Unraveling the Structural Sensitivity of CO2 Electroreduction at Facet-Defined Nanocrystals via Correlative Single-Entity and Macroelectrode Measurements.

The conversion of CO2 into value-added products is a compelling way of storing energy derived from intermittent renewable sources and can bring us closer to a closed-loop anthropogenic carbon cycle. The ability to synthesize nanocrystals of well-defined structure and composition has invigorated catalysis science with the promise of nanocrystals that selectively express the most favorable sites for efficient catalysis. The performance of nanocrystal catalysts for the CO2 reduction reaction (CO2RR) is typically evaluated with nanocrystal ensembles, which returns an averaged system-level response of complex catalyst-modified electrodes with each nanocrystal likely contributing a different (unknown) amount. Measurements at single nanocrystals, taken in the context of statistical analysis of a population, and comparison to macroscale measurements are necessary to untangle the complexity of the ever-present heterogeneity in nanocrystal catalysts, achieve true structure-property correlation, and potentially identify nanocrystals with outlier performance. Here, we employ environment-controlled scanning electrochemical cell microscopy to isolate and investigate the electrocatalytic CO2RR response of individual facet-defined gold nanocrystals. Using correlative microscopy approaches, we conclusively demonstrate that {110}-terminated gold rhombohedra possess superior activity and selectivity for CO2RR compared with {111}-terminated octahedra and high-index {310}-terminated truncated ditetragonal prisms, especially at low overpotentials where electrode kinetics is anticipated to dominate the current response. The methodology framework described here could inform future studies of complex electrocatalytic processes through correlative single-entity and macroscale measurement techniques.

Electroceutical fabric lowers zeta potential and eradicates coronavirus infectivity upon contact.

Coronavirus with intact infectivity attached to PPE surfaces pose significant threat to the spread of COVID-19. We tested the hypothesis that an electroceutical fabric, generating weak potential difference of 0.5 V, disrupts the infectivity of coronavirus upon contact by destabilizing the electrokinetic properties of the virion. Porcine respiratory coronavirus AR310 particles (105) were placed in direct contact with the fabric for 1 or 5 min. Following one minute of contact, zeta potential of the porcine coronavirus was significantly lowered indicating destabilization of its electrokinetic properties. Size-distribution plot showed appearance of aggregation of the virus. Testing of the cytopathic effects of the virus showed eradication of infectivity as quantitatively assessed by PI-calcein and MTT cell viability tests. This work provides the rationale to consider the studied electroceutical fabric, or other materials with comparable property, as material of choice for the development of PPE in the fight against COVID-19.

Electrospray deposition for single nanoparticle studies.

Single entity electrochemical (SEE) studies that can probe activities and heterogeneity in activities at nanoscale require samples that contain single and isolated particles. Single, isolated nanoparticles are achieved here with electrospray deposition of colloidal nanoparticle solutions, with simple instrumentation. Role of three electrospray (ES) parameters, viz. spray distance (emitter tip-to-substrate distance), ES current and emitter tip diameter, in the ES deposition of single Au nano-octahedra (Au ODs) is examined. The ES deposition of single, isolated Au ODs are analyzed in terms of percentage of single NPs and local surface density of deposition. The local surface density of ES deposition of single Au ODs was found to increase with decrease in spray distance and emitter tip diameter, and increase in ES current. While the percentage of single particle ES deposition increased with increase in spray distance and decrease in emitter tip size. No significant change in the single Au ODs ES deposition percentage was observed with change in ES current values included in this study. The most favourable conditions in the ES deposition of Au ODs in this study resulted in the local surface density of 0.26 ± 0.05 single particles per µm2 and observation of 96.3% single Au OD deposition.

Ketoconazole resistant Candida albicans is sensitive to a wireless electroceutical wound care dressing.

Wireless electroceutical dressing (WED) fabric kills bacteria and disrupts bacterial biofilm. This work tested, comparing with standard of care topical antibiotic ketoconazole, whether the weak electric field generated by WED is effective to manage infection caused by ketoconazole-resistant yeast Candida albicans. WED inhibited Candida albicans biofilm formation and planktonic growth. Unlike ketoconazole, WED inhibited yeast to hyphal transition and downregulated EAP1 curbing cell attachment. In response to WED-dependent down-regulation of biofilm-forming BRG1 and ROB1, BCR1 expression was markedly induced in what seems to be a futile compensatory response. WED induced NRG1 and TUP1, negative regulators of filamentation; it down-regulated EFG1, a positive regulator of hyphal pathway. Consistent with the anti-hyphal properties of WED, the expression of ALS3 and HWP1 were diminished. Ketoconazole failed to reproduce the effects of WED on NRG1, TUP1 and EFG1. WED blunted efflux pump activity; this effect was in direct contrast to that of ketoconazole. WED exposure compromised cellular metabolism. In the presence of ketoconazole, the effect was synergistic. Unlike ketoconazole, WED caused membrane depolarization, changes in cell wall composition and loss of membrane integrity. This work presents first evidence that weak electric field is useful in managing pathogens which are otherwise known to be antibiotic resistant.

Surface Charge Measurements with Scanning Ion Conductance Microscopy Provide Insights into Nitrous Acid Speciation at the Kaolin Mineral-Air Interface.

Unique surface properties of aluminosilicate clay minerals arise from anisotropic distribution of surface charge across their layered structures. Yet, a molecular-level understanding of clay mineral surfaces has been hampered by the lack of analytical techniques capable of measuring surface charges at the nanoscale. This is important for understanding the reactivity, colloidal stability, and ion-exchange capacity properties of clay minerals, which constitute a major fraction of global soils. In this work, scanning ion conductance microscopy (SICM) is used for the first time to visualize the surface charge and topography of dickite, a well-ordered member of the kaolin subgroup of clay minerals. Dickite displayed a pH-independent negative charge on basal surfaces whereas the positive charge on edges increased from pH 6 to 3. Surface charges responded to malonate addition, which promoted dissolution/precipitation reactions. Results from SICM were used to interpret heterogeneous reactivity studies showing that gas-phase nitrous acid (HONO) is released from the protonation of nitrite at Al-OH2+ groups on dickite edges at pH well above the aqueous pKa of HONO. This study provides nanoscale insights into mineral surface processes that affect environmental processes on the local and global scale.

Probing Single-Particle Electrocatalytic Activity at Facet-Controlled Gold Nanocrystals.

Electrocatalytic reduction reactions (i.e., the hydrogen evolution reaction (HER) and oxygen reduction reaction) at individual, faceted Au nanocubes (NCs) and nano-octahedra (ODs) expressing predominantly {100} and {111} crystal planes on the surface, respectively, were studied by nanoscale voltammetric mapping. Cyclic voltammograms were collected at individual nanoparticles (NPs) with scanning electrochemical cell microscopy (SECCM) and correlated with particle morphology imaged by electron microscopy. Nanoscale measurements from a statistically informative set of individual NPs revealed that Au NCs have superior HER electrocatalytic activity compared to that of Au ODs, in good agreement with macroscale cyclic voltammetry measurements. Au NCs exhibited more particle-to-particle variation in catalytic activity compared to that with Au ODs. The approach of single-particle SECCM imaging coupled with macroscale CV on well-defined NPs provides a powerful toolset for the design and activity assessment of nanoscale electrocatalysts.

Ion Mobility and Surface Collisions: Submicrometer Capillaries Can Produce Native-like Protein Complexes.

The use of submicrometer capillaries for nanoelectrospray ionization of native proteins and protein complexes effectively reduces the number of nonspecific salt adducts to biological molecules, therefore increasing the apparent resolution of a mass spectrometer without any further instrument modifications or increased ion activation. However, the increased interaction between proteins and the surface of the capillary has been shown to promote protein expansion and therefore loss of native structure. Here, we compare the effect of micrometer and submicrometer sized capillaries on the native structures of the protein complexes streptavidin, concanavalin A, and C-reactive protein under charge reducing conditions. We observe that the use of submicrometer capillaries did not result in a significantly higher charge state distribution, indicative of expansion, when compared to micrometer sized capillaries for complexes in 100 mM ammonium acetate and 100 mM triethylammonium acetate and for streptavidin in 200 mM ammonium acetate with no charge reduction. Additionally, no significant differences in collision cross sections were observed using ion mobility mass spectrometry. Finally, the dissociation behaviors of protein complexes ionized using micrometer and submicrometer capillaries were compared to determine if any structural perturbation occurred during ionization. Protein complexes from both capillary sizes displayed similar surface-induced dissociation patterns at similar activation energies. The results suggest that submicrometer capillaries do not result in significant changes to protein complex structure under charge reducing conditions and may be used for native mass spectrometry experiments. Submicrometer capillaries can be used to resolve small mass differences of biological systems on a QTOF platform; however, a laser tip puller is required for pulling reproducible submicrometer capillaries, and disruption in spray due to clogging was observed for larger protein complexes.

Array Microcell Method (AMCM) for Serial Electroanalysis.

We describe a method for electrochemical measurement and synthesis based on the combination of a mobile micropipette and a microelectrode array, which we term the array microcell method (AMCM). AMCM has the ability to address single electrodes within a microelectrode array (MEA) and provides a simple, low-cost format to enable versatile electrochemical measurements. In AMCM, a droplet at the tip of a movable micropipette (inner diameter of 50 µm) functions as an electrochemical cell, in which the electrode area is defined by a microelectrode of the array. We also report carbon MEAs that are well suited for AMCM and are fabricated from pyrolyzed photoresist films (PPFs). PPF-MEAs with nominal electrode diameters of 5.5 µm are characterized by AMCM, standard macroscale electrochemical methods, and finite element modeling. The versatility of AMCM is demonstrated by measurement of single Pt microparticles and by electrodeposition of shapecontrolled Pt nanoparticles.

On the intersection of electrochemistry and mass spectrometry.

The application of nanopipettes, developed first as a tool for electrochemistry and electrophysiology, as tools for mass spectrometry is considered. Recent examples of advances in electrospray ionization and sampling for mass spectrometry with nanopipettes is discussed. These examples show a scientific intersection that is ripe for further development.