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.

Water Droplet Self-Assembly to Au Nanoporous Films with Special Light Trapping and Surface Electromagnetic Field Enhancement.

Gold nano "breath figure" films are for the first time reported and their function as ideal systems for plasmonics demonstrated. Metal nano-breath figure substrates are metal thin films containing nanohole arrays supported on a solid substrate. Au nanohole arrays are prepared from the dynamic breath figure phenomenon, in which the pore formation is controlled to provide holes smaller than 100 nm. Au layer is deposited on polymer substrates containing breath figure topology. The breath figure topology can be fully translated to the Au layer. The nanofabrication process is completed within few minutes. A simplified preparation process but very impressive light trapping and surface electromagnetic field enhancement are related to the Au breath figure films obtained in this work. The porous films demonstrated higher absorbance in the region of 500-1100 nm than nonporous Au films. In the case of 10 nm Au film, the plasmon absorbance becomes more intense than the electronic band absorbance. The electromagnetic enhancement is proved by surface enhanced Raman spectroscopy effect, which is found to be very close to the maximum possible value predicted for nonresonant species.

The Inclusion of Chitosan in Poly-ε-caprolactone Nanoparticles: Impact on the Delivery System Characteristics and on the Adsorbed Ovalbumin Secondary Structure.

This report extensively explores the benefits of including chitosan into poly-ε-caprolactone (PCL) nanoparticles (NPs) to obtain an improved protein/antigen delivery system. Blend NPs (PCL/chitosan NPs) showed improved protein adsorption efficacy (84%) in low shear stress and aqueous environment, suggesting that a synergistic effect between PCL hydrophobic nature and the positive charges of chitosan present at the particle surface was responsible for protein interaction. Additionally, thermal analysis suggested the blend NPs were more stable than the isolated polymers and cytotoxicity assays in a primary cell culture revealed chitosan inclusion in PCL NPs reduced the toxicity of the delivery system. A quantitative 6-month stability study showed that the inclusion of chitosan in PCL NPs did not induce a change in adsorbed ovalbumin (OVA) secondary structure characterized by the increase in the unordered conformation (random coil), as it was observed for OVA adsorbed to chitosan NPs. Additionally, the slight conformational changes occurred, are not expected to compromise ovalbumin secondary structure and activity, during a 6-month storage even at high temperatures (45°C). In simulated biological fluids, PCL/chitosan NPs showed an advantageous release profile for oral delivery. Overall, the combination of PCL and chitosan characteristics provide PCL/chitosan NPs valuable features particularly important to the development of vaccines for developing countries, where it is difficult to ensure cold chain transportation and non-parenteral formulations would be preferred.

Preparing silk fibroin nanofibers through electrospinning: further heparin immobilization toward hemocompatibility improvement.

Sodium heparin (HS) was immobilized on the surface of the silk fibroin nanofibers (FS) prepared by electrospinning with the objective of improving the hemocompatibility of the fibers for application as scaffolds in tissue engineering. The nanofiber mats of silk fibroin without (MF-FS) and with (MF-FS/HS) immobilized heparin were characterized through scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR), thermogravimetric analyses (TGA), energy dispersive spectroscopy (EDS), contact angle, chemical analysis, and biological tests. The formation of hydrogen bonds between the silk fibroin and heparin was discussed based on FTIR-ATR spectra. The amount of immobilized heparin was quantified through papain/N-acetyl-l-cysteine digestion followed by dimethylmethylene blue complexation. Furthermore, the samples with immobilized HS showed higher hydrophilic capability compared to samples without HS due to lower contact angles. It was possible to verify that the capillary end-to-collector distance of 8.5 cm and flow rate of 0.35 mL h(-1) used in the electrospinning process at 20 kV are good conditions for obtaining a small average fiber diameter maintaining the amount of immobilized heparin on MF-FS/HS in ca. 4% w/w. Biological analysis showed that no hemolysis is provoked by MF-FS and MF-FS/HS mat fragments and those such mats are not toxic to Vero cells. However, the MF-FS/HS showed higher cell growth and proliferation than MF-FS, indicating an improvement in the hemocompatibility of the material due to heparin immobilization.

Recent advances in food-packing, pharmaceutical and biomedical applications of zein and zein-based materials.

Zein is a biodegradable and biocompatible material extracted from renewable resources; it comprises almost 80% of the whole protein content in corn. This review highlights and describes some zein and zein-based materials, focusing on biomedical applications. It was demonstrated in this review that the biodegradation and biocompatibility of zein are key parameters for its uses in the food-packing, biomedical and pharmaceutical fields. Furthermore, it was pointed out that the presence of hydrophilic-hydrophobic groups in zein chains is a very important aspect for obtaining material with different hydrophobicities by mixing with other moieties (polymeric or not), but also for obtaining derivatives with different properties. The physical and chemical characteristics and special structure (at the molecular, nano and micro scales) make zein molecules inherently superior to many other polymers from natural sources and synthetic ones. The film-forming property of zein and zein-based materials is important for several applications. The good electrospinnability of zein is important for producing zein and zein-based nanofibers for applications in tissue engineering and drug delivery. The use of zein's hydrolysate peptides for reducing blood pressure is another important issue related to the application of derivatives of zein in the biomedical field. It is pointed out that the biodegradability and biocompatibility of zein and other inherent properties associated with zein's structure allow a myriad of applications of such materials with great potential in the near future.

Antimicrobial activity of chitosan derivatives containing N-quaternized moieties in its backbone: a review.

Chitosan, which is derived from a deacetylation reaction of chitin, has attractive antimicrobial activity. However, chitosan applications as a biocide are only effective in acidic medium due to its low solubility in neutral and basic conditions. Also, the positive charges carried by the protonated amine groups of chitosan (in acidic conditions) that are the driving force for its solubilization are also associated with its antimicrobial activity. Therefore, chemical modifications of chitosan are required to enhance its solubility and broaden the spectrum of its applications, including as biocide. Quaternization on the nitrogen atom of chitosan is the most used route to render water-soluble chitosan-derivatives, especially at physiological pH conditions. Recent reports in the literature demonstrate that such chitosan-derivatives present excellent antimicrobial activity due to permanent positive charge on nitrogen atoms side-bonded to the polymer backbone. This review presents some relevant work regarding the use of quaternized chitosan-derivatives obtained by different synthetic paths in applications as antimicrobial agents.

Covalent albumin microparticles as an adjuvant for production of mucosal vaccines against hepatitis B.

Covalently modified albumin (BSA) microparticles were developed for potential use as an adjuvant in mucosal vaccines against hepatitis B. To synthesize consistent protein particles, a covalent approach was proposed to modify BSA. Our strategy was to bond maleic anhydride (MA) molecules to BSA structure by nucleophilic reaction for further radical cross-linking/polymerization reaction with N',N'-dimethylacrylamide (DMAAm). The presence of poly(N',N'-dimethylacrylamide) in the protein network enables the microparticles to show well-defined, homogeneous forms. Cytotoxicity tests showed that the cytotoxic concentration for 50% of VERO cells (CC50) was 216.25 ± 5.30 µg mL(-1) in 72 h of incubation. The obtained CC50 value is relatively low for an incubation time of 72 h, suggesting an acceptable biocompatibility. Assay of total protein showed that the encapsulation efficiency of the microparticles with hepatitis B surface antigen (HBsAg) was 77.7 ± 0.2%. For the reference sample, which was incubated without HBsAg, the quantity of protein was below the limit of detection.

Carboxymethylcellulose hydrogels crosslinked with keratin nanoparticles for efficient prednisolone delivery.

Carboxymethylcellulose (CMC) and keratin nanoparticle (KNP) hydrogels were obtained, characterized, and applied as drug delivery systems (DDSs) for the first time. Lyophilized CMC/KNP mixtures containing 10, 25, and 50 wt% of KNPs were kept at 170 °C for 90 min to crosslink CMC chains through a solid-state reaction with the KNPs. The hydrogels were characterized by infrared spectroscopy, thermal analyses, X-ray diffraction, mechanical measurements, and scanning electron microscopy. The infrared spectra indicated the formation of ester and amide linkages between crosslinked CMC and KNPs. The elastic modulus of the hydrogel containing 10 wt% KNPs was 2-fold higher than that of the hydrogel containing 50 wt% KNPs. The mechanical properties influenced the hydrogel stability and water uptake. The anti-inflammatory prednisolone (PRED) drug was incorporated into the hydrogels, and the release mechanism was investigated. The hydrogels supported PRED release by drug desorption for approximately 360 h. A sustained release mechanism was achieved. The CMC/KNP and CMC/KNP/PRED hydrogels were cytocompatible toward mammalian cells. The CMC/KNP/PRED set imparted the highest cell viability after 7 days of incubation. This study showed a straightforward procedure to create DDSs (chemically crosslinked) based on polysaccharides and proteins for efficient PRED delivery.

Antiadhesive and antibacterial multilayer films via layer-by-layer assembly of TMC/heparin complexes.

N-Trimethyl chitosan (TMC), an antibacterial agent, and heparin (HP), an antiadhesive biopolymer, were alternately deposited on modified polystyrene films, as substrates, to built antiadhesive and antibacterial multilayer films. The properties of the multilayer films were investigated by Fourier transform infrared spectroscopy, atomic force microscopy, scanning electron microscopy, and Kelvin force microscopy. In vitro studies of controlled release of HP were evaluated in simulated intestinal fluid and simulated gastric fluid. The initial adhesion test of E. coli on multilayer films surface showed effective antiadhesive properties. The in vitro antibacterial test indicated that the multilayer films of TMC/HP based on TMC80 can kill the E. coli bacteria. Therefore, antiadhesive and antibacterial multilayer films may have good potential for coatings and surface modification of biomedical applications.

FTIR-Assisted Electroreduction of CO2 and H2O to CO and H2 by Electrochemically Deposited Copper on Oxidized Graphite Felt.

Obtaining CO and H2 from electrochemical CO2 reduction (CO2RR) offers a viable alternative to reduce CO2 emissions and produce chemicals and fuels. Herein, we report a simple strategy for obtaining polycrystalline copper deposited on oxidized graphite felt (Cu-OGF) and its performance on the selective conversion of CO2 and H2O to CO and H2. For the electrode obtaining, graphite felt (GF) was first oxidized (OGF) in order to make the substrate hydrophilic and then copper particles were electrochemically deposited onto OGF. The pH of deposition was investigated, and the CO2RR activity was assessed for the prepared electrodes at each pH (2.0, 4.0, 6.0, 8.0, and 10.0). It was found that pH 2.0 was the most promising for CO2RR due to the presence of hexagonal copper microparticles. Fourier transform infrared analysis of the produced gases showed that this is a low-cost catalyst capable of reducing CO2 and H2O to CO and H2, with Faradaic efficiencies between 0.50 and 5.21% for CO and 50.87 to 98.30% for H2, depending on the experimental conditions. Hence, it is possible for this gas mixture to be used as a fuel gas or to be enriched with CO for use in Fischer-Tropsch processes.

Magnetic-responsive polysaccharide hydrogels as smart biomaterials: Synthesis, properties, and biomedical applications.

This review reports recent advances in polysaccharide-based magnetic hydrogels as smart platforms for different biomedical applications. These hydrogels have proved to be excellent, viable, eco-friendly alternative materials for the biomedical field due to their biocompatibility, biodegradability, and possibility of controlling delivery processes via modulation of the remote magnetic field. We first present their main synthesis methods and compare their advantages and disadvantages. Next, the synergic properties of hydrogels prepared with polysaccharides and magnetic nanoparticles (MNPs) are discussed. Finally, we describe the main contributions of polysaccharide-based magnetic hydrogels in the targeted drug delivery, tissue regeneration, and hyperthermia therapy fields. Overall, this review aims to motivate the synthesis of novel composite biomaterials, based on the combination of magnetic nanoparticles and natural polysaccharides, to overcome challenges that still exist in the treatment of several diseases.

Chemically crosslinked guar gum hydrogels: An investigation on the water transport and its relationship with hydrocortisone release.

In this work, we describe the synthesis, the characterization, and the potential application of a pH-responsive guar gum-based hydrogel. The polysaccharide produced permanent hydrogels with improved biocompatibility. In this work, we report the chemical modification of guar gum (with glycidyl methacrylate) and its use, as the main constituent, in obtaining chemically cross-linked hydrogels. The morphology, swelling properties, and cytotoxicity of the resulting materials were studied in-depth. The hydrogels showed to be pH-responsive, and non-toxic being safe to use it as a biomaterial. In addition, we tested the potential of this one as a drug carrier. Herein, we have chosen hydrocortisone (HCS) as a drug model. The mechanism of HCS release changed as a function of pH, owing to different responses in each medium. Our results indicate that the guar gum hydrogels have great potential to be used, with safety, as a drug carrier.

Effect of chitin nanowhiskers on mechanical and swelling properties of Gum Arabic hydrogels nanocomposites.

Hydrogels based on biopolymers like Gum Arabic (GA) usually show low applicability due to weak mechanical properties. To overcome this issue, (nano)fillers are utilized as reinforcing agents. Here, GA hydrogels were reinforced by chitin nanowhiskers (CtNWs, aspect ratio of 14) isolated from the biopolymer chitin through acid hydrolysis. Firstly, GA was chemically modified with glycidyl methacrylate (GMA), which allowed its crosslinking by free radical reactions. Next, hydrogel samples containing different concentrations of CtNWs (0-10 wt%) were prepared and fully characterized. Mechanical characterization revealed that 10 wt% of CtNWs promoted an increase of 44% in the Young's modulus and 96% the rupture force values compared to the pristine hydrogel. Overall, all nanocomposites were stiffer and more resistant to elastic deformation. Due to this feature, the swelling capacity of the nanocomposites decreased. GA hydrogel without CtNWs exhibited a swelling degree of 975%, whereas nanocomposites containing CtNWs exhibited swelling degrees under 725%.

Development of composite hydrogel based on hydroxyapatite mineralization over pectin reinforced with cellulose nanocrystal.

Hydrogels based on pectin and cellulose nanocrystals (CNC) were used in our study to nucleation and growth of hydroxyapatite (HAp) by the biomimetic method. In this study, we evaluated the direct impact of the different percentages of CNC on pectin hydrogel and the influence of HAp obtained through two methods. CNC were obtained from HCl hydrolysis following chemical functionalization through vinyl groups. The percentage of CNC positively induces thermal stability, mechanical properties and HAp mineralization from biomimetic using simulated body fluid (1.5 SBF). Hydrogels with 5% of CNC showed a higher amount of HAp immersed for 14 days, about 28% of HAp. The obtained hydrogels were compared with hydrogels containing 20% of HAp nanoparticles obtained by chemical precipitation. Biocompatibility of the hydrogels was evaluated by cell viability using fibroblasts (L929). In general, the hydrogels obtained through the biomimetic method show slightly larger biocompatibility compared to the hybrid hydrogels obtained from chemical precipitation.

pH-responsive hybrid hydrogels: Chondroitin sulfate/casein trapped silica nanospheres for controlled drug release.

In this study, the materials were synthesized by chemically crosslinking chondroitin sulfate (CS), casein (CAS), and silica nanospheres (SiO2), creating a highly crosslinked network. The hydrogel release profile was adaptable (that is, it could be faster or slower as needed) simply by changing the polymeric proportion. The incorporation of 5% of silica nanospheres, in mass, for all CAS/CS matrices promoted a better-controlled and sustained release of l-dopa, focusing on the matrix based on 70% of CAS, 30% of CS and 5% of silica, whose l-dopa release lasted for 87 h. Besides, hydrogels are cytocompatible. These new hydrogels can be considered highly attractive materials to be used for controlled and sustained drug release purposes, as well as scaffolds and wound dressing systems.

Nanofibrous silica microparticles/polymer hybrid aerogels for sustained delivery of poorly water-soluble camptothecin.

The surface functionalization of nanoporous silica materials with chemical agents opens up numerous possibilities, including improvement in the materials' ability to carry high payloads of drugs. In this study, KCC-1 nanofibrous silica microparticles are functionalized with methyl groups and then combined with poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) to produce hybrid aerogels that can deliver a poorly water-soluble anticancer drug. The synthetic steps involve freeze-drying a polymer solution of PVA and PAA that contains methyl-modified KCC-1 microparticles and then cross-linking the two polymers via a solid-state reaction. Benefiting from the incorporated methyl-modified KCC-1 microparticles, the hybrid aerogels can load and deliver a payload of camptothecin (CPT), an anticancer drug with antitumor activity but limited clinical application due to its hydrophobicity. The aerogels also show a sustained release of CPT for more than two weeks. The drug release profile can further be tuned by varying the relative amounts of PVA, PAA, and methyl-modified KCC-1. The aerogels are biocompatible to healthy cells, such as immortalized human epithelial (HaCaT), African green monkey kidney (Vero) and murine fibroblast (L929) cells. When loaded with CPT, they show potent antitumor activity against HeLa (HPV18-positive), SiHa (HPV16-positive) and C33A (HPV-negative) cancer cells, significantly inhibiting cell growth.

Enhancing Near-Infrared Photothermal Efficiency of Biocompatible Flame-Synthesized Carbon Nano-Onions with Metal Dopants and Silica Coating.

As an alternative to eliminating cancer cells with minimal impacts on the nearby tissues, biocompatible nanoparticles based on silica-coated carbon nano-onions, with outstanding photothermal efficiency, are presented. Metal-doped carbon nano-onion@SiO2 materials are produced using flame synthesis. Metal complexes are injected in the flame to tune the carbon organization levels, which results in materials with excellent photostability and total photothermal conversion efficiency, regarding the incident light input, as higher as 48% for 785 nm laser. It was found that the metal dopant, even at a very low content, plays an interesting role in photothermal efficiency. We tested the effect of thin silica layers on the carbon nanosphere, first as a way to improve biocompatibility and provide a more reactive surface toward the modifications process to add vectorizing agents. Despite the primary goal of the silica shell, a notable increase in photothermal efficiency was observed. In vivo studies of the biological response to the materials as probed by the zebrafish model found that the as-prepared carbon nanospheres and the SiO2-coated particles are highly biocompatible. The SiO2-coated samples were found to be more suitable for photothermal application, due to the higher colloidal stability and higher photothermal efficiency.

Uncommon Sorption Mechanism of Aromatic Compounds onto Poly(Vinyl Alcohol)/Chitosan/Maleic Anhydride-ß-Cyclodextrin Hydrogels.

Aromatic hydrocarbons are extensive environmental pollutants occurring in both water and air media, and their removal is a priority effort for a healthy environment. The use of adsorbents is among the several strategies used for the remediation of these compounds. In this paper, we aim the synthesis of an amphiphilic hydrogel with the potential for the simultaneous sorption of a set of monocyclic and polycyclic aromatic hydrocarbons associated with toxicity effects in humans. Thus, we start by the synthesis of a copolymer-based in chitosan and ß-cyclodextrin previously functionalized with the maleic anhydride. The presence of ß-cyclodextrin will confer the ability to interact with hydrophobic compounds. The resulting material is posteriorly incorporated in a cryogel of poly(vinyl alcohol) matrix. We aim to improve the amphiphilic ability of the hydrogel matrix. The obtained hydrogel was characterized by swelling water kinetics, thermogravimetric analysis, rheological measurements, and scanning electron microscopy. The sorption of aromatic hydrocarbons onto the gel is characterized by pseudo-first-order kinetics and Henry isotherm, suggesting a physisorption mechanism. The results show that the presence of maleic anhydride-ß-cyclodextrin and chitosan into hydrogels leads to an increase in the removal efficiency of the aromatic compounds. Additionally, the capacity of this hydrogel for removing these pollutants from a fossil fuel sample has also been tested.

Drug polarity effect over the controlled release in casein and chondroitin sulfate-based hydrogels.

This study compared the controlled release of two drugs: vitamin-B12, and l-dopa from hydrogels based on 50% of casein (CAS, a protein), 50% of chondroitin sulfate (CS, a polysaccharide) and different amounts of SiO2. The results indicated that the incorporation of 5% of SiO2 to the materials, allowed the best organization, distribution, and diameter of the pores, which are responsible for ensuring a more controlled release. Also, the matrices were not efficient in releasing vitamin-B12, but it successfully released l-dopa. It happened because vitamin-B12 is highly hydrophilic, interacting more with the medium than with the CAS/CS matrix, while l-dopa is less polar than vitamin-B12, interacting more with the CAS/CS matrix. It is worth mentioning that all synthesized hydrogels were non-toxic to the cells as showed by the in vitro assay. This work also demonstrated the importance of evaluating drug delivery devices using drugs of different polarities before stating if they are efficient or not.

Synthesis and water absorption transport mechanism of a pH-sensitive polymer network structured on vinyl-functionalized pectin.

Polysaccharide-structured copolymer hydrogel having excellent pH-sensitivity was developed from N,N-dimethylacrylamide (DMAc) and vinyl-functionalized Pectin (Pec). The Pec was vinyl-functionalized by way of chemical reaction with glycidyl metacrylate (GMA) in water under acidic and thermal stimuli. 13C NMR, 1H NMR, and FT-IR spectra revealed that the vinyl groups coming from the GMA were attached onto backbone of the polysaccharide. The hydrogels were obtained by polymerization of the Pec-vinyl with the DMAc. 13C-CP/MAS NMR and FTIR spectra confirmed that the gelling process occurred by way of the vinyl groups attached on Pec-vinyl backbone. The values of apparent swelling rate constant (k) decreased appreciably for pH greater than 6, demonstrating the swelling process of the hydrogel becomes slower at more alkaline conditions. There was an increase of diffusional exponent (n) with increasing pH of the surrounding liquid. This means the water absorption profile becomes more dependent on the polymer relaxation in basified swelling media. In this condition, a longer water absorption half-time (t1/2) was verified, suggesting the polymer relaxation mechanism of the hydrogel would have a considerable effect on the t1/2.