Polymer-coated Silver Nanoparticles Research Articles

Drug-loaded polymer-coated silver nanoparticles for lung cancer theranostics.

Lung cancer is the leading cause of death in cancer across the globe. To minimize these deaths, the replacement of traditional chemotherapy with novel strategies is significant. We have developed a nanotheranostic approach using silver nanoparticles for imaging and treatment. Silver nanoparticles (AgNPs) are fabricated by chemical reduction method. The formulation of AgNPs was confirmed by different characterization techniques like stability test, UV-Visible spectroscopy, Confocal Raman Spectroscopy, and Energy-Dispersive X-ray analysis. Further, AgNPs are coated with poly lactic-co-glycolic acid (PLGA) and then loaded with paclitaxel(Pac). Then the drug-loaded PLGA-coated AgNPs were characterized for size and zeta potential measurement by zetasizer, surface morphology study by atomic force microscopy, Fourier transform infrared spectroscopy, and release kinetics study. The imaging and anticancer properties of these nanoformulations are investigated using lung cancer cell lines. The results proved that the particles are in the nanometer range with smooth surface morphology. Moreover, the drug-loaded NPs showed a sustained release of the drug for a longer period of time. Further the formulations showed imaging property with greater anticancer efficacy. Thus, the results suggest the effective use of these nanoformulation in both lung cancer imaging and treatment using a simple and efficient approach.

Amino Acid-Based Polymer-Coated Silver Nanoparticles as Insulin Fibril Inhibitors

To explore the impact of polymer-coated silver nanoparticles (PC-AgNPs) on the extent of the insulin aggregation process, herein, we have synthesized three copolymers comprising poly(ethylene glycol) methyl ether methacrylate (PEGMA) and tert-butoxycarbonyl (Boc)-protected amino acid (alanine, leucine, and phenylalanine) containing methacrylate monomers, via reversible addition-fragmentation chain transfer (RAFT) polymerization. After deprotection of the Boc groups, the as-prepared water-soluble copolymers were coated on silver nanoparticles (Ag NPs), and the role of these NPs on insulin aggregation pathways was examined by multifarious spectroscopic and microscopic techniques. The extent of the inhibitory effect against the insulin fibrillation process was found to be related to the surface properties of the NPs, with the highest inhibitory effect detected for phenylalanine-based polymer-coated Ag NPs (PPhe-AgNPs). Using circular dichroism (CD) spectroscopy and Nile red (NR) fluorescence spectroscopy, we investigated the conformational changes and examined the role of hydrophobic interaction in inhibiting the aggregation properties of insulin upon treatment with PC-AgNPs. Furthermore, PC-AgNPs were also able to disintegrate the matured insulin fibrils and efficiently decreased the fibril-induced cytotoxicity, as confirmed by transmission electron microscopy (TEM) and the hemolysis study, respectively. Together, our findings established the novel amino acid-based PC-AgNPs as potent nanomaterials with 77–96% insulin fibril inhibition and marked disaggregation of matured insulin fibrils.

Highly Stable Polymer Coating on Silver Nanoparticles for Efficient Plasmonic Enhancement of Fluorescence.

Surface coating of plasmonic nanoparticles is of huge importance to suppress fluorescence quenching in plasmon-enhanced fluorescence sensing. Herein, a one-pot method for synthesizing polymer-coated silver nanoparticles was developed using a functional polymer conjugated with disulfide-containing anchoring groups. The disulfides played a crucial role in covalently bonding polymers to the surface of the silver nanoparticles. The covalent bond enabled the polymer layer to form a long-term stable coating on the silver nanoparticles. The polymer layer coated was adequately thin to efficiently achieve plasmonic enhancement of fluorescence and also thick enough to effectively suppress quenching of fluorescence, achieving a huge net enhancement of fluorescence. The polymer-coated plasmonic nanoparticles are a promising platform for demonstrating highly sensitive biosensing for medical diagnostics.

Characterization, bio-uptake and toxicity of polymer-coated silver nanoparticles and their interaction with human peripheral blood mononuclear cells.

Silver nanoparticles (AgNPs) are widely used in medical applications due to their antibacterial and antiviral properties. Despite the extensive study of AgNPs, their toxicity and their effect on human health is poorly understood, as a result of issues such as poor control of NP properties and lack of proper characterization. The aim of this study was to investigate the combined characterization, bio-uptake, and toxicity of well-characterized polyvinylpyrrolidone (PVP)-coated AgNPs in exposure media during exposure time using primary human cells (peripheral blood mononuclear cells (PBMCs)). AgNPs were synthesized in-house and characterized using a multimethod approach. Results indicated the transformation of NPs in RPMI medium with a change in size and polydispersity over 24 h of exposure due to dissolution and reprecipitation. No aggregation of NPs was observed in the RPMI medium over the exposure time (24 h). A dose-dependent relationship between PBMC uptake and Ag concentration was detected for both AgNP and AgNO3 treatment. There was approximately a two-fold increase in cellular Ag uptake in the AgNO3 vs the NP treatment. Cytotoxicity, using LDH and MTS assays and based on exposure concentrations was not significantly different when comparing NPs and Ag ions. Based on differential uptake, AgNPs were more toxic after normalizing toxicity to the amount of cellular Ag uptake. Our data highlights the importance of correct synthesis, characterization, and study of transformations to obtain a better understanding of NP uptake and toxicity. Statistical analysis indicated that there might be an individual variability in response to NPs, although more research is required.

Effect of polymer coating composition on the aggregation rates of Ag nanoparticles in NaCl solutions and seawaters

The aggregation behaviour of polymer-coated silver nanoparticles (AgNPs) was characterized in NaCl solutions, and in two seawaters of different salinities and dissolved organic matter (DOM) contents. Representative organic coatings i.e. tannic acid (TA), alginic acid (ALG), two gum Arabic samples (GAL and GAH), branched polyethylenimine (BPEI), and non-ionic surfactants (reference material NM-300K) were selected to cover a wide range of zeta-potentials. The stability in NaCl solutions, as determined from the rate of variation in hydrodynamic size within a timeframe of one hour, followed the order BPEI≫NM-300K≈GAL≫ALG≈TA≫GAH. In the seawater samples the order was NM-300K≈GAL≫ALG>GAH>TA≈BPEI, and only TA, GAL and NM-300K batches behaved as expected from the NaCl experiments. Remarkably, the BPEI sample showed the largest aggregation rate in the seawater sample with the highest DOM concentration (277μM C). The GAH sample displayed a non-monotonic variation in aggregation rate with NaCl concentration, apparently due to concomitant precipitation of AgCl. The results indicate that non-electrostatic stabilization mechanisms and DOM-coating interactions are important for the prediction of stability and persistence of polymer-coated AgNPs in seawater.

Transport and long-term release behavior of polymer-coated silver nanoparticles in saturated quartz sand: The impacts of input concentration, grain size and flow rate

This study investigated the transport and long-term release of stabilized poly vinylpyrrolidone-coated silver nanoparticles (PVP-AgNPs) in a quartz sand column with various sand grain sizes (0.3–0.5 μm, 0.5–1.0 μm, 1.0–2.0 μm), input concentrations of PVP-AgNP solution (1, 5, 15, 25 mg/L), and flow rates corresponding to a filter velocities (1.0, 1.5, 2.0, 2.5 mL/min–0.14, 0.21, 0.28, 0.35 cm/min) by determining breakthrough curves, retention profiles, and long-term release curves. Breakthrough curves and retention profiles were simulated by a mathematical model based on the advection dispersion equation coupled with second-order kinetics. The increased transport of PVP-AgNPs in quartz sand occurred with increased grain sizes and reduced input concentrations, and the transport can be predicted by the colloid filtration theory and DLVO theory.The long-term (one week) release amounts of retained PVP-AgNPs were 42.78%, 31.45%, and 10.95% in the fine, medium, and coarse sand columns, respectively, and were 34.70%, 40.79%, 47.24%, and 57.32% at flow rates of 0.0363, 0.0436, 0.0545, and 0.0726 mL/min, respectively. The released quantity of retained PVP-AgNPs decreased as the sand grain size increased. This phenomenon is opposite with the trend of increased transport of PVP-AgNPs with increased grain size in the transport test, which most likely because colloidal filtration regulates the transport process and adsorption (and desorption) dominates the release process. Increasing the flow rate increased the shear force on the particles, which improved the release of PVP-AgNPs. The results of the release tests further verified our previous published studies showing that the long-term release of retained PVP-AgNPs in the quartz sand was mostly in the form of released nanoparticles rather than ions. The results of this study indicated that sand grain size, input concentration, and flow rate have a prominent influence on the transport and long-term release behavior of PVP-AgNPs in saturated quartz sand.

Transport, retention, and long-term release behavior of polymer-coated silver nanoparticles in saturated quartz sand: The impact of natural organic matters and electrolyte

This study investigated the transport and long-term release of stabilized silver nanoparticles (AgNPs), including polyvinylpyrrolidone-coated AgNPs (PVP–AgNPs) and bare AgNPs (Bare–AgNPs), in the presence of natural organic matters (NOMs; both humic acids (HA) and alginate (Alg)) and an electrolyte (Ca2+) in a sand-packed column. Very low breakthrough rate (C/C0) of AgNPs (below 0.04) occurred in the absence of NOM and the electrolyte. Increasing the concentration of NOM and decreasing the influent NOM solution's ionic strength (IS) reduced the retention of AgNPs. The reduced NP retention at high NOM and low IS was mainly attributed to the increased energy barrier between the AgNPs and the sand grain surface. Notably, the retention of PVP–AgNPs was enhanced at high Alg concentration and low IS, which mainly resulted from the improved hydrophobicity that could increase the interaction between the PVP-AgNPs and the collector. The total release amount of PVP–AgNPs (10.03%, 9.50%, 28.42%, 6.37%) and Bare–AgNPs (3.28%, 2.58%, 10.36%, 1.54%) were gained when exposed to four kinds of NOM solutions, including deionized water, an electrolyte solution (1 mM Ca2+), HA with an electrolyte (1 mM Ca2+), and a Alg (40 mg/L) solution with an electrolyte (1 mM Ca2+). The long-term release of retained silver nanoparticles in the quartz sand was mostly through the form of released Ag NPs. The factors that increased the mobility of AgNPs in quartz sand could improve the release of the AgNPs. The release of AgNPs had no significant change in the presence Ca2+ but were increased in the presence of HA. The Alg slightly decreased the release of AgNPs by increasing the hydrophobicity of AgNPs. The results of the study indicated that all the tested NOM and Ca2+ have prominent influence on the transport and long-term release behavior of silver nanoparticles in saturated quartz sand.

Toxicological interactions of silver nanoparticles and organochlorine pesticides in mouse peritoneal macrophages

Nanotechnology occupies a prominent space in economy and science due to the beneficial properties of nanomaterials. However, nanoparticles may pose risks to living organisms due to their adsorption and pro-oxidative properties. The aim of the current study was to investigate the effects of polymer-coated silver nanoparticles (AgNPs) and organochlorine pesticides (OCPs), as well as their combined effects on mouse peritoneal macrophages. Macrophages were isolated and exposed to three concentrations of AgNPs (groups: N1 = 30, N2 = 300 and N3 = 3000 ng.ml−1), two concentrations of OCPs (groups: P1 = 30 and P2 = 300 ng.ml−1) and the six possible combinations of these two contaminants for 24 h. AgNPs had irregular shape, Feret diameter of 8.7 ± 7.5 nm and zeta potential of −28.7 ± 3.9 mV in water and −10.7 ± 1.04 mV in culture medium. OCP mixtures and the lower concentrations of AgNPs had no detectable effects on cell parameters, but the highest AgNPs concentration showed high toxicity (trypan blue and MTT assays) resulting in morphological changes, increase of nitric oxide levels and phagocytic index. Foremost, the association of N3 and P2 led to distinct effects from those observed under single exposure.

Toxicity mechanisms of ionic silver and polymer-coated silver nanoparticles with interactions of functionalized carbon nanotubes on early development stages of sea urchin

Exposures of aquatic organisms to multiple contaminants are likely to take place in estuarine and coastal areas and combined effects on early life stages have to be examined. Among emerging contaminants, ionic silver (Ag+) and silver nanoparticles (AgNps) have demonstrated contrasting effects on marine invertebrates, but their interactions with functionalized carbon nanotubes (f-SWCNTs) have not yet been investigated in details. In order to observe the impacts and understand the toxicity mechanism of Ag+ and polymer-coated AgNps, and their combined effects with f-SWCNTs, successive development stages of embryos of sea urchin, Strongylocentrotus droebachiensis, were exposed to Ag+, AgNps and f-SWCNTs, separately and in mixtures using moderate environmental concentrations. We also assessed long-term effects of treatments under recovery conditions. Morphological endpoints such as archenteron elongation, primary and secondary mesenchyme cells fate, pigment cells migration, spiculogenic cells and gut development indicated different effects of silver and nanosilver forms during successive development stages. Whereas Ag+ induced vegetalization and extrusion of mesenchyme cells on early embryos; f-SWCNTs+Ag+ strongly interfered with gut regionalization in late larvae. Sensitive blastocoelar cells got vacuolized and shapeless with AgNps, but not with mixtures with f-SWCNTs. Increased concentrations of Ag+ and f-SWCNTs+Ag+ led to the most disruptive effects during development, but f-SWCNTs+Ag+ caused the highest mortality rate during the recovery period, which indicated far-reaching effects driven by f-SWCNTs and their ability to keep silver more available during exposure period.

High-performance polyvinylidene fluoride/poly(styrene–butadiene–styrene)/functionalized MWCNTs-SCN-Ag nanocomposite membranes

In this work, solution blending technique was used to fabricate nano-filtration membranes of polyvinylidene fluoride (PVDF) and poly(styrene–butadiene–styrene) (SBS) blend matrix and modified multi-walled carbon nanotubes (MWCNTs) as filler. In this regard, two types of nanofiller, thiocyanate-modified nanotubes (MWCNTs-SCN) and silver-modified nanotubes (MWCNTs-SCN-Ag), were used as reinforced nanofiller in PVDF/SBS blend to form PVDF/SBS-MWCNTs-SCN 0.01–0.1 and PVDF/SBS-MWCNTs-SCN-Ag 0.01–0.1 membranes. Fourier transform infrared; field emission scanning electron microscopy; transmission electron microscopy; X-ray photoelectron spectroscopy; Brunauer, Emmett and Teller; and tensile tests were used for the exploration of structural and physical properties. Morphology studies showed the dispersion of polymer-coated silver nanoparticles with smooth and homogeneous surface in the spongy matrix. Porous nature of membranes was also observed in high-resolution cross-section micrographs. Tensile strength of PVDF/SBS-MWCNTs-SCN 0.01–1 nanocomposite series increased from 10.2 to 13.9 MPa, while PVDF/SBS-MWCNTs-SCN-Ag 0.01–1 had values in the range of 12.6–20.1 MPa. According to TGA, PVDF/SBS-MWCNTs-SCN revealed maximum decomposition temperature around 550–580 °C, while PVDF/SBS-MWCNTs-SCN-Ag had T max of 567–599 °C. The influence of various filler content on membrane performance and structure was studied using pertinent methods and techniques. Percentage of water content of PVDF/SBS-MWCNTs-SCN 0.01–0.1 was estimated around 1.08–2.80 % and this value was further increased to 1.94–4.65 % in silver nanoparticle-modified system. Moreover, the porosity of silver nanoparticle-modified system was found superior compared with the other composites. Pure water flux, salt rejection, and recovery were also found optimal for 0.05 wt% silver nanoparticle-based modified system. According to the consequences, novel membranes have fine nano-filtration characteristics to be utilized in advance water treatment industrial units.

Organic matter induced mobilization of polymer-coated silver nanoparticles from water-saturated sand

Mobilization of polymer-coated silver nanoparticles (AgNPs) by anionic surfactant (sodium dodecylbenzenesulphonate: SDBS), amino acid derivative (N-acetylcysteine: NAC), and chelate (ethylenediaminetetraacetic acid: EDTA) in water-saturated sand medium was explored based on carefully designed column tests. Exposure experiments monitoring the size evolution of polyvinylpyrrolidone (PVP) coated AgNPs in organic solutions confirm the capacity of SDBS, NAC and EDTA to partly displace PVP. Single Pulse Column Experiment (SPCE) results show both the PVP polymer and the silver core controlled AgNP deposition while the effect of the PVP was dominant. Results of Co-injected Pulse Column Experiments (CPCEs) where AgNP and SDBS or NAC were co-injected into the column following a very short mixing (<1s) disprove our hypothesis that coating-alternation by particle associated organic would mobilize irreversibly deposited particles from the uncoated sand, while surface charge modification by adsorbed NAC was identified as a potential mobilizing mechanism for AgNP from the iron-oxide-coated sand. Triple Pulse Column Experiment (TPCE) results confirm that such a charging effect of the adsorbed organic molecules may enable SDBS and NAC to mobilize AgNPs from the iron-oxide-coated sands. TPCE results with five distinct levels of SDBS indicate that concentration-stimulated change in the SDBS format from an individual to a micelle significantly increased the mobilizing efficiency and site blockage of SDBS. Although being an electrolyte, EDTA did not mobilize AgNPs, as the case with SDBS or NAC, as it dissolved the iron oxides which in turn prevented EDTA adsorption on sand. The findings have implications for better understanding the behavior of polymer-coated nanoparticles in organic-presented groundwater systems, i.e., detachment-associated uncertainty in exposure prediction of the nanomaterials.

Preparation of silver core-chitosan shell nanoparticles using catechol-functionalized chitosan and antibacterial studies

In this paper, we report the preparation and stabilization of colloidal silver nanoparticle solution, with the assistance of chitosan dihydroxyphenyl acetamide (CDHPA), or oligochitosan dihydroxyphenyl acetamide (OCDHPA). The structure of the chitosan derivatives were characterized by nuclear magnetic resonance (1H NMR) spectroscopy. The morphology of the synthesized silver core-chitosan shell nanoparticles were observed by transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques, and showed a well-defined core-shell structure of polymer-coated silver nanoparticles (AgNPs). The core-shell NPs exhibited a strong antibacterial activity against E. coli and S. aureus, at a very low concentration of AgNPs (2.5 ppm). Our studies offer a new method for the preparation and protection of silver nanoparticles for antibacterial applications. Open image in new window

Influence of natural organic matter on transport and retention of polymer coated silver nanoparticles in porous media

Interactions between organic matter (OM) and engineered polymer coatings as they affect the retention of polyvinylpyrrolidone (PVP) polymer-coated silver nanoparticles (AgNPs) were studied. Two distinct types of OM—cysteine representing low molecular weight multivalent functional groups, and Suwannee River Humic Acid (HA) representing high molecular weight polymers, were investigated with respect to their effects on particle stability in aggregation and deposition. Aggregation of the PVP coated AgNPs (PVP-AgNPs) was enhanced by cysteine addition at high ionic strengths, which was attributed to cysteine binding to the AgNPs and replacing the otherwise steric stabilizing agent PVP. In contrast the addition of HA did not increase aggregation rates and decreased PVP-AgNP deposition to the silica porous medium, consistent with enhanced electrosteric stabilization by the HA. Although cysteine also reduced deposition in the porous medium, the mechanisms of reduced deposition appear to be enhanced electric double layer (EDL) interaction at low ionic strengths. At higher ionic strengths, aggregation was favored leading to lower deposition due to smaller diffusion coefficients and single collector efficiencies despite the reduced EDL interactions.

Incorporation of silver nanoparticles coated with mercaptosuccinic acid/poly(ethylene glycol) copolymer into epoxy for enhancement of dielectric properties

A novel route to the synthesis of polymer-coated silver nanoparticles (NPs) was developed on the basis of the reduction of Tollens' reagent using mercaptosuccinic acid/poly(ethylene glycol) (MSA/PEG) copolymer as reducing agent and stabilizer simultaneously. The average size of the polymer-coated silver NPs could be controlled in a wide range from 10 to 120 nm by changing the MSA/PEG molar ratio. These surface-coated silver NPs can be uniformly dispersed in polar solvent and a homogeneous silver NPs/acetone dispersion has been prepared. Silver–epoxy nanocomposites have been developed by incorporating these silver NPs into epoxy. The nanocomposites with silver volume content of 25% showed a more than 3000% increase in dielectric constant as compared to neat matrix and a relatively low dielectric loss below 0.05, which meets the main requirement for embedded decoupling capacitors. Moreover, thermal properties of the silver–epoxy nanocomposites were also characterized by thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). The initial decomposition temperature and glass transition temperature were elevated with the increase of silver content, which exhibit great thermal stability and facilitate electrical applications requiring higher heat-resistance.

Impact of polymer-coated silver nanoparticles on marine microbial communities: A microcosm study

The use of silver nanoparticles (AgNPs) in consumer products is increasing drastically and their potential environmental impacts on aquatic organisms from bacterial communities to vertebrates are not well understood. This study reports on changes in marine bacterial richness using denaturing gradient gel electrophoresis (DGGE), and overall community abundance determined by flow cytometry in marine microcosms exposed to polymer-coated AgNPs (20±5nm) and ionic silver (Ag+). Our study clearly demonstrated that at low concentrations (5 and 50μgL−1 total silver), un-aggregated polymer-coated AgNPs and dissolved Ag+ contamination produced similar effects: a longer lag phase suggesting an adaptation period for microorganisms. As richness decreased in the treated samples, this longer lag phase could correspond to the selection of a fraction of the initial community that is insensitive to silver contamination. Polymer-coated AgNPs preserved their bactericidal properties even under the high ionic strength of estuarine waters.

Highly dispersible polymer-coated silver Nanoparticles

Highly dispersible silver nano-material was obtained by surface functionalization of silver nanoparticles with polylactic acid. The thiolation method was used for attaching carboxyl groups to the silver surface by treatment with 3-mercaptopropionic acid. The carboxyl groups were further activated by diisopropylcarbodiimide and reacted with polylactic acid. The functionalized nanoparticles contained 1.88 wt.% organic phase. While the as-received silver nanopowder exhibited poor colloidal stability in tetrahydrofuran, particle size analysis revealed that the functionalized material displayed high dispersibility in this solvent.

Enhancement of Thermal Properties of Polyvinylpyrrolidone (PVP)-Coated Silver Nanoparticles by Using Plasmid DNA and their Localized Surface Plasmon Resonance (LSPR) Characteristics

In this paper, the enhancement of thermal properties of polymer-coated silver nanoparticles by the addition of plasmid DNA is described. Nanoparticles of noble metals such as gold and silver possess specific characteristics by virtue of their quantum size effects. Therefore, noble metal nanoparticles are used for chemical sensing and biosensing applications based on their localized surface plasmon resonance absorption that can be measured in the visible region. The polyvinylpyrrolidone (PVP)-coated noble metal nanoparticles, in particular, with high dispersion ability in water, offer several advantages for sensing applications. However, some difficulties are encountered in the use of these PVP-coated noble metal nanoparticles for sensing applications due to their poor thermal properties. To improve the thermal properties of PVP-coated noble metal nanoparticles, we found that the addition of plasmid DNA to PVP-coated silver nanoparticles enhances their thermal properties due to good thermal stability of DNA. The introduction of plasmid DNA into PVP-coated silver nanoparticle dispersion enhanced the thermal properties through the formation of a complex between the nanoparticles and plasmid DNA. Furthermore, other polymers such as proteins and polyethylene glycol did not enhance the thermal properties of PVP-coated silver nanoparticles. Thus, the PVP-coated silver nanoparticle–plasmid DNA complex with enhanced thermal properties has a great potential for use in medical and drug delivery applications.