Mechanistic Basis of Conductivity in Carbon Dioxide-Expanded Electrolytes: A Joint Experimental-Theoretical Study.

Electrolyte conductivity contributes to the efficiency of devices for electrochemical conversion of carbon dioxide (CO2) into useful chemicals, but the effect of the dissolution of CO2 gas on conductivity has received little attention. Here, we report a joint experimental-theoretical study of the properties of acetonitrile-based CO2-expanded electrolytes (CXEs) that contain high concentrations of CO2 (up to 12 M), achieved by CO2 pressurization. Cyclic voltammetry data and paired simulations show that high concentrations of dissolved CO2 do not impede the kinetics of outer-sphere electron transfer but decrease the solution conductivity at higher pressures. In contrast with conventional behaviors, Jones reactor-based measurements of conductivity show a nonmonotonic dependence on CO2 pressure: a plateau region of constant conductivity up to ca. 4 M CO2 and a region showing reduced conductivity at higher [CO2]. Molecular dynamics simulations reveal that while the intrinsic ionic strength decreases as [CO2] increases, there is a concomitant increase in ionic mobility upon CO2 addition that contributes to stable solution conductivities up to 4 M CO2. Taken together, these results shed light on the mechanisms underpinning electrolyte conductivity in the presence of CO2 and reveal that the dissolution of CO2, although nonpolar by nature, can be leveraged to improve mass transport rates, a result of fundamental and practical significance that could impact the design of next-generation systems for CO2 conversion. Additionally, these results show that conditions in which ample CO2 is available at the electrode surface are achievable without sacrificing the conductivity needed to reach high electrocatalytic currents.

Deconvoluting Kinetic Rate Constants of Catalytic Substrates from Scanning Electrochemical Approach Curves with Artificial Neural Networks.

Extracting information from experimental measurements in the chemical sciences typically requires curve fitting, deconvolution, and/or solving the governing partial differential equations via numerical (e.g., finite element analysis) or analytical methods. However, using numerical or analytical methods for high-throughput data analysis typically requires significant postprocessing efforts. Here, we show that deep learning artificial neural networks can be a very effective tool for extracting information from experimental data. As an example, reactivity and topography information from scanning electrochemical microscopy (SECM) approach curves are highly convoluted. This study utilized multilayer perceptrons and convolutional neural networks trained on simulated SECM data to extract kinetic rate constants of catalytic substrates. Our key findings were that multilayer perceptron models performed very well when the experimental data were close to the ideal conditions with which the model was trained. However, convolutional neural networks, which analyze images as opposed to direct data, were able to accurately predict the kinetic rate constant of Fe-doped nickel (oxy)hydroxide catalyst at different applied potentials even though the experimental approach curves were not ideal. Due to the speed at which machine learning models can analyze data, we believe this study shows that artificial neural networks could become powerful tools in high-throughput data analysis.

Relational complexity influences analogical reasoning ability.

Human language without analogy is like a zebra without stripes. The ability to understand analogies, or to engage in relational reasoning, has been argued to be an important distinction between the cognitive abilities of human and non-human animals. Current studies have failed to robustly show that animals can perform more complex, relational discriminations, in part because such tests rely on linguistic or symbolic experiences, and therefore are not suitable for evaluating analogical reasoning in animals. We report on a methodological approach allowing for direct comparisons of analogical reasoning ability across species. We show that human participants spontaneously make analogical discriminations with minimal verbal instructions, and that the ability to reason analogically is affected by analogical complexity. Furthermore, performance on our task correlated with participants' fluid intelligence scores. These results show the nuance of analogical reasoning abilities by humans, and provide a means of robustly comparing this capacity across species.

Distinguishing the mechanism of electrochemical carboxylation in CO2 eXpanded Electrolytes.

We shed light on the mechanism and rate-determining steps of the electrochemical carboxylation of acetophenone as a function of CO2 concentration by using a robust finite element analysis model that incorporates each reaction step. Specifically, we show that the first electrochemical reduction of acetophenone is followed by the homogeneous chemical addition of CO2. The electrochemical reduction of the acetophenone-CO2 adduct is more facile than that of acetophenone, resulting in an Electrochemical-Chemical-Electrochemical (ECE) reaction pathway that appears as a single voltammetric wave. These modeling results provide new fundamental insights into the complex microenvironment in CO2-rich media that produces an optimum electrochemical carboxylation rate as a function of CO2 pressure.

Nanogap-Resolved Adsorption-Coupled Electron Transfer by Scanning Electrochemical Microscopy: Implications for Electrocatalysis.

Here, we demonstrate for the first time that the mechanism of adsorption-coupled electron-transfer (ACET) reactions can be identified experimentally. The electron transfer (ET) and specific adsorption of redox-active molecules are coupled in many electrode reactions with practical importance and fundamental interest. ACET reactions are often represented by a concerted mechanism. In reductive adsorption, an oxidant is simultaneously reduced and adsorbed as a reductant on the electrode surface through the ACET step. Alternatively, the non-concerted mechanism mediates outer-sphere reduction and adsorption separately when the reductant adsorption is reversible. In electrocatalysis, reversibly adsorbed reductants are ubiquitous and crucial intermediates. Moreover, electrocatalysis is complicated by the mixed mechanism based on simultaneous ACET and outer-sphere ET steps. In this work, we reveal the non-concerted mechanism for ferrocene derivatives adsorbed at highly oriented pyrolytic graphite as simple models. We enable the transient voltammetric mode of nanoscale scanning electrochemical microscopy (SECM) to kinetically control the adsorption step, which is required for the discrimination of non-concerted, concerted, and mixed mechanisms. Experimental voltammograms are compared with each mechanism by employing finite element simulation. The non-concerted mechanism is supported to indicate that the ACET step is intrinsically slower than its outer-sphere counterpart by at least four orders of magnitude. This finding implies that an ACET step is facilitated thermodynamically but may not be necessarily accelerated or catalyzed by the adsorption of the reductant. SECM-based transient voltammetry will become a powerful tool to resolve and understand electrocatalytic ACET reactions at the elementary level.

Age-related reduction of hemispheric asymmetry by pigeons: A behavioral and FDG-PET imaging investigation of visual discrimination.

Pigeons are long-lived and slowly aging animals that present a distinct opportunity to further our understanding of age-related brain changes. Generally, for pigeons, the left hemisphere contributes to discrimination of local information, whereas the right contributes to processing of global information. The function of each hemisphere may be examined by covering one eye, as the optic nerves decussate almost completely in birds, directing the majority of visual information to the contralateral hemisphere. Using this eye-capping technique, we investigated pigeons' ability to select grains from among grit while under binocular and monocular viewing conditions, across three different age groups. Prior to the grit-grain discrimination task, pigeons were injected with a radioactive tracer, which was taken up by the brain as the pigeons performed the task. Upon completion of the discrimination task, the pigeons' brains were imaged via [18F] fluorodeoxyglucose positron emission tomography (FDG-PET) scans. This process allowed us to compare hemispheric activity during the discrimination task for each individual within each age group. The Very Old subjects showed significantly worse discrimination performance compared to the Adult and Old subjects, particularly when needing to search primarily with their right hemisphere. Furthermore, the Very Old subjects did not show differences in hemispheric activation when performing the task, whereas the left hemisphere was most active for the Adult and Old groups. To our knowledge, this is the first study to use FDG-PET imaging to evaluate whether the pigeon brain shows evidence of age-related reduction in hemispheric asymmetry during a visual discrimination task.

Simultaneous Intelligent Imaging of Nanoscale Reactivity and Topography by Scanning Electrochemical Microscopy.

Scanning electrochemical microscopy (SECM) enables reactivity and topography imaging of single nanostructures in the electrolyte solution. The in situ reactivity and topography, however, are convoluted in the real-time image, thus requiring another imaging method for subsequent deconvolution. Herein, we develop an intelligent mode of nanoscale SECM to simultaneously obtain separate reactivity and topography images of non-flat substrates with reactive and inert regions. Specifically, an ∼0.5 µm-diameter Pt tip approaches a substrate with an ∼0.15 µm-height active Au band adjacent to an ∼0.4 µm-wide slope of the inactive glass surface followed by a flat inactive glass region. The amperometric tip current versus tip-substrate distance is measured to observe feedback effects including redox-mediated electron tunneling from the substrate. The intelligent SECM software automatically terminates the tip approach depending on the local reactivity and topography of the substrate under the tip. The resultant short tip-substrate distances allow for non-contact and high-resolution imaging in contrast to other imaging modes based on approach curves. The numerical post-analysis of each approach curve locates the substrate under the tip for quantitative topography imaging and determines the tip current at a constant distance for topography-independent reactivity imaging. The nanoscale grooves are revealed by intelligent topography SECM imaging as compared to scanning electron microscopy and atomic force microscopy without reactivity information and as unnoticed by constant-height SECM imaging owing to the convolution of topography with reactivity. Additionally, intelligent reactivity imaging traces abrupt changes in the constant-distance tip current across the Au/glass boundary, which prevents constant-current SECM imaging.

Adaptive specialization for spatial memory does not improve route efficiency: Comparing the ability of Clark's nutcrackers (Nucifraga columbiana) and pigeons (Columba livia) to solve traveling salesperson problems.

An important question in comparative cognition is whether animals are capable of planning ahead. Todd and Hills (Current Directions in Psychological Science, 29(3), 309-315, 2020) recently suggested that the ability to plan and choose internally may have scaffolded upon the cognitive mechanisms required by animals to search among patchy resources in their external environment. The traveling salesperson problem (TSP) is a spatial optimization problem in which a traveler is faced with the task of finding the best route from a start location to two or more destinations or targets. The Clark's nutcracker (Nucifraga columbiana) is a food-storing corvid with a highly specialized spatial memory. Spatial memory would appear to be deeply rooted in the cognitive mechanisms required for choosing efficiently among multiple alternative routes during a TSP. If so, then species like nutcrackers that are more dependent upon spatial memory for survival may have a greater ability to plan ahead or choose more efficiently among different route options than species that have less selective pressure for remembering the location of food, like pigeons. We examined the ability of nutcrackers to solve TSPs using the same procedures and target configurations as in our past research (Gibson, Wilkerson, & Kelly, Animal Cognition, 15, 379-391, 2012) to explore if nutcrackers can efficiently solve TSPs and how their route solutions compare with those of pigeons. Nutcrackers did not display an advantage in route efficiency and performed comparably to pigeons. Both species tended to prefer a nearest-neighbor strategy to more globally efficient routes. Having a more robust spatial memory may not improve the ability of animals to determine routes to multiple locations.

Abstract-concept learning in two species of new world corvids, pinyon jays (Gymnorhinus Cyanocephalus) and California scrub jays (Aphelocoma Californica).

concepts require individuals to identify relationships between novel stimuli. Previous studies have reported that the ability to learn abstract concepts is found in a wide range of species. In regard to a same/different concept, Clark's nutcrackers (Nucifraga columbiana) and black-billed magpies (Pica hudsonia), two corvid species, were shown to outperform other avian and primate species (Wright et al., 2017). Two additional corvid species, pinyon jays (Gymnorhinus cyanocephalus) and California scrub jays (Aphelocoma californica) chosen as they belong to a different clade than nutcrackers and magpies, were examined using the same set-size expansion procedure of the same/different task (the task used with nutcrackers and magpies) to evaluate whether this trait is common across the Corvidae lineage. During this task, concept learning is assessed with novel images after training. Results from the current study showed that when presented with novel stimuli after training with an 8-image set, discrimination accuracy did not differ significantly from chance for pinyon jays and California scrub jays, unlike the magpies and nutcrackers from previous studies that showed partial transfer at that stage. However, concept learning improved with each set-size expansion, and the jays reached full concept learning with a 128-image set. This performance is similar to the other corvids and monkeys tested, all of which outperform pigeons. Results from the current study show a qualitative similarity in full abstract-concept learning in all species tested with a quantitative difference in the set-size functions, highlighting the shared survival importance of mechanisms supporting abstract-concept learning for corvids and primates. (PsycInfo Database Record (c) 2021 APA, all rights reserved).

Enhancing Molecular Electrocatalysis of CO2 Reduction with Pressure-Tunable CO2 -Expanded Electrolytes.

Electrochemical studies of CO2 conversion by molecular catalysts are typically carried out in a narrow range of near-ambient CO2 pressures wherein low CO2 solubilities in the liquid phase can limit the rate of CO2 reduction. In this study, five-fold rate enhancements are enabled by pairing CO2 -expanded electrolytes (CXEs), a class of media that accommodate multimolar concentrations of CO2 in organic solvents at modest pressures, with a homogeneous molecular electrocatalyst, [Re(CO)3 (bpy)Cl] (1, bpy=2,2'-bipyridyl). Analysis of cyclic voltammetry data reveals pressure-tunable rate behavior, with first-order kinetics at moderate CO2 pressures giving way to zero-order kinetics at higher pressures. The significant enhancement in the space-time yield of CO demonstrates that CXEs offer a simple yet powerful strategy for unlocking the intrinsic potential of molecular catalysts by mitigating CO2 solubility limitations commonly encountered in conventional liquid electrolytes. Moreover, our findings reveal that 1, a workhorse molecular catalyst, performs with intrinsic kinetic behavior, which is competitive with fast enzymes under optimal conditions in CXEs.

Reorientation by features and geometry: Effects of healthy and degenerative age-related cognitive decline.

The ability to orient is critical for mobile species. Two visual cues, geometry (e.g., distance and direction) and features (e.g., colour and texture) are often used when establishing one's orientation. Previous research has shown the use of these cues, in particular, geometry, may decline with healthy aging. Few studies have examined whether degenerative aging processes show similar time points for the decline of geometry use. The present study examined this issue by training adult and aged mice from two strains, a healthy wild-type and an Alzheimer's model, to search for a hidden platform in a rectangular water maze. The shape of the maze provided geometric information, and distinctive features were displayed on the walls. Following training, manipulations to the features were made to examine whether the mice were able to use the features and geometry, and whether they showed a preference between these two cue types. Results showed that although Alzheimer's transgenic mice were slower to learn the task, overall age rather than strain, was associated with a degradation in use of geometry. However, the presence of seemingly uninformative features (due to their redundancy) facilitated the use of geometry. Additionally, when features and geometry provided conflicting information, only young wild-type mice showed a primary use of features. Our results suggest the failure to use geometry may be a generalized function of aging, and not a diagnostic feature of degeneration for mice. Whether this is also the case for other mammals, such as humans for which the mouse is an important medical model, remains to be examined.

Nanoscale Intelligent Imaging Based on Real-Time Analysis of Approach Curve by Scanning Electrochemical Microscopy.

Scanning electrochemical microscopy (SECM) enables high-resolution imaging by examining the amperometric response of an ultramicroelectrode tip near a substrate. Spatial resolution, however, is compromised for nonflat substrates, where distances from a tip far exceed the tip size to avoid artifacts caused by the tip-substrate contact. Herein, we propose a new imaging mode of SECM based on real-time analysis of the approach curve to actively control nanoscale tip-substrate distances without contact. The power of this software-based method is demonstrated by imaging an insulating substrate with step edges using standard instrumentation without combination of another method for distance measurement, e.g., atomic force microscopy. An ∼500 nm diameter Pt tip approaches down to ∼50 nm from upper and lower terraces of a 500 nm height step edge, which are located by real-time theoretical fitting of an experimental approach curve to ensure the lack of electrochemical reactivity. The tip approach to the step edge can be terminated at <20 nm prior to the tip-substrate contact as soon as the theory deviates from the tip current, which is analyzed numerically afterward to locate the inert edge. The advantageous local adjustment of tip height and tip current at the final point of tip approach distinguishes the proposed imaging mode from other modes based on standard instrumentation. In addition, the glass sheath of the Pt tip is thinned to ∼150 nm to rarely contact the step edge, which is unavoidable and instantaneously detected as an abrupt change in the slope of approach curve to prevent damage of the fragile nanotip.

Intensified Electrocatalytic CO2 Conversion in Pressure-Tunable CO2 -Expanded Electrolytes.

Multimolar CO2 concentrations are achieved in acetonitrile solutions containing supporting electrolyte at relatively mild CO2 pressures (<5 MPa) and ambient temperature. Such CO2 -rich, electrolyte-containing solutions are termed as CO2 -eXpanded Electrolytes (CXEs) because significant volumetric expansion of the liquid phase accompanies CO2 dissolution. Cathodic polarization of a model polycrystalline gold electrode-catalyst in CXE media enhances CO2 to CO conversion rates by up to an order of magnitude compared with those attainable at near-ambient pressures, without loss of selectivity. The observed catalytic process intensification stems primarily from markedly increased CO2 availability. However, a non-monotonic correlation between the dissolved CO2 concentration and catalytic activity is observed, with an optimum occurring at approximately 5 m CO2 concentration. At the highest applied CO2 pressures, catalysis is significantly attenuated despite higher CO2 concentrations and improved mass-transport characteristics, attributed in part to increased solution resistance. These results reveal that pressure-tunable CXE media can significantly intensify CO2 reduction rates over known electrocatalysts by alleviating substrate starvation, with CO2 pressure as a crucial variable for optimizing the efficiency of electrocatalytic CO2 conversion.

Probing High Permeability of Nuclear Pore Complexes by Scanning Electrochemical Microscopy: Ca2+ Effects on Transport Barriers.

The nuclear pore complex (NPC) solely mediates molecular transport between the nucleus and cytoplasm of a eukaryotic cell to play important biological and biomedical roles. However, it is not well-understood chemically how this biological nanopore selectively and efficiently transports various substances, including small molecules, proteins, and RNAs by using transport barriers that are rich in highly disordered repeats of hydrophobic phenylalanine and glycine intermingled with charged amino acids. Herein, we employ scanning electrochemical microscopy to image and measure the high permeability of NPCs to small redox molecules. The effective medium theory demonstrates that the measured permeability is controlled by diffusional translocation of probe molecules through water-filled nanopores without steric or electrostatic hindrance from hydrophobic or charged regions of transport barriers, respectively. However, the permeability of NPCs is reduced by a low millimolar concentration of Ca2+, which can interact with anionic regions of transport barriers to alter their spatial distributions within the nanopore. We employ atomic force microscopy to confirm that transport barriers of NPCs are dominantly recessed (∼80%) or entangled (∼20%) at the high Ca2+ level in contrast to authentic populations of entangled (∼50%), recessed (∼25%), and "plugged" (∼25%) conformations at a physiological Ca2+ level of submicromolar. We propose a model for synchronized Ca2+ effects on the conformation and permeability of NPCs, where transport barriers are viscosified to lower permeability. Significantly, this result supports a hypothesis that the functional structure of transport barriers is maintained not only by their hydrophobic regions, but also by charged regions.

Hot-Tip Scanning Electrochemical Microscopy: Theory and Experiments Under Positive and Negative Feedback Conditions.

Hot-tip scanning electrochemical microscopy (HT-SECM) is a novel surface characterization technique utilizing an alternating current (ac) polarized disk microelectrode as a probe. A high-frequency (∼100 MHz) ac waveform applied between the tip and a counter electrode causes the resistive heating of the surrounding electrolyte solution that leads also to the electrothermal fluid flow (ETF). The effects of the temperature and the convection driven by the ETF result in the increased rate of mass transfer of the redox species. In this paper, HT-SECM was studied in positive and negative feedback modes, for which approach curves and cyclic voltammograms were recorded. The experimental data showed that the use of a hot tip leads to a more pronounced feedback compared to that at room temperature. Numerical simulations performed in COMSOL Multiphysics supported the experimental findings. Additional analytical approximations were developed that could be used to predict the faradaic response in HT-SECM experiments. Finally, a possible contribution to the current from the Soret effect was studied theoretically. A good understanding of HT-SECM was achieved, both experimentally and theoretically, suggesting that this methodology could be applied to investigate electrode kinetics under the conditions of elevated temperature and increased rate of mass transfer.

Examination of long-term visual memorization capacity in the Clark's nutcracker (Nucifraga columbiana).

Clark's nutcrackers exhibit remarkable cache recovery behavior, remembering thousands of seed locations over the winter. No direct laboratory test of their visual memory capacity, however, has yet been performed. Here, two nutcrackers were tested in an operant procedure used to measure different species' visual memory capacities. The nutcrackers were incrementally tested with an ever-expanding pool of pictorial stimuli in a two-alternative discrimination task. Each picture was randomly assigned to either a right or a left choice response, forcing the nutcrackers to memorize each picture-response association. The nutcrackers' visual memorization capacity was estimated at a little over 500 pictures, and the testing suggested effects of primacy, recency, and memory decay over time. The size of this long-term visual memory was less than the approximately 800-picture capacity established for pigeons. These results support the hypothesis that nutcrackers' spatial memory is a specialized adaptation tied to their natural history of food-caching and recovery, and not to a larger long-term, general memory capacity. Furthermore, despite millennia of separate and divergent evolution, the mechanisms of visual information retention seem to reflect common memory systems of differing capacities across the different species tested in this design.

Experience with featural-cue reliability influences featural- and geometric-cue use by mice (Mus musculus).

Orienting is a critical skill for all mobile animals. Two commonly studied visual components used to guide orientation in an environment are geometric (e.g., distance or direction) and featural cues (e.g., color or texture). Previous research has shown that visual-cue use and cue weighing can depend on the navigator's previous experience, the nature and reliability of the cues, and genetic factors. Accordingly, the domestic mouse (Mus musculus) is a species of increasing interest because of its potential as a model for human neurological disorders with associated spatial disorientation, as is seen in Alzheimer's disease. In the present study, adult C57BL/6 mice were trained to search for a hidden food reward in one corner of a rectangular environment with featural information displayed continuously along the walls. After training, one group of mice was given a block of testing in which the featural information was removed, followed by a second block of testing in which the featural information was put in conflict with the learned configuration of featural and geometric cues. A second group of mice was given the same set of tests, but in the reverse order. Our results show that the mice incidentally encoded the geometry of the environment if they had experience with featural cues being unreliable prior to tests, during which featural cues were completely removed (unstable). Furthermore, we found when featural and geometric cues provide conflicting spatial information, this unreliability of featural cues over the course of the study may influence cue weighing. (PsycINFO Database Record

Corvids Outperform Pigeons and Primates in Learning a Basic Concept.

Corvids (birds of the family Corvidae) display intelligent behavior previously ascribed only to primates, but such feats are not directly comparable across species. To make direct species comparisons, we used a same/different task in the laboratory to assess abstract-concept learning in black-billed magpies ( Pica hudsonia). Concept learning was tested with novel pictures after training. Concept learning improved with training-set size, and test accuracy eventually matched training accuracy-full concept learning-with a 128-picture set; this magpie performance was equivalent to that of Clark's nutcrackers (a species of corvid) and monkeys (rhesus, capuchin) and better than that of pigeons. Even with an initial 8-item picture set, both corvid species showed partial concept learning, outperforming both monkeys and pigeons. Similar corvid performance refutes the hypothesis that nutcrackers' prolific cache-location memory accounts for their superior concept learning, because magpies rely less on caching. That corvids with "primitive" neural architectures evolved to equal primates in full concept learning and even to outperform them on the initial 8-item picture test is a testament to the shared (convergent) survival importance of abstract-concept learning.

Abstract-concept learning in Black-billed magpies (Pica hudsonia).

relational concepts depend upon relationships between stimuli (e.g., same vs. different) and transcend features of the training stimuli. Recent evidence shows that learning abstract concepts is shared across a variety species including birds. Our recent work with a highly-skilled food-storing bird, Clark's nutcracker, revealed superior same/different abstract-concept learning compared to rhesus monkeys, capuchin monkeys, and pigeons. Here we test a more social, but less reliant on food-storing, corvid species, the Black-billed magpie (Pica hudsonia). We used the same procedures and training exemplars (eight pairs of the same rule, and 56 pairs of the different rule) as were used to test the other species. Magpies (n = 10) showed a level of abstract-concept learning that was equivalent to nutcrackers and greater than the primates and pigeons tested with these same exemplars. These findings suggest that superior initial abstract-concept learning abilities may be shared across corvids generally, rather than confined to those strongly reliant on spatial memory.