Antimicrobial Functionalization of Silicone-graft-poly(N-vinylimidazole) Catheters.

In this work, we present the modification of a medical-grade silicone catheter with the N-vinylimidazole monomer using the grafting-from method at room temperature and induced by gamma rays. The catheters were modified by varying the monomer concentration (20-100 vol%) and the irradiation dose (20-100 kGy). Unlike the pristine material, the grafted poly(N-vinylimidazole) chains provided the catheter with hydrophilicity and pH response. This change allowed for the functionalization of the catheters to endow it with antimicrobial features. Thus, the quaternization of amines with iodomethane and bromoethane was performed, as well as the immobilization of silver and ampicillin. The inhibitory capacity of these materials, functionalized with antimicrobial agents, was challenged against Escherichia coli and Staphylococcus aureus strains, showing variable results, where loaded ampicillin was amply better at eliminating bacteria.

Lignocellulosic Membranes Grafted with N-Vinylcaprolactam Using Radiation Chemistry: Load and Release Capacity of Vancomycin.

Radiation chemistry presents a unique avenue for developing innovative polymeric materials with desirable properties, eliminating the need for chemical initiators, which can be potentially detrimental, especially in sensitive sectors like medicine. In this investigation, we employed a radiation-induced graft polymerization process with N-vinylcaprolactam (NVCL) to modify lignocellulosic membranes derived from Agave salmiana, commonly known as maguey. The membranes underwent thorough characterization employing diverse techniques, including contact angle measurement, degree of swelling, scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier-transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR), nuclear magnetic resonance (CP-MAS 13C-NMR), X-ray photoelectron spectroscopy (XPS), and uniaxial tensile mechanical tests. The membranes' ability to load and release an antimicrobial glycopeptide drug was assessed, revealing significant enhancements in both drug loading and sustained release. The grafting of PNVCL contributed to prolonged sustained release by decreasing the drug release rate at temperatures above the LCST. The release profiles were analyzed using the Higuchi, Peppas-Sahlin, and Korsmeyer-Peppas models, suggesting a Fickian transport mechanism as indicated by the Korsmeyer-Peppas model.

Crosslinked Chitosan Films Supplemented with Randia sp. Fruit Extract.

This work proposes the development of a polymer film made up of affordable components for its use as a healthcare material. Chitosan, itaconic acid, and Randia capitata fruit extract (Mexican variation) are the unique ingredients of this biomaterial prospect. Chitosan (from crustacean chitin) is crosslinked with itaconic acid, and in situ added R. capitata fruit extract in a one-pot reaction carried out in water as the sole solvent. Structurally, the film formed is an ionically crosslinked composite characterized by IR spectroscopy and thermal analysis (DSC and TGA); cell viability was also performed in vitro using fibroblasts BALB/3T3. Dry and swollen films were analyzed to determine affinity and stability in water. This chitosan-based hydrogel is designed as a wound dressing due to the combined properties of the chitosan with R. capitata fruit extract, which has potential as bioactive material due to its properties in epithelial regeneration.

Catheters with Dual-Antimicrobial Properties by Gamma Radiation-Induced Grafting.

Dual antimicrobial materials that have a combination of antimicrobial and antifouling properties were developed. They were developed through modification using gamma radiation of poly (vinyl chloride) (PVC) catheters with 4-vinyl pyridine (4VP) and subsequent functionalization with 1,3-propane sultone (PS). These materials were characterized by infrared spectroscopy, thermogravimetric analysis, swelling tests, and contact angle to determine their surface characteristics. In addition, the capacity of the materials to deliver ciprofloxacin, inhibit bacterial growth, decrease bacterial and protein adhesion, and stimulate cell growth were evaluated. These materials have potential applications in the manufacturing of medical devices with antimicrobial properties, which can reinforce prophylactic potential or even help treat infections, through localized delivery systems for antibiotics.

Binary Graft of Poly(acrylic acid) and Poly(vinyl pyrrolidone) onto PDMS Films for Load and Release of Ciprofloxacin.

Polymers are versatile compounds which physical and chemical properties can be taken advantage of in wide applications. Particularly, in the biomedical field, polydimethylsiloxane (PDMS) is one of the most used for its high biocompatibility, easy manipulation, thermal, and chemical stability. Nonetheless, its hydrophobic nature makes it susceptible to bacterial pollution, which represents a disadvantage in this field. A potential solution to this is through the graft of stimuli-sensitive polymers that, besides providing hydrophilicity, allow the creation of a drug delivery system. In this research, PDMS was grafted with acrylic acid (AAc) and vinyl pyrrolidone (VP) in two steps using gamma radiation. The resulting material was analyzed by several characterization techniques such as infrared spectroscopy (FTIR), swelling, contact angle, critical pH, and thermogravimetric analysis (TGA), demonstrating the presence of both polymers onto PDMS films and showing hydrophilic and pH-response properties. Among the performed methods to graft, the loading and release of ciprofloxacin were successful in those samples obtained by direct irradiation method. Furthermore, the antimicrobial assays showed zones of inhibition for microorganisms such as Staphylococcus aureus and Escherichia coli.

Recent Trends in Magnetic Polymer Nanocomposites for Aerospace Applications: A Review.

Polymers have had an enormous impact on science and technology, and their interest relating to the development of new macromolecular materials has exponentially increased. Polymer nanocomposites, materials based on a polymeric matrix covalently coupled to reinforcement, display properties of both components. In the aerospace industry, polymer nanocomposites are attractive due to their promising characteristics, among which lightness, mechanical and thermal resistance, radiation and corrosion resistance, and conductive and magnetic properties stand out. The use of them, instead of metal-based materials, has allowed the optimization of design processes and applications in order to provide safer, faster, and eventually cheaper transportation in the future. This comparative review collects the most relevant and prominent advances in the development of polymer nanocomposites with aerospace applications starting from basic aspects such as the definition of polymer nanocomposite to more specialized details such as synthesis, characterization, and applications, in addition to proposing new research branches related to this topic.

Polymer-Magnetic Semiconductor Nanocomposites for Industrial Electronic Applications.

Nanocomposite materials have acquired great importance, as have similar composite materials on a macroscopic scale, because the reinforcement complements the defects in the properties of the matrix, thus obtaining materials with better mechanical, thermal, and electrical properties, among others. At the same time, the importance and research of polymeric nanocomposites reinforced with nanoparticles of various types have grown. Among those that have stood out the most in the electronics industry are polymeric matrices reinforced with nanoparticles that present dual behavior, that is, both magnetic and semiconductor. This property has been very well used in developing electronic devices such as televisions, computers, and smartphones, which are part of everyday life. In this sense, this review presents a compilation of the synthetic methods to produce polymer nanocomposites with dual magnetic and semiconductor behavior and their potential applications within electronic fields and new relevant trends.

Antifouling PVC Catheters by Gamma Radiation-Induced Zwitterionic Polymer Grafting.

In medical environments, polymeric surfaces tend to become contaminated, hindering the treatment and recovery from diseases. Biofouling-resistant materials, such as zwitterionic polymers, may mitigate this problem. In this work, the modification of PVC catheters with a binary graft of 4-vinylpyridine (4VP) and sulfobetaine methacrylate (SBMA) by the oxidative pre-irradiation method is proposed to develop pH-responsive catheters with an antifouling capacity. The ionizing radiation allowed us to overcome limitations in the synthesis associated with the monomer characteristics. In addition, the grafted materials showed a considerable increase in their hydrophilic character and antifouling capacity, significantly decreasing the protein adsorption compared to the unmodified catheters. These materials have potential for the development of a combined antimicrobial and antifouling capabilities system to enhance prophylactic activity or even to help treat infections.

Polymeric Composite of Magnetite Iron Oxide Nanoparticles and Their Application in Biomedicine: A Review.

A broad spectrum of nanomaterials has been investigated for multiple purposes in recent years. Some of these studied materials are magnetics nanoparticles (MNPs). Iron oxide nanoparticles (IONPs) and superparamagnetic iron oxide nanoparticles (SPIONs) are MNPs that have received extensive attention because of their physicochemical and magnetic properties and their ease of combination with organic or inorganic compounds. Furthermore, the arresting of these MNPs into a cross-linked matrix known as hydrogel has attracted significant interest in the biomedical field. Commonly, MNPs act as a reinforcing material for the polymer matrix. In the present review, several methods, such as co-precipitation, polyol, hydrothermal, microemulsion, and sol-gel methods, are reported to synthesize magnetite nanoparticles with controllable physical and chemical properties that suit the required application. Due to the potential of magnetite-based nanocomposites, specifically in hydrogels, processing methods, including physical blending, in situ precipitation, and grafting methods, are introduced. Moreover, the most common characterization techniques employed to study MNPs and magnetic gel are discussed.

Silver Nanoparticles Loaded on Polyethylene Terephthalate Films Grafted with Chitosan.

Currently, polyethylene terephthalate (PET) is one of the most widely used polymeric materials in different sectors such as medicine, engineering, and food, among others, due to its benefits, including biocompatibility, mechanical resistance, and tolerance to chemicals and/or abrasion. However, despite all these excellent characteristics, it is not capable of preventing the proliferation of microorganisms on its surface. Therefore, providing this property to PET remains a difficult challenge. Fortunately, different strategies can be applied to remove microorganisms from the PET surface. In this work, the surface of the PET film was functionalized with amino groups and later with a dicarboxylic acid, allowing a grafting reaction with chitosan chains. Finally, the chitosan coating was loaded with silver nanoparticles with an average size of 130 ± 37 nm, presenting these materials with an average cell viability of 80%. The characterization of these new PET-based materials showed considerable changes in surface morphology as well as increased surface hydrophilicity without significantly affecting their mechanical properties. In general, the implemented method can open an alternative pathway to design new PET-based materials due to its good cell viability with possible bacteriostatic activity due to the biocidal properties of silver nanoparticles and chitosan.

Hydrogels Classification According to the Physical or Chemical Interactions and as Stimuli-Sensitive Materials.

Hydrogels are attractive biomaterials with favorable characteristics due to their water uptake capacity. However, hydrogel properties are determined by the cross-linking degree and nature, the tacticity, and the crystallinity of the polymer. These biomaterials can be sorted out according to the internal structure and by their response to external factors. In this case, the internal interaction can be reversible when the internal chains are led by physicochemical interactions. These physical hydrogels can be synthesized through several techniques such as crystallization, amphiphilic copolymers, charge interactions, hydrogen bonds, stereo-complexing, and protein interactions. In contrast, the internal interaction can be irreversible through covalent cross-linking. Synthesized hydrogels by chemical interactions present a high cross-linking density and are employed using graft copolymerization, reactive functional groups, and enzymatic methods. Moreover, specific smart hydrogels have also been denoted by their external response, pH, temperature, electric, light, and enzyme. This review deeply details the type of hydrogel, either the internal structure or the external response. Furthermore, we detail some of the main applications of these hydrogels in the biomedicine field, such as drug delivery systems, scaffolds for tissue engineering, actuators, biosensors, and many other applications.

Highly Crosslinked Agar/Acrylic Acid Hydrogels with Antimicrobial Properties.

Hydrogels are three-dimensional soft polymeric materials that can entrap huge amounts of water. They are widely attractive in the biomedicine area because of their outstanding applications such as biosensors, drug delivery vectors, or matrices for cell scaffolds. Generally, the low mechanical strength and fragile structure of the hydrogels limit their feasibility, but this is not the case. In this work, acrylic acid-agar hydrogels with excellent mechanical properties were synthesized using gamma radiation as a crosslinking promoter. The obtained hydrogels exhibited a water absorption capacity up to 6000% in weight without breaking and keeping their shape; additionally, they showed a noticeable adhesion to the skin. The synthesized materials were characterized by infrared spectroscopy (FTIR-ATR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and mechanical testing. Additionally, their water uptake capacity and critical pH were studied. Net(Agar/AAc) hydrogel exhibited a noticeable capacity to load silver nanoparticles (AgNPs), which endowed it with antimicrobial activity that was demonstrated when challenged against Escherichia coli and methicillin-resistant Staphylococcus aureus (MRSA) on in vitro conditions.

Interaction between Filler and Polymeric Matrix in Nanocomposites: Magnetic Approach and Applications.

In recent years, polymer nanocomposites produced by combining nanofillers and a polymeric matrix are emerging as interesting materials. Polymeric composites have a wide range of applications due to the outstanding and enhanced properties that are obtained thanks to the introduction of nanoparticles. Therefore, understanding the filler-matrix relationship is an important factor in the continued growth of this scientific area and the development of new materials with desired properties and specific applications. Due to their performance in response to a magnetic field magnetic nanocomposites represent an important class of functional nanocomposites. Due to their properties, magnetic nanocomposites have found numerous applications in biomedical applications such as drug delivery, theranostics, etc. This article aims to provide an overview of the filler-polymeric matrix relationship, with a special focus on magnetic nanocomposites and their potential applications in the biomedical field.

Synthesis and Antimicrobial Properties of Highly Cross-Linked pH-Sensitive Hydrogels through Gamma Radiation.

The design of new polymeric systems for antimicrobial drug release focused on medical/surgical procedures is of great interest in the biomedical area due to the high prevalence of bacterial infections in patients with wounds or burns. For this reason, in this work, we present a new design of pH-sensitive hydrogels copolymerized by a graft polymerization method (gamma rays), intended for localized prophylactic release of ciprofloxacin and silver nanoparticles (AgNPs) for potential topical bacterial infections. The synthesized hydrogels were copolymerized from acrylic acid (AAc) and agar. Cross-linked hydrogel film formation depended on monomer concentrations and the degree of radiation used (Cobalt-60). The obtained hydrogel films were characterized by attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mechanical testing. The swelling of the hydrogels was evidenced by the influence of their pH-sensitiveness. The hydrogel was loaded with antimicrobial agents (AgNPs or ciprofloxacin), and their related activity was evaluated. Finally, the antimicrobial activity of biocidal-loaded hydrogel was tested against Escherichia coli (E. coli) and methicillin-resistant Staphylococcus aureus (MRSA) on in vitro conditions.

Simultaneous Grafting Polymerization of Acrylic Acid and Silver Aggregates Formation by Direct Reduction Using γ Radiation onto Silicone Surface and Their Antimicrobial Activity and Biocompatibility.

The modification of medical devices is an area that has attracted a lot of attention in recent years; particularly, those developments which search to modify existing devices to render them antimicrobial. Most of these modifications involve at least two stages (modification of the base material with a polymer graft and immobilization of an antimicrobial agent) which are both time-consuming and complicate synthetic procedures; therefore, as an improvement, this project sought to produce antimicrobial silicone (PDMS) in a single step. Using gamma radiation as both an energy source for polymerization initiation and as a source of reducing agents in solution, PDMS was simultaneously grafted with acrylic acid and ethylene glycol dimethacrylate (AAc:EGDMA) while producing antimicrobial silver nanoparticles (AgNPs) onto the surface of the material. To obtain reproducible materials, experimental variables such as the effect of the dose, the intensity of radiation, and the concentration of the silver salt were evaluated, finding the optimal reaction conditions to obtain materials with valuable properties. The characterization of the material was performed using electronic microscopy and spectroscopic techniques such as 13C-CPMAS-SS-NMR and FTIR. Finally, these materials demonstrated good antimicrobial activity against S. aureus while retaining good cell viabilities (above 90%) for fibroblasts BALB/3T3.

Poly(N-vinylcaprolactam) and Salicylic Acid Polymeric Prodrug Grafted onto Medical Silicone to Obtain a Novel Thermo- and pH-Responsive Drug Delivery System for Potential Medical Devices.

New medical devices with anti-inflammatory properties are critical to prevent inflammatory processes and infections in medical/surgical procedures. In this work, we present a novel functionalization of silicone for medical use with a polymeric prodrug and a thermosensitive polymer, by graft polymerization (gamma rays), for the localized release of salicylic acid, an analgesic, and anti-inflammatory drug. Silicone rubber (SR) films were functionalized in two stages using graft polymerization from ionizing radiation (60Co). The first stage was grafting poly(N-vinylcaprolactam) (PNVCL), a thermo-sensitive polymer, onto SR to obtain SR-g-PNVCL. In the second stage, poly(2-methacryloyloxy-benzoic acid) (P2MBA), a polymeric prodrug, was grafted to obtain (SR-g-PNVCL)-g-P2MBA. The degree of functionalization depended on the concentrations of monomers and the irradiation dose. The films were characterized by attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy/energy-dispersive X-ray spectrometry (SEM-EDX), thermogravimetric analysis (TGA), and contact angle. An upper critical solution temperature (UCST) of the films was demonstrated by the swelling degree as a temperature function. (SR-g-PNVCL)-g-P2MBA films demonstrated hydrolysis-mediated drug release from the polymeric prodrug, pH, and temperature sensitivity. GC-MS confirmed the presence of the drug (salicylic acid), after polymer hydrolysis. The concentration of the drug in the release media was quantified by HPLC. Cytocompatibility and thermo-/pH sensitivity of functionalized medical silicone were demonstrated in cancer and non-cancer cells.

Polypropylene Graft Poly(methyl methacrylate) Graft Poly(N-vinylimidazole) as a Smart Material for pH-Controlled Drug Delivery.

Surface modification of polypropylene (PP) films was achieved using gamma-irradiation-induced grafting to provide an adequate surface capable of carrying glycopeptide antibiotics. The copolymer was obtained following a versatile two-step route; pristine PP was exposed to gamma rays and grafted with methyl methacrylate (MMA), and afterward, the film was grafted with N-vinylimidazole (NVI) by simultaneous irradiation. Characterization included Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and physicochemical analysis of swelling and contact angle. The new material (PP-g-MMA)-g-NVI was loaded with vancomycin to quantify the release by UV-vis spectrophotometry at different pH. The surface of (PP-g-MMA)-g-NVI exhibited pH-responsiveness and moderate hydrophilicity, which are suitable properties for controlled drug release.

An Updated Review of Macro, Micro, and Nanostructured Hydrogels for Biomedical and Pharmaceutical Applications.

Hydrogels are materials with wide applications in several fields, including the biomedical and pharmaceutical industries. Their properties such as the capacity of absorbing great amounts of aqueous solutions without losing shape and mechanical properties, as well as loading drugs of different nature, including hydrophobic ones and biomolecules, give an idea of their versatility and promising demand. As they have been explored in a great number of studies for years, many routes of synthesis have been developed, especially for chemical/permanent hydrogels. In the same way, stimuli-responsive hydrogels, also known as intelligent materials, have been explored too, enhancing the regulation of properties such as targeting and drug release. By controlling the particle size, hydrogel on the micro- and nanoscale have been studied likewise and have increased, even more, the possibilities for applications of the so-called XXI century materials. In this paper, we aimed to produce an overview of the recent studies concerning methods of synthesis, biomedical, and pharmaceutical applications of macro-, micro, and nanogels.

Radiation Grafting of a Polymeric Prodrug onto Silicone Rubber for Potential Medical/Surgical Procedures.

Silicone rubber (SR) is a material used for medical procedures, with a common example of its application being in implants for cosmetic or plastic surgeries. It is also an essential component for the development of medical devices. SR was functionalized with the polymeric prodrug of poly(2-methacryloyloxy-benzoic acid) (poly(2MBA)) to render the analgesic anti-inflammatory drug salicylic acid by hydrolysis. The system was designed by functionalizing SR films (0.5 cm × 1 cm) with a direct grafting method, using gamma irradiation (60Co source) to induce the polymerization process. The absorbed dose (from 20 to 100 kGy) and the monomer concentration (between 0.4 and 1.5 M) were critical in controlling the surface and the bulk modifications of SR. Grafting poly(2MBA) onto SR (SR-g-2MBA) were characterized by attenuated total reflectance Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy/energy-dispersive X-ray spectrometry, fluorescence microscopy, the contact angle, and the swelling. SR-g-2MBA demonstrated the drug's sustained and pH-dependent release in simulated physiological mediums (pH = 5.5 and 7.4). The drug's release was quantified by high-performance liquid chromatography and confirmed by gas chromatography-mass spectrometry. Finally, cytocompatibility was demonstrated in murine fibroblast and human cervical cancer cell lines. The developed systems provide new polymeric drug release systems for medical silicone applications.

Gamma rays: An alternative energy source for the preparation of manganese carbonyls-based new materials.

We report on the synthesis of new manganese carbonyls-based materials prepared using gamma-rays radiation (at doses of 10 and 40 kGy) as energy source. Characterization was achieved using nuclear magnetic resonance, infrared spectroscopy, elemental analysis, single-crystal X-ray diffraction, differential scan calorimetry, thermogravimetric analysis, and mass spectrometry. The irradiated materials presented enhanced thermal stability along with formation of spherical shaped microparticles sized around 0.95 µm attested by scanning electron microscopy and energy-dispersive X-ray spectroscopy.