Antimicrobial Composites Based on Methacrylic Acid-Methyl Methacrylate Electrospun Fibers Stabilized with Copper(II).

This study presents fibers based on methacrylic acid-methyl methacrylate (Eudragit L100) as Cu(II) adsorbents, resulting in antimicrobial complexes. Eudragit L100, an anionic copolymer synthesized by radical polymerization, was electrospun in dimethylformamide (DMF) and ethanol (EtOH). The electrospinning process was optimized through a 22-factorial design, with independent variables (copolymer concentration and EtOH/DMF volume ratio) and three repetitions at the central point. The smallest average fiber diameter (259 ± 53 nm) was obtained at 14% w/v Eudragit L100 and 80/20 EtOH/DMF volume ratio. The fibers were characterized using scanning electron microscopy (SEM), infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), and differential scanning calorimetry (DSC). The pseudo-second-order mechanism explained the kinetic adsorption toward Cu(II). The fibers exhibited a maximum adsorption capacity (qe) of 43.70 mg/g. The DSC analysis confirmed the Cu(II) absorption, indicating complexation between metallic ions and copolymer networks. The complexed fibers showed a lower degree of swelling than the non-complexed fibers. The complexed fibers exhibited bacteriostatic activity against Gram-negative (Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus) bacteria. This study successfully optimized the electrospinning process to produce thin fibers based on Eudragit L100 for potential applications as adsorbents for Cu(II) ions in aqueous media and for controlling bacterial growth.

Zinc oxide nanoparticle-reinforced pectin/starch functionalized films: A sustainable solution for biodegradable packaging.

Environmental pollution caused by non-biodegradable plastic pollutants adversely affects various ecosystems. This study proposes the development of novel functional and biodegradable films based on corn starch (CST) and pectin (PEC) containing zinc oxide nanoparticles (ZnONPs) from the casting method. The films exhibited processability, transparency, low water vapor permeation, and desirable mechanical properties for food packaging and coating applications. The ZnONPs acted as a plasticizer, enhancing the film elongation at the break, increasing the pec25-1 (PEC 25 wt% and ZnONPs 1 wt%) elongation from 79.85 to 162.32 %. The improved film elasticity supported by ZnONPs reduced the material stiffness. However, the films still demonstrated an average tensile strength (0.69 MPa) 17-fold higher than the tensile strength (0.04 MPa) of the non-biodegradable commercial film based on poly(vinyl chloride). Furthermore, the ZnONPs enhanced the UV-blocking capabilities of the films, leading to wettable materials with water contact angles lower than 90°. The films showed high biodegradation rates under natural disposal conditions. The results indicated that the pec25-1/ZnONPs film is a promising eco-friendly coating in food preservation due to its biodegradability, suitable mechanical properties, low water vapor permeability, and UV-blocking properties.

κ-Carrageenan/poly(vinyl alcohol) functionalized films with gallic acid and stabilized with metallic ions.

Given the environmental issues caused by the extensive use of conventional petroleum-based packaging, this work proposes functional films based on commercial κ-carrageenan (κc), poly(vinyl alcohol) (PVA), and gallic acid (GA) prepared by the "casting" method. Metallic ions in the κc composition stabilized the films, supporting processability and suitable mechanical properties. However, the incorporated GA amount (6.25 and 10 wt%) in the films created from an aqueous κc solution at 3.0 % wt/v (κc3) prevented crystalline domains in the resulting materials. The κc3/GA6.25 and κc3/GA10 films had less tensile strength (8.50 ± 0.61 and 10.28 ± 0.65 MPa) and high elongation at break (2.36 ± 0.16 and 1.19 ± 0.17 %) compared to the other samples, respectively. Low κc contents (κc2.5/GA6.25 and κc2.5/GA10) promoted stiff films and less permeability to water vapor (5.36 ± 0.51 and 3.76 ± 0.02 [×10-12 g(Pa × m × s)-1], respectively. The κc/GA weight ratio also influenced the film wettability, indicating water contact angles (WCAs) between 55 and 74°. The surface wettability implies a low oil permeability and high water swelling capacity of up to 1600 %. The κc/GA also played an essential role in the film's antimicrobial action against Staphylococcus aureus and Escherichia coli. Thus, the κc3/GA10 film showed suitable physical, chemical, and biological properties, having the potential to be applied as food coatings.

Natural carbohydrate-based thermosensitive chitosan/pectin adsorbent for removal of Pb(II) from aqueous solutions.

Biodegradable and eco-friendly adsorbents composed of natural carbohydrates have been used to replace carbon-based materials. This study presents a natural carbohydrate-based chitosan/pectin (CS/Pec) hydrogel adsorbent to remove Pb(II) from aqueous solutions. The physical CS/Pec hydrogel was prepared by blending aqueous CS and Pec solutions at 65 °C, preventing the use of toxic chemistries (crosslinking agents). The thermosensitive CS/Pec hydrogel was quickly created by cooling CS/Pec blend at room temperature. The used strategy created stable CS/Pec hydrogel against disintegration and water dissolution. The as-prepared hydrogel was characterized by infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The adsorbent had 1.688 mmol -COO- for each gram. These ionized sites bind Pb(II) ions, promoting their adsorption. The adsorption kinetic and equilibrium studies indicated that the Elovich and pseudo-second-order models adjusted well to the experimental data, respectively. The maximum removal capacities (qm) predicted by the Langmuir and Sips isotherms achieved 108.2 and 97.55 mg/g at 0.83 g/L adsorbent dosage (pH 4.0). The hydrogel/Pb(II) pair was characterized by scanning electron microscopy (SEM), X-ray dispersive energy (EDS), and differential scanning calorimetry (DSC). The chemisorption seems to play an essential role in the Pb(II) adsorption. Therefore, the adsorbent was not recovered, showing low potential for reusability.

Biodegradable films based on commercial κ-carrageenan and cassava starch to achieve low production costs.

Biodegradable films have been a great alternative compared to non-renewable sources because of their cytocompatibility, biodegradability, and antimicrobial features. These properties may raise the foodstuff shelf life, reducing costs and economic losses. Indeed, biodegradable films can also reduce the environmental pollution promoted by non-biodegradable conventional packs. For the first time, biodegradable films were produced by casting commercials kappa-carrageenan (κ-car) and cassava starch at different κ-carrageenan/cassava starch weight ratios. Physical, thermal, and mechanical properties were evaluated. Apparent opacity and color analyses suggest that the films present high transparency. The sample 0κ-c supported a film with high water solubility (39.22%) and a low swelling degree (391.6%). The lowest water vapor permeability (WVP) was observed for 50κ-c (3.01×10-8g (Pams)-1). The oil permeability varied from 0.0033 to 0.0043mmm2 d-1. The 100κ-c and 75κ-c films (with high κ-carrageenan contents) had higher stiffness (19.23 and 25.88MPa, respectively) than the 25κ-c and 0κ-c films with elongation at break (ε) of 21.60 and 67.65%, respectively. The thermal stability increased as the starch concentration raised in the blend. We produced low-cost biodegradable films from commercial polysaccharides. These films can be used as food packs.

Removal of Cu(II) from aqueous solutions imparted by a pectin-based film: Cytocompatibility, antimicrobial, kinetic, and equilibrium studies.

To obtain pectin-based films is challenging due to the aqueous instability of polyelectrolyte mixtures. We overcome this issue by blending chitosan to pectin of high O-methoxylation degree (56%), followed by solvent evaporation. A durable film containing 74 wt% pectin content was produced and used as an adsorbent material toward Cu(II) ions. Kinetic and adsorption equilibrium studies showed that the pseudo-second-order and Sips isotherm models adjusted well to the experimental data, respectively. Langmuir isotherm indicated a maximum adsorption capacity (qm) for Cu(II) removal of 29.20 mg g-1. Differential scanning calorimetry, contact angle measurements, and X-ray photoelectron spectroscopy confirm the adsorption. The chemisorption plays an essential role in the process; thereby, the film reusability is low. After adsorption, the cytocompatible film/Cu(II) pair prevents the proliferation of Escherichia coli.

Pectin-capped gold nanoparticles synthesis in-situ for producing durable, cytocompatible, and superabsorbent hydrogel composites with chitosan.

Studies report the production of gold nanoparticles (AuNPs) and polysaccharides-based composites. However, there are few reports about AuNPs synthesis in-situ followed by the formation of hydrogel composites. Here, we show AuNPs synthesis in-situ into the pectin solutions to yield cytocompatible pectin-capped AuNPs/chitosan hydrogel composites. Visible spectroscopy and dynamic light scattering measurements confirm the AuNPs synthesis. The hydrodynamic radius of the pectin-capped AuNPs ranges from approximately 510 to 721 nm, while the Zeta potential is around -43 mV. Scanning electron microscopy shows that the composites present compact structures. Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy characterize the composites as well. Hydrogels (with or without AuNPs) containing the highest pectin content (at 4.12 pectin/chitosan weight ratio) have low stability (disintegrates approximately 60% after 14 days in phosphate buffer). Composites obtained at 3.75 pectin/chitosan weight ratio disintegrate between 25 and 30% after 14 days in phosphate buffer (physiological condition = pH 7.4). The AuNPs reinforce the hydrogel structures, increasing the elastic modulus (from 3.5 to 7.6 Pa) and decreasing the water uptake from 4465 to 2976%. 3.75 PT/CS weight ratio and 3.0 × 10-4 M Au(III) content provide a durable, cytocompatible, and superabsorbent hydrogel composite. These properties can support materials for drug delivery purposes.

Properties of a commercial κ-carrageenan food ingredient and its durable superabsorbent hydrogels.

Physical kappa-carrageenan-based hydrogels are often prepared from dilute aqueous kappa-carrageenan (κ-carrageenan) solutions at the presence of metallic ions or by mixing these solutions with proteins and other polysaccharides. The κ-carrageenan hydrogels have been used for technological purposes; however, there are no reports about the properties of a commercial GENUGEL® κ-carrageenan produced by the CP Kelco. The flame atomic absorption spectrometry shows that the commercial κ-carrageenan comprises a high content of metallic ions (K+ = 216.1 g kg-1, Na+ = 6.3 g kg-1 and Ca2+ = 12.5 g kg-1). The X-ray photoelectron spectroscopy (XPS) indicates the presence of sodium, calcium, and potassium atoms on the as-received κ-carrageenan and its physical hydrogel surfaces. XPS supports the occurrence of a low protein content onto the sample surfaces, as well. The metallic level (especially for K+) in the commercial κ-carrageenan plays an essential role in the preparation of durable hydrogels. These materials are prepared by cooling aqueous κ-carrageenan solutions at 4.0 and 5.0 wt%. The gelation temperature is determined by measuring G' &G″ as a function of the temperature. The gelation behavior depends on the κ-carrageenan concentration, as well as the metallic content in the commercial sample. Scanning electron microscopy shows that hydrogels have porous and smooth surfaces. The dried materials swell from 2400 to 3100%, while the disintegration/dissolution test confirms that the samples present high stability in distilled water throughout 14 days. These hydrogels are superabsorbent materials and can be applied in agriculture as soil conditioners.

Chitosan content modulates durability and structural homogeneity of chitosan-gellan gum assemblies.

Here we report a new and straightforward method to yield durable polyelectrolyte complexes (hydrogel PECs) from gellan gum (GG) and chitosan (CS) assemblies, without metallic and covalent crosslinking agents, commonly used to produce GG and CS-based hydrogels, respectively. This new approach overcomes challenges of obtaining stable and durable GG-based hydrogels with structural homogeneity, avoiding precipitation and aqueous instability, typical of PEC-based materials. PECs are created by blending CS:GG solutions (at 60 °C) with GG:CS weight ratios between 80:20 to 40:60. X-ray photoelectron spectroscopy (XPS) analysis shows that CS-GG chains are interacting by electrostatic and intermolecular forces, conferring a high degree of association to the washed PECs, characteristic of self-assembling of polymer chains. The CS:GG weight ratio can be tuned to improve polyelectrolyte complex (PEC) high porosity, stability, porous homogeneity, and degradation rate. Physical and thermosensitive CS/GG-based hydrogels can have advantages over conventional materials produced by chemical processes.

Scaffolds based on chitosan/pectin thermosensitive hydrogels containing gold nanoparticles.

Thermosensitive hydrogels based on chitosan/pectin (CS/Pec) and CS/Pec/gold nanoparticles (CS/Pec/AuNPs) were successfully prepared with different AuNP levels. Using a tilting method, gelation temperature was demonstrated to decrease when the amount of AuNPs increased and pectin concentrations decreased. The presence of AuNPs in the CS/Pec composite was evaluated via WAXS and UV-vis techniques, while SEM analysis assessed the average size of pores (350-600µm). All samples were extremely cytocompatible with many cell types, such as normal kidney epithelial cells (VERO cells), epithelial colorectal adenocarcinoma cells (HT-29 cells), HPV-16 positive human cervical tumour cells (SiHa cells), kidney epithelial cells (LLCMK2 cells) and murine macrophage cells (J774A1 cells). Cell viability assays using the MTT method upon mouse preosteoblastic cells (MC3T3-E1 cells) showed that CS/Pec and CS/Pec/AuNPs composites had the potential to foster proliferation and growth of bone cells, making them possible stimulators for reconstruction of bone tissues.

Polyelectrolyte complexes based on alginate/tanfloc: Optimization, characterization and medical application.

Hydrogels based on alginate and tanfloc (a cationic biopolymer obtained from natural condensed tannins) were successfully prepared. Tanfloc (TN) presents high aqueous solubility at pHs lower than 10; it contains substituted amino sites and molar weight of ca. 600,000gmol-1. A factorial design (22) was used to optimize the yield of alginate/tanfloc polyelectrolyte complexes (PECs). Dialysis recovered the overplus of alginate (AG) no complexed with TN. These materials were characterized by thermal analyses (TGA/DTG and DSC), zeta potential, and FTIR, while SEM technique depicted a rough surface on AG/TN complex, containing non-homogeneous pores. Indeed, the AG and TN were tailored to elicit scaffold materials with outstanding cytocompatibility, mainly upon mouse preosteoblastic cells because of reconstruction of bone tissues (119% at 10days). The AG/TN complex also displayed antioxidant and bactericidal activities against Staphylococcus aureus (S. aureus). Besides, the pristine TN fostered bacteriostatic and bactericidal performances towards S. aureus and Escherichia coli. However, for our best knowledge, no studies were still carried out on TN and TN-based materials for medical purpose.

Polysaccharide-Based Materials Associated with or Coordinated to Gold Nanoparticles: Synthesis and Medical Application.

BACKGROUND: Gold nanoparticles (AuNPs) have enormous potential for application in imaging, diagnosis, and therapies in the medical field. AuNPs are renowned for their localized surface plasmon resonance (LSPR) properties, large surface area, and biocompatibility with body fluids. Further, AuNPs have featured prominently in new methodologies for cancer treatments, like photothermal and imaging therapies. Although AuNPs present enormous potential for application in the medical field, their instability under physiological conditions prevents further uses. However, this limitation may be overcome by associating AuNPs with biopolymers. To the best of our knowledge, a revision paper rationalizing the structure/property relationship and applications of AuNPspolysaccharide composites in the medical field has not been published yet. METHODS: This manuscript discusses the most relevant aspects and state-of-art concepts surrounding the synthesis of AuNPs based on green chemistry and their association with polysaccharides that can efficiently function both as stabilizing and reducing agents of Au nanoparticles. Even more, polysaccharide devices may inhibit non-specific interactions between AuNPs and biological macromolecules, suppressing unsuitable "protein corona" formations on AuNP surfaces, thereby increasing the potential of AuNP composites of being employing as drug delivery matrices and wound-healing devices as well as in photothermal/ imaging purposes for cancer treatments and biosensors.

SPR platform based on image acquisition for HER2 antigen detection.

HER2 antigen is a marker used for breast cancer diagnosis and prevention. Its determination has great importance since breast cancer is one of the most insidious types of cancer in women. HER2 antigen assessment in human serum is traditionally achieved by enzyme-linked immunosorbent assay (ELISA method), but it has some disadvantages, such as suppressing the thermodynamic-kinetic studies regarding the antibody-antigen interaction, and the use of labeled molecules that can promote false positive responses. Biosensors based on surface plasmon resonance (SPR) are sensitive optical techniques widely applied on bioassays. The plasmonic devices do not operate with labeled molecules, overcoming conventional immunoassay limitations, and enabling a direct detection of target analytes. In this way, a new SPR biosensor to assess HER2 antigen has been proposed, using nanohole arrays on a gold thin film by signal transduction of transmitted light measurements from array image acquisitions. These metallic nanostructures may couple the light directly on surface plasmons using a simple collinear arrangement. The proposed device reached an average sensitivity for refractive index (RI) variation on a metal surface of 4146 intensity units/RIU (RIU = RI units). The device feasibility on biomolecular assessment was evaluated. For this, 3 ng ml-1 known HER2 antigen concentration was efficiently flowed (using a microfluidic system) and detected from aqueous solutions. This outcome shows that the device may be a powerful apparatus for bioassays, particularly toward breast cancer diagnosis and prognosis.

Incorporation of conjugated fatty acids into Nile tilapia (Oreochromis niloticus).

BACKGROUND: The aim of this work was to improve the nutritional quality of Nile tilapia meat through enriched diets with conjugated isomers of linolenic acid from tung oil. The transfer process of conjugated fatty acids (CFAs) into fish muscle tissue was evaluated by gas chromatography-flame ionization detection (GC-FID) and easy ambient sonic-spray ionization mass spectrometry (EASI-MS). RESULTS: The results showed that conjugated fatty acids were transferred from enriched diet for muscle tissue of Nile tilapia. Conjugated linoleic acids biosynthesis from conjugated linolenic acids was also observed after 10 days. Other important fatty acids such as docosahexaenoic (DHA), eicosapentaenoic (EPA) and arachidonic (AA) acids were also identified over time; however, DHA showed the highest concentration when compared with EPA and AA compounds. CONCLUSION: Therefore, the nutritional quality of Nile tilapia was improved through feeding with enriched diets. The ingestion of these fish may contribute to reaching adequate levels of daily CFA consumption. Furthermore, other important substances which play an important role in human metabolism, such as EPA, DHA and AA, can also be ingested together with CFA. © 2016 Society of Chemical Industry.

Preparation and cytotoxicity of N-modified chitosan nanoparticles applied in curcumin delivery.

Nanoparticles (NPs) based on N,N-dimethyl chitosan (DMC) and N,N,N-trimethyl chitosan (TMC), physical crosslinked with sodium tripolyphosphate (TPP) were successful obtained, using water/benzyl alcohol emulsion system. NPs morphologies were evaluated by Scanning Electron Microscopy and Transmission Electron Microscopy. NPs were characterized by Infrared Spectroscopy (FTIR), Thermogravimetric Analysis, Zeta Potential, Differential Scanning Calorimetry and Wide-angle X-ray Scattering. Curcumin (CUR) was loaded onto NPs and controlled release studies were evaluated in simulated intestinal fluid and in simulated gastric fluid. Cytotoxicity assays showed only loaded TMC/TPP particles containing CUR were slightly cytotoxic on human cervical tumor cells (SiHa cells), concerning unloaded TMC/TPP particles. Conversely, loaded NPs (TMC/TPP/CUR and DMC/TPP/CUR), especially TMC/TPP/CUR sample presented greater biocompatibility toward healthy VERO cells than unloaded NPs (TMC/TPP and DMC/TPP).

Polyelectrolyte complex containing silver nanoparticles with antitumor property on Caco-2 colon cancer cells.

Polyelectrolyte complex (beads) based on N,N,N-trimethyl chitosan/alginate was successful obtained and silver nanoparticles (AgNPs) were loaded within beads. In vitro cytotoxicity assays using beads/silver nanoparticles (beads/AgNPs) provided results, indicating that this material significantly inhibited the growth of colon cancer cells (Caco-2). In vitro release studies showed that the beads stabilized AgNPs and repressed Ag(0) oxidation under gastric conditions (pH 2.0). On the other hand, at physiological condition (pH 7.4) the beads/AgNPs released 3.3 µg of Ag(+) per each beads milligram. These studies showed that the concentration of Ag(+) released (3.3 µg) was cytotoxic for the Caco-2 cells and was not cytotoxic on healthy VERO cells. This result opens new perspectives for the manufacture of biomaterials based on beads/AgNPs with anti-tumor properties.