C. albicans. TEM evidenced PX micelles of around 20 nm on NDBNC nanofibrils. The FTIR and XRD analyses revealed that the binary hydrogels are dominated by PX signals, and that the ternary hydrogel is dominated by CS, with additional particular fingerprints for the biocompounds and the hydrogel interaction with mucin. Rheology evidenced the gel transition temperatures of 18-22 °C for the binary hydrogels with thixotropic behavior and, respectively, no gel transition, with rheopectic behavior for the ternary hydrogel. The adhesion energies of the binary and ternary hydrogels were evaluated to be around 1.2 J/m2 and 9.1 J/m2, respectively. The hydrogels exhibited a high degree of biocompatibility, with the potential to support cell proliferation and also to promote the growth of lactobacilli. The hydrogel systems also presented significant antimicrobial and antibiofilm activity.

Extraction of Cellulose from Ulva lactuca Algae and Its Use for Membrane Synthesis.

Green algae are a sustainable source of biopolymers for the global demand due to their high photosynthetic efficiency. This article describes the extraction of cellulose from plant systems represented by Ulva lactuca species. In order to extract various substances, algae were finely ground with the help of solvents (liquid media). This was carried out to achieve the necessary conditions that help reduce the resistance this phase shows in regard to the transport and transfer of the species being extracted. The highest yield of extracted cellulose (20,944%) was obtained for the following factors: S/L = 1/20; conc. ethanol = 90%, conc. salts = 4 g/L. Hydrogel membranes are a unique class of macromolecular networks that contain a large fraction of aqueous solvent within their structure. With the cellulose extracted from algae, we obtained membranes which underwent the process of swelling in liquid media (ethyl alcohol) of different concentrations. The swelling of biocellulose membranes in alcoholic solutions of high concentrations was investigated. It was observed that the process of absorption of the alcoholic solution by the membrane occurred rapidly in the first part. After stabilization, the membranes continued to absorb at a slower rate until stabilization or saturation concentration was reached.

Peelable Alginate Films Reinforced by Carbon Nanofibers Decorated with Antimicrobial Nanoparticles for Immediate Biological Decontamination of Surfaces.

This study presents the synthesis and characterization of alginate-based nanocomposite peelable films, reinforced by carbon nanofibers (CNFs) decorated with nanoparticles that possess remarkable antimicrobial properties. These materials are suitable for immediate decontamination applications, being designed as fluid formulations that can be applied on contaminated surfaces, and subsequently, they can rapidly form a peelable film via divalent ion crosslinking and can be easily peeled and disposed of. Silver, copper, and zinc oxide nanoparticles (NPs) were synthesized using superficial oxidized carbon nanofibers (CNF-ox) as support. To obtain the decontaminating formulations, sodium alginate (ALG) was further incorporated into the colloidal solutions containing the antimicrobial nanoparticles. The properties of the initial CNF-ox-NP-ALG solutions and the resulting peelable nanocomposite hydrogels (obtained by crosslinking with zinc acetate) were assessed by rheological measurements, and mechanical investigations, respectively. The evaluation of Minimal Inhibitory Concentration (MIC) and Minimal Bactericidal Concentration (MBC) for the synthesized nanoparticles (silver, copper, and zinc oxide) was performed. The best values for MIC and MBC were obtained for CNF-ox decorated with AgNPs for both types of bacterial strains: Gram-negative (MIC and MBC values (mg/L): E. coli-3 and 108; P. aeruginosa-3 and 54) and Gram-positive (MIC and MBC values (mg/L): S. aureus-13 and 27). The film-forming decontaminating formulations were also subjected to a microbiology assay consisting of the time-kill test, MIC and MBC estimations, and evaluation of the efficacity of peelable coatings in removing the biological agents from the contaminated surfaces. The best decontamination efficiencies against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa varied between 97.40% and 99.95% when employing silver-decorated CNF-ox in the decontaminating formulations. These results reveal an enhanced antimicrobial activity brought about by the synergistic effect of silver and CNF-ox, coupled with an efficient incorporation of the contaminants inside the peelable films.

Selenium-Fortified Kombucha-Pollen Beverage by In Situ Biosynthesized Selenium Nanoparticles with High Biocompatibility and Antioxidant Activity.

Biogenic selenium nanoparticles (SeNPs) have been shown to exhibit increased bioavailability. Fermentation of pollen by a symbiotic culture of bacteria and yeasts (SCOBY/Kombucha) leads to the release of pollen content and enhances the prebiotic and probiotic effects of Kombucha. The aim of this study was to fortify Kombucha beverage with SeNPs formed in situ by Kombucha fermentation with pollen. Response Surface Methodology (RSM) was used to optimize the biosynthesis of SeNPs and the pollen-fermented Kombucha beverage. SeNPs were characterized by Transmission electron microscopy energy-dispersive X-ray spectroscopy (TEM-EDX), Fourier-transform infrared spectroscopy (FTIR), Dynamic light scattering (DLS), and Zeta potential. The pollen-fermented Kombucha beverage enriched with SeNPs was characterized by measuring the total phenolic content, antioxidant activity, soluble silicon, saccharides, lactic acid, and the total content of Se0. The polyphenols were identified by liquid chromatography-mass spectrometry (LC-MS). The pollen and the bacterial (nano)cellulose were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX), FTIR, and X-Ray diffraction (XRD). We also assessed the in vitro biocompatibility in terms of gingival fibroblast viability and proliferation, as well as the antioxidant activity of SeNPs and the pollen-fermented Kombucha beverage enriched with SeNPs. The results highlight their increased biological performance in this regard.

Trametes versicolor laccase activity modulated by the interaction with gold nanoparticles.

In this study, the impact of gold nanoparticles (AuNPs) on the structure and activity of laccase from Trametes versicolor (Lc) was described. Fluorescence experiments revealed that AuNPs efficiently quench Lc's tryptophan fluorescence by a static and dynamic process. By using differential scanning microcalorimetry and circular dichroism spectroscopy, it was determined how the concentration of nanoparticles and the composition of the medium affected the secondary structure of Lc. The data revealed that upon binding with AuNPs, conformational changes take place mainly in presence of high amounts of nanoparticles. The complex kinetic analysis unveiled the Lc activity enhancement at low concentrations of AuNPs as opposed to the concentrated regime, where it can be reduced by up to 55%. The Michaelis-Menten tests highlighted that the activity of the biocatalyst is closely related to the concentration of AuNPs, while the Selwyn analysis demonstrated that even in a concentrated regime of Lc it is not deactivated regardless of the amount of AuNPs added. The thermal parameters improved by twofold in the presence of low AuNPs concentration, whereas the activation energy increased with AuNPs content, implying that not all collisions are beneficial to the enzyme structure. The effect of AuNPs on the decomposition of a recalcitrant dye (naphthol green B, NG) by Lc was also evaluated, and the Michaelis-Menten model revealed that only the high AuNPs content influenced negatively the Lc activity. The isothermal titration calorimetry revealed that hydrogen bonds are the main intermolecular forces between Lc and AuNPs, while electrostatic interactions are responsible for NG adsorption to AuNPs. The results of the docking analysis show the binding of NG near the copper T1 site of Lc with hydrogen bonds, electrostatic and hydrophobic interactions. The findings of this work provide important knowledge for laccase-based bio-nanoconjugates and their use in the field of environmental remediation.

Nanocomposite Hydrogel Films Based on Sequential Interpenetrating Polymeric Networks as Drug Delivery Platforms.

In this study, novel materials have been obtained via a dual covalent and ionic crosslinking strategies, leading to the formation of a fully interpenetrated polymeric network with remarkable mechanical performances as drug delivery platforms for dermal patches. The polymeric network was obtained by the free-radical photopolymerization of N-vinylpyrrolidone using tri(ethylene glycol) divinyl ether as crosslinker in the presence of sodium alginate (1%, weight%). The ionic crosslinking was achieved by the addition of Zn2+, ions which were coordinated by the alginate chains. Bentonite nanoclay was incorporated in hydrogel formulations to capitalize on its mechanical reinforcement and adsorptive capacity. TiO2 and ZnO nanoparticles were also included in two of the samples to evaluate their influence on the morphology, mechanical properties and/or the antimicrobial activity of the hydrogels. The double-crosslinked nanocomposite hydrogels presented a good tensile resistance (1.5 MPa at 70% strain) and compression resistance (12.5 MPa at a strain of 70%). Nafcillin was loaded into nanocomposite hydrogel films with a loading efficiency of up to 30%. The drug release characteristics were evaluated, and the profile was fitted by mathematical models that describe the physical processes taking place during the drug transfer from the polymer to a PBS (phosphate-buffered saline) solution. Depending on the design of the polymeric network and the nanofillers included, it was demonstrated that the nafcillin loaded into the nanocomposite hydrogel films ensured a high to moderate activity against S. aureus and S. pyogenes and no activity against E. coli. Furthermore, it was demonstrated that the presence of zinc ions in these polymeric matrices can be correlated with the inactivation of E. coli.

Nafcillin-Loaded Photocrosslinkable Nanocomposite Hydrogels for Biomedical Applications.

Skin infections are frequently treated via intravenous or oral administration of antibiotics, which can lead to serious adverse effects and may sometimes contribute to the proliferation of resistant bacterial strains. Skin represents a convenient pathway for delivering therapeutic compounds, ensured by the high number of blood vessels and amount of lymphatic fluids in the cutaneous tissues, which are systematically connected to the rest of the body. This study provides a novel, straightforward method to obtain nafcillin-loaded photocrosslinkable nanocomposite hydrogels and demonstrates their performance as drug carriers and antimicrobial efficacy against Gram-positive bacteria. The novel formulations obtained, based on polyvinylpyrrolidone, tri(ethylene glycol) divinyl ether crosslinker, hydrophilic bentonite nanoclay, and/or two types of photoactive (TiO2 and ZnO) nanofillers, were characterized using various analytical methods (transmission electron microscopy (TEM), scanning electron microscopy-energy-dispersive X-ray analysis (SEM-EDX), mechanical tests (tension, compression, and shear), ultraviolet-visible spectroscopy (UV-Vis), swelling investigations, and via specific microbiological assays ("agar disc diffusion method" and "time-kill test"). The results reveal that the nanocomposite hydrogel possessed high mechanical resistance, good swelling abilities, and good antimicrobial activity, demonstrating a decrease in the bacteria growth between 3log10 and 2log10 after one hour of direct contact with S. aureus.

Microbial Polysaccharide-Based Formulation with Silica Nanoparticles; A New Hydrogel Nanocomposite for 3D Printing.

Natural polysaccharides are highly attractive biopolymers recommended for medical applications due to their low cytotoxicity and hydrophilicity. Polysaccharides and their derivatives are also suitable for additive manufacturing, a process in which various customized geometries of 3D structures/scaffolds can be achieved. Polysaccharide-based hydrogel materials are widely used in 3D hydrogel printing of tissue substitutes. In this context, our goal was to obtain printable hydrogel nanocomposites by adding silica nanoparticles to a microbial polysaccharide's polymer network. Several amounts of silica nanoparticles were added to the biopolymer, and their effects on the morpho-structural characteristics of the resulting nanocomposite hydrogel inks and subsequent 3D printed constructs were studied. FTIR, TGA, and microscopy analysis were used to investigate the resulting crosslinked structures. Assessment of the swelling characteristics and mechanical stability of the nanocomposite materials in a wet state was also conducted. The salecan-based hydrogels displayed excellent biocompatibility and could be employed for biomedical purposes, according to the results of the MTT, LDH, and Live/Dead tests. The innovative, crosslinked, nanocomposite materials are recommended for use in regenerative medicine.

New Biodegradable Materials for Re-Thought Packaging from Pre-Consumer Wastes by Controlling the Storage Time as Method to Increase the Mechanical Recycling Efficiency.

The influence of storage conditions on the mechanical recycling of pre-consumer waste (PRE-CW) from the manufacture of multilayer packaging films starting from starch compounds using a renewable-based polymer with PCL and PBAT, which are biodegradable conventional-based polyesters, was studied. It was found that, unlike materials based on conventional-origin polymers that accumulate in the environment for hundreds of years, the studied compounds degraded, even in the solid state, duringstorage in unventilated spaces and during the rainy hot summers with alternatingheat and rain. The degradation of the mechanically recycled compounds obtained from PRE-CW stored in such conditions was highlighted by the comparative analysis with the primary compounds, which proved the following: specific FTIR spectra changes; 2-3-times higher melt fluidity than for primary compounds; melting in successive processes over the entire positive temperatures range, up to 115 °C, such as in cases of compositional de-mixing of incompatible blends, faced to a single melting endotherm with a maximum at around 120 °C for the primar thermal degradation with the movement of the main destruction stages towards higher temperatures; a high quantity residue at 750 °C in air; dispersed mechanical resistance properties y compounds; crystallization at temperatures 10 °C-15 °C higher. The elimination of storage before the mechanical recycling of the pre-consumer waste from this type of polymeric compound fabrication is a way to increase the mechanical recycling efficiency while obtaining new materials with functional properties required by the applications.

Novel Nanocomposite Hydrogels Based on Crosslinked Microbial Polysaccharide as Potential Bioactive Wound Dressings.

A multitude of dressings have been developed to promote wound repair, such as membranes, foams, hydrocolloids and hydrogels. In this study, a crosslinked polysaccharide hydrogel was mixed with a bioactive ingredient to synthesize a novel nanocomposite material to be used in wound healing. Variation of the ratio between hydrogel components was followed and its effect was analyzed in regard to swelling, degradation rate and thermo-mechanical behavior. The resulting crosslinked structures were characterized by FTIR and microscopy analyses. The antimicrobial activity of the crosslinked hydrogels loaded with bioactive agent was evaluated using two bacterial strains (Gram-positive Staphylococcus aureus and Gram-negative bacteria Escherichia Coli). All the results showed that the new synthesized biopolymer nanocomposites have adequate properties to be used as antibacterial wound dressings.

Cytocompatibility, Antimicrobial and Antioxidant Activity of a Mucoadhesive Biopolymeric Hydrogel Embedding Selenium Nanoparticles Phytosynthesized by Sea Buckthorn Leaf Extract.

Phytosynthesized selenium nanoparticles (SeNPs) are less toxic than the inorganic salts of selenium and show high antioxidant and antibacterial activity. Chitosan prevents microbial biofilm formation and can also determine microbial biofilm dispersal. Never-dried bacterial nanocellulose (NDBNC) is an efficient carrier of bioactive compounds and a flexible nanofibrillar hydrophilic biopolymer. This study aimed to develop a selenium-enriched hydrogel nanoformulation (Se-HNF) based on NDBNC from kombucha fermentation and fungal chitosan with embedded biogenic SeNPs phytosynthesized by an aqueous extract of sea buckthorn leaves (SbLEx)-SeNPsSb-in order to both disperse gingival dysbiotic biofilm and prevent its development. We determined the total phenolic content and antioxidant activity of SbLEx. Liquid chromatography-mass spectrometry (LC-MS) and high-performance liquid chromatography (HPLC) were used for the identification of polyphenols from SbLEx. SeNPsSb were characterized by transmission electron microscopy-energy-dispersive X-ray spectroscopy (TEM-EDX), dynamic light scattering (DLS), zeta potential, Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) in small- and wide-angle X-ray scattering (SAXS and WAXS). The hydrogel nanoformulation with embedded SeNPsSb was characterized by SEM, FTIR, XRD, rheology, mucin binding efficiency, contact angle and interfacial tension measurements. We also assessed the in vitro biocompatibility, antioxidant activity and antimicrobial and antibiofilm potential of SeNPsSb and Se-HNF. TEM, DLS and SAXS evidenced polydisperse SeNPsSb, whereas FTIR highlighted a heterogeneous biocorona with various biocompounds. The contact angle on the polar surface was smaller (52.82 ± 1.23°) than that obtained on the non-polar surface (73.85 ± 0.39°). The interfacial tension was 97.6 ± 0.47 mN/m. The mucin binding efficiency of Se-HNF decreased as the amount of hydrogel decreased, and the SEM analysis showed a relatively compact structure upon mucin contact. FTIR and XRD analyses of Se-HNF evidenced an interaction between BNC and CS through characteristic peak shifting, and the rheological measurements highlighted a pseudoplastic behavior, 0.186 N adhesion force and 0.386 adhesion energy. The results showed a high degree of cytocompatibility and the significant antioxidant and antimicrobial efficiency of SeNPsSb and Se-HNF.

Molecularly Imprinted Ligand-Free Nanogels for Recognizing Bee Venom-Originated Phospholipase A2 Enzyme.

In this study, ligand-free nanogels (LFNGs) as potential antivenom mimics were developed with the aim of preventing hypersensitivity and other side effects following massive bee attacks. For this purpose, poly (ethylene glycol) diacrylate was chosen as a main synthetic biocompatible matrix to prepare the experimental LFNGs. The overall concept uses inverse mini-emulsion polymerization as the main route to deliver nanogel caps with complementary cavities for phospholipase A2 (PLA2) from bee venom, created artificially with the use of molecular imprinting (MI) technologies. The morphology and the hydrodynamic features of the nanogels were confirmed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) analysis. The following rebinding experiments evidenced the specificity of molecularly imprinted LFNG for PLA2, with rebinding capacities up to 8-fold higher compared to the reference non-imprinted nanogel, while the in vitro binding assays of PLA2 from commercial bee venom indicated that such synthetic nanogels are able to recognize and retain the targeted PLA2 enzyme. The results were finally collaborated with in vitro cell-viability experiments and resulted in a strong belief that such LFNG may actually be used for future therapies against bee envenomation.

Poly(N-vinylpyrrolidone)-Laponite XLG Nanocomposite Hydrogels: Characterization, Properties and Comparison with Divinyl Monomer-Crosslinked Hydrogels.

The present work investigates, for the first time, the synthesis and properties of some nanocomposite (NC) hydrogels obtained by the aqueous solution free radical polymerization of N-vinylpyrrolidone (NVP) in the presence of Laponite XLG (XLG) as a crosslinker, in comparison with the corresponding hydrogels prepared by using two conventional crosslinking divinyl monomers: N,N'-methylenebisacrylamide (MBA) and tri(ethylene glycol) divinyl ether (DVE). The structure and properties of the hydrogels were studied by FTIR, TEM, XRD, SEM, swelling and rheological and compressive mechanical measurements. The results showed that DVE and XLG are much better crosslinking agents for the synthesis of PNVP hydrogels than MBA, leading to larger gel fractions and more homogeneous network hydrogels. The hydrogels crosslinked by either DVE or XLG displayed comparable viscoelastic and compressive mechanical properties under the experimental conditions employed. The properties of the XLG-crosslinked hydrogels steadily improved as the clay content increased. The addition of XLG as a second crosslinker together with a divinyl monomer strongly enhanced the material properties in comparison with the hydrogels crosslinked by only one of the crosslinkers involved. The FTIR analyses suggested that the crosslinking of the NC hydrogels was the result of two different interactions occurring between the clay platelets and the PNVP chains. Laponite XLG displayed a uniform distribution within the NC hydrogels, the clay being mostly exfoliated. However, a small number of platelet agglomerations were still present. The PNVP hydrogels described here may find applications for water purification and in the biomedical field as drug delivery systems or wound dressings.

Adjusting Some Properties of Poly(methacrylic acid) (Nano)Composite Hydrogels by Means of Silicon-Containing Inorganic Fillers.

The present work aims to show how the main properties of poly(methacrylic acid) (PMAA) hydrogels can be engineered by means of several silicon-based fillers (Laponite XLS/XLG, montmorillonite (Mt), pyrogenic silica (PS)) employed at 10 wt% concentration based on MAA. Various techniques (FT-IR, XRD, TGA, SEM, TEM, DLS, rheological measurements, UV-VIS) were used to comparatively study the effect of these fillers, in correlation with their characteristics, upon the structure and swelling, viscoelastic, and water decontamination properties of (nano)composite hydrogels. The experiments demonstrated that the nanocomposite hydrogel morphology was dictated by the way the filler particles dispersed in water. The equilibrium swelling degree (SDe) depended on both the pH of the environment and the filler nature. At pH 1.2, a slight crosslinking effect of the fillers was evidenced, increasing in the order Mt < Laponite < PS. At pH > pKaMAA (pH 5.4; 7.4; 9.5), the Laponite/Mt-containing hydrogels displayed a higher SDe as compared to the neat one, while at pH 7.4/9.5 the PS-filled hydrogels surprisingly displayed the highest SDe. Rheological measurements on as-prepared hydrogels showed that the filler addition improved the mechanical properties. After equilibrium swelling at pH 5.4, G' and G" depended on the filler, the Laponite-reinforced hydrogels proving to be the strongest. The (nano)composite hydrogels synthesized displayed filler-dependent absorption properties of two cationic dyes used as model water pollutants, Laponite XLS-reinforced hydrogel demonstrating both the highest absorption rate and absorption capacity. Besides wastewater purification, the (nano)composite hydrogels described here may also find applications in the pharmaceutical field as devices for the controlled release of drugs.

Embedded Target Filler and Natural Fibres as Interface Agents in Controlling the Stretchability of New Starch and PVOH-Based Materials for Rethinked Sustainable Packaging.

A structuring solution converting starch into a multiphase polymeric material was obtained through a melt compounding sequence, which can be irreversibly shaped by thermoforming into rethinked, sustainable packaging, based on the physical modification of starch with polyvinyl alcohol (PVOH), target fillers, (CaCO3 and wood flour), and a good plasticizer compatible with the polar components. Polymeric material can be thermoformed if it can be stretched without breaking in the positive temperature range, have functional properties required by the application, and keep its shape and properties after stretching for more than six months. The properties of the selected quaternary starch-based compound, fulfil the requirements for a thermoformable polymeric material due to the chemical compatibility between the components and the compounding in a selected procedure and optimal conditions wich ensure a comfortable miscibility. Most likely, the obtained miscibility can be explained only by the arrangement of the wood flour at the interface, where it acts as compatibilizer with a main role in structuring the new starch-based materials. The compatibilizer role of the wood flour was proved for the quaternary selected blend by the changing of the thermal degradation mechanism, from one with two stages for binary and tertiary blends, to one consisting of a single stage: decreasing till elimination of morphological defects, the reproducibility of the mechanical properties, stretching without breaking, and dimensional stability after stretching. Future studies will aim to achieve rethinked packaging for applications that require higher strength properties.

3D Printing of Alginate-Natural Clay Hydrogel-Based Nanocomposites.

Biocompatibility, biodegradability, shear tinning behavior, quick gelation and an easy crosslinking process makes alginate one of the most studied polysaccharides in the field of regenerative medicine. The main purpose of this study was to obtain tissue-like materials suitable for use in bone regeneration. In this respect, alginate and several types of clay were investigated as components of 3D-printing, nanocomposite inks. Using the extrusion-based nozzle, the nanocomposites inks were printed to obtain 3D multilayered scaffolds. To observe the behavior induced by each type of clay on alginate-based inks, rheology studies were performed on composite inks. The structure of the nanocomposites samples was examined using Fourier Transform Infrared Spectrometry and X-ray Diffraction (XRD), while the morphology of the 3D-printed scaffolds was evaluated using Electron Microscopy (SEM, TEM) and Micro-Computed Tomography (Micro-CT). The swelling and dissolvability of each composite scaffold in phosfate buffer solution were followed as function of time. Biological studies indicated that the cells grew in the presence of the alginate sample containing unmodified clay, and were able to proliferate and generate calcium deposits in MG-63 cells in the absence of specific signaling molecules. This study provides novel information on potential manufacturing methods for obtaining nanocomposite hydrogels suitable for 3D printing processes, as well as valuable information on the clay type selection for enabling accurate 3D-printed constructs. Moreover, this study constitutes the first comprehensive report related to the screening of several natural clays for the additive manufacturing of 3D constructs designed for bone reconstruction therapy.

Effects of Siliceous Natural Nanomaterials Applied in Combination with Foliar Fertilizers on Physiology, Yield and Fruit Quality of the Apricot and Peach Trees.

Siliceous natural nanomaterials (SNNMs), i.e., diatomaceous earth and natural zeolites, have a nanoporous structure with large active surfaces that adsorb cations or polarized molecules. Such nanoporous feature determines the effects related to SNNM utilization as low-risk plant protectants and soil improvers. This work used SNNMs from Romanian quarries as carriers for foliar fertilizers applied to stone-fruit trees, apricot and peach. We determined the effects of SNNMs on the physiology, yield and fruit quality of the treated stone-fruit trees. SNNM application determined impacts specific to the formation of particle films on leaves: reduced leaf temperature (up to 4.5 °C) and enhanced water use efficiency (up to 30%). Foliar fertilizers' effects on yield are amplified by their application with SNNMs. Yield is increased up to 8.1% by the utilization of SNNMs with foliar fertilizers, compared to applying foliar fertilizer alone. Diatomaceous earth and natural zeolites promote the accumulation of polyphenols in apricot and peach fruits. The combined application of SNNMs and foliar fertilizer enhance the performance of peach and apricot trees.