Assembly Of Nanoparticle Films Research Articles

Size-Selective Nanoparticle Assembly on Substrates by DNA Density Patterning.

The vision of nanoscale self-assembly research is the programmable synthesis of macroscale structures with controlled long and short-range order that exhibit a desired set of properties and functionality. However, strategies to reliably isolate and manipulate the nanoscale building blocks based on their size, shape, or chemistry are still in their infancy. Among the promising candidates, DNA-mediated self-assembly has enabled the programmable assembly of nanoparticles into complex architectures. In particular, two-dimensional assembly on substrates has potential for the development of integrated functional devices and analytical systems. Here, we combine the high-resolution patterning capabilities afforded by electron-beam lithography with the DNA-mediated assembly process to enable direct-write grayscale DNA density patterning. This method allows modulation of the functionally active DNA surface density to control the thermodynamics of interactions between nanoparticles and the substrate. We demonstrate that size-selective directed assembly of nanoparticle films from solutions containing a bimodal distribution of particles can be realized by exploiting the cooperativity of DNA binding in this system. To support this result, we study the temperature-dependence of nanoparticle assembly, analyze the DNA damage by X-ray photoelectron spectroscopy and fluorescence microscopy, and employ molecular dynamics simulations to explore the size-selection behavior.

Electrochemical characterization of self-assembled monolayers on gold substrates derived from thermal decomposition of monolayer-protected cluster films

Networked films of monolayer-protected clusters (MPCs), alkanethiolate-stabilized gold nanoparticles, can be thermally decomposed to form stable gold on glass substrates that are subsequently modified with self-assembled monolayers (SAMs) for use as modified electrodes. Electrochemical assessment of these SAM-modified gold substrates, including double-layer capacitance measurements, linear sweep desorption of the alkanethiolates, and diffusional redox probing, all show that SAMs formed on gold supports formed from thermolysis of MPC films possess substantially higher defect density compared to SAMs formed on traditional evaporated gold. The density of defects in the SAMs on thermolyzed gold is directly related to the strategies used to assemble the MPC film prior to thermolysis. Specifically, gold substrates formed from thermally decomposing MPC films formed with electrostatic bridges between carboxylic acid-modified MPCs and metal ion linkers are particularly sensitive to the degree of metal exposure during the assembly process. While specific metal dependence was observed, metal concentration within the MPC precursor film was determined to be a more significant factor. Specific MPC film linking strategies and pretreatment methods that emphasized lower metal exposure resulted in gold films that supported SAMs of lower defect density. The defect density of a SAM-modified electrode is shown to be critical in certain electrochemical experiments such as protein monolayer electrochemistry of adsorbed cytochrome c. While the thermal decomposition of nanoparticle film assemblies remains a viable and interesting technique for coating both flat and irregular shaped substrates, this study provides electrochemical assessment tools and tactics for determining and controlling SAM defect density on this type of gold structure, a property critical to their effective use in subsequent electrochemical applications.

Nanoparticle Film Assemblies as Platforms for Electrochemical Biosensing—Factors Affecting the Amperometric Signal Enhancement of Hydrogen Peroxide

Factors affecting the enhanced amperometric signal observed at electrodes modified with polyelectrolyte-gold nanoparticle (Au-NP) composite films, which are potential interfaces for first-generation biosensors, were systematically investigated and optimized for hydrogen peroxide (H2O2) detection. Polyelectrolyte multilayer films embedded with citrate-stabilized gold nanoparticles exhibited high sensitivity toward the oxidation of H2O2. From this Au-NP film assembly, the importance of Au-NP ligand protection, film permeability, the density of Au-NPs within the film, and electronic coupling between Au-NPs (interparticle) and between the film and the electrode (interfacial) were evaluated. Using alternative Au-NPs, including those stabilized with thiols, polymers, and bulky ligands, suggests that the amperometric enhancement of H2O2 is optimized at poly-L-lysine-linked film assemblies embedded with Au-NPs possessing small, charged, and conductive (conjugated) peripheral ligands. As a potential application of these Au-NP film assemblies, an enhanced amperometric signal for H2O2 oxidation was shown for modified "needle" electrodes. The overall aim of this research is to gain a greater understanding of designing electrochemical sensing strategies that incorporate Au-NPs and target specific analytes.

Flame spray pyrolysis synthesis and aerosol deposition of nanoparticle films

AbstractThe assembly of nanoparticle films by flame spray pyrolysis (FSP) synthesis and deposition on temperature‐controlled substrates (323–723 K) was investigated for several application‐relevant conditions. An exemplary SnO2 nanoparticle aerosol was generated by FSP and its properties (e.g., particle size distribution), and deposition dynamics were studied in details aiming to a simple correlation between process settings and film growth rate. At high precursor concentrations (0.05–0.5·mol/L), typically used for FSP synthesis, the nanoparticles agglomerated rapidly in the aerosol leading to large (>100 nm) fractal‐like structures with low diffusivity. As a result, thermophoresis was confirmed as the dominant nanoparticle deposition mechanism down to small (≈40 K) temperature differences (ΔT) between the aerosol and the substrate surface. For moderate‐high ΔT (>120 K), thermal equilibrium was rapidly obtained yielding a constant thermophoretic flux and film growth rate. A model was developed to predict the nanoparticle deposition rates by FSP synthesis at moderate‐high ΔT that does not require detailed analysis of the aerosol composition. Comparison with previous studies having similar nozzle geometries showed that the deposition rates of FSP‐made aerosols can be reasonably well predicted for various materials and flame conditions. © 2012 American Institute of Chemical Engineers AIChE J, 2012

Synthesis, Assembly, and Characterization of Monolayer Protected Gold Nanoparticle Films for Protein Monolayer Electrochemistry

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently incorporated into film assemblies that serve as adsorption platforms for protein monolayer electrochemistry (PME). PME is utilized as the model system for studying electrochemical properties of redox proteins by confining them to an adsorption platform at a modified electrode, which also serves as a redox partner for electron transfer (ET) reactions. Studies have shown that gold nanoparticle film assemblies of this nature provide for a more homogeneous protein adsorption environment and promote ET without distance dependence compared to the more traditional systems modified with alkanethiol self-assembled monolayers (SAM). In this paper, MPCs functionalized with hexanethiolate ligands are synthesized using a modified Brust reaction and characterized with ultraviolet visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and proton (¹H) nuclear magnetic resonance (NMR). MPC films are assembled on SAM modified gold electrode interfaces by using a "dip cycle" method of alternating MPC layers and dithiol linking molecules. Film growth at gold electrode is tracked electrochemically by measuring changes to the double layer charging current of the system. Analogous films assembled on silane modified glass slides allow for optical monitoring of film growth and cross-sectional TEM analysis provides an estimated film thickness. During film assembly, manipulation of the MPC ligand protection as well as the interparticle linkage mechanism allow for networked films, that are readily adaptable, to interface with redox protein having different adsorption mechanism. For example, Pseudomonas aeruginosa azurin (AZ) can be adsorbed hydrophobically to dithiol-linked films of hexanethiolate MPCs and cytochrome c (cyt c) can be immobilized electrostatically at a carboxylic acid modified MPC interfacial layer. In this report, we focus on the film protocol for the AZ system exclusively. Investigations involving the adsorption of proteins on MPC modified synthetic platforms could further the understanding of interactions between biomolecules and man-made materials, and consequently aid the development of biosensor schemes, ET modeling systems, and synthetic biocompatible materials.

Synthesis, Assembly, and Characterization of Monolayer Protected Gold Nanoparticle Films for Protein Monolayer Electrochemistry

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently incorporated into film assemblies that serve as adsorption platforms for protein monolayer electrochemistry (PME). PME is utilized as the model system for studying electrochemical properties of redox proteins by confining them to an adsorption platform at a modified electrode, which also serves as a redox partner for electron transfer (ET) reactions. Studies have shown that gold nanoparticle film assemblies of this nature provide for a more homogeneous protein adsorption environment and promote ET without distance dependence compared to the more traditional systems modified with alkanethiol self-assembled monolayers (SAM).1-3 In this paper, MPCs functionalized with hexanethiolate ligands are synthesized using a modified Brust reaction4 and characterized with ultraviolet visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and proton (1H) nuclear magnetic resonance (NMR). MPC films are assembled on SAM modified gold electrode interfaces by using a "dip cycle" method of alternating MPC layers and dithiol linking molecules. Film growth at gold electrode is tracked electrochemically by measuring changes to the double layer charging current of the system. Analogous films assembled on silane modified glass slides allow for optical monitoring of film growth and cross-sectional TEM analysis provides an estimated film thickness. During film assembly, manipulation of the MPC ligand protection as well as the interparticle linkage mechanism allow for networked films, that are readily adaptable, to interface with redox protein having different adsorption mechanism. For example, Pseudomonas aeruginosa azurin (AZ) can be adsorbed hydrophobically to dithiol-linked films of hexanethiolate MPCs and cytochrome c (cyt c) can be immobilized electrostatically at a carboxylic acid modified MPC interfacial layer. In this report, we focus on the film protocol for the AZ system exclusively. Investigations involving the adsorption of proteins on MPC modified synthetic platforms could further the understanding of interactions between biomolecules and man-made materials, and consequently aid the development of biosensor schemes, ET modeling systems, and synthetic biocompatible materials.5-8

Molecularly Mediated Thin Film Assembly of Nanoparticles on Flexible Devices: Electrical Conductivity versus Device Strains in Different Gas/Vapor Environment

The ability to precisely control nanoparticle-enabled electrical devices for applications involving conformal wrapping/bending adaptability in various complex sensing environments requires an understanding of the electrical correlation with the device strain and exposure to the molecular environment. This report describes novel findings of an investigation of molecularly mediated thin film assembly of gold nanoparticles on flexible chemiresistor devices under different device strains and exposure molecules. Both theoretical and experimental data have revealed that the electrical conductivity of the nanoparticle assembly depends on a combination of the device strain and the exposure molecules. Under no device strain, the electrical conductivity is sensitive to the molecular nature in the exposure environment, revealing a clear increase in electrical conductivity with the dielectric constant of vapor molecules. Under small device strains, the electrical conductivity is shown to respond sensitively to the strain directions (tensile vs compressive strain) and also to the dielectric constant of the vapor molecules in a way resembling the characteristic under no device strain. Under large device strains, the electrical conductivity is shown to respond to the difference in dielectric constant of the vapor molecules but, more significantly, to the device tensile and compressive strains than those under small device strains. This combination of device strain and dielectric characteristic is also dependent on the orientation of the microelectrode patterns with respect to the device strain direction, a finding that has important implications to the design of flexible arrays for a complex sensing environment.

Distance Dependence of Electron Transfer Kinetics for Azurin Protein Adsorbed to Monolayer Protected Nanoparticle Film Assemblies

The distance dependence and kinetics of the heterogeneous electron transfer (ET) reaction for the redox protein azurin adsorbed to an electrode modified with a gold nanoparticle film are investigated using cyclic voltammetry. The nanoparticle films are comprised of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), which are covalently networked with dithiol linkers. The MPC film assembly serves as an alternative adsorption platform to the traditional alkanethiolate self-assembled monolayer (SAM) modified electrodes that are commonly employed to study the ET kinetics of immobilized redox proteins, a strategy known as protein monolayer electrochemistry. Voltammetric analysis of the ET kinetics for azurin adsorbed to SAMs of increasing chain length results in quasi-reversible voltammetry with significant peak splitting. We observed rate constants (k degrees (ET)) of 12-20 s(-1) for the protein at SAMs of shorter alkanethiolates that decays exponentially (beta = 0.9/CH(2) or 0.8/A) at SAMs of longer alkanethiolates (9-11 methylene units) or an estimated distance of 1.23 nm and is representative of classical electronic tunneling behavior over increasing distance. Azurin adsorbed to the MPC film platforms of increasing thickness results in reversible voltammetry with very little voltammetric peaks splitting and nearly negligible decay of the ET rate over significant distances up to 20 nm. The apparent lack of distance dependence for heterogeneous ET reactions at MPC film assemblies is attributed to a two-step mechanism involving extremely fast electronic hopping through the MPC film architecture. These results suggest that MPC platforms may be used in protein monolayer electrochemistry to create adsorption platforms of higher architecture that can accommodate greater than monolayer protein coverage and increase the Faradaic signal, a finding with significant implications for amperometric biosensor design and development.

Polyelectrolyte-linked film assemblies of nanoparticles and nanoshells: Growth, stability, and optical properties

Multi-layer films of nanoparticles and nanoshells featuring various polymeric linkage molecules have been assembled and their optical properties characterized. The growth dynamics, including molecular weight effects, and stability of the various nanoparticle film constructions, using both single polymer as well as combinations of alternating charge polyelectrolytes as linking mechanisms, are presented. The polymeric linkers studied include poly-L-lysine, poly-L-arginine, poly(allylamine hydrochloride), and polyamidoamine dendrimers. Significantly air stable films were achieved with the use of multi-layered polymeric bridges between the nanoparticles and nanoshells. Optical sensitivity normally observed with these nanomaterials in solution was observed for their corresponding film geometries, with the nanoshell films exhibiting a markedly higher ability to report their local dielectric environment.

Assessment of Morphological and Optical Properties of Molecularly Mediated Thin Film Assembly of Gold Nanoparticles

This paper reports the results of an investigation of the optical properties of molecularly mediated thin film assemblies of nanoparticles. Thin film assemblies of gold nanoparticles of different sizes that are linked by dithiols and carboxylic acid functionalized thiols of different alkyl chain lengths are studied as a model system. These thin films have been assembled on different substrates for the systematic measurements of the morphological and optical properties. The correlation of the d-spacing values between the experimental and theoretical results has revealed the presence of ordered nanostructures in the thin film assemblies. The wavelength of the surface plasmon resonance band of the nanoparticles in these thin film assemblies is shown to be linearly dependent on the particle size and the interparticle linker chain length. The analyses of the optical properties theoretically using Mie theory and experimentally using reflectometry and spectroscopic ellipsometry have provided important information for the assessment of the optical constants for these nanostructured thin films. Implications of the results to the understanding of the interparticle structural properties are also discussed.

Monolayer-Protected Nanoparticle Film Assemblies as Platforms for Controlling Interfacial and Adsorption Properties in Protein Monolayer Electrochemistry

Assembled films of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), are investigated as adsorption platforms in protein monolayer electrochemistry (PME), a strategy for studying the electron transfer (ET) of redox proteins. Modified electrodes featuring MPC films assembled with various linking methods, including both electrostatic and covalent mechanisms, are employed to immobilize cytochrome c (cyt c) for electrochemical analysis. The background signal (non-Faradaic current) of these systems is directly related to the structure and composition of the MPC films, including nanoparticle core size, protecting ligand properties, as well as the linking mechanism utilized during assembly. Dithiol-linked films of Au225(C6)75 are identified as optimal films for PME by sufficiently discriminating against detrimental background current and exhibiting interfacial properties that are readily engineered for cyt c adsorption and electroactivity (Faradaic current). Surface concentrations and denaturation rates of adsorbed cyt c are dictated by specific manipulation of the individual MPCs composing the outer layer of the film. The use of specially designed, hydrophilic MPCs as a terminal film layer results in near-ideal cyt c voltammetry, attributed to a high degree of molecular level control of the necessary interfacial interactions and flexibility needed to create a uniform and effective binding of protein across large areas of a substrate. The electrochemical properties of cyt c at MPC films, including ET rate constants that are unaffected by the large ET distance introduced by MPC assemblies, are compared to traditional strategies employing self-assembled monolayers to immobilize cyt c. The incorporation of nanoparticles as protein adsorption platforms has implications for biosensor engineering as well as fundamental biological ET studies.

Stable Aqueous Nanoparticle Film Assemblies with Covalent and Charged Polymer Linking Networks

The construction of highly stable and efficiently assembled multilayer films of purely water soluble gold nanoparticles is reported. Citrate-stabilized nanoparticles (CS-NPs) of average core diameter of 10 nm are used as templates for stabilization-based exchange reactions with thioctic acid to form more robust aqueous NPs that can be assembled into multilayer films. The thioctic acid stabilized nanoparticles (TAS-NPs) are networked via covalent and electrostatic linking systems, employing dithiols and the cationic polymer poly(L-lysine), respectively. Multilayer films of up to 150 nm in thickness are successfully grown at biological pH with no observable degradation of the NPs within the film. The characteristic surface plasmon band, an optical feature of certain NP film assemblies that can be used to report the local environment and core spacing within the film, is preserved. Growth dynamics and film stability in solution and in the air are examined, with poly(L-lysine) linked films showing no evidence of aggregation for at least 50 days. We believe these films represent a pivotal step toward exploring the potential of aqueous NP film assemblies as a sensing apparatus.

Array of Molecularly Mediated Thin Film Assemblies of Nanoparticles: Correlation of Vapor Sensing with Interparticle Spatial Properties

The ability to tune interparticle spatial properties of nanoparticle assemblies is essential for the design of sensing materials toward desired sensitivity and selectivity. This paper reports findings of an investigation of molecularly mediated thin film assemblies of metal nanoparticles with controllable interparticle spatial properties as a sensing array. The interparticle spatial properties are controlled by a combination of alpha,omega-difunctional alkyl mediators (X-(CH(2))(n)-X) such as alkyl dithiols, dicarboxylate acids, and alkanethiol shells capped on nanoparticles. Alkanethiolate-capped gold and gold-silver alloy nanoparticles (2-3 nm) were studied as model building blocks toward the thin film assemblies, whereas the variation of alkyl chain length manipulates the interparticle spacing. The thin films assembled on an interdigitated microelectrode array platform are characterized for determining their responses to the sorption of volatile organic compounds (VOCs). The correlation between the response sensitivity and the interparticle spacing properties revealed not only a clear dependence of the sensitivity on alkyl chain length but also the occurrence of a dramatic change of the sensitivity in a region of chain length for the alkyl mediator comparable with that of the capping alkyl chains. This finding reflects a balance between the interparticle chain-chain cohesive interdigitation and the nanostructure-vapor interaction which determines the relative change of the electrical conductivity of the inked nanoparticle thin film in response to vapor sorption. The results, along with statistical analysis of the sensor array data in terms of sensitivity and selectivity, have provided important insights into the detailed delineation between the interparticle spacing and the nanostructured sensing properties.

Correlation between nanostructural parameters and conductivity properties for molecularly-mediated thin film assemblies of gold nanoparticles

The understanding of the particle size and interparticle spatial effects on the electrical conductivity properties of molecularly mediated thin film assemblies of nanoparticles is important for exploring the unique electrical properties in applications such as chemical sensors and biosensors. This paper reports findings of an investigation of such effects for thin film assemblies of gold nanoparticles of highly-monodispersed sizes (2–4 nm) using alkyl dithiols of different chain lengths (0.8–2 nm). The conductivities of the thin films were measured using interdigitated microelectrodes as the platform. Experimental results have shown that the activation energy increases with chain length and decreases with particle size, and the electron tunneling decay term decreases with particle size. The results have revealed that the experimentally determined conductivity and activation energy data for the nanoparticle films quantitatively match the calculations from electrostatic model of granular metals through the electron tunneling mechanism. The strong correlation between the experimental and calculated data was attributed to a combination of the high monodispersity of the nanoparticles and the uniformity and stability of the thin film assemblies. These findings have provided an important set of systematic data supporting the applicability of the activated electron tunneling theory to the molecularly-mediated thin film assemblies of gold nanoparticles, which have important implications for the design and fine-tuning of nanostructured thin films as chemical and biological sensing materials.

Ultra-fast formation and characterization of stable nanoparticle film assemblies

Novel assembled films of monolayer-protected clusters (MPCs) can be grown on gold and glass substrates with a 20-fold higher efficiency than established procedures. Thick MPC films grown using this new method, which can easily be scaled up or automated, are extremely stable and have properties identical to traditionally formed nanoparticle films, including unique quantized double layer charging effects. This new procedure for growing nanoparticle films shares the versatility of the traditional method but exhibits accelerated growth attributed to highly efficient sorption and mobility of metal ion linkers within swelled films and improved mass transfer of nanoparticles to assembly sites. Concentration and pH effects on the mechanism of film growth are shown to have substantial impact on the efficiency.

Gold and alloy nanoparticles in solution and thin film assembly: spectrophotometric determination of molar absorptivity

The spectrophotometric determination of molar absorptivities of the surface plasmon (SP) resonance for gold and gold–silver nanoparticles is reported. The importance of the optical parameter for assessing concentrations of nanoparticles in solution reactions and for estimating thickness of thin film assembly of nanoparticles is highlighted. The high monodispersity (5.6±0.4 nm) of decanethiolate-capped gold nanoparticles produced by thermally activated processing protocol served as a model system, which yielded an ε value of 1.1×10 7 M −1 cm −1. This value was also compared with values determined similarly for nanoparticles of different core sizes and compositions, including decanethiolate-capped gold (1.9 nm), gold–silver alloy (2.7 and 5.6 nm), and citrate-capped gold nanoparticles (13.4 nm). The determined ε values are used for the thickness estimation of thin film assembly of gold nanoparticles linked by 1,9-nonanedithiol (NDT) and the concentration calculation of nanoparticles in a solution reaction. The results have important implications for quantitative assessment of nanoparticle-related reactivities and structures.