Monolayer Of Silver Nanoparticles Research Articles

Laser-Driven Hybridization of a Surface Plasmon Resonance Collective Mode in a Monolayer of Silver Nanoparticles

Laser-driven hybridization of a collective surface plasmon mode of a monolayer of silver nanoparticles has been studied as a function of irradiation power density. Two collective surface plasmon modes were identified in the spectra, namely, T- and P-modes, associated with the induced particle dipoles parallel and perpendicular to the plane of the layer. The P-mode was in resonance with the laser irradiation wavelength (488 nm). The magnitude, spectral position, and bandwidth of the two modes depend significantly differently on the laser power density. The laser-driven changes of the T-mode were attributed to the thermal effects caused by laser heating of the sample. Meanwhile, the spectral behavior of the P-mode is governed by resonant excitation by an Ar laser.

High Raman-to-fluorescence ratio of Rhodamine 6G excited with 532 nm laser wavelength using a closely packed, self-assembled monolayer of silver nanoparticles.

A highly efficient Raman-to-fluorescence ratio of Rhodamine 6G is obtained by means of 532 nm laser wavelength, which is in close proximity of the dye's absorption maximum. Closely packed, gap-filled self-assembled monolayers of silver nanoparticles were produced to observe the Raman signals of Rhodamine 6G. Two mechanisms contribute to detect the Raman signals of the fluorescent sample: surface-enhanced Raman scattering (SERS) and nanomaterial surface energy transfer (NSET). Self-assembled monolayers of silver nanoparticles with different coverage densities and also those filled with probe molecules were prepared through variations of the substrate's immersion time in a nanoparticle solution and drying the substrate, respectively. Examination of the effects of these two factors on the plasmonic response and SERS efficiency of the substrate revealed that in a gap-filled dense coverage, near-field interactions dominate, which remarkably increase the Raman-to-fluorescence ratio (RFR). To have a perfect dense coverage, the efficient immersion time was obtained at about 48 h. Drying the substrates also caused further enhancement in RFR through filling interparticle spaces with dye molecules and, accordingly, an increase in NSET efficiency.

Titanium dioxide/silver nanoparticle bilayers prepared in self-assembly processes

<p>A new method for the preparation of TiO<sub>2</sub>/Ag bilayers via colloid <br /> self-assembly process using well-characterized titanium dioxide and silver suspensions was developed. The titanium dioxide nanoparticles, forming a supporting layer, were 46 nm in diameter, exhibiting an isoelectric point at pH 6.4. The silver nanoparticles, forming an external layer of the diameter of 50 nm were prepared via a chemical reduction method with the presence inorganic phosphate salts. The electrophoretic mobility measurements revealed that the zeta potential of silver nanoparticles was highly negative for a broad range of pH and ionic strengths. By explaining this information, the optimum condition for the silver nanoparticle immobilization on TiO<sub>2</sub> supporting layers were selected. The coverage of the first layer was adjusted by ionic strength of the suspensions and by the deposition time. Afterward, the silver nanoparticle monolayers of controlled coverage were deposited under the diffusion-controlled transport. Their coverage was determined by a direct enumeration of deposited nanoparticles from AFM images and SEM micrographs. The experimental results showed that for extended deposition times, the coverage of silver nanoparticle layers significantly increases with ionic strength. Therefore, it was proven that the formation of bilayers is mainly controlled by electrostatic interactions and that it is feasible to produce uniform TiO<sub>2</sub>/Ag materials of desired coverage and structure.</p>

Monolayers of silver nanoparticles on positively charged polymer microspheres

Abstract The deposition of silver nanoparticles on positively charged polystyrene microspheres was studied by micro-electrophoretic and concentration depletion methods involving UV–vis spectrometry. The influence of ionic strength varied between 10 −4 to 3 × 10 −2 M, was determined. Primarily, the electrophoretic mobility variations of latex upon the addition of controlled amount of silver nanoparticles were measured. These dependencies were quantitatively interpreted in terms of the 3D electrokinetic model previously used for planar interface. This allowed to determine the coverage of nanoparticles on microspheres under in situ conditions for incomplete monolayer range. Additionally, the maximum coverage of silver nanoparticles was precisely determined by measuring the absorption spectrum of the silver suspension acquired by ultrafiltration after the deposition step. It was shown that maximum coverage monotonically increased with ionic strength attaining 0.52 for the ionic strength of 3 × 10 −2 M. This effect, attributed to the decreasing range of lateral electrostatic interactions among deposited particles, was accounted for by the random sequential adsorption model. The obtained results proved the feasibility of preparing silver nanoparticle shells on polymeric carrier microspheres having well-defined coverage and structure. Also, our measurements confirmed the validity of the 3D electrokinetic method for a quantitative interpretation of nanoparticle deposition on microspheres.

Effect of electron irradiation on the size and concentration of silver nanoparticles on the surface of silicate glass

Experiments show that electron irradiation of silicate glass with a monolayer of silver nanoparticles (NPs) at energies of 3–5 keV leads to a decrease in the NP concentration due to elimination of small-size NPs and an increase in the mean diameter of the remaining NPs. It is demonstrated that the main processes that take place upon irradiation of the NP monolayer on the glass surface involve secondary electron emission, charging of NPs and near-surface glass layers with the generation of high-intensity electric fields, surface ionization that leads to the detachment of silver ions from NPs, and migration of charged NPs over glass surface.

Surface Plasmon Modes of Sandwich-Like Metal–Dielectric Nanostructures

We established that metal–dielectric nanostructures (consisting of three stacked monolayers of silver nanoparticles incorporated into polymer cross-linked film) can demonstrate three different surface plasmon collective modes. The modes were detected when the extinction spectra of the nanostructures were studied as a function of the incident angle and polarization of the incident light. Two previously known surface plasmon collective modes, namely T and P, associated with particle dipoles parallel and perpendicular to plane of the layer were identified for the polymer films containing one, two, and three monolayers of the particles. The extinction bands of T and P modes exhibited different intensity and frequency dependences on the angle of incidence. More pronounced angular dependences for P mode band indicated the stronger coupling of dipoles for P mode than for T one. A new N mode was observed for the structures consisting of three nanoparticle layers. This mode originated from surface plasmon coupling between adjacent layers. The additional mode significantly increases amount of information that can be obtained from optical response of the nanostructures.

Monolayers of silver nanoparticles obtained by chemical reduction methods

Charge-stabilized silver particle suspensions were prepared by the chemical reduction of silver nitrate using various organic and inorganic reducing agents such as gallic acid, tannin, hydroxylamine hydrochloride, hypophospite, sodium hexametaphosphate, borohydride and trisodium citrate. The control of the size of nanoparticles was achieved by varying the stoichiometric ratio of reagents, resulting in monodisperse nanoparticles with the diameter in the range of 13–17 nm. Surface properties of obtained nanoparticles were determined by electrophoretic measurements over a wide range of ionic strength and pH. Knowing the mobility and size of particles, their effective electrokinetic charge and 2D electrokinetic charge densities were calculated. It was also confirmed by dynamic light scattering measurements that these sols were stable for ionic strength up to 0·03 M, and in the case of tannin, up to 0·1 M. Using these negatively charged suspensions, monolayers of silver particles on poly(allylamine hydrochloride)-covered mica were prepared by a diffusion controlled self-assembly process. The kinetics of monolayer formation was quantitatively determined by atomic force microscopy and scanning electron microscopy imaging of deposited nanoparticles. These experimental results were interpreted in terms of the theoretical modeling based on the random sequential adsorption approach.

Fast self-assembly of silver nanoparticle monolayer in hydrophobic environment and its application as SERS substrate

We present a method which allows the straightforward wet-chemical synthesis of silver nanoparticles (AgNPs), hydrophobic coating assembling into monolayer, and their utilization as substrates for surface-enhanced Raman spectroscopy (SERS). In order to fabricate the SERS-active substrates, AgNPs were synthesized in water by chemical reduction of Ag+, coated with a hydrophobic shell (dodecanethiol), transferred to a non-polar solvent, and finally assembled through precipitation into a SERS-active self-assembled monolayer (SAM). Simple approaches for concentration and purification of the coated AgNPs are shown. The synthesized particles and SAMs were characterized by transmission electron microscopy, optical imaging, and spectroscopic measurements. This manuscript can be used as a do-it-yourself (DIY) tutorial which allows making SAMs from coated AgNPs (<15 nm) in every laboratory within less than 1 h and their utilization as potential low-cost SERS substrates (movie 1–4).

Plasmon-assisted photocurrent generation from silver nanoparticle monolayers combined with porphyrins via their different chain-length alkylcarboxylates.

Three-typed porphyrin derivatives with a different chain-length alkylcarboxylic acid as their peripheral anchor group have been prepared. Anodic photocurrents were observed in a simple system where the porphyrin derivatives were directly anchored on an indium tin oxide (ITO) electrode. Cathodic photocurrents and their plasmon-assisted enhancement appeared from an Ag nanoparticle (Ag NP) composite monolayer combined with the porphyrin derivatives on the ITO electrode. In the photocurrent generation mechanism, Ag NPs played both the roles as photon- and energy-transfer to the porphyrin derivatives. The plasmon-assisted enhancement was affected by the chain-lengths of the peripheral anchor groups.

Hematite/silver nanoparticle bilayers on mica – AFM, SEM and streaming potential studies

Bilayers of hematite/silver nanoparticles were obtained in the self-assembly process and thoroughly characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), and in situ streaming potential measurements. The hematite nanoparticles, forming a supporting layer, were 22nm in diameter, exhibiting an isoelectric point at pH 8.9. The silver nanoparticles, used to obtain an external layer, were 29nm in diameter, and remained negative within the pH range 3 to 11. In order to investigate the particle deposition, mica sheets were used as a model solid substrate. The coverage of the supporting layer was adjusted by changing the bulk concentration of the hematite suspension and the deposition time. Afterward, silver nanoparticle monolayers of controlled coverage were deposited under the diffusion-controlled transport. The coverage of bilayers was determined by a direct enumeration of deposited particles from SEM micrographs and AFM images. Additionally, the formation of the hematite/silver bilayers was investigated by streaming potential measurements carried out under in situ conditions. The effect of the mica substrate and the coverage of a supporting layer on the zeta potential of bilayers was systematically studied. It was established that for the coverage exceeding 0.20, the zeta potential of bilayers was independent on the substrate and the supporting layer coverage. This behavior was theoretically interpreted in terms of the 3D electrokinetic model. Beside significance for basic sciences, these measurements allowed to develop a robust method of preparing nanoparticle bilayers of controlled properties, having potential applications in catalytic processes.

Two dimensional dipolar coupling in monolayers of silver and gold nanoparticles on a dielectric substrate.

The dimensionality of assembled nanoparticles plays an important role in their optical and magnetic properties, via dipolar effects and the interaction with their environment. In this work we develop a methodology for distinguishing between two (2D) and three (3D) dimensional collective interactions on the surface plasmon resonance of assembled metal nanoparticles. Towards that goal, we elaborate different sets of Au and Ag nanoparticles as suspensions, random 3D arrangements and well organized 2D arrays. Then we model their scattering cross-section using effective field methods in dimension n, including interparticle as well as particle-substrate dipolar interactions. For this modelling, two effective field medium approaches are employed, taking into account the filling factors of the assemblies. Our results are important for realizing photonic amplifier devices.

Antibiofilm activity of a monolayer of silver nanoparticles anchored to an amino-silanized glass surface

Biofilm production is the crucial pathogenic mechanism of the implant-associated infection and a primary target for new anti-infective strategies. Silver nanoparticles (AgNPs) are attracting interest for their multifaceted potential biomedical applications. As endowed with highest surface/mass ratio and potent antibacterial activity, they can profitably be applied as monolayers at biomaterial surfaces. Desirably, in order to minimize the risks of toxic effects from freely circulating detached nanoparticles, AgNPs should firmly be anchored to the modified biomaterial surfaces. Here we focus on a newly designed glass surface modified with AgNPs and on its antibiofilm properties. Link of a self-assembled monolayer of AgNPs to glass was obtained through preliminary amino-silanization of the glass followed by immersion in an AgNPs colloidal suspension. Static contact angle measure, AFM, TEM, UV-Vis spectroscopy, ICP atomic emission spectroscopy were used for characterization. Antibiofilm activity against the biofilm-producer Staphylococcus epidermidis RP62A was assayed by both CFU method and CLSM. Performances of AgNPs-glasses were: i) excellent stability in aqueous medium; ii) prolonged release and high local concentration of Ag+ without any detaching of AgNPs; iii) strong antibiofilm activity against S. epidermidis RP62A. This AgNPs surface-modification can be applied to a large variety of biomaterials by simply depositing glass-like SiO2 films on their surfaces.

Stability of silver nanoparticle monolayers determined by in situ streaming potential measurements

A silver particle suspension obtained by a chemical reduction was used in this work. Monolayers of these particles (average size 28 nm) on mica modified by poly(allylamine hydrochloride) were produced under diffusion-controlled transport. Monolayer coverages, quantitatively determined by atomic force microscopy (AFM) and SEM, was regulated by adjusting the nanoparticle deposition time and the suspension concentration. The zeta potential of the monolayers was determined by streaming potential measurements carried out under in situ (wet) conditions. These measurements performed for various ionic strengths and pH were interpreted in terms of the three-dimensional (3D) electrokinetic model. The stability of silver monolayers was also investigated using streaming potential and the AFM methods. The decrease in the surface coverage of particles as a function of time and ionic strength varied between 10−1 and 10−4 M was investigated. This allowed one to determine the equilibrium adsorption constant K a and the binding energy of silver particles (energy minima depth). Energy minima depth were calculated that varied between −18 kT for I = 10−1 M and −19 kT for I = 10−4 for pH 5.5 and T = 298 K. Our investigations suggest that the interactions between surface and nanoparticles are controlled by the electrostatic interactions among ion pairs. It was also shown that the in situ electrokinetic measurements are in accordance with those obtained by more tedious ex situ AFM measurements. This confirmed the utility of the streaming potential method for direct kinetic studies of nanoparticle deposition/release processes.Graphical

Metal nanoparticles in organic field-effect transistor: Transition from charge trapping to conduction mechanism

Self-assembled monolayers of metal nanoparticles (NPs) are envisioned for various devices and have been investigated for possible applications. However, organic envelope of NPs which is required for self-assembling must be often removed prior further device fabrication. Here, we report on effect of ozonolysis on monolayer of silver NPs (Ag NPs) with size of 8nm and its impact on Ag NPs utilization in organic field-effect transistor. It was found that Ag NPs covered by organics serve like a traps and removal of insulating organics decreases number of traps and consequently increases Ag NPs monolayer conductivity.

A Stable Sandwich-Type Hydrogen Peroxide Sensor Based on Immobilizing Horseradish Peroxidase to a Silver Nanoparticle Monolayer Supported by PEDOT:PSS-Nafion Composite Electrode

A Stable Sandwich-Type Hydrogen Peroxide Sensor Based on Immobilizing Horseradish Peroxidase to a Silver Nanoparticle Monolayer Supported by PEDOT:PSS-Nafion Composite Electrode

Can a novel silver nano coating reduce infections and maintain cell viability in vitro?

Herein we report a facile layer-by-layer method for creating an antimicrobial coating composed of silver nanoparticles on medical grade titanium test discs. Nanoscale silver nanoparticle layers are attached to the titanium orthopedic implant material via aminopropyltriethoxy silane crosslinker that reacts with neighboring silane moieties to create an interconnected network. A monolayer of silane, followed by a monolayer of silver nanoparticles would form one self-assembled layer and this process can be repeated serially, resulting in increased silver nanoparticles deposition. The release rate of silver ion increases predictably with increasing numbers of layers and at appropriate thicknesses these coatings demonstrate 3-4 log reduction of viable Escherichia coli and Staphylococcus aureus bacteria. Increasing the thickness of the coatings resulted in reduced bacterial colonization as determined by fluorescent staining and image analysis. Interestingly, the cytotoxicity of murine 3T3 cells as quantified by fluorescent staining and flow cytometry, was minimal and did not vary significantly with the coating thickness. Additionally, these coatings are mechanically stable and resist delamination by orthogonal stress test. This simple layer-by-layer coating technique may provide a cost-effective and biocompatible method for reducing microbial colonization of implantable orthopedic devices.

Influence of surface oxidation on plasmon resonance in monolayer of gold and silver nanoparticles

Surface plasmon resonance of gold and silver nanoparticle (NP) layers is investigated by the experiment as well as simulations. Although the good agreement was found for gold NP film, a significant mismatch in the resonance energy for silver NP film was observed. The deviation was assigned to the presence of silver oxide (Ag2O) in silver NPs. As an alternative to the NP size-dependent Drude model, the analysis based on effective medium approximation for refractive index of Ag-Ag2O material system is carried out and compared with the core-shell model. Both Mie's model and numerical simulation results illustrate shift of the surface plasmon resonance due to silver NP surface oxidation.

A method for the coating of a polymer inclusion membrane with a monolayer of silver nanoparticles

The preparation of silver nanoparticles (AgNPs) is described using a polymer inclusion membrane (PIM) consisting of 45% (m/m) di-(2-ethylhexyl)phosphoric acid (D2EHPA) and 55% (m/m) poly(vinyl chloride) (PVC) as a template. The Ag(I) ion was firstly extracted into the membrane via cation-exchange and then subsequently reduced with NaBH4, trisodium citrate, citric acid, or l-ascorbic acid to form AgNPs. The most effective reducing agent was found to be l-ascorbic acid which at pH 2.0 formed a uniform monolayer of AgNPs of an average size of 360nm on the surface of the PIM. Citric acid also produced AgNPs but these were embedded in the bulk of the membrane and did not provide a good surface coverage. NaBH4 and trisodium citrate, on the other hand, gave rise to the formation of black silver oxide on the membrane surface.Factors such as the membrane loading with Ag(I), PIM composition, reduction time, temperature and shaking time were found to have a significant influence on the surface coverage and size of the AgNPs.

Optical Method for Predicting the Composition of Self-Assembled Monolayers of Mixed Thiols on Surfaces Coated with Silver Nanoparticles

With a simple optical method, based on UV-vis absorption spectra on glass slides, it is possible to predict the composition of self-assembled monolayers of mixed thiols, grafted on monolayers of silver nanoparticles. Glass slides are modified with the layer-by-layer technique, first forming a monolayer of mercaptopropyltrimethoxysilane, then grafting a monolayer of silver nanoparticles on it. These surfaces are further coated by single or mixed thiol monolayers, by dipping the slides in toluene solutions of the chosen thiols. Exchange constants are calculated for the competitive deposition between the colorless 1-dodecanethiol or PEG5000 thiol and BDP-SH, with the latter being a thiol-bearing molecule containing the strongly absorbing BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) moiety, synthesized on purpose. The constants are calculated by determining the fraction of BDP-SH deposited on the surface from a solution with a given molar fraction, directly measuring the absorption spectra of BDP-SH on the slides. Then, the exchange constant for the competitive deposition between 1-dodecanethiol and PEG5000 thiol is calculated by combining their exchange constants with BDP-SH. This allows to predict the fraction of the two colorless thiols coating the silver nanoparticles slides obtained from a toluene solution with a given molar fraction, for example, of PEG5000 thiol. The correctness of the calculated surface fraction is verified by studying the coating competition between 1-dodecanethiol and a PEG5000 thiol remotely modified with a strongly absorbing fluorescein fragment.

High density silver nanoparticle monolayers produced by colloid self-assembly on polyelectrolyte supporting layers

A stable silver nanoparticle suspension was synthesized via the reduction of silver nitrate using sodium borohydride and sodium citrate. The particle’s shape and size distribution were measured by various methods. The electrophoretic mobility measurements revealed that the zeta potential of particles was highly negative, increasing slightly with the ionic strength, from −52 mV for I = 10 –5 M to −35 mV for I = 3 × 10 −2 M (for pH = 5.5). The zeta potential of mica modified by the adsorption of cationic polyelectrolytes: PEI and PAH was also determined using the streaming potential measurements. The modified mica sheets were used as substrates for particle monolayers formed via colloid self assembly. The kinetics of this process, proceeding under diffusion-controlled transport conditions, was quantitatively evaluated by a direct enumeration of particles using the AFM and SEM techniques. Both the kinetics of particle deposition and the maximum surface concentration were determined. From the slope of the initial deposition rates, the equivalent diameter of particles was determined to be 16 nm, in agreement with previous measurements. Based on this finding, an efficient method of determining particle size in suspension was proposed. It was also demonstrated that for higher ionic strengths, the maximum coverage of particle monolayers on PAH modified mica exceeded 0.39. The kinetic data were quantitatively interpreted in terms of the random sequential adsorption (RSA) model using the effective hard particle concept.