Magdalena Oćwieja

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 particles 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.

Tuning properties of silver particle monolayers via controlled adsorption-desorption processes.

Using the well-defined silver particle suspension, systematic studies of adsorption kinetics on mica modified by poly(allylamine hydrochloride) (PAH) were carried out. The coverage of adsorbed particles was directly determined by AFM and SEM imaging. The dependence of the coverage on adsorption time, bulk suspension concentration, and ionic strength was systematically studied. It was confirmed that adsorption was diffusion controlled, with the initial rate proportional to the bulk concentration of particles. On the other hand, for long adsorption times, the saturation coverage was attained, which increased systematically with the ionic strength of the particle suspension. The adsorption kinetic runs were adequately reflected for the entire range of times and bulk concentration by the random sequential adsorption (RSA) model. Additionally, particle desorption kinetics from previously formed monolayers were studied. The decrease in the surface coverage of particles as a function of time was measured, which allowed one to determine the equilibrium adsorption constant K(a). The binding energy of silver particles (energy minimum depth) derived form these measurements varied between -16.9 kT and -17.8 kT, which suggests that it is mainly controlled by electrostatic interactions. Knowing the equilibrium adsorption constant, a particle adsorption isotherm was theoretically derived using the RSA model. Experimental data obtained for various bulk concentration of particles were in agreement with these theoretical predictions. These measurements suggest that it is feasible to produce uniform silver particle monolayers of desired coverage in the self-assembly process of particles.

Silver particle monolayers — Formation, stability, applications

The formation of silver particle monolayers at solid substrates in self-assembly processes is thoroughly reviewed. Initially, various silver nanoparticle synthesis routes are discussed with the emphasis focused on the chemical reduction in aqueous media. Subsequently, the main experimental methods aimed at bulk suspension characterization are critically reviewed by pointing out their advantages and limitations. Also, various methods enabling the in situ studies of particle deposition and release kinetics, especially the streaming potential method are discussed. In the next section, experimental data are invoked illustrating the most important features of particle monolayer formation, in particular, the role of bulk suspension concentration, particle size, ionic strength, temperature and pH. Afterward, the stability of monolayers and particle release kinetics are extensively discussed. The results obtained by the ex situ AFM/SEM imaging of particles are compared with the in situ streaming potential measurements. An equivalency of both methods is demonstrated, especially in respect to the binding energy determination. It is shown that these experimental results can be adequately interpreted in terms of the hybrid theoretical approach that combines the bulk transport step with the surface blocking effects derived from the random sequential adsorption model. It is also concluded that the particle release kinetics is governed by the discrete electrostatic interactions among ion pairs on particle and substrate surfaces. The classical theories based on the mean-field (averaged) zeta potential concept proved inadequate. Using the ion pair concept the minor dependence of the binding energy on particle size, ionic strength, pH and temperature is properly explained. The final sections of this review are devoted to the application of silver nanoparticles and their monolayers in medicine, analytical chemistry and catalysis.

Controlled Release of Silver Nanoparticles from Monolayers Deposited on PAH Covered Mica

Systematic studies of silver particle deposition kinetics under diffusion transport on poly(allylamine hydrochloride) (PAH) modified mica were carried out. Monolayer coverage, quantitatively determined by AFM and SEM, was regulated within broad limits by adjusting the deposition time and the ionic strength. The stability of obtained silver films was determined in controlled release experiments also carried out under diffusion transport for pronged time periods reaching 240 h. The decrease in the surface coverage of particles was followed by SEM and AFM imaging. The role of particle size, ionic strength, and temperature was systematically studied. It was determined that particle release kinetics was enhanced by increase in ionic strength and temperature, whereas the effect of particle size was less significant. These results were theoretically interpreted in terms of the random sequential adsorption model (RSA), which allowed one to determine the equilibrium adsorption constant Ka and the binding energy (energy minimum depth). For particles of the average size 15 nm and T = 298 K, the energy varied between -16.9 kT for ionic strength 0.1 M and -18.8 kT for ionic strength 10(-4) M. For the largest nanoparticles 54 nm, the energy varied between -17.7 kT for ionic strength 0.1 M and -20.8 kT for ionic strength 10(-4) M. These results suggest that the interactions between surface and nanoparticles are mainly controlled by electrostatic attraction between ion pairs. Our studies indicate that there is a possibility of a controlled release of silver nanoparticles from films formed at solid substrates, which can be significant for biological application, e.g., in respect to antibacterial activity.

Hematite nanoparticle monolayers on mica preparation by controlled self-assembly.

A stable suspension of α-Fe(2)O(3) (hematite) was synthesized according to the method of Matijevic and Scheiner by an acidic hydrolysis of ferric chloride. The average size of the particles was determined by dynamic light scattering (DLS) and atomic force microscopy (AFM) and was 22 nm. The electrophoretic mobility and zeta potential of particles were determined as a function of ionic strength and pH. The zeta potential of the hematite particles was positive for pH<8.9 (isoelectric point) and negative otherwise. Using the suspension, systematic studies of particle deposition kinetics on mica were carried out. The coverage of self-assembled particle monolayers was determined by AFM and SEM imaging. Particle deposition was diffusion controlled, with the initial rate proportional to the bulk concentration of particles. On the other hand, for long times, the saturation coverage was attained, increasing systematically with ionic strength. The deposition kinetic runs were adequately reflected by the random sequential adsorption (RSA) model. Additionally, particle desorption kinetics, from previously formed monolayers, were studied using the AFM and SEM methods. It was confirmed that hematite particle desorption was practically negligible within the time period of 60 h. Our experimental data proved, therefore, that it is feasible to produce uniform and stable hematite particle monolayers of desired coverage in self-assembly processes controlled by the bulk suspension concentration and the ionic strength.

Kinetics of Silver Nanoparticle Deposition at PAH Monolayers: Reference QCM Results

The deposition kinetics of silver nanoparticles on Au/SiO2 /PAH substrate was studied under in situ conditions using the QCM method and the ex situ SEM imaging. Because of low dissipation, the Sauerbrey equation was used for calculating the mass per unit area (coverage). Measurements were done for various bulk suspension concentrations, flow rates, and ionic strengths. It was shown that particle deposition for the low coverage regime is governed by the bulk mass transfer step that results in a linear increase of the coverage with the time. A comparison of QCM and SEM results showed that the hydration of the silver monolayers was negligible. This allowed one to derive a universal kinetic equation that describes the mass transfer rates in the cell as a function of the bulk concentration, flow rate, and diffusion coefficient. Measurements were also performed for longer times and for various ionic strengths where the deposition kinetics and the maximum coverage of particles were determined. The experimental data confirmed a significant increase in the maximum coverage with ionic strength. This was interpreted as due to the decreasing range of the electrostatic interactions among deposited particles. These results were adequately interpreted in terms of the extended random sequential adsorption (eRSA) model. Additionally, it was shown that the QCM data matched the ex situ SEM results, indicating that the monolayer hydration was also negligible for higher coverage range. These results derived for the model silver nanoparticle system can be exploited as reference data for the interpretation of protein adsorption kinetics where the dry mass is needed in order to assess the extent of hydration.

Adsorption of tannic acid on polyelectrolyte monolayers determined in situ by streaming potential measurements.

Physicochemical characteristics of tannic acid (tannin) suspensions comprising its stability for a wide range of ionic strength and pH were thoroughly investigated using UV-vis spectrophotometry, dynamic light scattering and microelectrophoretic measurements. These studies allowed to determine the hydrodynamic diameter of the tannic acid that was 1.63 nm for the pH range 3.5-5.5. For pH above 6.0 the hydrodynamic diameter significantly decreased as a result of the tannin hydrolysis. The electrophoretic mobility measurements confirmed that tannic acid is negatively charged for these values of pH and ionic strength 10(-4)-10(-2) M. Therefore, in order to promote adsorption of tannin molecules on negatively charged mica, the poly(allylamine hydrochloride) (PAH) supporting monolayers were first adsorbed under diffusion transport conditions. The coverage of polyelectrolyte monolayers was regulated by changing bulk concentration of PAH and the adsorption time. The electrokinetic characteristics of bare and PAH-covered mica were determined using the streaming potential measurements. The zeta potential of these PAH monolayers was highly positive, equal to 46 mV for ionic strength of 10(-2) M. The kinetics of tannin adsorption on these PAH supporting monolayers was evaluated by the in situ the streaming potential measurements. The zeta potential of PAH monolayers abruptly decreases with the adsorption of tannin molecules that was quantitatively interpreted in terms of the three-dimensional electrokinetic model. The acid-base characteristics of tannin monolayers were acquired via the streaming potential measurements for a broad range of pH. The obtained results indicate that it is possible to control adsorption of tannin on positively charged surfaces in order to designed new multilayer structures of desirable electrokinetic properties and stability.

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 22 nm in diameter, exhibiting an isoelectric point at pH 8.9. The silver nanoparticles, used to obtain an external layer, were 29 nm 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.

Silver nanoparticle monolayers on poly(ethylene imine) covered mica produced by colloidal self-assembly

Monodisperse silver particles were synthesized according to the method of Creighton et al. by reduction of AgNO(3) solutions with NaBH(4) in the presence of polyvinyl alcohol as the stabilizing agent. Bulk characteristics of silver nanoparticles in aqueous solutions were carried out by measuring their extinction spectrum, fluorescence, diffusion coefficients using the PCS method and the electrophoretic mobilities. The average hydrodynamic diameter of PVA covered silver particles was 44 nm, being fairly independent of ionic strength and pH in the range of 3-9. It was also shown that the hydrodynamic radius did not change within prolonged storage of suspensions (up to 75 days), indicating that the sols were quite stable. A similar value of 45±8 nm was determined from SEM measurements. The electrophoretic mobility measurements showed that the zeta potential of silver nanoparticles was insensitive to pH and decreased with the ionic strength, attaining -45 mV for I=10(-5) M and -25 mV for I=10(-2) M. Additionally, the kinetics of silver particle deposition on mica modified by adsorption of a saturated layer of poly(ethylene imine) (PEI) was studied. Surface concentration was determined directly by counting the number of particles over various surface areas using the atomic force microscopy working in the semicontact mode. The maximum surface concentration for I=10(-3)M was 102 μm(-2), which corresponds to the coverage degree of 16%. The kinetic run and the maximum coverage value was in a good agreement with theoretical predictions stemming from the random sequential adsorption (RSA) model. This kinetic run allowed one to determine the size of Ag core, which was 20 nm and the thickness of the PVA layer, equal to 12 nm.

Hematite nanoparticle monolayers on mica electrokinetic characteristics.

Electrokinetic properties of α-Fe(2)O(3) (hematite) nanoparticle monolayers on mica were thoroughly characterized using the streaming potential method. Hematite suspensions were obtained by acidic hydrolysis of ferric chloride. The average size of particles (hydrodynamic diameter), determined by dynamic light scattering (DLS) and AFM, was 22 nm (pH=5.5, I=10(-2)M). The hematite monolayers on mica were produced under diffusion-controlled transport from the suspensions of various bulk concentration. The monolayer coverage, quantitatively determined by AFM and SEM, was regulated within broad limits by adjusting the nanoparticle deposition time. This allowed one to uniquely express zeta potential of hematite monolayers, determined by the streaming potential measurements, in terms of the particle coverage. Such dependencies, obtained for various pH, were successfully interpreted in terms of the three-dimensional electrokinetic model. A universal calibrating graph was produced enabling one to determine hematite monolayer coverage from the measured value of the streaming potential. The influence of the ionic strength, varied between 10(-4) and 10(-2)M, on the zeta potential of hematite monolayers was also studied. Additionally, the stability of monolayers (desorption kinetics) was determined under in situ conditions using the streaming potential method. Our experimental data prove that it is feasible to produce uniform and stable hematite particle monolayers of well-controlled coverage. Such monolayers may find practical applications as universal substrates for protein immobilization (biosensors) and in electrocatalytic applications.