Nanocomposites based on crosslinked polyacrylic latex/silver nanoparticles for waterborne high‐performance antibacterial coatings

Functional polymer/AgNPs nanocomposites have been prepared. Silver nanoparticles (NPs) were synthesized to which polyacrylamide, PAAm, was covalently bound. PAAm was synthesized via a RAFT reaction and carried thiol and carboxylic acid end groups. Thiol was used to bind the polymer to the metal surface and carboxyl for further reactions. The AgNPs were used in a post‐crosslinking reaction with a separately synthesized poly(butyl acrylate‐co‐methyl methacrylate)/polyglycidyl methacrylate core/shell latex bearing epoxy functional groups. Dynamic mechanical analysis showed that the functional AgNPs effectively crosslinked the latex polymer, and that the final product had excellent mechanical strength. Antibacterial tests revealed that the nanocomposite films had strong antibacterial activity against all types of the bacteria and the immobilization of silver NPs by crosslinking retarded the release of silver in comparison to the uncrosslinked ones. With the presented method, it is possible to obtain ductile antibacterial nanocomposites to be used as waterborne functional coatings. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1435–1447     

In-situ synthesis and immobilization of silver nanoparticles on microfibrillated cellulose for long-term antibacterial applications

Cellulose - Synthesis of nanocomposites containing silver nanoparticles (AgNPs) has drawn growing interest owing to their antimicrobial activity and tuneable physicochemical properties. In this...     

Biosynthesis,Characterization and Antibacterial Application of Novel Silver Nanoparticles against Drug Resistant Pathogenic Klebsiella pneumoniae and Salmonella Enteritidis

The present study highlights the biosynthesis of silver nanoparticles (AgNPs) using culture supernatant of Massilia sp. MAHUQ-52 as well as the antimicrobial application of synthesized AgNPs against multi-drug resistant pathogenic Klebsiella pneumoniae and Salmonella Enteritidis. Well-defined AgNPs formation occurred from the reaction mixture of cell-free supernatant and silver nitrate (AgNO₃) solution within 48 h of incubation. UV-visible spectroscopy analysis showed a strong peak at 435 nm, which corresponds to the surface plasmon resonance of AgNPs. The synthesized AgNPs were characterized by FE-TEM, EDX, XRD, DLS and FT-IR. From FE-TEM analysis, it was found that most of the particles were spherical shape, and the size of synthesized nanoparticles (NPs) was 15–55 nm. EDX spectrum revealed a strong silver signal at 3 keV. XRD analysis determined the crystalline, pure, face-centered cubic AgNPs. FT-IR analysis identified various functional molecules that may be involved with the synthesis and stabilization of AgNPs. The antimicrobial activity of Massilia sp. MAHUQ-52 mediated synthesized AgNPs was determined using the disk diffusion method against K. pneumoniae and S. Enteritidis. Biosynthesized AgNPs showed strong antimicrobial activity against both K. pneumoniae and S. Enteritidis. The MICs of synthesized AgNPs against K. pneumoniae and S. Enteritidis were 12.5 and 25.0 μg/mL, respectively. The MBC of biosynthesized AgNPs against both pathogens was 50.0 μg/mL. From FE-SEM analysis, it was found that the AgNPs-treated cells showed morphological changes with irregular and damaged cell walls that culminated in cell death.     

Exploitation of Haloferax alexandrinus for Biogenic Synthesis of Silver Nanoparticles Antagonistic to Human and Lower Mammalian Pathogens

In the present study we report the use of cells of a Haloarchaeon for the green synthesis of silver nanoparticles. Biosynthesis of AgNPs occurred within 30 s on exposure of cells of Haloferax alexandrinus to silver nitrate in direct sunlight. Maximum AgNPs production was achieved within 4 min of exposure of silver nitrate (0.05 %) to cells (5 mg/ml), at pH 7, at ambient day temperature (26–34 °C). The AgNPs had characteristic surface plasmon resonance at 420 nm in UV–Vis spectra. Spherical and irregular crystals ranging from 2 to 60 nm in size with an average size of 18 nm were observed in TEM analysis. The FTIR spectral analysis indicated involvement of N–H, –OH, C=O, C–O functional groups present in cells of Haloferax alexandrinus MTCC 3265. The biogenic AgNPs exhibited broad spectrum antimicrobial activity against human and mammalian pathogens, in the order of Pseudomonas aeruginosa ATCC 9027 > Bordetella bronchiseptica ATCC 4617 > Bacillus subtilis ATCC 6633 > Staphylococcus aureus ATCC 6538P > Staphylococcus epidermidis ATCC 12228 > Escherichia coli ATCC 8739 > Salmonella typhimurium ATCC 14028.     

Antioxidant and antibacterial activity of silver nanoparticles biosynthesized using Chenopodium murale leaf extract

Silver is known for its antimicrobial effects and silver nanoparticles are gaining their importance due to their antimicrobial activities. The aims of the current study were to use plant extract for the biosynthesis of silver nanoparticles and to evaluate their antibacterial and antioxidant activity in vitro. The results indicated that silver nanoparticles (AgNPs) can be synthesized in a simple method using Chenopodium murale leaf extract. The TEM analysis showed that the sizes of the synthesized AgNps ranged from 30 to 50 nm. The essential oil of C. murale leaf extract was formed mainly of α-Terpinene, (Z)-Ascaridole and cis-Ascaridole. The total phenolic compounds and total flavonides were higher in AgNPs-containing plant extract compared to the plant extract. AgNPs-containing leaf extract showed a higher antioxidant and antimicrobial activity compared to C. murale leaf extract alone or silver nitrate. It could be concluded that C. murale leaf extract can be used effectively in the production of potential antioxidant and antimicrobial AgNPs for commercial application.     

Facile preparation and characterization of highly antimicrobial colloid Ag or Au nanoparticles

A series of colloid silver or gold nanoparticles (AgNPs or AuNPs) were successfully prepared by in situ reduction and stabilization of hyperbranched poly(amidoamine) with terminal dimethylamine groups (HPAMAM-N(CH(3))(2)) in water, and they all exhibited highly antimicrobial activity. The particle size could be controlled easily by adjusting the molar ratio of N/Ag (or N/Au) in feed. When the molar ratio was 2, some aggregates of the nanoparticles separated from the colloidal solution, which showed some limited antimicrobial activity with the bacterial inhibition ratio of below 15%. As the molar ratio increased from 10 to 30, the average particle diameters decreased (from ca. 7.1 to 1.0 nm for AgNPs and from ca. 7.7 to 3.9 nm for AuNPs, respectively) and they all showed high dispersion stability and excellent antimicrobial efficiency. All the bacterial inhibition ratios reached up to ca. 98% at the low silver content of ca. 2.0 microg/mL or at the low gold content of ca. 2.8 microg/mL. The AgNPs or AuNPs with smaller particle size can provide much more effective contact surface with the bacteria, thus enhancing their antimicrobial efficiency. Besides, the cationic HPAMAM-N(CH(3))(2) can also do some contribution to the antimicrobial activity through the strong ionic interaction with the bacteria.     

Silver polymeric nanocomposites as advanced antimicrobial agents: classification, synthetic paths, applications, and perspectives

Utilization of metallic nanoparticles in various biotechnological and medical applications represents one of the most extensively investigated areas of the current materials science. These advanced applications require the appropriate chemical functionalization of the nanoparticles with organic molecules or their incorporation in suitable polymer matrices. The intensified interest in polymer nanocomposites with silver nanoparticles is due to the high antimicrobial effect of nanosilver as well as the unique characteristics of polymers which include their excellent structural uniformity, multivalency, high degree of branching, miscellaneous morphologies and architectures, and highly variable chemical composition. In this review, we explore several aspects of antimicrobial polymer silver nanocomposites, giving special focus to the critical analysis of the reported synthetic routes including their advantages, drawbacks, possible improvements, and real applicability in antibacterial and antifungal therapy. A special attention is given to "green" synthetic routes exploiting the biopolymeric matrix and to the methods allowing preparing magnetically controllable antimicrobial polymers for targeting to an active place. The controversial mechanism of the action of silver against bacteria, fungi and yeasts as well as perspectives and new applications of silver polymeric nanocomposites is also briefly discussed.     

Biosynthesis and Characterization of Extracellular Silver Nanoparticles from Streptomyces aizuneusis: Antimicrobial,Anti Larval,and Anticancer Activities

The ability of microorganisms to reduce inorganic metals has launched an exciting eco-friendly approach towards developing green nanotechnology. Thus, the synthesis of metal nanoparticles through a biological approach is an important aspect of current nanotechnology. In this study, Streptomyces aizuneusis ATCC 14921 gave the small particle of silver nanoparticles (AgNPs) a size of 38.45 nm, with 1.342 optical density. AgNPs produced by Streptomyces aizuneusis were characterized by means of UV-VIS spectroscopy and transmission electron microscopy (TEM). The UV-Vis spectrum of the aqueous solution containing silver ion showed a peak between 410 to 430. Moreover, the majority of nanoparticles were found to be a spherical shape with variables between 11 to 42 nm, as seen under TEM. The purity of extracted AgNPs was investigated by energy dispersive X-ray analysis (EDXA), and the identification of the possible biomolecules responsible for the reduction of Ag⁺ ions by the cell filtrate was carried out by Fourier Transform Infrared spectrum (FTIR). High antimicrobial activities were observed by AgNPs at a low concentration of 0.01 ppm, however, no deleterious effect of AgNPs was observed on the development and occurrence of Drosophila melanogaster phenotype. The highest reduction in the viability of the human lung carcinoma and normal cells was attained at 0.2 AgNPs ppm.     

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.     

Development of silver-containing nanocellulosics for effective water disinfection

Electrospun cellulose nanofibers and cellulose-graft-polyacrylonitrile (Cell-g-PAN) copolymer nanofibers containing silver nanoparticles (AgNPs) were synthesized for effective water disinfection. Surface morphology, AgNPs content, physical distribution of AgNPs, levels of silver leaching from the fibers in water and antimicrobial efficacy were studied. Scanning electron microscope images revealed that AgNPs in cellulose nanofibers were more evenly dispersed than in Cell-g-PAN copolymer nanofibers, but with the certainty that Cell-g-PAN copolymer nanofibers had higher AgNPs content. This was confirmed by energy dispersive X-ray analysis and atomic absorption analysis. Both cellulose nanofibers and Cell-g-PAN copolymer nanofibers containing AgNPs had excellent antimicrobial activity against Escherichia coli, Salmonella typhi, and Staphylococcus aureus, with cellulose-nAg nanofibers killing between 91 and 99 % of bacteria in a contaminated water sample and Cell-g-PAN-nAg copolymer nanofibers killed 100 %. Neither Cell-g-PAN copolymer nanofibers nor cellulose nanofibers leached silver into water.     

Structure-Morphology-Antimicrobial and Antiviral Activity Relationship in Silver-Containing Nanocomposites Based on Polylactide

Green synthesis of silver-containing nanocomposites based on polylactide (PLA) was carried out in two ways. With the use of green tea extract, Ag⁺ ions were reduced to silver nanoparticles with their subsequent introduction into the PLA (mechanical method) and Ag⁺ ions were reduced in the polymer matrix of PLA-AgPalmitate (PLA-AgPalm) (in situ method). Structure, morphology and thermophysical properties of nanocomposites PLA-Ag were studied by FTIR spectroscopy, wide-angle X-ray scattering (WAXS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) methods. The antimicrobial, antiviral, and cytotoxic properties were studied as well. It was found that the mechanical method provides the average size of silver nanoparticles in the PLA of about 16 nm, while in the formation of samples by the in situ method their average size was 3.7 nm. The strong influence of smaller silver nanoparticles (3.7 nm) on the properties of nanocomposites was revealed, as with increasing nanosilver concentration the heat resistance and glass transition temperature of the samples decreases, while the influence of larger particles (16 nm) on these parameters was not detected. It was shown that silver-containing nanocomposites formed in situ demonstrate antimicrobial activity against gram-positive bacterium S. aureus, gram-negative bacteria E. coli, P. aeruginosa, and the fungal pathogen of C. albicans, and the activity of the samples increases with increasing nanoparticle concentration. Silver-containing nanocomposites formed by the mechanical method have not shown antimicrobial activity. The relative antiviral activity of nanocomposites obtained by two methods against influenza A virus, and adenovirus serotype 2 was also revealed. The obtained nanocomposites were not-cytotoxic, and they did not inhibit the viability of MDCK or Hep-2 cell cultures.     

Effect of filler incorporation route on the properties of polysulfone–silver nanocomposite membranes of different porosities

Flat sheet porous polysulfone–silver nanocomposite membranes were synthesized by the wet phase inversion process. The effects of casting mixture composition and nanoparticle incorporation route on the morphological and separation properties of prepared membranes were studied by comparing nanocomposites of different preparations with silver-free controls. Silver nanoparticles were either synthesized ex situ and then added to the casting solution as an organosol or produced in the casting solution via in situ reduction of ionic silver by the polymer solvent. Nanocomposite membranes of three types differing in skin porosity and macrovoid structure were prepared. The structure and properties of nanocomposites were interpreted in terms of the coupling between the processes of nanoparticle formation and gelling of the polymer-rich phase during phase inversion. Larger nanoparticles preferentially located in the skin layer were observed in composites prepared via the ex situ method while in situ reduction of silver led to formation of smaller nanoparticles homogeneously distributed along the membrane cross-section. In some cases, incorporation of nanoscale silver formed ex situ resulted in macrovoid widening and an order of magnitude decrease in hydraulic resistance accompanied by only a moderate decrease in rejection. The accessibility of the silver nanoparticles embedded in the membrane was quantitatively assessed by the degree of the growth inhibition of a membrane biofilm due to the ionic silver released by the nanocomposites and was found to depend on the method of silver incorporation.     

Intelligent colloidal hybrids via reversible pH-induced complexation of polyelectrolyte and silica nanoparticles

We present novel intelligent colloidal polymer/silica nanocomposites, in which the complexation of cationic silica nanoparticles and a weak anionic polyelectrolyte can be manipulated simply by pH change through a hydrogen-bonding interaction and ionic complexation caused by hydrogen-transfer interactions between the constituents. Special silica particles which have nanometer size (diameter approximately 3.0 nm) and two independent proton-accepting sites were developed in this study. Both the silica and poly(acrylic acid) form transparent colloidal solutions in water, while a white turbid dispersion was obtained just after mixing the two solutions due to the complexation. The pH-induced association-dissociation behavior was confirmed by the turbidity and potentiometric titration measurements. The assembled structures of the hybrids were visualized by scanning force microscopy.     

Bio-based thermostable, biodegradable and biocompatible hyperbranched polyurethane/Ag nanocomposites with antimicrobial activity

The enhanced thermal and antimicrobial activity of silver nanoparticles prompts their uses in many medical devices. Mesua ferrea L. seed oil based antimicrobial biocompatible hyperbranched and linear polyurethane/Ag nanocomposites have been prepared in dimethylformamide without using any extra reducing agent. Formation of the stable and well-dispersed Ag nanoparticles was confirmed by ultra violet, X-ray diffractometeric, transmission electron microscopic and Fourier transform infra-red spectroscopic analyses. The enhancement of properties like thermal stability by (46-53)°C and 42 °C, tensile strength to ∼170% and ∼180% for hyperbranched and linear polyurethanes respectively was observed by the formation of nanocomposites. The cytocompatibility test based on the inhibition of RBC hemolysis showed that the materials lack cytotoxicity. The nanocomposites showed biodegradability as conferred from the bacterial degradation. Dose dependent excellent antibacterial activity of the nanocomposites against Gram positive (Staphylococcus aureus) and Gram negative (Escherichia coli) bacteria and antifouling activity against Candida albicans was observed.     

Evaluating the antimicrobial activity and cytotoxicity of polydopamine capped silver and silver/polydopamine core-shell nanocomposites

Fabrication of bioactive nanomaterials with improved stability and low toxicity towards healthy mammalian cells have recently been a topic of interest. Bioactive metal nanomaterials such as silver nanoparticles (AgNPs) tend to lose their stability with time and become toxic to some extent, limiting their biological applications. AgNPs were separately encapsulated and loaded on the surface of a biocompatible polydopamine (PDA) to produce Ag-PDA and Ag@PDA nanocomposites to unravel the issue of agglomeration. PDA was coated through the self-polymerization of dopamine on the surface of AgNPs to produce Ag-PDA core-shells nanocomposites. For Ag@PDA, PDA spheres were first designed through self-polymerization of dopamine followed by in situ reduction of silver nitrate (AgNO3) without any reductant. AgNPs sizes were controlled by varying the concentration of AgNO₃. The TEM micrograms showed monodispersed PDA spheres with an average diameter of 238 nm for Ag-PDA and Ag@PDA nanocomposites. Compared to Ag@PDA, Ag-PDA nanocomposites have shown insignificant toxicity towards human embryonic kidney (HEK-293T) and human dermal fibroblasts (HDF) cells with cell viability of over 95% at concentration of 250 µg/mL. A excellent antimicrobial activity of the nanocomposites was observed; with Ag@PDA possessing bactericidal effect at concentration as low as 12.5 µg/mL. Ag-PDA on the other hand were only found to be bacteriostatic against gram-positive and gram-negative bacteria was also observed.     

Ganoderma applanatum-mediated green synthesis of silver nanoparticles: Structural characterization,and in vitro and in vivo biomedical and agrochemical properties

This study presents the use of basidiomycete extracts as an effective platform for “green synthesis” of silver nanoparticles (AgNPs). Out of seven basidiomycete species, Ganoderma applanatum displayed the highest antimicrobial properties against the tested pathogens. Thus, G. applanatum methanol crude extract was fractionated using column chromatography, and the obtained fractions were subjected to an antimicrobial assay followed by phytochemical analyses using high-performance liquid chromatography to select the best fraction for synthesis of AgNPs. Fraction 3 displayed potent antimicrobial activities as evidenced by its high phenolic content, and thus was used for AgNP biosynthesis. The G. applanatum fraction 3-synthesized AgNPs were then characterized using various microscopy, spectroscopy and X-ray diffraction techniques. The characteristic features of the synthesized AgNPs indicated the spherical shape of AgNPs with an average size of 20–25 nm. The synthesized AgNPs exhibit high antioxidant capacity, in vitro antibacterial activity against Staphylococcus aureus and Escherichia coli, and in vivo antifungal properties against Botrytis cinerea and Colletotrichum gloeosporioides in tomato and strawberry leaflet assays, respectively. Our results demonstrated that G. applanatum can be efficiently used in synthesis of AgNPs with potent antimicrobial properties, which can be used for both clinical and agrochemical purposes.     

Polymeric coatings on silver nanoparticles hinder autoaggregation but enhance attachment to uncoated surfaces

The propensity of silver nanoparticles (AgNPs) having two different polymer coatings (poly(vinylpyrrolidone), PVP, or gum arabic, GA) to aggregate, or to deposit to a reference surface (silica), was explored as a basis for differentiating the effect of surface coating on the stability of nanoparticles in aggregation and in deposition. Surface polymeric coatings stabilize nanoparticles against aggregation as shown by either an increased critical coagulation concentration as for PVP-coated AgNPs (AgPVP) or the absence of observable aggregation even at a high ionic strength as for GA-coated AgNPs (AgGA). In experiments of AgNPs deposition in a silica porous medium, dissimilar surfaces favored deposition, such as the case where polymer coatings were present on the AgNPs but were absent on the porous medium. The increased affinity of the AgNPs for the porous medium in this case may be explained by a shifted contact frontier where electrical double layer interaction is weaker. When coating polymers were introduced to the porous medium and allowed to preadsorb to the silica surfaces, the attachment efficiencies for both the AgPVP and AgGA were reduced due to steric and electrosteric stabilization, respectively. The results suggest that polymeric coatings that are usually deemed as stabilizers (as they indeed are in the case of autoaggregation) might not necessarily stabilize nanoparticles against deposition unless the collector surfaces are also coated with polymer.     

Antibacterial Activity and Synergistic Effect of Biosynthesized AgNPs with Antibiotics Against Multidrug-Resistant Biofilm-Forming Coagulase-Negative Staphylococci Isolated from Clinical Samples

Silver nanoparticles form promising template for designing antimicrobial agents against drug resistant pathogenic microorganisms. Thus, the development of a reliable green approach for the synthesis of nanoparticles is an important aspect of current nanotechnology research. In the present investigation, silver nanoparticles synthesized by a soil Bacillus sp. were characterized using UV–vis spectroscopy, FTIR, SEM, and EDS. The antibacterial potential of biosynthesized silver nanoparticles, standard antibiotics, and their conjugates were evaluated against multidrug-resistant biofilm-forming coagulase-negative S. epidermidis strains, S. aureus, Salmonella Typhi, Salmonella Paratyphi, and V. cholerae. Interestingly, silver nanoparticles (AgNPs) showed remarkable antibacterial activity against all the test strains with the highest activity against S. epidermidis strains 145 and 152. In addition, the highest synergistic effect of AgNPs was observed with chloramphenicol against Salmonella typhi. The results of the study clearly indicate the promising biomedical applications of biosynthesized AgNPs.     

Synthesis and optical properties of poly(N-isopropylacrylamide) nanogel containing silver nanoparticles

Composite nanoparticles representing silver nanoparticle-containing polymer gels have been synthesized. The synthesis comprises two main stages. Initially, monodisperse hydrogel particles with a controlled diameter of approximately 500 nm are obtained by N-isopropylacrylamide polymerization. Then, silver ions are reduced on the surface of the polymer network. Variations in the concentration ratio between reductants and silver nitrate make it possible to produce silver nanoparticles with sizes in a range of 10–30 nm and different packing densities on the gel particle surface. The resultant nanocomposites have been studied by transmission electron microscopy, spectrophotometry, and dynamic light scattering. Depending on the size and packing density of the silver nanoparticles on the polymer particle surface, the plasmon resonance of the nanocomposites varies in a range of 420–750 nm, which determines variations in the color of the colloid from yellow, orange, and red to blue and blue-green. After the inclusion of silver nanoparticles, nanogels of poly(N-isopropylacrylamide) retain their capability for thermosensitive phase transition with a lower critical mixing temperature of 31°C.     

Effects of pH,salt, surfactant and composition on phase transition of poly(NIPAm/MAA) nanoparticles

The volume phase transition of poly(NIPAm/MAA) copolymer nanoparticles in buffer solutions at various pH and in aqueous solutions of KCl or ionic surfactants (SDS and DTMAB) was systematically studied using dynamic laser scattering technique. It was found that ionizable MAA groups imparted a responsiveness of the particles to pH and electrolytes. At pH > pKa of the copolymer, electrostatic repulsion of negative charges, mostly from COO⁻ groups, was a governing mechanism for preventing the particles from collapse at T > T_tr. The particles exhibited a sharp volume phase transition upon elimination of the negative charges by decreasing the pH of the medium or by the addition of cationic surfactant. At pH < pKa, the presence of MAA groups enhanced the hydrophobicity of the particles as indicated by a lower T_tr and a sharper volume phase transition. A pH 4 buffer at the same ionic strength exhibited the most significant effect on the particle size and phase transition, followed by the ionic surfactant with an opposite charge (e.g., DTMAB), KCl, and finally the ionic surfactant with the same charge (e.g. SDS). © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2667–2676, 1999