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We report a systematic study of the electrocatalytic properties and stability of a series of 1-2 nm Au, Pd, and AuPd alloy nanoparticles (NPs) for the ethanol oxidation reaction (EOR). Following EOR electrocatalysis, NP sizes and compositions were characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and energy dispersive spectroscopy (EDS). Two main findings emerge from this study. First, alloyed AuPd NPs exhibit enhanced electrocatalytic EOR activity compared to either monometallic Au or Pd NPs. Specifically, NPs having a 3:1 ratio of Au:Pd exhibit an ~8-fold increase in peak current density compared to Pd NPs, with an onset potential shifted ~200 mV more to the negative compared to Au NPs. Second, the size and composition of AuPd alloy NPs do not (within experimental error) change following 1.0 or 2.0 h chronoamperometry experiments, while monometallic Au NPs increase in size from 2 to 5 nm under the same conditions. Notably, this report demonstrates the importance of post-catalytic ac-STEM/EDS characterization for fully evaluating NP activity and stability, especially for 1-2 nm NPs that may change in size or structure during electrocatalysis.

In recent years, microplastics have been found in seawater, soil, food, and even human blood and tissues. The ubiquity of microplastics is alarming, but the health and environmental impacts of microplastics are just beginning to be understood. Accordingly, sampling, separating, and quantifying exposure to microplastics to devise a total risk assessment is the focus of ongoing research. Unfortunately, traditional separation methods ( i.e. , size- and density-based methods) unintentionally exclude the smallest microplastics (<10 μm). Limited data about the smallest microplastics is problematic because they are likely the most pervasive and have distinct properties from their larger plastic counterparts. To that end, in this Perspective, we discuss using electrokinetic methods for separating the smallest microplastics. Specifically, we describe three methods for forming electric field gradients, discuss key results within the field for continuously separating microplastics, and lastly discuss research avenues which we deem critical for advancing electrokinetic separation platforms for targeting the smallest microplastics., Competing Interests: The authors state that there are no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

A key goal of nanoparticle-based catalysis research is to correlate the structure of nanoparticles (NPs) to their catalytic function. The most common approach for achieving this goal is to synthesize ensembles of NPs, characterize the ensemble, and then evaluate its catalytic properties. This approach is effective, but it excludes the certainty of structural heterogeneity in the NP ensemble. One means of addressing this shortcoming is to carry out analyses on individual NPs. This approach makes it possible to establish direct correlations between structures of single NPs and, in the case reported here, their electrocatalytic properties. Accordingly, we report on enhanced electrocatalytic formic acid oxidation (FAO) activity using individual Cu-modified, high-indexed Pt NPs. The results show that the Cu-modified Pt NPs exhibit significantly higher currents for FAO than the Pt-only analogs. The increased activity is enabled by the Cu submonolayer on the highly stepped Pt surface, which enhances the direct FAO pathway but not the indirect pathway which proceeds via surface-absorbed CO*., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

We report the presence of small clusters of atoms (<1 nm) (SCs) and single atoms (SAs) in solutions containing 1-2 nm dendrimer-encapsulated nanoparticles (DENs). Au and Pd DENs were imaged using aberration-corrected scanning transmission electron microscopy (ac-STEM), and energy dispersive spectroscopy (EDS) was used to identify and quantify the SAs/SCs. Two main findings have emerged from this work. First, the presence or absence of SAs/SCs depends on both the terminal functional group of the dendrimer (-NH 2 or -OH) and the elemental composition of the DENs (Au or Pd). Second, dialysis can be used to remove the majority of SAs/SCs in cases where a high density of SAs/SCs are present. The foregoing conclusions provide insights into the mechanisms for Au and Pd DEN synthesis and stability. Ultimately, these results demonstrate the need for careful characterization of systems containing nanoparticles to ensure that SAs/SCs, which may be below the detection limit of most analytical methods, are taken into consideration (especially for catalysis experiments).

We report on the use of silver nanodisks (AgNDs), having a diameter of 50 ± 8 nm and a thickness of 8 ± 2 nm, as electrochemical labels for the detection of a model metalloimmunoassay for the heart failure biomarker NT-proBNP. The detection method is based on an electrochemically activated galvanic exchange (GE) followed by the detection of Ag using anodic stripping voltammetry (ASV). The AgNDs labels are superior to Ag nanocubes and Ag nanospheres in terms of the dynamic range for both the model and NT-proBNP metalloimmunoassays. The linear dynamic range for the model composite is 1.5 to 30.0 pM AgNDs. When AgND labels are used for the NT-proBNP assay, the dynamic range is 0.03-4.0 nM NT-proBNP. The latter range fully overlaps the risk stratification range for heart failure from 53 pM to 590 pM. The performance improvement of the AgNDs is a result of the specific GE mechanism for nanodisks. Specifically, GE is complete across the face of the AgNDs, leaving behind an incompletely exchanged ring structure composed of both Ag and Au.

Here we report an easily fabricated, plastic-based lateral flow device for carrying out metalloimmunoassays. The device is called oc Flow to emphasize the open-channel design. We have shown that the oc Flow is capable of magnetic microbead (MμB)-based metalloimmunoassays for the detection of two types of immunoconjugates: a model composite (MC) and a sandwich immunoassay for the heart failure marker NT-proBNP. In both assays, Ag nanoparticles (AgNPs) were used as electrochemically detectable labels. NT-proBNP and MC concentrations as low as 750.0 pM and 10.0 pM, respectively, could be detected using the oc Flow device. Four key conclusions can be drawn from the results presented herein. First, immunoconjugates attached to the MμBs can be transported in the flow channel using combined hydrodynamic and capillary pressure passive pumping. Second, the oc Flow device is capable of on-chip storage, resolvation, and conjugate formation of both the MC and NT-proBNP composites. Third, electrochemical detection can be conducted on analytes suspended in serum by rinsing the electrodes with a wash buffer. Finally, and perhaps most significantly, the assay is quantitative and has a detection limit for NT-proBNP in the high picomolar range when the necessary reagents are stored on the device in a dry form.

In this article, we compare linear sweep anodic stripping voltammetry (LASV) and square-wave anodic stripping voltammetry (SWASV) for detection of a nano metalloimmunoassay. Two separate immunoassays were examined: a model assay, based on interactions between antibodies, and a sandwich assay for the heart failure marker NT-proBNP. In both cases, one antibody is linked to a magnetic microbead, and one is linked to a spherical Ag nanoparticle label. Electrochemical detection is carried out on a paper device. The three analytical figures of merit studied were the precision of the measurements, the calibration sensitivity, and the limit of detection (LOD). For the NT-proBNP assay, the results show that after optimization of the pulse amplitude and frequency of the potential input for SWASV, the detection efficiency is substantially higher compared to LASV. Specifically, the calibration sensitivity increased by up to ~40 fold, the average coefficient of variation decreased by ~40%, and the (LOD) decreased to 300.0 pM. Finally, for a model immunoassay, a ~10-fold decrease in the LOD was observed for SWASV compared to LASV.

The concept of nanoparticle-mediated electron transfer (eT) across insulating thin films was elucidated theoretically by Allongue and Chazalviel in 2011. In their model, metal nanoparticles (NPs) are immobilized atop passivating, self-assembled monolayers (SAMs). They found that under certain conditions, related to the thickness of the SAM and the size of the NPs, efficient faradaic oxidation and reduction reactions could proceed at the NP surface. In the absence of NPs, however, eT was suppressed by the insulating SAM thin films. Allongue and Chazalviel concluded that, within certain bounds, eT is mediated by fast tunneling between the conductive electrode and the metal NPs, while the kinetics of the redox reaction are controlled by the NPs. This understanding has been confirmed using a variety of experimental models. The theory is based on electron tunneling; therefore, the nature of the intervening medium (the insulator in prior studies) should not affect the eT rate. In the present manuscript, however, we show that the theory breaks down under certain electrochemical conditions when the medium between conductors is an n -type semiconductor. Specifically, we find that in the presence of either Au or Pt NPs immobilized on a thin film of TiO x , CO electrooxidation does not proceed. In contrast, the exact same systems lead to the efficient reduction of oxygen. At present, we are unable to explain this finding within the context of the model of Allongue and Chazalviel.

We report a method for electrochemical pH regulation in microdroplets generated in a microfluidic device. The key finding is that controlled quantities of reagents can be generated electrochemically in moving microdroplets confined within a microfluidic channel. Additionally, products generated at the anode and cathode can be isolated within descendant microdroplets. Specifically, ∼5 nL water-in-oil microdroplets are produced at a T-junction and then later split into two descendant droplets. During splitting, floor-patterned microelectrodes drive water electrolysis within the aqueous microdroplets to produce H + and OH - . This results in a change in the pHs of the descendant droplets. The droplet pH can be regulated over a range of 5.9 to 7.7 by injecting controlled amounts of charge into the droplets. When the injected charge is between -6.3 and 54.5 nC nL -1 , the measured pH of the resulting droplets is within ±0.1 pH units of that predicted based on the magnitude of the injected charge. This technique can likely be adapted to electrogeneration of other reagents within microdroplets.