Donald A. Robinson

Mixed dithiolate durene-DT and monothiolate phenylethanethiolate protected Au130 nanoparticles with discrete core and core-ligand energy states.

A new type of gold nanoparticle with interesting energetics has been created by employing a mixture of dithiol durene (Durene-DT) and monothiol phenylethanethiol (PhC2S) in the synthesis. The average composition of these mixed thiolate clusters is characterized to be Au(130)(Durene-DT)(29)(PhC2S)(22). Continuous quantized core charging behaviors were observed at lower potentials in voltammetric measurements, while ligand reaction and core-ligand interactions were observed at higher potentials. The absorbance spectrum displays discrete absorption bands at ca. 355, 490, 584, and 718 nm. The electrochemical and absorbance features are correlated through the determined energy states and charging energy. Broad near-IR luminescence was observed, associated with significant relaxation of excitation energy. Such interesting optical and electrochemical properties are attributed to the nanoparticle core size, ligand composition, and core-ligand charge delocalization determined by the dithiolate molecular structure.

Increasing the Collision Rate of Particle Impact Electroanalysis with Magnetically Guided Pt-Decorated Iron Oxide Nanoparticles

An integrated microfluidic/magnetophoretic methodology was developed for improving signal response time and detection limits for the chronoamperometric observation of discrete nanoparticle/electrode interactions by electrocatalytic amplification. The strategy relied on Pt-decorated iron oxide nanoparticles which exhibit both superparamagnetism and electrocatalytic activity for the oxidation of hydrazine. A wet chemical synthetic approach succeeded in the controlled growth of Pt on the surface of FeO/Fe3O4 core/shell nanocubes, resulting in highly uniform Pt-decorated iron oxide hybrid nanoparticles with good dispersibility in water. The unique mechanism of hybrid nanoparticle formation was investigated by electron microscopy and spectroscopic analysis of isolated nanoparticle intermediates and final products. Discrete hybrid nanoparticle collision events were detected in the presence of hydrazine, an electrochemical indicator probe, using a gold microband electrode integrated into a microfluidic channel. In contrast with related systems, the experimental nanoparticle/electrode collision rate correlates more closely with simple theoretical approximations, primarily due to the accuracy of the nanoparticle tracking analysis method used to quantify nanoparticle concentrations and diffusion coefficients. Further modification of the microfluidic device was made by applying a tightly focused magnetic field to the detection volume to attract the magnetic nanoprobes to the microband working electrode, thereby resulting in a 6-fold increase to the relative frequency of chronoamperometric signals corresponding to discrete nanoparticle impact events.

Addressing Colloidal Stability for Unambiguous Electroanalysis of Single Nanoparticle Impacts

Herein the problem of colloidal instability on electrochemically detected nanoparticle (NP) collisions with a Hg ultramicroelectrode (UME) by electrocatalytic amplification is addressed. NP tracking analysis (NTA) shows that rapid aggregation occurs in solution after diluting citrate-stabilized Pt NPs with hydrazine/phosphate buffers of net ionic strength greater than 70 mM. Colloidal stability improves by lowering the ionic strength, indicating that aggregation processes were strongly affected by charge screening of the NP double layer interactions at high cation concentrations. For the system of lowest ionic strength, the overwhelming majority of observed electrocatalytic current signals represent single NP/electrode impacts, as confirmed by NTA kinetic monitoring. NP diffusion coefficients determined by NTA and NP impact electroanalysis are in excellent agreement for the stable colloids, which signifies that the sticking probability of Pt NPs interacting with Hg is unity and that the observed NP impact rate agrees with the expected steady-state diffusive flux expression for the spherical cap Hg UME.

Uniform epitaxial growth of Pt on Fe3O4 nanoparticles; synergetic enhancement to Pt activity for the oxygen reduction reaction

A synthetic strategy for achieving uniform shell-like epitaxial growth of Pt on Fe3O4 nanoparticles is introduced. The method involves the controlled high-density loading of Pt2+ by the linear growth of repeatedly stacked units of [Pt(NH2OH)4]2+ and [PtCl4]2−, followed by a subsequent reduction step. In comparison to commercial Pt-based fuel cell catalysts, the resulting Pt–Fe3O4 hybrid nanostructures were found to exhibit improved Pt specific activity for the electroreduction of oxygen in alkaline media, which is attributed to charge transfer from Fe3O4 to Pt. The Pt shell-type structure of the Pt–Fe3O4 hybrids was found to protect the Fe3O4 cores from corrosion, thus ensuring catalyst stability. A uniform Pt coating was also deposited evenly over SiO2 microspheres using this method, thus demonstrating its potential as a general strategy for platinum deposition on essentially any amine-functionalized surface.

Mechanistic aspects of hydrazine-induced Pt colloid instability and monitoring aggregation kinetics with nanoparticle impact electroanalysis

Here we investigate the mechanistic aspects of Pt nanoparticle (NP) aggregation in solutions typically used for detecting NP/electrode impacts by electrocatalytic amplification (ECA). We previously proposed a general mechanism for Pt colloid destabilization that involved the participation of both the hydrazine redox probe and the pH buffer species as coagulants. Herein the Pt NP coagulation and aggregation mechanisms were further investigated with microscopic kinetic NP concentration monitoring and zeta potential measurements using nanoparticle tracking analysis (NTA), as well as open circuit potential experiments with a citrate-treated polycrystalline Pt surface to assess electrical double layer potential. After considering the combined results of these experiments we propose that the colloidal stability of citrate-capped platinum nanoparticles involves much more than the typical physicochemical interactions predicted by DLVO theory. A structure based on intermolecular H-bonding in the citrate capping layer is the most plausible explanation for the exceptional stability of large Pt NPs in high ionic strength buffers. Thus, the mechanism of Pt NP aggregation includes specific reactive contributions from hydrazine. The catalytic decomposition of hydrazine, in particular, is thought to occur to some extent at the citrate-coated Pt surface while the citrate remains adsorbed. Evolved gases such as ammonia and possible surface bound intermediates from Pt-catalyzed decomposition of hydrazine may disrupt the stability of the citrate layer, causing colloidal instability and thus promoting Pt NP coagulation. In the closing section, we demonstrate nanoparticle impact electroanalysis by ECA detection as a method to quantify Pt NP concentration with adequate time resolution for monitoring the kinetics of Pt NP coagulation.

What is Your Fitness Tracker Communicating?: Exploring Messages and Effects of Wearable Fitness Devices

Although studies have investigated how the technical features of wearable fitness trackers promote physical activity, we understand less about how communication surrounding such devices may contribute to their success. Addressing current opportunities for inquiry is important, as the popularity of fitness trackers and other wearable devices grows. Through interviews with 25 people wearing fitness devices, this study elucidates how and with whom people communicate fitness tracker messages and explains the effects of sociomaterial practice on interactions between wearable fitness device users. Our findings show the vital role of communication in sharing and encouraging physical activity.