Influence of triphenylphosphonium pendant groups on the rheological and morphological properties of new quaternized polysulfone

A new quaternized polysulfone with triphenylphosphonium pendant groups was synthesized by reacting chloromethylated polysulfone with triphenylphosphine. The molecular restructurations, generated by hydrogen bonding, electrostatic interactions, and association phenomena in ternary quaternized polysulfone/N,N‐dimethylformamide (solvent)/water (nonsolvent) systems, were evaluated by rheological investigations. The polyelectrolyte effect, induced by enhanced dissociation of the ionizable groups and by mixed solvents' quality, modify the rheological functions, that is, dynamic viscosity, elastic shear modulus, and viscous shear modulus, as well as the thermodynamic parameters obtained from the rheological properties, such as apparent activation energy. These results were correlated with the morphological properties of the films obtained from solutions in solvent/nonsolvent mixtures and compared with other quaternized polysulfones, having different hydrophobic characteristics. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Miscibility and morphological properties of quaternized polysulfone blends with polystyrene and poly(4‐vinylpyridine)

Quaternized polysulfones were synthesized by the quaternization reaction of chloromethylated polysulfone with different tertiary amines −N,N‐dimethylethylamine (DMEA) and N,N‐dimethyloctylamine (DMOA), respectively. New blends from these quaternized polysulfones (PSF‐DMEA or PSF‐DMOA) with polystyrene (PS) or poly(4‐vinylpyridine) (P4VP) were prepared by the solution casting method. Pure quaternized polysulfones, in N,N‐dimethylformamide (DMF)/methanol (MeOH) and DMF/water solvent/nonsolvent mixtures, and their blends with PS and P4VP, as well, were investigated by shear viscometry and viscoelasticity, atomic force microscopy, differential scanning calorimetry, and surface properties. The results obtained revealed that the blends have good miscibility. Surface morphology is characterized by roughness and nodules formations, depending on the alkyl radical lengths, composition of the polymer mixtures, including specific electron‐donor or electron‐acceptor characteristics of polymers. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Surface properties and antibacterial activity of quaternized polysulfones

Novel quaternized polysulfones (PSFs) with two ionic chlorine contents were investigated, namely, their morphology and antimicrobial activity. Atomic force microscopy (AFM) studies on their membranes showed ordered domains, in which pores and nodules of different sizes and intensities were distributed. The charge density of the quaternized PSFs and the history of the membranes formed from solutions in solvent/nonsolvent mixtures influenced the different aspects of the surface images. The adhesion of Escherichia coli ATCC 10536 and Staphylococcus aureus ATCCC 6538 microorganisms to solutions of the modified PSFs is discussed in correlation with the hydrophobic/hydrophilic properties of the studied polymers and microorganisms. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Impact of Some Properties of Quaternized Polysulfone/Poly(Vinylidene Fluoride) Blend on the Potential Biomedical Applications

Blends of quaternized polysulfones with triphenylphosphonium pendant groups/poly(vinylidene fluoride) were analyzed to establish their impact on the rheological, morphological and surface properties, as well as their interactions with some blood compounds. The rheological functions reflect the influence of both polymers’ chemical structures. Blend compositions of the corresponding films influence the surface tension parameters, increase blend hydrophobicity and, implicitly, decrease the polar surface tension parameters. The specific surface characteristics of polymer blends are related to their interactions with some blood constituents and plasma proteins. Also, the specific microarchitecture of the blend represents an excellent scaffold for medical applications.     

Antibacterial poly{(4‐vinyl phenylboronic acid)‐co‐[2‐(dimethylamino)ethyl methacrylate]} copolymers and their application in water‐based paints

Herein, we report the synthesis of poly(4‐vinylphenylboronic acid) (PVPBA) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) homopolymers, copolymers, and their methyl, pentyl, and octyl quaternized forms as dopant in water‐based permanent antibacterial paints. Both quaternized and nonquaternized forms of P(VPBA‐co‐DMAEMA) copolymers have reflected higher MIC values relative to PDMAEMA homopolymers. High molecular weight copolymers were more active against Escherichia coli ATCC 25922, contrarily, lower molecular weight copolymers showed higher antibacterial activity against Staphylococcus aureus ATCC 25923. The paint films prepared with quaternized PDMAEMA homopolymers with a weight of 10% showed better antibacterial activity in water and airborne tests than the copolymers. However, it has been shown that the inadequate anti‐biofilm properties of homopolymer‐containing paint films are overcome with the VPBA content of the copolymer structure and the most effective antibacterial and anti‐biofilm properties have been obtained with paint films containing P(VPBA‐co‐5QDMAEMA) copolymers. These paint films, which can maintain antibacterial and anti‐biofilm properties for at least 1 year, have the potential to be an alternative to Ag/Cl based solid surfaces which require the active substance to be regenerated. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46245.     

Biodegradable antimicrobial films based on poly(lactic acid) matrices and active azo compounds

Using solvent casting and melt compounding methods, we realized antibacterial and antifungal poly(lactic acid)‐based films by introducing different percentages of antimicrobial azo dyes into polymer matrices. Concentration up to 0.01% (w/w) of azo compounds permitted the preparation of antimicrobial and transparent films. The thin films retained the properties of the pure PLA matrices, such as glass transition temperature, flexibility, and amorphous nature. The films exhibited antimicrobial activity and the capability to inhibit biofilms formation of Staphylococcus aureus and Candida albicans. Spectrophotometric investigation of azo compounds release from the polymer matrices confirmed that the materials might have applications in fields where an intrinsic antimicrobial ability of the material is required, such as biomedical tools, biodegradable antibacterial coatings, and films for active packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42357.     

Antimicrobial and anti-quorum-sensing properties and paint film usage of novel diazaborine-based copolymers

To meet high hygiene requirements, intensive studies are being carried out on antimicrobial materials. This study reports the synthesis of 3-((1-hydroxybenzo[d][1,2,3]diazaborinin-2(1H)-yl)sulfonyl)propyl methacrylate (DAZBMA) and its polymer, which is antimicrobial [tested with Staphylococcus aureus (ATCC 25923 and MU 40) and Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853, and Candida albicans ATCC 10239] on solid surfaces. Antibiofilm capability was tested against MU 40. Although DAZBMA and its polymer show a high quorum-sensing inhibition property (tested with Chromobacterium violaceum CV 026 and CV 12472 and P. aeruginosa PA01), the lesser antibacterial activity of the polymer was improved by copolymerizing DAZBMA with quaternized 2-dimethylaminoethyl methacrylate. The paint films containing the prepared copolymer are highly active against all tested bacteria and show an antibiofilm effect against hospital-acquired multiple-antibiotic-resistant MU 40. The novel copolymer can be used in water-soluble paints to reduce its biofilm production and pathogenicity, especially for paints used in hospitals. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46907.     

Phosphonic acid‐containing polysulfones as anticorrosive layers

As a part of research work to elaborate polymeric materials for metal corrosion protection, we have developed a new family of phosphonic acid‐containing polymers. The synthesis and the characterization of polysulfones bearing alkyl phosphonate ester side groups are first described. These polymers are synthesized by direct polycondensation of a phosphonate ester‐containing bisphenol by aromatic nucleophilic substitution. The physicochemical properties of the resulting polymers are described. Acidic hydrolysis of phosphonate esters results in the formation of phosphonic acid groups. A series of phosphonic acid‐containing polysulfones is therefore obtained and characterized. A preliminary evaluation of the anticorrosive properties of these polymers is described. In 0.25M Na₂SO₄ solution, the corrosion rate of a polymer‐coated mild steel sample is much lower than of the free metal substrate. These results suggest that phosphonic acid‐containing polysulfones might be interesting as anticorrosive coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41890.     

Biocidal activity of cellulose materials for medical implants

Surface wettability trends, and blood component adhesion of some cellulose acetate phthalate/hydroxypropyl cellulose blend films are analyzed in view of adapting the system to biomedical applications. The results show that intermediate blend compositions of the corresponding films influence the surface tension parameters—controlled by the interactions occurring in the system. Increasing hydrophobicity and, implicitly, decreasing the polar surface tension components, are correlated with the adhesion/cohesion of blood components and plasma proteins. Thus, the work of spreading proteins on the hydrophobic blend surfaces indicated that albumin is not absorbed preferentially, while fibrinogen is characterized by a higher degree of adhesion on the surfaces, and also that selective adsorption of plasma proteins modifies blood compatibility. In addition, the obtained results and the ascertained antimicrobial activity of the studied blends contribute to the development of new applications in the biomedical field. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41932     

Electrical conductivity and optical properties of a new quaternized polysulfone

Quaternized polysulfone with triphenylphosphonium pendant groups was investigated, as to its optical and electronic properties. Optical properties were analyzed by refractivity and transmission spectra. To obtain the optical parameters, the approach proposed by Tauc for amorphous semiconductors has been used, because of the similarity of the absorption edges. Values of pseudogap energy and Urbach energy of 3.89 eV and 168 meV, respectively, were obtained. The dielectric properties and AC-conductivity were also studied as a function of temperature and frequency. Decrease in the dielectric constant was observed with the increase in frequency and decrease in temperature. Also, quaternized polysulfone films were characterized by two relaxation processes, γ and β relaxation, which appear at different temperatures, depending on the pendant group. The frequency–temperature-dependent conductivity showed that conductivity increases with frequency and also that the quaternized polysulfones possess typical semiconducting properties. All parameters have been found as slightly influenced by the polymer chain structure.     

Protein‐based bioplastics and their antibacterial potential

The use of conventional petroleum‐based plastics in many applications poses the risk of contamination, potentially causing infection when used in medical applications, and contamination when used in food packaging. Nontraditional materials such as protein are being examined for their potential use in the production of bioplastics for applications that require uncontaminated materials. The proteins of albumin, soy, and whey provide possible sources of raw material for bioplastic production, as they have already been utilized in the area of edible films and low‐stress applications. We conducted this study to investigate the thermal, viscoelastic, and antibacterial properties of the albumin, soy, and whey bioplastics with the use of three plasticizers—water, glycerol, and natural rubber latex (NRL). Bacillus subtilis and Escherichia coli were utilized as Gram (+) and Gram (?) species, respectively, for antimicrobial analysis. Albumin and whey bioplastics exhibited similar thermal and viscoelastic properties, whereas soy bioplastics had varied viscoelastic properties based on the plasticizer used. In terms of antibacterial activity, the albumin–glycerol and whey–glycerol were the best bioplastics, as no bacterial growth was observed on the plastics after 24 h of inoculation. In terms of the future impact of this research, the aim will be to scale up production of the bioplastics for use in food packaging as well as biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41931.     

Enhanced Antimicrobial Activity of Biocompatible Bacterial Cellulose Films via Dual Synergistic Action of Curcumin and Triangular Silver Nanoplates

Curcumin and triangular silver nanoplates (TSNP)-incorporated bacterial cellulose (BC) films present an ideal antimicrobial material for biomedical applications as they afford a complete set of requirements, including a broad range of long-lasting potency and superior efficacy antimicrobial activity, combined with low toxicity. Here, BC was produced by Komagataeibacter medellinensis ID13488 strain in the presence of curcumin in the production medium (2 and 10%). TSNP were incorporated in the produced BC/curcumin films using ex situ method (21.34 ppm) and the antimicrobial activity was evaluated against Escherichia coli ATCC95922 and Staphylococcus aureus ATCC25923 bacterial strains. Biological activity of these natural products was assessed in cytotoxicity assay against lung fibroblasts and in vivo using Caenorhabditis elegans and Danio rerio as model organisms. Derived films have shown excellent antimicrobial performance with growth inhibition up to 67% for E. coli and 95% for S. aureus. In a highly positive synergistic interaction, BC films with 10% curcumin and incorporated TSNP have shown reduced toxicity with 80% MRC5 cells survival rate. It was shown that only 100% concentrations of film extracts induce low toxicity effect on model organisms’ development. The combined and synergistic advanced anti-infective functionalities of the curcumin and TSNP incorporated in BC have a high potential for development for application within the clinical setting.     

Polysulfone‐based anion exchange polymers for catalyst binders in alkaline electrolyzers

The preparation of quaternized bisphenol A polysulfone (PSf) by chloromethylation and quaternization with trimethylamine (TMA), 1,4‐diazabicyclo[2.2.2]octane (DABCO), 1‐methylimidazole (MI), or 1,2‐dimethylimidazole (DMI) is described. While the ion‐exchange capacities (IECs) of MI or DMI quaternized PSf significantly decrease in concentrated KOH solutions at 60°C, the IECs of TMA or DABCO quaternized PSf are not much affected, but the membranes of these polymers become brittle. TMA quaternized PSf (IEC = 1.21 meq/g; IC = 2.45 S/m) and DABCO quaternized PSf (IEC = 1.09 meq/g; IC = 2.49 S/m) were used to bind a NiCo₂O₄ spinel electrocatalyst on the anode of Ni foam. Both the quaternized PSfs were quite effective in water electrolysis when used as binders, but not more effective than PTFE when rear sides of electrodes were fed with 10 wt % aqueous KOH solution. For long‐term electrolysis, binders based on more stable anion‐conductive polymers should be developed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42581.     

Synthesis and thermal stability,dielectric, and conductivity characteristics of some carbazole-bearing pendant and backbone sulfones

A group of poly(N-vinylcarbazole) pendant polysulfones has been prepared by reacting it with benzene, toluene, p-chlorobenzene- and p-nitrobenzenesulfonyl chloride and N-methyl carbazole, 3,6-disulfonyl chloride by the Friedel Crafts reaction. Carbazole-based backbone polysulfones have also been prepared by the reaction of N-methyl carbazole, 3,6-disulfonyl chloride and biphenyl, naphthalene, anthracene, and carbazole in presence of anhydrous aluminum chloride. The various sulfone polymers, thus prepared, have been structurally characterized by elemental analysis and IR spectroscopy. Detailed analyses of thermal stability, dielectric, and conductivity characteristics have revealed certain significant differences between these two types of sulfone polymers.     

Improving thermo-responsive hydrogel films by gamma rays and loading of Cu and Ag nanoparticles

This paper presents two modified copolymeric hydrogel films with thermo-responsiveness. The final films are hydrogels containing N-isopropylacrylamide, N-N-dimethylacrylamide, methyl methacrylate, and ethoxyethyl methacrylate. The incorporation of Ag and Cu in the smart hydrogel films endowed them with specific properties that could be useful in developing biological sensors, smart membranes, or flexible electronic components, which are proper for design and improvement on technology and biomedical applications. The films were synthesized in solution by gamma radiation at a dose rate of 10 kGy h⁻¹, and an absorbed dose of 50 kGy. The characterization was realized by different spectroscopic and microscopic techniques as FTIR-ATR, atomic force microscopy, SEM–EDX, TGA, and DSC. The hydrogel films were grafted with glycidyl methacrylate showing high resistance, biocompatibility, adequate adaptability, flexibility, in addition to the capacity of metal doping with silver and copper.     

Structure–rheology relationship in complex quaternized polysulfones/solvent/nonsolvent systems

Polymer chains consisting of water-soluble polysulfones with various amounts of ionic chlorine have been prepared via the quaternization reaction of chloromethylated polysulfones with N,N-dimethylethanolamine. Rheological investigations have reflected the importance of electrostatic interactions, hydrogen bonding, and association phenomena from the ternary systems consisting of a proton-acceptor polymer (polysulfones with different ionic chlorine content), a proton-donor solvent (N,N-dimethylformamide), and a proton-donor solvent (methanol). The specific interactions, the polyelectrolyte effect induced by enhanced dissociation of the ionizable groups and mixed solvents’ quality modify the rheological functions, i.e., dynamic viscosity, elastic shear modulus and viscous shear modulus, as well as the thermodynamic parameters obtained from the rheological properties, such as apparent energy of activation and flow activation entropy. These results were correlated with the surface properties of the polysulfonic films formed from solutions in solvent/nonsolvent mixtures.     

Preparation of antibacterial biocompatible polycaprolactone/keratin nanofibrous mats by electrospinning

Keratin-based materials are widely used in biomedical applications due to excellent biocompatibility and biodegradability. In this study, keratin was extracted from waste wool fibers and blended with polycaprolactone (PCL) to produce PCL/keratin nanofibrous mats by electrospinning. The electrospun PCL/keratin nanofibrous mats were chlorinated in diluted sodium hypochlorite solution to endow antibacterial properties. The prepared nanofibrous mats were characterized by scanning electron microscopy, X-ray photoelectron, and Fourier infrared spectroscopy. The effect of the chlorination time on the active chlorine loading of the mats was investigated. The chlorinated PCL/keratin nanofibrous mats with 0.78 ± 0.009 wt% active chlorine displayed potent antibacterial activity against Gram-positive Staphylococcus aureus (ATCC 6538) and Gram-negative Escherichia coli O157:H7 (ATCC 43895) with 6.88 and 6.81 log reductions, respectively. It was found that the mats were compatible with mouse fibroblast cells (L929). The chlorinated PCL/keratin nanofibrous mats might find promising applications in the biomedical field.     

Properties of nanocrystalline diamond thin films grown by MPCVD for biomedical implant purposes

Nanocrystalline diamond (NCD) thin films have been grown by microwave plasma chemical vapor deposition (MPCVD) and investigated to determine their suitability for biomedical applications. Growth conditions were chosen to produce very uniform films over the surface of curved temporomandibular joint implants. These parameters include methane flow rates exceeding 20% of the hydrogen gas flow rate, and chamber pressure and microwave power were maintained at 30 Torr and 0.73 kW, respectively, in a Wavemat 6 kW MPCVD device. Films (3 μm thick) that completely coated 2.54-cm-diameter Ti–6Al–4V disks under these conditions exhibit mean grain size of 30.4 nm as determined by XRD peak broadening, hardness of 80 GPa as determined by nanoindentation, RMS mean roughness of 15.3±5.3 nm as determined by stylus profilometry, and film adhesion toughness (Γ_C) of 158 J/m² as determined by a Rockwell indentation method. Similar deposition performed on small Ti–6Al–4V hemispheres produce films with smaller mean grain size of 21.1 nm and correspondingly lower hardness and roughness. Overall, these films exhibit properties well suited for use in biomedical applications.     

Biostatic Behavior of Side Chain Charged Polycations and Polymer-Ag Complexes

Summary Poly[(3-methacryloylamino)propyl]trimethylammonium)chloride (PMF'TA), and poly (2-acrylamido-2-methyl-1-propane sulfonic acid) (PAPSA) were synthesized by radical polymerization. Three copolymers of (3-methacryloylamino)propyl] trimethylammonium chloride and 2-acrylamido-2-methyl-1-propane sulfonic acid P(MPTA-co-APSA) with different feed monomer mol ratios were also synthesized by radical polymerization. These polymer materials and the commercial poly(vinylpyrro1idone-co-2-dimethylaminoethyl methacrylate) quaternized P(VP-co- DMAEM) were purified by ultrafiltration membranes and subsequently their complexes with Ag(I) were prepared. Antibacterial activity of all these polymers, was investigated against Escherichia coli (6538P), and Staphylococcus aureus (ATCC 28922), using the National Comittee for Clinical Laboratory Standards method [1]. None of these compounds exhibited biocidal or biostatic action against E. coli, and only PMTA and P(VP-co-DMAEM) exhibited some action against S. aureus.     

Antibacterial porous xanthan-based films containing flavoring agents evaluated by near infrared chemical imaging technique

Xanthan gum (XG) is a widely applied natural polysaccharide in food industry as thickening agent. Nowadays, one of the major problems is that some food products are found to be contaminated by pathogenic bacteria such as Escherichia coli and Staphylococcus aureus reducing so, their shelf life. This research aims to demonstrate the antibacterial activity of some biodegradable formulation XG-lignin hydrogel films and their potential application as carriers for controlled release of flavoring compounds. The XG-lignin films containing an aspen wood lignin type showed a high antibacterial activity against Salmonella Typhymurium ATCC 14028, E. coli ATCC 25922 and Listeria monocytogenes ATCC 25922 bacteria compared with those containing softwood lignin, or lignin from annual plants. Surface morphology indicated a homogeneous distribution of both components within the hydrogel network and the generation of a porous structure after swelling and lyophilization. Additionally, near infrared chemical imaging technique was used as nondestructive method to observe the spatial distribution of the polymeric components and vanillin into the hydrogel films as well as its release profile. The vanillin release rate dependence on the lignin type was also evidenced, a retarded release of vanillin being observed. These results give an important insight into the use of XG, lignin, and vanillin for the development of new edible films for active packaging materials.