Antibacterial effect of nanometer-size grafted layer of quaternary ammonium polymer on poly(ether ether ketone) substrate

Owing to its excellent physicochemical properties, poly(ether ether ketone) (PEEK) has been used clinically for medical implants. However, its surface properties should be improved to further enhance its compatibility with a living organism and infection resistance. Here, we examined the surface construction via a combined process, that is, the self-initiated photoinduced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMA) on PEEK substrate followed by polymer quaternization using various bromoalkanes (Q-PDMA-g-PEEK). Using a Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, the grafting and quaternarization of poly(DMA) (PDMA) on the PEEK substrate was confirmed. The degree of quaternizations was at least 60% even when the various bromoalkanes were reacted. The Q-PDMA-g-PEEK with 1-bromooctane (BrC₈) (C₈-Q-PDMA-g-PEEK) substrate exhibited the highest ζ-potential of other Q-PDMA-g-PEEK substrates. However, no significant differences were observed in the degree of quaternization, thickness of the polymer layer, and hydrophilicity of all modified PEEK substrates. In addition, from antibacterial test with Escherichia coli, the C₈Q-PDMA-g-PEEK substrate exhibited the highest antibacterial rate (80%) among Q-PDMA-g-PEEK substrates examined. Therefore, we concluded that the surface ζ-potential is the one an important parameter for manufacturing PEEK substrates with bactericidal properties.     

Radiopaque iodinated ethers of poly(vinyl iodobenzyl ether)s: Synthesis and evaluation for endovascular embolization

Leachable‐free radiopaque iodinated polymers were designed as long‐lived embolization materials visible by X‐ray tomography. This is a definite improvement over liquid embolics incorporating either radiopaque inorganic particles or iodinated polymers having hydrolysable ester bonds. Grafting 4‐iodobenzyl or 2,3,5‐triiodobenzyl groups to poly(vinyl alcohol) (PVAL) yields iodobenzyl ethers of PVAL having iodine contents in the range 40–70 wt %. Their solubility in solvents accepted for medical devices (DMSO and NMP), viscosity of concentrated solutions, precipitation behavior, radiopacity, and stability with respect to sterilization and hydrolysis were assessed. The solvent NMP allows the preparation of concentrated solutions of suitable viscosity for their application as liquid embolics. Precipitation in water yields a cohesive mass of material that can plug vascular malformations. A rationale to the properties is given in terms of the Hansen contributions to the Hildebrand solubility parameters. Iodobenzyl ethers of PVA resist hydrolysis whereas their corresponding iodobenzoyl esters leach iodinated fragments. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41791.     

Polyester functionalization for mycobacterial capture

Tuberculosis (TB) is one of the deadliest diseases known to man and ranks among the top ten global causes of fatalities. Children often develop a paucibacillary form of this disease which makes diagnosis arduous even with the aid of sophisticated techniques. In these cases, the concentration of bacteria in their sputum falls below the lowest limit of detection for sputum smear microscopy, the technique predominantly used in developing countries. In this study we aim to test the hypothesis that modifying a polymer, often used in buccal swabs, could assist in creating a capturing and concentrating oral swab for Mycobacterium tuberculosis (Mtb), the pathogenic bacterial species responsible for TB. Such a device will assist in meeting the detection limit and allow for rapid detection of the disease. The polymer used was a micro fibrous form of poly(ethylene terephthalate) (PET) which was surface functionalized with Concanavalin A (Con A), a lectin based adhesin with an affinity for the mannose groups on the Mtb cell wall. The functionalization was mediated with glutaraldehyde as bioconjugate molecule and found to produce a surface uniformly covered with Con A. Affinity studies between the modified fibers and the Mycobacterium bovis bacillus Calmette-Guérin (BCG), as Mtb mimic, were conducted to evaluate the capturing abilities of the substrate. The results indicate that the fibers avidly captured BCG and that the fibrous matrix aided in its function. Dilution studies showed successful capturing of the bacterial species at concentrations characteristic of paucibacillary cases. In this study a commercial polymeric material was successfully surface modified with a biological entity to create a substrate to which Mtb could adhere and accordingly be captured.     

Conjugated polymers with anionic dyes: Synthesis,properties, and sensing ability for nucleosides,DNA, and BSA

The reaction of N-(2,4-dinitrophenyl)pyridinium chloride (salt[Cl⁻]) with sodium salts of anionic dyes, such as acid red 52 (AR52), acid violet 49 (AV49), and coomassie brilliant blue G-250 (CBBG250) involves an anion exchange between the chloride anion of salt(Cl⁻) and sulfonium anion of the dyes, resulting in the generation of novel Zincke salts, namely, salt(AR52), salt(AV49), and salt(CBBG250), respectively. Reactions of salt(AR52), salt(AV49), and salt(CBBG250) with piperazine in the absence of catalysts resulted in the opening of the pyridinium ring to yield ionic polymers comprising units of 5-piperazinium-2,4-dienylideneammonium and the corresponding dye anion, namely polymer(AR52), polymer(AV49), and polymer(SBBG250), respectively. The corresponding model compounds for the polymers were also synthesized by reacting salt(AR52), salt(AV49), and salt(CBBG250) with piperidine. Polymer(AV49) and polymer(SBBG250) were found to be suitable for the detection of nucleosides, DNA, and proteins, realized by monitoring the changes in their UV–vis absorption spectra, arising from the anionic dyes within the polymers. The polymers and the model compounds were electrochemically oxidized in solution.     

Different real-time degradation scenarios of functionalized poly(ε-caprolactone) for biomedical applications

Anterior cruciate ligament (ACL) ruptures are a much-commented injury as it can end the season or even career of professional athletes. However, the recovery of a patient from the general population is no less painful during the long period required by current treatments. Artificial ligaments could improve this healing, yet, orthopedic surgeons are still cautious about permanent ACL implants. Therefore, combining biodegradation and bioactivity could be a key feature for the popularization of these devices. This study aim at evaluating the real-time degradation of poly(ε-caprolactone) (PCL) grafted with the bioactive polymer sodium polystyrene sulfonate in different scenarios. PCL physical–chemical properties were evaluated before and after degradation. In addition, in vitro experiments were realized to confirm the long term influence of the grafting on cell response. Altogether, we were able to show different degradations scenarios, enabling to study the impact of degradation environment on degradation mode and rate of functionalized PCL.     

Recent advances in nanocellulose for biomedical applications

Nanocellulose materials have undergone rapid development in recent years as promising biomedical materials because of their excellent physical and biological properties, in particular their biocompatibility, biodegradability, and low cytotoxicity. Recently, a significant amount of research has been directed toward the fabrication of advanced cellulose nanofibers with different morphologies and functional properties. These nanocellulose fibers are widely applied in medical implants, tissue engineering, drug delivery, wound‐healing, cardiovascular applications, and other medical applications. In this review, we reflect on recent advancements in the design and fabrication of advanced nanocellulose‐based biomaterials (cellulose nanocrystals, bacterial nanocellulose, and cellulose nanofibrils) that are promising for biomedical applications and discuss material requirements for each application, along with the challenges that the materials might face. Finally, we give an overview on future directions of nanocellulose‐based materials in the biomedical field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41719.     

Performance of silk-polypyrrole bilayer actuators under biologically relevant conditions

Biocompatible actuators that are capable of controlled movement and can function under biologically relevant conditions are of significant interest for biomedical applications. Previously, we have demonstrated that a composite material of silk biopolymer and the conducting polymer poly(pyrrole) (PPy) can be formed into a functional bilayer bending actuator. Further, these silk-PPy composites can generate forces comparable to human muscle (>0.1 MPa) making them ideal candidates for interfacing with biological tissues. Here, we explore the performance of these silk-PPy composite bilayer actuators under biologically relevant conditions including exposure to proteins, serum, enzymes, and biologically relevant temperatures. Free-end bending actuation performance, current response, force generation, and mass degradation under these conditions were investigated. We find that under the conditions tested here, the performance of our silk-PPy composites is sensitive to both protein serum and enzyme type, as well as to the temperature at which the devices are actuated. However, the silk-PPy actuators retained their functionality under all conditions tested, demonstrating the ability to bend, generate forces, and conduct currents at comparable levels to devices tested under standard operating conditions. The results suggest that our silk-PPy actuators are promising candidates for implantation in vivo and for interfacing with biological systems. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46922.     

Dielectric properties of thin films of Babassu‐based polymer and polyaniline blends

In the present work, we describe the preparation and subsequent characterization of polymeric blends consisting of a monoglyceride (MG) synthesized from the Babassu's oil and the already commonly employed polyaniline (PAni). By following changes in the complex impedance of capacitor‐like devices we observe that the presence of MG in the PAni/MG blends decreases electrical conductivity and that this decrease is a function of the content of MG in the blend, i.e., the blend with 30% of MG shows Z′ about seven times greater than the one with 10% of MG. Fourier transform infrared measurements prove the formation of MG and the presence of secondary amine groups (N? H bonds) in the blends, which allow for the chemical doping of PAni by protonation, further studies are necessary to access the viability of employing this new material as active layer in electronic organic devices. Atomic force microscopy images show the formation of agglomerates due to the presence of MG. In addition, the polymeric mixture acts only as a blend, providing a physical interaction between different components. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46198.     

New biomaterial based on cotton with incorporated Biomolecules

The aim of this study was to investigate a method of embedding l ‐cysteine (l ‐cys), an antimicrobial agent, between layers of chitosan (CH) and sodium alginate (ALG) onto cotton samples obtained via a layer‐by‐layer electrostatic deposition technique via several embedding methods. The results show that the best way to incorporate l ‐cys into the layers was the one that used the property of gelling ALG. To monitor the l ‐cys embedding into the CH/ALG multilayer film, different methods were used: energy‐dispersive X‐ray spectrometry analysis to assess the presence of sulfur on the sample, Ellman's reagent method to analyze l ‐cys release from the sample, and attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FTIR) to compare the ATR–FTIR spectra of the pure l ‐cys and l ‐cys embedded in the CH/ALG multilayer film to study the interaction between the l ‐cys and the CH/ALG multilayer films. Functionalized CH/ALG cotton samples were also investigated for their antibacterial properties toward Staphylococcus aureus and Klebsiella pneumonia with the Japanese Industrial Standard method JIS L 1902:2002, and the results show an enhancement of the antibacterial effect due to the presence of l ‐cys. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40519.     

Comparison of the antibacterial activity of modified‐cotton with magainin I and LL‐37 with potential as wound‐dressings

Wounds are the ideal setting for the development of micro‐organisms, so it is often necessary to apply a dressing to control bacterial colonization. Cotton is commonly used in dressings, as it exhibits important hydrophilic characteristics such as high moisture and fluid retention properties, but it may provide a sustainable media for the development of micro‐organisms. In this way, the development of new strategies to provide cotton materials with lasting and effective antimicrobial properties is of the utmost importance. Consequently, here we described two processes to develop cotton‐dressings functionalized with antimicrobial peptides (AMPs) magainin I (MagI) and LL‐37, in order to give cotton‐dressings an antibacterial effect. The AMPs showed no cytotoxic effect against human fibroblasts so they are safe to contact with skin. In addition, the functionalized materials with either LL‐37 or MagI present an antimicrobial effect exhibiting inhibition ratios of 89% against Klebsiella pneumoniae and 58% against Staphylococcus aureus, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40997.     

Human organ phantoms for catheterization using the radiation crosslinking technique

An artificial organ based on polyvinyl alcohol (PVA) hydrogel was developed to train medical staff to improve their ablation therapy skills, by using the radiation cross-linking technique. The aqueous PVA solution was irradiated with γ-rays or electron beams to produce a highly transparent, high-strength, and flexible crosslinked hydrogel without using a crosslinking agent. Physical properties of the hydrogel, such as, gel fraction, swelling, and elastic modulus, were controlled by changing the radiation dose. The catheter ablation region on the surface of the cardiac phantom produced from PVA hydrogel with temperature-responsive pigment inks can be visually identified by the color change. The tumor organ phantom consists of the PVA hydrogel with the purple pigment ink (healthy organ site) and red PVA hydrogel with cellulose (the tumor sites) was developed by applying this radiation crosslinking technique. The positions of the tumor hydrogel and the ablation electrode needle can be confirmed through ultrasound echography. It is possible to practice ablation on the tumor site while observing the echo images under conditions similar to the actual treatment. These novel human organ phantoms are created as a means for ablation training for treating cardiac arrhythmia and liver cancer using the radiation crosslinking technology.     

Electrochemical stability of PEDOT for wearable on-skin application

Conducting polymers are promising candidates for wearable devices due to mechanical flexibility combined with electroactivity. While electrochemical measurements have been adopted as a central transduction method in many on-skin sensors, less studied is the stability of the active materials (in particular poly3,4-ethylenedioxythiophene, PEDOT) in such systems, particularly for “on-skin” applications. In this study, several different variants of doped PEDOT are fabricated and characterized in terms of their (electrical, physical, and chemical) stability in biological fluid. PEDOT doped with tosylate (TOS) or polystyrenesulfonate (PSS) are selected as prototypical forms of conducting polymers. These are compared with a new variant of PEDOT co-doped with both TOS and PSS. Artificial interstitial fluid (aISF) loaded with 1% wt/vol bovine serum albumin is adopted as the testing medium to demonstrate the stability in dermal applications (i.e., conducting polymer microneedles or coatings on microneedles). A range of techniques such as cyclic voltammetry and electrochemical impedance spectroscopy are used to qualify and quantify the stability of the doped conducting polymers. Furthermore, this study is extended by using human skin lysate in the aISF to demonstrate proof-of-concept for stable use of PEDOT in wearable “on-skin” electronics.     

Facile fabrication of superhydrophobic polyaniline structures and their anticorrosive properties

We report a simple approach for the preparation of superhydrophobic polyaniline (PANI) and its application for the corrosion protection coatings. First, PANI was synthesized conventionally by oxidative polymerization with APS. Subsequently, PANI with different wettability was obtained by modification with different surfactants. The surface modification of PANI with three different surfactants (sodium dodecylbenzenesulfonate, polyethylene glycol, and cetyltrimethylammonium bromide) provided excellent surface superhydrophobicity (water contact angle >150°). The structure and morphology of as‐prepared PANI were characterized with Fourier transform infrared, Energy dispersive X‐ray spectroscopy, and Scanning electron microscopy. Corrosion protection performance of PANI with different wettability was evaluated in 3.5% NaCl electrolyte using Tafel polarization curves and electrochemical impedance spectroscopy. The results indicated that various superhydrophobic PANI coatings have better anticorrosion performance as compared to the hydrophilic PANI. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44248.     

Green electrospun nanocuprous oxide–poly(ethylene oxide)–silk fibroin composite nanofibrous scaffolds for antibacterial dressings

Cuprous oxide (Cu₂O) nanoparticles have attracted extensive attention because of their excellent optical, catalytic, antibacterial, and antifungal properties and low cost. Nano-Cu₂O–poly(ethylene oxide) (PEO)–silk fibroin (SF) composite nanofibrous scaffolds (CNSs) were fabricated through green electrospinning to impart excellent antibacterial properties onto nanofibrous scaffolds. Scanning electron microscopy revealed that the nanofibers became more nonuniform and appeared more and more as beads in the nanofibers with increasing nano-Cu₂O concentration, and no obvious morphological changes were observed after 75% EtOH vapor treatment. Transmission electron microscopy and X-ray photoelectron spectroscopy demonstrated that nano-cuprous oxide (nano-Cu₂O) was successfully loaded into the PEO–SF nanofibers. Fourier transform infrared–attenuated total reflectance spectroscopy results indicate that nano-Cu₂O did not induce SF conformation from random coils to β sheets. The SF conformation converted from random coils to β sheets after 75% EtOH vapor treatment. The results of water contact angle testing and swelling property measurement clarified that nano-Cu₂O–PEO–SF CNSs possessed outstanding hydrophilicity. Nano-Cu₂O–PEO–SF CNSs exhibited better antibacterial activity against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus bacteria than PEO–SF nanofibrous scaffolds, and the antibacterial activity increased with increasing nano-Cu₂O concentration. Cell viability studies with pig iliac endothelial cells demonstrated that nano-Cu₂O–PEO–SF CNSs had no cytotoxicity. Nano-Cu₂O–PEO–SF CNSs are expected to be ideal biomimetic antibacterial dressings for wound healing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47730.     

Imidazole functionalized polyaniline: Synthesis,characterization, and Cu (II) coordination studies

Polyaniline functionalized with imidazole as strategically designed receptor group in its backbone was synthesized for copper binding. The synthesized polymer has been characterized using FTIR, NMR, and UV‐Vis spectroscopic techniques. The addition of copper (II) to the polymer distinctly changes the properties such as crystallinity, molecular weight, aggregation, and electronic properties. XRD, DLS, SEM, and four‐point probe techniques have been used for study of these changes. It is observed that the secondary ion generated as a result of copper coordination results in the doping of the polyaniline backbone, which enhances the conductivity by one order of magnitude. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Antimicrobial silica and sand particles functionalized with an N‐halamine acrylamidesiloxane copolymer

The monomer 2‐acrylamido‐2‐methyl‐1‐(5‐methylhydantoinyl)propane (HA) was copolymerized with 3‐(trimethoxysilyl)propyl methacrylate (SL) and covalently attached onto silica gel and sand particles. As a result HASL copolymer‐grafted silica gel and sand particles (HASL SGPs and SPs) were obtained. These two types of HASL SGPs and SPs provided excellent biocidal efficacy against Gram positive S. aureus and Gram negative E. coli O157:H7 bacteria when the copolymer‐grafted particles were exposed to dilute sodium hypochlorite (household bleach) solution. In a flowing water application, seven logs of bacteria were inactivated within 10 s of contact time with the particles packed into a column. The treated particles also exhibited good washing and storage stabilities. The chlorine loss during extensive flow could be recovered by further exposure to dilute bleach solution. The antimicrobial particles have potential application for use in inexpensive disinfecting water filters for slow water flows. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43413.     

Soft mixed ionic–electronic conductive electrodes for noninvasive stimulation

A new material, classified as a soft mixed ionic–electronic conductor (MIEC), was fabricated through casting and curing of different ratios of single walled carbon nanotube (SWNTs), hyaluronic acid (HA), and acrylonitrile butadiene copolymer latex (NBR) and developed for noninvasive stimulation for electrotherapeutics. The morphology of the composite yielded high electrical conductivity and retention of elasticity. The interfacial charge transfer of the material showed that by increasing the HA loading the capacitive contribution decreased, while increasing SWNT loading decreased the interfacial resistance. The soft MIEC materials interfacial charge transfer was superior than current state-of-the art electrodes on the market. A layered configuration with high HA ratio at the skin interface and high SWNTs ratio at the stainless-steel interface was created to induce the most optimal charge transfer. These soft MIEC electrodes will be extremely helpful in electrotherapeutic applications to eliminate the need for hydrogels, which can be unsuitable due the their lack long term durability and instability.     

Antibacterial and antifungal dressings obtained by photochemical deposition of silver nanoparticles

The antimicrobial activity of silver against a wide spectrum of bacteria, fungi and viruses is known since antiquity. Silver has been used as topical antimicrobial agent in the treatment of wounds since many years and advanced silver‐based dressings have been designed so far. The aim of this study was the development of low‐cost antibacterial and antifungal dressings through the surface modification of conventional cotton gauzes. Different percentages of silver were deposited on textile substrates by adopting an innovative silver deposition technique based on the photochemical deposition of silver nanoparticles. The uniformity of the coating and the distribution of the silver clusters on the surface were evaluated by scanning electron microscopy (SEM). The amount of silver was quantified by thermogravimetric analysis (TGA) and the presence of metallic silver nanoparticles was also assesses through UV–Vis–NIR with integrating sphere and energy dispersive X‐ray spectroscopy EDX. The effectiveness of the silver treated textile was verified on different microorganisms, namely Escherichia coli, Staphylococcus aureus, Pseudomonas p43 and Candida albicans derived from a clinical isolate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40326.     

Facile synthesis of amphiphilic chitosan‐g‐poly(lactic acid) derivatives and the study of their controlled drug release

We report here a simple and green procedure for the synthesis of amphiphilic chitosan (CS) derivatives with poly(lactic acid) (PLA) side chains, without the use of high pure lactide, high temperatures, or large amounts of organic solvent. The chemical structure and physical properties of these CS derivatives were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, thermogravimetric analysis, and X‐ray diffraction. The formation and characteristics of polymeric micelles based on these CS derivatives were studied by fluorescence spectroscopy and dynamic light scattering. The critical aggregation concentration in water varied from 0.048 to 0.021 mg/mL, and the mean diameter was in the range 169.8–260.7 nm in aqueous solution at 25°C when the PLA grafting percentage increased from 92 to 132%. Transmission electron microscopy showed that the micelles exhibited a nanospheric morphology within a size range of 60–120 nm. For the resulting micellar aggregates, the drug loading and in vitro drug‐release characteristics were studied with indomethacin as the model drug. We found that such micellar aggregates could be potentially used as nanocarriers for drug delivery. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 908‐915, 2013     

Cellulose/polyaniline derivatives nanocomposites: Synthesis and their performance in removal of anionic dyes from simulated industrial effluents

A series of cellulose/polyaniline derivatives [polyaniline (PANI), poly(N‐methylaniline) (PNMANI), and poly(N‐ethylaniline) (PNEANI)] nanocomposites were synthesized by in situ chemical oxidation polymerization method and successfully applied for removal of acid red 4 and direct red 23 dyes from simulated industrial effluents. The synthesized nanocomposites were analyzed using Fourier transform infrared and ultraviolet‐visible spectroscopies, thermogravimetric analysis and scanning electron microscope. The effect of some parameters including pH, adsorbent amount, and initial dyes concentrations on adsorption processes were evaluated. The maximum adsorption capacities (Q_m) for the synthesized nanocomposites were calculated, and among them the Cell/PANI sample showed the highest Q_m for both AR4 (117 mg g^–1) and DR23 (56 mg g^–1) dyes. The regeneration and reusability tests exhibited that the synthesized nanocomposites had the relatively good reusability after five repetitions of the adsorption–desorption cycles. According to results, we envision that these nanocomposites, especially Cell/PANI, find application for removal of anionic dyes from industrial effluents mainly due to their low production costs, high adsorption effectiveness, and relatively good reusability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45352.