Polymer-coated Nanoparticles Research Articles

Surface-enhanced Raman encoded polymer stabilized gold nanoparticles: Demonstration of potential for use in bioassays

The preparation of biotinylated, self-assembled polymer stabilized gold nanoparticle hybrids encoded with a SERS active compound is described. The polymers used for nanoparticle stabilization are carefully designed for this purpose and are synthesized by the RAFT polymerization process, as the thiocarbonylthio end group provides a functional handle for anchoring the polymers to the gold surface. Functionalised biotin moieties are attached to the hybrid nanoparticles via Cu-catalyzed azide-alkyne cycloaddition. Binding of the biotinylated hybrid nanoparticles to streptavidin was confirmed by nanoparticle detection and identification by the SERS spectrum of the surface-bound SERS active compound, quinolinethiol. This investigation includes the requisites that constitute a bioassay, demonstrating the potential of polymer-coated hybrid nanoparticles for this purpose.

Simultaneous hyperthermia and doxorubicin delivery from polymer-coated magnetite nanoparticles

In this work, the hyperthermia response, (i.e., heating induced by an externally applied alternating magnetic field) and the simultaneous release of an anti-cancer drug (doxorubicin) by polymer-coated magnetite nanoparticles have been investigated. After describing the setup for hyperthermia measurements in suspensions of magnetic nanoparticles, the hyperthermia (represented by the rate of suspension heating and, ultimately, by the specific absorption rate or SAR) of magnetite nanoparticles (both bare and polymer-coated as drug nanocarriers) is discussed. The effect of the applied ac magnetic field on doxorubicin release is also studied, and it is concluded that the field does not interfere with the release process, demonstrating the double functionality of the investigated particles.

Impact of polymer-modified gold nanoparticles on brain endothelial cells: exclusion of endoplasmic reticulum stress as a potential risk factor

A library of polymer-coated gold nanoparticles (AuNPs) differing in size and surface modifications was examined for uptake and induction of cellular stress responses in the endoplasmic reticulum (ER stress) in human brain endothelial cells (hCMEC/D3). ER stress is known to affect the physiology of endothelial cells (ECs) and may lead to inflammation or apoptosis. Thus, even if applied at non-cytotoxic concentrations ER stress caused by nanoparticles should be prevented to reduce the risk of vascular diseases and negative effects on the integrity of barriers (e.g. blood–brain barrier). We exposed hCMEC/D3 to twelve different AuNPs (three sizes: 18, 35, and 65 nm, each with four surface-modifications) for various times and evaluated their effects on cytotoxicity, proinflammatory mediators, barrier functions and factors involved in ER stress. We demonstrated a time-dependent uptake of all AuNPs and no cytotoxicity for up to 72 h of exposure. Exposure to certain AuNPs resulted in a time-dependent increase in the proinflammatory markers IL-8, MCP-1, sVCAM, sICAM. However, none of the AuNPs induced an increase in expression of the chaperones and stress sensor proteins BiP and GRP94, respectively, or the transcription factors ATF4 and ATF6. Furthermore, no upregulation of the UPR stress sensor receptor PERK, no active splicing product of the transcription factor XBP1 and no upregulation of the transcription factor CHOP were detectable. In conclusion, the results of the present study indicate that effects of different-sized gold nanoparticles modified with various polymers were not related to the induction of ER stress in brain microvascular endothelial cells or led to apoptosis.

Mixed Polymer-Coated Magnetic Nanoparticles as Forward Osmosis Draw Agents of Tuned Hydrophilicity.

We recently reported a polymer-coated magnetic nanoparticle (MNP) draw agent for the forward osmosis (FO) water desalination process. The water flux was found to increase when the polymer poly(sodium acrylate) (PSA) was anchored to the MNP surface as compared to the polymer (or polyelectrolyte solution) alone, due to the polymer chains being stretched out and most of the hydrophilic groups on the polymer contributing to water flux. We herein report the use of a secondary polymer poly(N-isopropylacrylamide) PNIPAM to manipulate the PSA polymer conformation and influence inter- and intrachain interactions to enhance the efficiency of the FO draw agent. These PSA-PNIPAM-coated MNPs generated a much higher water flux of ∼11.66 LMH when compared to the 100 % PSA-coated MNPs featuring a value of ∼5.32 LMH under identical FO conditions. The osmotic pressure and water flux driven by the mixed polymer-coated MNPs were found to be a strong function of the net polymer coverage on MNPs, that is, net available hydrophilic groups. Our new draw agent demonstrates potential for use in the water industry due to its improved efficiency and cost effectiveness as it uses only ∼0.062 % (w/v) of the draw agent solution.

Magnetic Properties of Polyvinyl Alcohol and Doxorubicine Loaded Iron Oxide Nanoparticles for Anticancer Drug Delivery Applications.

The current study emphasizes the synthesis of iron oxide nanoparticles (IONPs) and impact of hydrophilic polymer polyvinyl alcohol (PVA) coating concentration as well as anticancer drug doxorubicin (DOX) loading on saturation magnetization for target drug delivery applications. Iron oxide nanoparticles particles were synthesized by a reformed version of the co-precipitation method. The coating of polyvinyl alcohol along with doxorubicin loading was carried out by the physical immobilization method. X-ray diffraction confirmed the magnetite (Fe3O4) structure of particles that remained unchanged before and after polyvinyl alcohol coating and drug loading. Microstructure and morphological analysis was carried out by transmission electron microscopy revealing the formation of nanoparticles with an average size of 10 nm with slight variation after coating and drug loading. Transmission electron microscopy, energy dispersive, and Fourier transform infrared spectra further confirmed the conjugation of polymer and doxorubicin with iron oxide nanoparticles. The room temperature superparamagnetic behavior of polymer-coated and drug-loaded magnetite nanoparticles were studied by vibrating sample magnetometer. The variation in saturation magnetization after coating evaluated that a sufficient amount of polyvinyl alcohol would be 3 wt. % regarding the externally controlled movement of IONPs in blood under the influence of applied magnetic field for in-vivo target drug delivery.

Salt-Driven Deposition of Thermoresponsive Polymer-Coated Metal Nanoparticles on Solid Substrates.

Here we report on a simple, generally applicable method for depositing metal nanoparticles on a wide variety of solid surfaces under all aqueous conditions. Noble-metal nanoparticles obtained by citrate reduction followed by coating with thermoresponsive polymers spontaneously form a monolayer-like structure on a wide variety of substrates in presence of sodium chloride whereas this phenomenon does not occur in salt-free medium. Interestingly, this phenomenon occurs below the cloud point temperature of the polymers and we hypothesize that salt ion-induced screening of electrostatic charges on the nanoparticle surface entropically favors hydrophobic association between the polymer-coated nanoparticles and a hydrophobic substrate.

Synthesis of Polymer-Coated Magnetic Nanoparticles from Red Mud Waste for Enhanced Oil Recovery in Offshore Reservoirs

Buried red mud waste from groundwater refineries can cause pollution. The aim of this paper is to utilize this mud for the synthesis of Fe3O4 magnetic nanoparticles (MNPs). Then, MNPs are encapsulated by a copolymer of methyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfonate via oleic acid linker. MNPs are prepared by a controlled co-precipitation method in the presence of a dispersant and surface-modified agents to achieve a high hydrophobic or hydrophilic surface. Mini-emulsion polymerization was conducted to construct a core–shell structure with MNPs as core and the copolymer as shell. The core–shell structure of the obtained particles enables them to disperse well in brine and to stabilize at high-temperature environments. The chemical structures and morphology of this nanocomposite were investigated by Fourier transform infrared spectroscopy, transmission electron microscopy, and field emission scanning electron microscopy. The thermal stability of the nanocomposite was evaluated via a thermogravimetric analysis method for the solid state and an annealing experiment for the liquid state. The nanocomposite is about 14 nm, disperses well in brine and is thermally stable in the solid state. The blends of synthesized nanocomposite and carboxylate surfactant effectively reduced the interfacial tension between crude oil and brine, and remained thermally stable after 31 days annealed at 100°C. Therefore, a nanofluid of copolymer/magnetic nanocomposite can be applied as an enhanced oil recovery agent for harsh environments in offshore reservoirs.

Application of Engineered Si Nanoparticles in Light-Induced Advanced Oxidation Remediation of a Water-Borne Model Contaminant.

Surface-engineered amphiphilic polymer-coated silicon nanoparticles (SiNPs) were employed as photocatalysts to capture and degrade a model organic contaminant (methanol) in water. This study represents the first time SiNPs have been employed in the initiation of advanced oxidation processes that are commonly used to degrade organic constituents in industrial wastewaters. The quantum yield of photocatalytic methanol oxidation and the corresponding yield factor for the generation of active OH radicals are reported. The size and surface defect dependent photocatalytic activity of SiNPs was investigated. The yield factors (η) decreased with increasing particle size and reached impressive values that exceeded that of equivalent TiO2 nanoparticle systems by 3-4 times and are comparable to the robust UV/Cl2 and UV/H2O2 systems. The higher photocatalytic efficiency of SiNPs is attributed to the combined effects of quantum confinement, effective band gap, and surface states, among which surface states play a dominant role. SiNPs provide a potentially tunable, biologically inert, and robust nanoparticle system for photocatalytic oxidation of wastewater contaminants.

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.

Diffusion of functionalized magnetite nanoparticles forced by a magnetic field studied by EPR method

The article shows the influence of time of the inhomogeneous magnetic field application and the type of coverage on the behavior of functionalized magnetite nanoparticles. TEMPO-functionalized and polymer-coated nanoparticles (Fe3O4@PEG) in water solution were subjected to a magnetic field for 1, 2 and 4 min, while the same nanoparticles mixed with bovine serum for 1 and 2 min. TEMPO-functionalized and silane-coated nanoparticles (Fe3O4@Silane) diluted in water, human blood or human serum were subjected to a magnetic field for 4 min. For each sample before and after its placement in an inhomogeneous magnetic field the electron paramagnetic resonance (EPR) spectra were recorded using an X-band (9.4 GHz) EPR spectrometer. On the basis of EPR spectra we developed a new method and software to study the effect of external magnetic field on the changes in nanoparticles distribution in the samples studied. It has been observed that the placement of the sample with the nanoparticles in the inhomogeneous magnetic field causes them to diffusion, wherein the speed of diffusion depends on the time during which the sample is hold in a magnetic field, the kind of coverage and the type of solvent.

Visible Light and pH Responsive Polymer-Coated Mesoporous Silica Nanohybrids for Controlled Release.

A visible light and pH responsive anticancer drug delivery system based on polymer-coated mesoporous silica nanoparticles (MSNs) has been developed. Perylene-functionalized poly(dimethylaminoethyl methacrylates) sensitive to visible light and pH are electrostatically attached on the surface of MSNs to seal the nanopores. Stimulation of visible light and acid can unseal the nanopores to induce controlled drug release from the MSNs. More interestingly, the release can be enhanced under the combined stimulation of the dual-stimuli. The synergistic effect of visible light and acid stimulation on the efficient release of anticancer drugs from the nanohybrids endows the system with great potential for cancer therapy.

Dual-modality self-heating and antibacterial polymer-coated nanoparticles for magnetic hyperthermia

Multifunctional nanoparticles for magnetic hyperthermia which simultaneously display antibacterial properties promise to decrease bacterial infections co-localized with cancers. Current methods synthesize such particles by multi-step procedures, and systematic comparisons of antibacterial properties between coatings, as well as measurements of specific absorption rate (SAR) during magnetic hyperthermia are lacking. Here we report the novel simple method for synthesis of magnetic nanoparticles with shells of oleic acid (OA), polyethyleneimine (PEI) and polyethyleneimine-methyl cellulose (PEI-mC). We compare their antibacterial properties against single gram-positive (Staphylococcus aureus) and gram-negative (Escherichia coli) bacteria as well as biofilms. Magnetite nanoparticles (MNPs) with PEI-methyl cellulose were found to be most effective against both S. aureus and E. coli with concentration for 10% growth inhibition (EC10) of <150mg/l. All the particles have high SAR and are effective for heat-generation in alternating magnetic fields.

The Importance of Excess Poly(N-isopropylacrylamide) for the Aggregation of Poly(N-isopropylacrylamide)-Coated Gold Nanoparticles.

Thermoresponsive materials are generating significant interest on account of the sharp and tunable temperature deswelling transition of the polymer chain. Such materials have shown promise in drug delivery devices, sensing systems, and self-assembly. Incorporation of nanoparticles (NPs), typically through covalent attachment of the polymer chains to the NP surface, can add additional functionality and tunability to such hybrid materials. The versatility of these thermoresponsive polymer/nanoparticle materials has been shown previously; however, significant and important differences exist in the published literature between virtually identical materials. Here we use poly(N-isopropylacrylamide) (PNIPAm)-AuNPs as a model system to understand the aggregation behavior of thermoresponsive polymer-coated nanoparticles in pure water, made by either grafting-to or grafting-from methods. We show that, contrary to popular belief, the aggregation of PNIPAm-coated AuNPs, and likely other such materials, relies on the size and concentration of unbound “free” PNIPAm in solution. It is this unbound polymer that also leads to an increase in solution turbidity, a characteristic that is typically used to prove nanoparticle aggregation. The size of PNIPAm used to coat the AuNPs, as well as the concentration of the resultant polymer–AuNP composites, is shown to have little effect on aggregation. Without free PNIPAm, contraction of the polymer corona in response to increasing temperature is observed, instead of nanoparticle aggregation, and is accompanied by no change in solution turbidity or color. We develop an alternative method for removing all traces of excess free polymer and develop an approach for analyzing the aggregation behavior of such materials, which truly allows for heat-triggered aggregation to be studied.

Low Adsorption of Magnetite Nanoparticles with Uniform Polyelectrolyte Coatings in Concentrated Brine on Model Silica and Sandstone

In subsurface imaging and oil recovery where temperatures and salinities are high, it is challenging to design polymer-coated nanoparticles with low retention (high mobility) in porous rock. Herein, the grafting of poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylic acid) (poly(AMPS-co-AA)) on magnetic iron oxide nanoparticles was sufficiently uniform to achieve low adsorption on model colloidal silica and crushed Berea sandstone in highly concentrated API brine (8% NaCl and 2% CaCl2 by weight). The polymer shell was grafted via amide bonds to an aminosilica layer, which was grown on silica-coated magnetite nanoparticles. The particles were found to be stable against aggregation in American Petroleum Institute (API) brine at 90 °C for 24 h. For IO nanoparticles with ∼23% polymer content, Langmuir adsorption capacities on colloidal silica and crushed Berea Sandstone in batch experiments were extremely low at only 0.07 and 0.09 mg of IO/m2, respectively. Furthermore, upon injection of a 2.5 mg/mL I...

Co-operative transitions of responsive-polymer coated gold nanoparticles; precision tuning and direct evidence for co-operative aggregation.

Responsive polymers and polymer-coated nanoparticles have many potential bio-applications with the crucial parameter being the exact temperature where the transition occurs. Chemical modification of hydrophobic/hydrophilic or ligand binding sites has been widely explored as a tool for controlling this transition, but requires the synthesis of many different components to achieve precise control. This study reports an extensive investigation into the use of blending (i.e. mixing) as a powerful tool to modulate the transition temperature of poly(N-isopropylacrylamide) (PNIPAM) coated gold nanoparticles. By simply mixing two nanoparticles of different compositions, precise control over the transition temperature can be imposed. This was shown to be flexible to all possible mixing parameters (different polymers on different particles, different polymers on same particles and different sized particles with identical/different polymers). Evidence of the co-operative aggregation of differently sized nanoparticles (with different cloud points) is shown using transmission electron microscopy; particles with higher cloud points aggregate with those with lower cloud points with homo-aggregates not seen, demonstrating the co-operative behaviour. These interactions, and the opportunities for transition tuning will have implications in the rational design of responsive biomaterials.

Preparation and Characterization of Inulin Coated Gold Nanoparticles for Selective Delivery of Doxorubicin to Breast Cancer Cells

A novel folate-targeted gold-based nanosystem for achieving selectivity towards folate receptor (FR) positive cells is proposed, by virtue of the fact that the FR is a molecularly targeted entity overexpressed in a wide spectrum of solid tumors. A new inulin-folate derivative (INU-FA) has been synthesized to act as coating agent for 40 nm gold nanoparticles. The obtained polymer-coated gold nanoparticles (Au@INU-FA) were characterized in terms of hydrodynamic radius, shape, zeta potential, and aqueous stability and were loaded with doxorubicin (Au@INU-FA/Doxo). Its release capability was tested in different release media. The selectivity of Au@INU-FA/Doxo system towards FRs-positive cancer cells was proved by the differences in the quantitative uptake using human breast cancer MCF7 as FR-positive cells and 16HBE epithelial as noncancer cell line. Furthermore, the folate-mediated uptake mechanism was studied by FRs-blocking experiments. On the whole Au@INU-FA/Doxo was able to be preferentially internalized into MCF7 cells proving a folate-mediated endocytosis mechanism which allowed a higher and selective cytotoxic effect towards cancer cells. The cytotoxicity profile was evaluated on both cancer and noncancer cell lines, displaying that folate-mediated targeting implied advantageous therapeutic effects, such as amplified drug uptake and increased anticancer activity towards MCF7 cancer cells.

Ultrasound-Mediated Surface Engineering of Theranostic Magnetic Nanoparticles: An Effective One-Pot Functionalization Process Using Mixed Polymers for siRNA Delivery

Nano-sized materials have been studied for diverse clinical applications, partly because their size-dependent physical properties and nanometer-scale dimensions have important roles in biological systems. Synergistic combinations of differently nanostructured materials, such as polymer-coated magnetic nanoparticles (NPs), strongly promoted various multifunctional nano-medical platforms for simultaneous diagnosis and therapy in the rapidly emerging area of theranostics. In this context, magnetically responsive Ce cation-doped maghemite (γ-Fe2O3) NPs form a useful NPs basis towards a new type of polycationic polymer/organic species-grafted maghemite NPs for both drug delivery and imaging. The versatility of the Ce cation-doped maghemite NPs fabrication process mediated by high-power ultrasound (US) enables the development of a new one-step time-saving US-driven variant fabrication of corresponding polymer/organic species-grafted NPs. Thus, two types of organic polycationic species, a branched 25 kDa polyethylene imine (b-PEI25) polymer and a generation 2 (G2) PAMAM (poly(amidoamine)) dendrimer biopolymer, were simultaneously used during this US-mediated NPs system fabrication to effectively deliver optimized small interfering RNA (siRNA) applications as a proof of concept. This unique one-step fabrication protocol affords a positively charged magnetic core grafted with mixed organic species nanocomposite particles that enables both gene silencing therapy and magnetic resonance imaging.

Taste masking of a drug by pH-responsive coordination polymer-coated mesoporous silica nanoparticles

We developed a simple and efficient method for fabricating a taste-masked oral drug delivery system (DDS) that regulates the release of unpleasant drug taste via the change in pH value in the physiological environment of the alimentary canal.

Evaluation of polymer-coated magnetic nanoparticles for oil separation under environmentally relevant conditions: effect of ionic strength and natural organic macromolecules

Fluorescence spectra for oil–water mixtures before and after oil removal using PVP-coated magnetic nanoparticles under different environmentally relevant conditions.

Fluorescent determination of poly(hexamethylene guanidine) via the aggregates it forms with quantum dots and magnetic nanoparticles

The authors report that the cationic polymer-oligomer poly(hexamethylene guanidine) (PHMG) in the form of its hydrochloride induces the formation of mixed aggregates composed of anionic magnetiс nanoparticles (magNPs), PHMG and anionic quantum dots (QDs). The magNPs consisted of polymer-coated magnetite nanoparticles, and the QDs consisted of polymer-coated CdSe@CdS/ZnS nanoparticles with an emission maximum at 617 nm. This finding is exploited in a semi-quantitative method for the determination of PHMG. The protocol includes magnetic separation of the mixed aggregates (magNPs/PHMG/QDs) from the sample and excess QDs, redispersion of the aggregates in water, and measurement of fluorescence intensity. The signal is proportional to the concentration of PHMG in the 0.05 to 0.2 mg L−1 concentration range, with intra-day RSDs of up to 27 %. The limit of detection (LOD) of PHMG in spiked run-off waters, swimming pool water and wastewater is 23 μg L−1. This PHMG assay is selective in that high concentrations of surfactants and inorganic salts are tolerated. Polyethyleneimine and poly(diallyldimethylammonium chloride) also cause the formation of mixed aggregates but only at higher concentrations. Both a fluorometer and a digital camera (using a 365-nm LED as a light source) were used to measure fluorescence. In case of using a digital camera, the LOD is 40 μg L−1 and the intraday RSDs are up to 23 %. The method is sensitive, fairly selective and rather simple.