Silver hydroxyapatite reinforced poly(vinyl alcohol)—starch cryogel nanocomposites and study of biodegradation,compressive strength and antibacterial activity

In the present work polyvinyl alcohol‐starch/silver hydroxyapatite (PVA‐starch/AgHap) cryogel nanocomposites were prepared by successive freezing‐thawing of a blend of PVA and starch solutions to fabricate a cryogel followed by its reinforcement with silver hydroxyapatite (AgHap). The prepared macroporous cryogel nanocomposites were characterized by Infra‐red spectroscopy (FTIR), environmental scanning electron microscopy (ESEM), and particle size and charge analysis. The amylase induced enzymatic degradation of nanocomposites was studied gravimetrically in phosphate buffer saline (PBS) and effect of various parameters like chemical composition of the nanocomposite, number of freeze‐thaw cycles, and enzyme activity were assessed on the extent of degradation of the nanocomposite. The influence of chemical composition and experimental conditions like the number of freeze thaw cycles was studied on the elastic modulii of the cryogels. The in vitro cytotoxicity and antibacterial activity of nanocomposites was also evaluated against L‐529 fibroblast cells and gram positive and gram negative bacteria, respectively. POLYM. ENG. SCI., 59:254–263, 2019. © 2018 Society of Plastics Engineers     

Studies on the synthesis of electrospun PAN‐Ag composite nanofibers for antibacterial application

We have successfully synthesized polyacrylonitrile (PAN) nanofibers impregnated with Ag nanoparticles by electrospinning method at room temperature. Briefly, the PAN‐Ag composite nanofibers were prepared by electrospinning PAN (10% w/v) in dimethyl formamide (DMF) solvent containing silver nitrate (AgNO₃) in the amounts of 8% by weight of PAN. The silver ions were reduced into silver particles in three different methods i.e., by refluxing the solution before electrospinning, treating with sodium borohydride (NaBH₄), as reducing agent, and heating the prepared composite nanofibers at 160°C. The prepared PAN nanofibers functionalized with Ag nanoparticles were characterized by field emission scanning electron microscopy (FESEM), SEM elemental detection X‐ray analysis (SEM‐EDAX), transmission electron microscopy (TEM), and ultraviolet‐visible spectroscopy (UV‐VIS) analytical techniques. UV‐VIS spectra analysis showed distinct absorption band at 410 nm, suggesting the formation of Ag nanoparticles. TEM micrographs confirmed homogeneous dispersion of Ag nanoparticles on the surface of PAN nanofibers, and particle diameter was found to be 5–15 nm. It was found that all the three electrospun PAN‐Ag composite nanofibers showed strong antibacterial activity toward both gram positive and gram negative bacteria. However, the antibacterial activity of PAN‐Ag composite nanofibers membrane prepared by refluxed method was most prominent against S. aureus bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of biocompatible spongy cryogels of poly(vinyl alcohol)–gelatin and study of water sorption behaviour

Porous biocompatible spongy hydrogels of poly(vinyl alcohol) (PVA)–gelatin were prepared by the freezing–thawing method and characterized by infrared and differential scanning calorimetry. The prepared so‐called ‘cryogels’ were evaluated for their water‐uptake potential and the influence of various factors, such as the chemical architecture of the spongy hydrogels, pH and the temperature of the swelling bath, on the degree of water sorption by the cryogels was investigated. It was found that the water sorption capacity constantly decreased with increasing concentration of PVA while initially an increase and thereafter a decrease in swelling was obtained with increasing amounts of gelatin in the cryogel. The water sorption capacity decreased with an increase in the number of freeze–thaw cycles. The hydrogels were also swollen in salt solutions and various simulated biological fluids and a fall in swelling ratio was noticed. The effect of the drying temperature of the cryogel on its water sorption capacity was also investigated, and a decrease in swelling was obtained with increasing temperature of drying. The biocompatibility of the prepared materials was assessed by in vitro methods of blood‐clot formation, platelet adhesion, and per cent haemolysis. It was noticed that with increasing concentration of PVA and gelatin the biocompatibility increased, while a reduced biocompatibility was noted with an increasing number of freeze–thaw cycles. Copyright © 2005 Society of Chemical Industry     

Radiation synthesis and characterization of poly(vinyl alcohol)/poly(N-vinyl-2-pyrrolidone) based hydrogels containing silver nanoparticles

A series of PVA/PVP based hydrogels at different compositions were prepared by gamma irradiation. The gel fraction degree of swelling were investigated. Highly stable and uniformly distributed silver nanoparticles have been obtained onto hydrogel networks. The morphology and structure of (PVA/PVP) hydrogel and dispersion of the silver nanoparticles in the polymeric matrix were examined by scanning electron microscopy (SEM) and infrared spectroscopy (FT-IR), respectively. The formation of silver nanoparticles has been confirmed by ultraviolet visible (UV–vis) spectroscopy. A strong characteristic absorption peak was found to be around 420 nm for the silver nanoparticles in the hydrogel nanocomposite. The X-ray diffraction pattern confirmed the formation of silver nanoparticles with average particle size of 12 nm. The diameter distribution of silver nanoparticles was determined by dynamic light scattering DLS. Transmission electron microscope (TEM) showed almost spherical and uniform distribution of silver nanoparticles through the hydrogel network and the mean size of silver nanoparticles ranging is 23 nm. The good swelling properties and antibacterial of PVA/PVP-Ag hydrogel suggest that it can be a good candidate as wound dressing.     

Swelling–deswelling kinetics of ionic poly(acrylamide) hydrogels and cryogels

A series of ionic poly(acrylamide) (PAAm) gels was prepared by free‐radical crosslinking copolymerization of acrylamide and N,N′‐methylenebisacrylamide in aqueous solutions. The gels were prepared both below and above the bulk freezing temperature of the polymerization solvent water, which are called as the cryogels and the hydrogels, respectively. The deswelling behavior of swollen gels in acetone as well as the reswelling behavior of the collapsed gels in water were investigated. It was shown that the cryogels respond against the external stimuli much faster than the hydrogels. The interior morphology of the cryogel networks exhibits a discontinuity and a two‐phase structure, compared to the continuous morphology of the hydrogel networks. Introduction of the ionic units in the network chains further increased the response rate of the cryogels. In contrast to these advantages of cryogels, they exhibit lower swelling capacities than the conventional hydrogels. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 319–325, 2006     

Development of Savlon Containing Polyvinyl Alcohol Based Cryogels as Potential Biomaterials for Burn Healing Applications

Novel membranes of hydrogels were prepared by freeze-thaw method and characterized by Fourier transform infrared (FTIR) and environmental scanning electron microscopy techniques. The FTIR spectra clearly reveal that savlon loaded poly (vinyl alcohol) cryogels are held together through hydrogen bonding. The scanning electron microscope analysis suggests that cryogels show a well-defined porous morphology. The cryogels were also studied for swelling and deswelling behaviors. The results show that the swelling and deswelling greatly depend on the factors such as chemical composition of the cryogels, number of freeze-thaw cycles, and pH and temperature of the swelling bath. The savlon loaded cryogels were also investigated for their in vitro blood compatibility and antibacterial activity.     

Preparation of atactic poly(vinyl alcohol)/silver composite nanofibers by electrospinning and their characterization

Poly(vinyl alcohol) (PVA)/silver composite nanofibers were successfully prepared by the electrospinning method. Water‐based colloidal silver in a PVA solution was directly mixed without any chemical or structural modifications into PVA polymer fibers to form organic–inorganic composite nanofibers. The ratio of silver colloidal solution to PVA played an important role in the formation of the PVA/silver composite nanofibers. We prepared two different atactic PVA/silver nanocomposites with number‐average degrees of polymerization of 1700 and 4000 through electrospinning with various processing parameters, such as initial polymer concentration, amount of silver colloidal solution, applied voltage, and tip‐to‐collector distance. The PVA/silver composite nanofibers were characterized by field emission scanning electron microscopy and transmission electron microscopy (TEM). TEM images showed that silver nanoparticles with an average diameter of 30–50 nm were obtained and were well distributed in the PVA nanofibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structural,morphological and thermal characterization of poly (2-hydroxyethyl methacrylate-co-acrylonitrile) (P (HEMA-co-AN)) Cryogels: evaluation of water sorption potential and cytotoxicity

Cryogels are macroporous hydrogels which are synthesized through cryogelation method. In the present study cryogels of poly (2-hydroxyethyl methacrylate-co-acrylonitrile) (P (HEMA-co-AN)) were synthesized by copolymerization of 2-hydroxyethyl methacrylate (HEMA) and acrylonitrile (AN) monomers by redox polymerization using cryogelation technique. The synthesized cryogels were characterized by FTIR, SEM, XRD, DSC and TGA techniques. Different compositions of the cryogels were prepared by varying concentrations of the monomers and redox initiators in the feed mixture. These cryogels were then subjected to swelling studies and porosity determination. The swelling behavior was studied as function of concentration of the monomers, redox initiators, temperature, pH, and simulated biological fluids. The prepared cryogels were also characterized for their network parameters using water sorption data. The biocompatibility of P (HEMA-co-AN) cryogel was evaluated by in vitro cytotoxicity test. The results indicated that the P (HEMA-co-AN) cryogel had macroporous morphology and exhibited good water absorption capacity. Moreover, the cryogel was thermally stable and biocompatible in nature.     

Preparation, characterization, and antibacterial properties of pH-responsive P(MMA-co-MAA)/silver nanocomposite hydrogels

A pH-responsive copolymer hydrogel was synthesized based on methyl methacrylate (MMA) and methacrylic acid (MAA) as monomers, and was adopted as a nanoreactor for assembling Ag nanoparticles. Fourier transform infrared spectroscope (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV-visible spectroscopy (UV-Vis) and thermogravimetric analysis (TGA) were used to fully characterize the formation of silver nanoparticles in P(MMA-co-MAA) hydrogels. The experimental results showed that the P(MMA-co-MAA) hydrogels assume a three-networks architecture in morphologies, and that nearly spherical Ag nanoparticles are formed in these hydrogel networks; the size of these Ag nanoparticles varies with the system composition. The swelling kinetics investigations demonstrated that the equilibrium swelling ratio (ESR) of the P(MMA-co-MAA)/Ag hydrogels depended on the content of the MAA and pH of the buffer solutions, and the ESR values were reduced with increasing MAA contents. The antibacterial properties against both S. aureus and B. subtilis bacteria demonstrated that the P(MMA-co-MAA)/silver nanocomposite hydrogels had higher antimicrobial efficacy than the pure P(MMA-co-MAA) counterparts. Therefore, the nanocomposite hydrogels turned out to be a potentially smart material in the range of applications of antibacterial activity.     

Preparation and antibacterial effects of PVA‐PVP hydrogels containing silver nanoparticles

The poly(vinyl alcohol)/poly(N‐vinyl pyrrolidone) (PVA–PVP) hydrogels containing silver nanoparticles were prepared by repeated freezing–thawing treatment. The silver content in the solid composition was in the range of 0.1–1.0 wt %, the silver particle size was from 20 to 100 nm, and the weight ratio of PVA to PVP was 70 : 30. The influence of silver nanoparticles on the properties of PVA–PVP matrix was investigated by differential scanning calorimeter, infrared spectroscopy and UV–vis spectroscopy, using PVA–PVP films containing silver particles as a model. The morphology of freeze‐dried PVA–PVP hydrogel matrix and dispersion of the silver nanoparticles in the matrix was examined by scanning electron microscopy. It was found that a three‐dimensional structure was formed during the process of freezing–thawing treatment and no serious aggregation of the silver nanoparticles occurred. Water absorption properties, release of silver ions from the hydrogels and the antibacterial effects of the hydrogels against Escherichia coli and Staphylococcus aureus were examined too. It was proved that the nanosilver‐containing hydrogels had an excellent antibacterial ability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 125–133, 2007     

The release of cefazolin from chitosan/polyvinyl alcohol/sepiolite nanocomposite hydrogel films

Films of chitosan/polyvinyl alcohol (PVA)/sepiolite nanocomposite were prepared by a simple and “green” route through solution mixing; followed by freezing–thawing cycles. The structures of nanocomposites were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis, X-ray diffractometry, and Fourier transform infrared spectroscopy. The SEM and TEM micrographs confirmed a needle-type dispersion of sepiolite nanoclay in the hydrogel nanocomposites. The effects of sepiolite and chitosan/PVA weight ratio on the swelling of nanocomposites were investigated. The water absorbency of nanocomposites was decreased by introducing sepiolite nanoclay. The nanocomposites with high content of chitosan showed high swelling capacity. The nanocomposite films showed pH-dependent swelling behavior with a maximum water absorbency under acidic pH. The cefazolin with a broad-spectrum activity toward gram-positive and gram-negative bacteria was loaded in hydrogels. The release of cefazolin from nanocomposites was evaluated at pH 7.4. The content of released drug was affected by both sepiolite amount and chitosan/PVA weight ratio. The nanocomposites films released more cefazolin than the neat hydrogel film. Cefazolin-loaded nanocomposites showed the antibacterial activity with a large zone of inhibition against gram-positive Bacillus cereus bacterium.     

Synthesis,Characterization, and Antibacterial Activity of Polyindole/Ag–Cuo Nanocomposites by Reflux Condensation Method

Polyindole-based silver and copper oxide (polyindole/Ag–CuO) nanocomposites were synthesized using reflux condensation method by varying the concentrations of polyindole and silver nitrate with copper oxide in N₂ atmosphere. They were characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), and scanning electron microscope (SEM) techniques. The SEM images revealed fascinating shapes of CuO nanoparticles. The FTIR and XRD confirmed the functional group transformation and crystalline natures of silver and CuO existed in the nanocomposites. The polyindole/Ag–CuO nanocomposites were examined for antibacterial activity and found to exhibit the antibacterial activity against pathogenic bacteria.     

Study of cryostructuration of polymer systems. XII. Poly(vinyl alcohol) cryogels: Influence of low-molecular electrolytes

The influence of the presence of low-molecular electrolytes in initial solutions of poly(vinyl alcohol) (PVA) on the results of cryotropic gelation of the polymer (gelation caused by the freezing thawing) and on the swelling characteristics of PVA cryogels prepared in a salt-free medium were studied. The reinforcing ability of the electrolytes with respect to the gel strength for both alkaline element cations and simple low-molecular anions has been shown to be in agreement with the positions of these ions in corresponding lyotropic (Hofmeister) series. Namely, the ions (chaotropic ones), which are capable to interfere the H-bonding, disturbed somewhat the cryotropic gel-formation of PVA and facilitated the marked additional swelling of cryogels preliminary prepared in pure water medium, whereas the ions (antichaotropic ones), which are capable to promote the H-bonding, caused the formation of reinforced cryogels and resulted in the shrinking of cryogels prepared without salt additives. More pronounced effects were observed for anions as compared with cations. Some anomalous swelling behavior of PVA cryogel in Cs⁺-containing solutions was supposed to be associated with the formation of weak chelates. In addition to antichaotropic inorganic salts like NaF, rather high salting-out effects in respect to PVA were exhibited by wellsoluble amino acid salts: glycine zwitter-ions, lysine monochlorohydrate, and monosodium aspartate. © 1996 John Wiley & Sons, Inc.     

A straightforward preparation and characterization of novel poly(vinyl alcohol)/organoclay/silver tricomponent nanocomposite films

In the present investigation, novel poly(vinyl alcohol)/organoclay/silver (PVA/OMMT/Ag) tricomponent nanocomposite (NC) films with different compositions were prepared by solution intercalation method under ultrasonic irradiation process. The NC films were obtained by mixing a colloidal solution consisting of Ag nanoparticles (NPs) (3, 5, 7 and 9 wt%) with a water solution of PVA and OMMT (10 wt%) via solution casting method. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis (TGA) were utilized to characterize the morphology and properties of the PVA/OMMT/Ag NC films. TGA confirmed that the heat stability of the nanocomposite was improved. The enhancement in the thermal properties of the hybrid materials was due to strong hydrogen bonding between OH groups of PVA, free acid functionalized groups of OMMT, and the Ag NPs. SEM and TEM results also showed that the OMMT and Ag NPs were dispersed homogeneously in the PVA matrix on nanoscale.     

In situ fabrication of polyaniline‐silver nanocomposites using soft template of sodium alginate

Polyaniline (PANI)‐Ag nanocomposites were synthesized by in situ chemical polymerization approach using ammonium persulfate and silver nitrate as oxidant. Characterizations of nanocomposites were done by ultraviolet–visible ( UV–vis), Fourier transform infrared (FTIR), X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM). UV–vis, XRD and FTIR analysis established the formation of PANI/Ag nanocomposites and face‐centered‐cubic phase of silver. PANInanofibers were of average diameter ～ 30 nm and several micrometers in length. Morphological analysis showed that the spherical‐shaped silver nanoparticles decorate the surface of PANI nanofibers. Silver nanoparticles of average diameter ～ 5–10 nm were observed on the TEM images for the PANI‐Ag nanocomposites. Such type of PANI‐Ag nanocomposites can be used as bistable switches as well as memory devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study of cryostructuration of polymer systems. XX. Foamed poly(vinyl alcohol) cryogels

Foamed poly(vinyl alcohol) (PVA) cryogels, which are formed as a result of freeze–thaw treatment of whipped PVA water solutions (polymer with MW of 69,000 Da and DD ～99 mol % was used), were obtained and their properties were studied. The rheological characteristics and macrostructure of these gel materials were controlled by the same factors as for the ordinary nonfoamed PVA cryogels (initial polymer concentration and freezing–thawing regimes) and also by the conditions of generation of fluid PVA foams. The study of the kinetics of the freeze–thaw‐induced gel formation of these foams revealed that the temperature dependence of the efficiency of cryotropic gelation showed a maximum at about ?1.5°C. The presence of low molecular weight admixtures in the initial polymer solution appears to be a rather important factor because the admixtures were capable of decreasing the stability of fluid PVA foams and weakening both foamed and nonfoamed cryogel samples. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1609–1619, 2001     

Polyaniline/Ag nanocomposite synthesized by using aniline as dispersant and stabilizer of nanosilver sol

Polyaniline/silver (PANI/Ag) nanocomposite was successfully prepared by in‐situ polymerization from nanosilver sol using aniline (An) as both dispersant and stabilizer and characterized by FT‐IR, XRD SEM, TEM and electrochemical methods, respectively. The results showed that core‐shelled composite particles of less than 100 nm were synthesized with PANI as shell formed around a core of silver nanoparticles at higher aniline levels. Compared to pure PANI, PANI/Ag nanocomposites have higher electrical conductivity (65.98 S/cm) and current response and capacitance as well. Potentio dynamic polarization showed the anodic shifting of zero current potential and a lower exchange current density for the PANI/Ag composite. Compared with PANI, the PANI/Ag nanocomposite is a promising candidate for coatings with improved anti‐corrosion performance. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhancement of pervaporation performance of composite membranes through in situ generation of silver nanoparticles in poly(vinyl alcohol) matrix

Composite membranes were prepared from an aqueous solution of poly(vinyl alcohol) (PVA) and silver sulphate. The silver nanoparticles were generated in situ before crosslinking PVA matrix by reduction of silver ions using sodium borohydride. Physico‐chemical properties of the resulting composite membranes were studied using Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy (UV–vis), thermogravimetric analysis (TGA), Wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), and universal testing machine (UTM). The UV–vis spectrum shows a single peak at 410 nm due to surface plasmon absorption of silver nanoparticles. This surely specified that silver nanoparticles are generated in PVA matrix. The membranes were under go pervaporation (PV) for separation of water from isopropanol at different temperatures. The results indicated that hydrophilicity and amorphous nature of the membranes were increased with increasing silver nanoparticles in PVA matrix. The swelling and separation performance of the membranes were studied. Both permeation flux and separation factor were increased with increasing silver nanoparticles in PVA matrix. The results showed that the membrane containing 2.5 mass% of Ag salt exhibited excellent PV performance. The values of total flux and flux of water are almost closed to each other, indicating that membranes could be effectively used to break the azeotropic point of water‐isopropanol. The long‐term test was performed at room temperature and ascertained that membranes were durable up to 30 days for the dehydration of IPA. On the basis of the estimate Arrhenius activation energy values, the efficiency of the membranes was discussed. The calculated ΔH_s values are negative for all the membranes, indicating that Longmuir's mode of sorption is predominant. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41248.     

Study of cryostructuration of polymer systems. XVII. Poly(vinyl alcohol) cryogels: Dynamics of the cryotropic gel formation

Freeze‐thaw treatment of concentrated (>5 g/dL) aqueous solutions of poly(vinyl alcohol) (PVA) (MW 115,000; DD ≈100%) resulted in the formation of opaque gels. The extent of such a cryostructuration process was exhibited in the rheological properties of similar PVA cryogels. The gels' strength depended on the initial polymer concentration in the solution to be frozen and on the conditions of a cryogenic influence. The key factor was the defrostation dynamics: the slower the thawing rate, the stronger the cryogel sample formed, provided other parameters of the process were identical. The observation for the kinetics of the freeze‐thaw–induced gel formation revealed the extreme character of the temperature dependence of the efficacy of PVA cryotropic gelation, the maximum point being in the vicinity of −2°C. It was shown that the effect of the strengthening of PVA cryogels prepared by means of a single‐cycle cryogenic treatment could be reached either with use of as slow as possible thawing regimes, or by the prolonged frozen storage of the samples at “high” subzero temperatures. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2017–2023, 2000     

Radiation synthesis and characterization of polyvinyl alcohol/chitosan/silver nanocomposite membranes: antimicrobial and blood compatibility studies

Polyvinyl alcohol/chitosan/silver (PVA/CS/Ag) nanocomposite membranes were synthesized by γ-radiation with promising antimicrobial and biomedical applications. The nanocomposite membranes were prepared by mixing PVA and CS solutions with different copolymer compositions in the presence of silver nitrate (AgNO₃) and glutaraldehyde as cross-linker, followed by in situ reduction with γ-radiation at different doses. The nanocomposite membranes were characterized by ultraviolet spectroscopy (UV), Fourier transform infrared, X-ray diffraction (XRD) and transmission electron microscopy (TEM). UV studies showed a strong peak around λ _max at 430 nm due to surface plasmon resonance of silver nanoparticles formed during irradiation. As the irradiation dose increased from 25 to 75 kGy, the plasmon band is shifted from 430 to 418 nm with high intensity, indicating the formation of smaller particles. TEM investigation showed uniform distribution of silver nanoparticles (AgNPs) in the membranes with mean diameter of 32–19 nm. XRD results confirmed that the mean diameter of AgNPs estimated from the Debye–Scherrer formula was in the range of 27.5–12.8 nm which confirms the TEM results. The PVA/CS/Ag nanocomposite membranes exhibited good antibacterial activity and were found to cause significant reduction in microbial growth. The nanocomposite membranes showed non-thrombogenicity effect and slightly haemolytic potential, suggesting their promising use in biomedical applications.