Enhanced Electrochemistry of Nanoparticle-Embedded Polyelectrolyte Films: Interfacial Electronic Coupling and Distance Dependence

Factors affecting the electronic communication believed to be responsible for the enhanced solution electrochemistry observed at electrodes modified with hybrid polyelectrolyte–nanoparticle (PE–NP) film assemblies were systematically investigated. Specifically, the faradaic current and voltammetric peak splitting recorded for cyclic voltammetry of ferricyanide redox species (Fe(CN)63−/4−) at films constructed with various architectures of citrate-stabilized gold NPs embedded in polyelectrolyte films composed of poly-l-lysine and poly-S-styrene were used to establish the relative importance of both distance and electronic coupling. Layer-by-layer construction of PE–NP films allowed for the position and density of NPs to be varied within the film to assess electronic coupling between particles (interparticle coupling) as well as at the electrode–film interface. The cumulative results observed at these films suggest that, while distance dependence prevails in nearly every case and interparticle coupling can contribute to facilitating the Fe(CN)63−/4− electrochemistry, interfacial electronic coupling of the PE–NP films is of critical importance and decoupling is easily achieved by disengaging NP–electrode interactions

Monolayer-Protected Nanoparticle Doped Xerogels as Functional Components of Amperometric Glucose Biosensors

First-generation amperometric glucose biosensors incorporating alkanethiolate-protected gold nanoparticles, monolayer protected clusters (MPCs), within a xerogel matrix are investigated as model systems for nanomaterial-assisted electrochemical sensing strategies. The xerogel biosensors are comprised of platinum electrodes modified with composite films of (3-mercaptopropyl)trimethoxy silane xerogel embedded with glucose oxidase enzyme, doped with Au225(C6)75 MPCs, and coated with an outer polyurethane layer. Electrochemistry and scanning/transmission electron microscopy, including cross-sectional TEM, show sensor construction, humidity effects on xerogel structure, and successful incorporation of MPCs. Analytical performance of the biosensor scheme with and without MPC doping of the xerogel is determined from direct glucose injection during amperometry. MPC-doped xerogels yield significant enhancement of several sensor attributes compared to analogous films without nanoparticles: doubling of the linear range, sensitivity enhancement by an order of magnitude, and 4-fold faster response times accompany long-term stability and resistance to common interfering agents that are competitive with current glucose biosensing literature. Ligand chain length and the MPC/silane ratio studies suggest the MPC-induced enhancements are critically related to structure–function relationships, particularly those affecting interparticle electronic communication where the MPC network behaves as a three-dimensional extension of the working electrode into the xerogel film, reducing the system’s dependence on diffusion and maximizing efficiency of the sensing mechanism. The integration of MPCs as a functional component of amperometric biosensor schemes has implications for future development of biosensors targeting clinically relevant species

Layered Xerogel Films Incorporating Monolayer Protected Cluster Networks on Platinum Black Modified Electrodes for Enhanced Sensitivity in 1st Generation Uric Acid Biosensing

Amperometric uric acid (UA) biosensing schemes incorporating networks of alkanethiolate‐protected gold nanoparticles, monolayer protected clusters (MPCs), and platinum black (Pt‐B) electrode modification through the layer‐by‐layer construction of xerogels are investigated. MPC doping and Pt‐B augmentation are implemented within hydroxymethyltriethoxysilane xerogel bilayers at platinum electrodes. The first xerogel adlayer is doped with an MPC network and houses uricase for the enzymatic reaction required for first‐generation schemes. Polyluminol–aniline and polyurethane are used as selective/stabilizing interfacial layers. The sensing performance with and without Pt‐B and/or MPC doping is assessed by amperometry with standardized UA injections. The use of each individual material results in an enhancement of UA sensitivity compared with analogous films without these materials. The use of Pt‐B and MPC doping in concert results in a biosensor design with the highest observed UA sensitivity (0.97 μA mm−1) and fast, linear responses over physiologically relevant UA concentrations. Enhancement is attributed to Pt‐B providing increased electrode surface area and integration into the xerogel for greater electronic coupling of the MPC network and more efficient reporting of H2O2 oxidation. The findings have implications for advancing clinical in vivo sensing devices that require scalability or additional biocompatibility layering, both of which would benefit from signal enhancement strategies

Ultra-fast Formation 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

Sintering-Induced Nucleation and Growth of Noble Metal Nanoparticles for Plasmonic Resonance Ceramic Color

This study demonstrates the formation of nanoparticles (NPs) from metal salts within ceramic glazes, such that the use of this colorant technology is more accessible to artisans, employs less metal content, is less environmentally harmful, and allows for the use of traditional kilns. Gold NPs have been demonstrated to possess a specific, low material loading use as a ceramic glaze colorant via plasmon resonance. Pre-synthesized gold NPs that are added to ceramic glazes have been found to significantly change in size after firing in both reductive and oxidative atmospheres, but still maintain some size relationships and color properties. Unfortunately, it is not viable for the art community to fabricate and employ gold NP systems with high precision in a studio setting; however, the use of noble metal salts or metal oxides are realistic. To that end, this work investigates spontaneous gold and silver NP synthesis by the firing-induced development of NPs from metallic salts included within the glaze materials. Glaze samples with gold and silver salts are fired in reductive and oxidative environments, yielding a range of surface plasmon coloring effects for ceramic coloring. Additionally, the use of gold NP waste (precipitated Au NPs waste) was added to wet ceramic glazes to investigate firing effects on NPs precipitate and potential use as an alternative colorant. Sintering-induced NP nucleation and growth was observed after firing in both oxidation and reduction environments, although to differing degrees. The direct noble metal salt application process eliminates the need for preliminary gold NP synthesis, thus allowing for more practical and environmentally friendly methods in creating plasmonic resonance ceramic coloring, potentially reflective of the processes employed in ancient nanoparticle glasses

Quantitative Analysis of Heavy Metals in Children’s Toys and Jewelry: A Multi-Instrument, Multi-Technique Exercise in Analytical Chemistry and Public Health

For most chemistry curricula, laboratory-based activities in quantitative and instrumental analysis continue to be an important aspect of student development/training, one that can be more effective if conceptual understanding is delivered through an inquiry-based process relating the material to relevant issues of public interest and student career trajectories. Laboratory experiences that actively engage students in this manner can be difficult to identify and execute. A special topics, project-based laboratory module is presented here that utilizes multiple techniques and instruments to investigate toxic metal content (lead, cadmium, and arsenic) in children’s toys and toy jewelry. The module effectively illustrates a considerable number of fundamental and advanced quantitative analysis principles including sample digestion, Beer–Lambert law, calibration curve, and standard addition analyses, as well as instrumental analysis considerations of atomic absorption spectroscopy including atomization efficiency (e.g., flames vs furnaces), matrix modifiers, and nondestructive spectroscopy. Module effectiveness stems from the illustration of critical chemical analysis principles in the context of projects with student-directed hypotheses and experimental results that are clearly relevant to the interface of basic science, medicine, and public health: primary career interests for a significant number of undergraduates in the physical and life sciences

Optical and Electrochemical Properties of Multi-layer Polyelectrolyte Thin Films Incorporating Spherical, Gold Colloid Nanomaterials

Polyelectrolyte multilayer (PEM) films incorporating various types of spherical, gold nanomaterials (NMs) were investigated to assess the existence of electrochemical and/or optical signal enhancement effects directly attributable to embedded NMs and the relationship of these effects to film structure and composition. Specifically, electrostatically assembled films of cationic poly-L-lysine (PLL) and anionic poly(4-styrene sulfonate) (PSS) incorporating one of four types of spherical, gold colloid NMs were constructed on 3-(aminopropyl)trimethoxysilane (3-APTMS)-modified glass substrates for optical studies or 11-mercaptoundecanoic (MUA)-modified gold electrodes for electrochemical studies. The NMs inserted into the PEM films include citrate-stabilized gold nanoparticles, thioctic acid-stabilized gold nanoparticles (TAS-NPs), MUA-modified monolayer protected gold clusters, and hollow gold nanoshells (Au-NSs). Optical sensitivity of the NM-embedded films, in terms of absorbance, surface plasmon band shifts, and the dependence of these optical responses on film thickness, varied depending on the type of NM within the film (e.g., TAS-NPs versus Au-NSs) but exhibited no corresponding electrochemical effects in the diffusional voltammetry of a ferricyanide redox probe. While not correlated to optical responses, the increased Faradaic current achieved during voltammetry at NM-embedded PEM films suggested that electrochemical effects of NMs were less dependent on the type of NMs and were, instead, more related to their location within the film and the electrostatic interactions built into the interfacial chemistry of the films. These results should prove useful for developing strategies constructing thin films with NMs that are specifically designed for optical or electrochemical sensing, taking full advantage of the signal enhancements provided by individual types of NMs

A Series of Vertically Integrated Nanotechnology Experiments for the Undergraduate Curriculum

We have designed three nanotechnology experiments that are vertically integrated for an undergraduate chemistry curriculum. They are an evolving set of experiments for sequential courses in an undergraduate chemistry program. These experiments are designed to match the student\u27s level of understanding for each particular course. The participating student is involved in a research project that progresses in both theory and experimental technique. Students benefit from these vertically integrated experiments by being involved in multiple facets of a simulated research project. This mimics a traditional research project under an advisor\u27s supervision without the undesired drawback of an unknown outcome

Functional Layer-By-Layer Design of Xerogel-Based 1st Generation Amperometric Glucose Biosensors

Xerogel-based first-generation amperometric glucose biosensors, constructed through specific layer-by-layer assembly of films featuring glucose oxidase doped xerogel, a diffusion-limiting xerogel layer, and capped with both electropolymerized polyphenol and blended polyurethane semipermeable membranes, are presented. The specific combination of xerogels formed from specific silane precursors, including propyl-trimethoxysilane, isobutyl-trimethoxysilane, octyl-trimethoxysilane, and hydroxymethyl-triethoxysilane, exhibit impressive dynamic and linear ranges of detection (e.g., ≥24–28 mM glucose) and low response times, as well as significant discrimination against common interferent species such as acetaminophen, ascorbic acid, sodium nitrite, oxalic acid, and uric acid as determined by selectivity coefficients. Additionally, systematic electrochemical and contact angle studies of different xerogel silane precursors, varying in structure, chain length, and/or functional group, reveal that sensor performance is more dependent on the tunable porosity/permeability of the layered interfaces rather than the hydrophobic character or functional groups within the films. While the sensing performance largely exceeds that of existing electrochemical glucose sensing schemes in the literature, the presented layered approach establishes the specific functionality of each layer working in concert with each other and suggests that the strategy may be readily adaptable to other clinically relevant targets and is amenable to miniaturization for eventual in situ or in vivo sensing

Sweep, Step, Pulse, and Frequency-Based Techniques Applied to Protein Monolayer Electrochemistry at Nanoparticle Interfaces

Protein monolayer electrochemistry (PME), a strategy using synthetic platforms to study the electron transfer (ET) properties of adsorbed proteins, has been successfully applied to proteins adsorbed at monolayer-protected gold cluster (MPCs) assembled films, an adsorption interface shown to be an effective alternative, compared to traditional self-assembled monolayer (SAM) films, for the immobilization and study of ET proteins. Within PME studies, cyclic voltammetry (CV) remains the most commonly applied electrochemical technique in spite of several limitations that occur when the sweep technique is used at either platform. In particular, CV for PME at MPC films results in analysis complications stemming from the increased charging current inherent to electrochemical interfaces incorporating MPCs with capacitive properties. In this study, multiple electroanalytical techniques, involving step (chronocoulometry, CC), pulse (square wave voltammetry, SWV), and frequency-based impedance (electrochemical impedance spectroscopy, EIS) measurements, are applied to monolayers of adsorbed Pseudomonas aeruginosa azurin and horse heart cytochrome c at both MPC film assemblies as well as traditional SAMs. Electrochemical parameters (formal potential, electroactive surface coverage, double-layer capacitance, and ET rate constant) measured from these various techniques are directly compared and offer insight into the performance and reliability of each technique’s effectiveness in PME. While certain techniques result in measurements indistinguishable from CV, others offer distinct differences. Moreover, the application of alternative techniques reveals systemic limitations and complications within the electrochemical analysis that we further explore, including strategies for applying fast scanning techniques like SWV as well as the construction of MPC platforms with controlled levels of charging current that enable successful impedance analysis. The application of more advanced electrochemical techniques to developing electrochemical interfaces such as MPC film assemblies allows for a greater understanding of not only PME but also the applicability and effectiveness of these techniques to optimize the measurement of specific electrochemical parameters