Next-Generation Nanopore Sensors Based on Conductive Pulse Sensing for Enhanced Detection of Nanoparticles.

Nanopore sensing has been successfully used to characterize biological molecules with single-molecule resolution based on the resistive pulse sensing approach. However, its use in nanoparticle characterization has been constrained by the need to tailor the nanopore aperture size to the size of the analyte, precluding the analysis of heterogeneous samples. Additionally, nanopore sensors often require the use of high salt concentrations to improve the signal-to-noise ratio, which further limits their ability to study a wide range of nanoparticles that are unstable at high ionic strength. Here, a new paradigm in nanopore research that takes advantage of a polymer electrolyte system to comprise a conductive pulse sensing approach is presented. A finite element model is developed to explain the conductive pulse signals observed and compare these results with experiments. This system enables the analytical characterization of heterogeneous nanoparticle mixtures at low ionic strength . Furthermore, the wide applicability of the method is demonstrated by characterizing metallic nanospheres of varied sizes, plasmonic nanostars with various degrees of branching, and protein-based spherical nucleic acids with different oligonucleotide loadings. This system will complement the toolbox of nanomaterials characterization techniques to enable real-time optimization workflow for engineering a wide range of nanomaterials.

Ocean climate and hydrodynamics drive decadal shifts in Northeast Atlantic dinoflagellates.

The abundance of large marine dinoflagellates has declined in the North Sea since 1958. Although hypotheses have been proposed to explain this diminution (increasing temperature and wind), the mechanisms behind this pattern have thus far remained elusive. In this article, we study the long-term changes in dinoflagellate biomass and biodiversity in relation to hydro-climatic conditions and circulation within the North Atlantic. Our results show that the decline in biomass has paralleled an increase in biodiversity caused by a temperature-induced northward movement of subtropical taxa along the European shelf-edge, and facilitated by changes in oceanic circulation (subpolar gyre contraction). However, major changes in North Atlantic hydrodynamics in the 2010s (subpolar gyre expansion and low-salinity anomaly) stopped this movement, which triggered a biodiversity collapse in the North Sea. Further, North Sea dinoflagellate biomass remained low because of warming. Our results, therefore, reveal that regional climate warming and changes in oceanic circulation strongly influenced shifts in dinoflagellate biomass and biodiversity.

Investigating the Brain Mechanisms of Externally Cued Sit-to-Stand Movement in Parkinson's Disease.

BACKGROUND: One of the more challenging daily-life actions for Parkinson's disease patients is starting to stand from a sitting position. Parkinson's disease patients are known to have difficulty with self-initiated movements and benefit from external cues. However, the brain processes underlying external cueing as an aid remain unknown. The advent of mobile electroencephalography (EEG) now enables the investigation of these processes in dynamic sit-to-stand movements. OBJECTIVE: To identify cortical correlates of the mechanisms underlying auditory cued sit-to-stand movement in Parkinson's disease. METHODS: Twenty-two Parkinson's disease patients and 24 healthy age-matched participants performed self-initiated and externally cued sit-to-stand movements while cortical activity was recorded through 32-channel mobile EEG. RESULTS: Overall impaired integration of sensory and motor information can be seen in the Parkinson's disease patients exhibiting less modulation in the θ band during movement compared to healthy age-matched controls. How Parkinson's disease patients use external cueing of sit-to-stand movements can be seen in larger high ß power over sensorimotor brain areas compared to healthy controls, signaling sensory integration supporting the maintenance of motor output. This appears to require changes in cognitive processing to update the motor plan, reflected in frontal θ power increases in Parkinson's disease patients when cued. CONCLUSION: These findings provide the first neural evidence for why and how cueing improves motor function in sit-to-stand movement in Parkinson's disease. The Parkinson's disease patients' neural correlates indicate that cueing induces greater activation of motor cortical areas supporting the maintenance of a more stable motor output, but involves the use of cognitive resources to update the motor plan. © 2024 International Parkinson and Movement Disorder Society.

Extended reality to assess post-stroke manual dexterity: contrasts between the classic box and block test, immersive virtual reality with controllers, with hand-tracking, and mixed-reality tests.

BACKGROUND: Recent technological advancements present promising opportunities to enhance the frequency and objectivity of functional assessments, aligning with recent stroke rehabilitation guidelines. Within this framework, we designed and adapted different manual dexterity tests in extended reality (XR), using immersive virtual reality (VR) with controllers (BBT-VR-C), immersive VR with hand-tracking (BBT-VR-HT), and mixed-reality (MD-MR). OBJECTIVE: This study primarily aimed to assess and compare the validity of the BBT-VR-C, BBT-VR-HT and MD-MR to assess post-stroke manual dexterity. Secondary objectives were to evaluate reliability, usability and to define arm kinematics measures. METHODS: A sample of 21 healthy control participants (HCP) and 21 stroke individuals with hemiparesis (IHP) completed three trials of the traditional BBT, the BBT-VR-C, BBT-VR-HT and MD-MR. Content validity of the different tests were evaluated by asking five healthcare professionals to rate the difficulty of performing each test in comparison to the traditional BBT. Convergent validity was evaluated through correlations between the scores of the traditional BBT and the XR tests. Test-retest reliability was assessed through correlations between the second and third trial and usability was assessed using the System Usability Scale (SUS). Lastly, upper limb movement smoothness (SPARC) was compared between IHP and HCP for both BBT-VR test versions. RESULTS: For content validity, healthcare professionals rated the BBT-VR-HT (0[0-1]) and BBT-MR (0[0-1]) as equally difficult to the traditional BBT, whereas they rated BBT-VR-C as more difficult than the traditional BBT (1[0-2]). For IHP convergent validity, the Pearson tests demonstrated larger correlations between the scores of BBT and BBT-VR-HT (r = 0.94;p < 0.001), and BBT and MD-MR (r = 0.95;p < 0.001) than BBT and BBT-VR-C (r = 0.65;p = 0.001). BBT-VR-HT and MD-MR usability were both rated as excellent, with median SUS scores of 83[57.5-91.3] and 83[53.8-92.5] respectively. Excellent reliability was found for the BBT-VR-C (ICC = 0.96;p < 0.001), BBT-VR-HT (ICC = 0.96;p < 0.001) and BBT-MR (ICC = 0.99;p < 0.001). The usability of the BBT-VR-C was rated as good with a median SUS of 70[43.8-83.8]. Upper limb movements of HCP were significantly smoother than for IHP when completing either the BBT-VR-C (t = 2.05;p = 0.043) and the BBT-VR-HT (t = 5.21;p < 0.001). CONCLUSION: The different XR manual tests are valid, short-term reliable and usable tools to assess post-stroke manual dexterity. TRIAL REGISTRATION: https://clinicaltrials.gov/ct2/show/NCT04694833 ; Unique identifier: NCT04694833, Date of registration: 11/24/2020.

Evaluating Analytical Expressions for Scanning Electrochemical Cell Microscopy (SECCM).

Scanning electrochemical cell microscopy (SECCM) maps the electrochemical activity of a surface with nanoscale resolution using an electrolyte-filled nanopipette. The meniscus at the end of the pipet is sequentially placed at an array of locations across the surface, forming a series of nanometric electrochemical cells where the current-voltage response is measured. Quantitative interpretation of these responses typically employs numerical modeling to solve the coupled equations of transport and electron transfer, which require costly software or self-written code. Expertise and time are required to build and solve numerical models, which must be rerun for each new experiment. In contrast, algebraic expressions directly relate the current response to physical parameters. They are simpler to use, faster to calculate, and can provide greater insight but frequently require simplifying assumptions. In this work, we provide algebraic expressions for current and concentration distributions in SECCM experiments, which are formulated by approximating the pipet and meniscus using 1-D spherical coordinates. Expressions for the current and concentration distributions as a function of experimental parameters and in various conditions (steady state and time dependent, diffusion limited, and including migration) all show excellent agreement with numerical simulations employing a full geometry. Uses of the analytical expressions include determination of expected currents in experiments and quantifying electron-transfer rate constants in SECCM experiments.

Phytoplankton life strategies, phenological shifts and climate change in the North Atlantic Ocean from 1850 to 2100.

Significant phenological shifts induced by climate change are projected within the phytoplankton community. However, projections from current Earth System Models (ESMs) understandably rely on simplified community responses that do not consider evolutionary strategies manifested as various phenotypes and trait groups. Here, we use a species-based modelling approach, combined with large-scale plankton observations, to investigate past, contemporary and future phenological shifts in diatoms (grouped by their morphological traits) and dinoflagellates in three key areas of the North Atlantic Ocean (North Sea, North-East Atlantic and Labrador Sea) from 1850 to 2100. Our study reveals that the three phytoplanktonic groups exhibit coherent and different shifts in phenology and abundance throughout the North Atlantic Ocean. The seasonal duration of large flattened (i.e. oblate) diatoms is predicted to shrink and their abundance to decline, whereas the phenology of slow-sinking elongated (i.e. prolate) diatoms and of dinoflagellates is expected to expand and their abundance to rise, which may alter carbon export in this important sink region. The increase in prolates and dinoflagellates, two groups currently not considered in ESMs, may alleviate the negative influence of global climate change on oblates, which are responsible of massive peaks of biomass and carbon export in spring. We suggest that including prolates and dinoflagellates in models may improve our understanding of the influence of global climate change on the biological carbon cycle in the oceans.

Simulation of the cyclic voltammetric response of an outer-sphere redox species with inclusion of electrical double layer structure and ohmic potential drop.

A finite-element model has been developed to simulate the cyclic voltammetric (CV) response of a planar electrode for a 1e outer-sphere redox process, which fully accounts for cell electrostatics, including ohmic potential drop, ion migration, and the structure of the potential-dependent electric double layer. Both reversible and quasi-reversible redox reactions are treated. The simulations compute the time-dependent electric potential and ion distributions across the entire cell during a voltammetric scan. In this way, it is possible to obtain the interdependent faradaic and non-faradaic contributions to a CV and rigorously include all effects of the electric potential distribution on the rate of electron transfer and the local concentrations of the redox species Oz and Rz-1. Importantly, we demonstrate that the driving force for electron transfer can be different to the applied potential when electrostatic interactions are included. We also show that the concentrations of Oz and Rz-1 at the plane of electron transfer (PET) significantly depart from those predicted by the Nernst equation, even when the system is characterised by fast electron transfer/diffusion control. A mechanistic rationalisation is also presented as to why the electric double layer has a negligible effect on the CV response of such reversible systems. In contrast, for quasi-reversible electron transfer the concentrations of redox species at the PET are shown to play an important role in determining CV wave shape, an effect also dependant on the charge of the redox species and the formal electrode potential of the redox couple. Failure to consider electrostatic effects could lead to incorrect interpretation of electron-transfer kinetics from the CV response. Simulated CVs at scan rates between 0.1 and 1000 V s-1 are found to be in good agreement with experimental data for the reduction of 1.0 mM Ru(NH3)63+ at a 2 mm diameter gold disk electrode in 1.0 M potassium nitrate.

Structures of Arabidopsis thaliana oxygen-sensing plant cysteine oxidases 4 and 5 enable targeted manipulation of their activity.

In higher plants, molecular responses to exogenous hypoxia are driven by group VII ethylene response factors (ERF-VIIs). These transcriptional regulators accumulate in the nucleus under hypoxia to activate anaerobic genes but are destabilized in normoxic conditions through the action of oxygen-sensing plant cysteine oxidases (PCOs). The PCOs catalyze the reaction of oxygen with the conserved N-terminal cysteine of ERF-VIIs to form cysteine sulfinic acid, triggering degradation via the Cys/Arg branch of the N-degron pathway. The PCOs are therefore a vital component of the plant oxygen signaling system, connecting environmental stimulus with cellular and physiological response. Rational manipulation of PCO activity could regulate ERF-VII levels and improve flood tolerance, but requires detailed structural information. We report crystal structures of the constitutively expressed PCO4 and PCO5 from Arabidopsis thaliana to 1.24 and 1.91 Å resolution, respectively. The structures reveal that the PCOs comprise a cupin-like scaffold, which supports a central metal cofactor coordinated by three histidines. While this overall structure is consistent with other thiol dioxygenases, closer inspection of the active site indicates that other catalytic features are not conserved, suggesting that the PCOs may use divergent mechanisms to oxidize their substrates. Conservative substitution of two active site residues had dramatic effects on PCO4 function both in vitro and in vivo, through yeast and plant complementation assays. Collectively, our data identify key structural elements that are required for PCO activity and provide a platform for engineering crops with improved hypoxia tolerance.

Evidence of Motor Skill Learning in Acute Stroke Patients Without Lesions to the Thalamus and Internal Capsule.

BACKGROUND: It is currently unknown whether motor skill learning (MSkL) with the paretic upper limb is possible during the acute phase after stroke and whether lesion localization impacts MSkL. Here, we investigated MSkL in acute (1-7 days post) stroke patients compared with healthy individuals (HIs) and in relation to voxel-based lesion symptom mapping. METHODS: Twenty patients with acute stroke and 35 HIs were trained over 3 consecutive days on a neurorehabilitation robot measuring speed, accuracy, and movement smoothness variables. Patients used their paretic upper limb and HI used their nondominant upper limb on an MSkL task involving a speed/accuracy trade-off. Generalization was evaluated on day 3. All patients underwent a 3-dimensional magnetic resonance imaging used for VSLM. RESULTS: Most patients achieved MSkL demonstrated by day-to-day retention and generalization of the newly learned skill on day 3. When comparing raw speed/accuracy trade-off values, HI achieved larger MSkL than patients. However, relative speed/accuracy trade-off values showed no significant differences in MSkL between patients and HI on day 3. In patients, MSkL progression correlated with acute motor and cognitive impairments. The voxel-based lesion symptom mapping showed that acute vascular damage to the thalamus or the posterior limb of the internal capsule reduced MSkL. CONCLUSIONS: Despite worse motor performance for acute stroke patients compared with HI, most patients were able to achieve MSkL with their paretic upper limb. Damage to the thalamus and posterior limb of the internal capsule, however, reduced MSkL. These data show that MSkL could be implemented into neurorehabilitation during the acute phase of stroke, particularly for patients without lesions to the thalamus and posterior limb of the internal capsule. REGISTRATION: URL: https://www. CLINICALTRIALS: gov; Unique identifier: NCT01519843.

Finite Element Modeling of the Combined Faradaic and Electrostatic Contributions to the Voltammetric Response of Monolayer Redox Films.

The voltammetric response of electrodes coated with a redox-active monolayer is computed by finite element simulations based on a generalized model that couples the Butler-Volmer, Nernst-Planck, and Poisson equations. This model represents the most complete treatment of the voltammetric response of a redox film to date and is made accessible to the experimentalist via the use of finite element modeling and a COMSOL-generated report. The model yields a full description of the electric potential and charge distributions across the monolayer and bulk solution, including the potential distribution associated with ohmic resistance. In this way, it is possible to properly account for electrostatic effects at the molecular film/electrolyte interface, which are present due to the changing charge states of the redox head groups as they undergo electron transfer, under both equilibrium and nonequilibrium conditions. Specifically, our numerical simulations significantly extend previous theoretical predictions by including the effects of finite electron-transfer rates (k0) and electrolyte conductivity. Distortion of the voltammetric wave due to ohmic potential drop is shown to be a function of electrolyte concentration and scan rate, in agreement with experimental observations. The commonly used Laviron analysis for the determination of k0 fails to account for ohmic drop effects, which may be non-negligible at high scan rates. This model provides a more accurate alternative for k0 determination at all scan rates. The electric potential and charge distributions across an electrochemically inactive monolayer and electrolyte solution are also simulated as a function of applied potential and are found to agree with the Gouy-Chapman-Stern theory.

Stepping stones towards Antarctica: Switch to southern spawning grounds explains an abrupt range shift in krill.

Poleward range shifts are a global-scale response to warming, but these vary greatly among taxa and are hard to predict for individual species, localized regions or over shorter (years to decadal) timescales. Moving poleward might be easier in the Arctic than in the Southern Ocean, where evidence for range shifts is sparse and contradictory. Here, we compiled a database of larval Antarctic krill, Euphausia superba and, together with an adult database, it showed how their range shift is out of step with the pace of warming. During a 70-year period of rapid warming (1920s-1990s), distribution centres of both larvae and adults in the SW Atlantic sector remained fixed, despite warming by 0.5-1.0°C and losing sea ice. This was followed by a hiatus in surface warming and ice loss, yet during this period the distributions of krill life stages shifted greatly, by ~1000 km, to the south-west. Understanding the mechanism of such step changes is essential, since they herald system reorganizations that are hard to predict with current modelling approaches. We propose that the abrupt shift was driven by climatic controls acting on localized recruitment hotspots, superimposed on thermal niche conservatism. During the warming hiatus, the Southern Annular Mode index continued to become increasingly positive and, likely through reduced feeding success for larvae, this led to a precipitous decline in recruitment from the main reproduction hotspot along the southern Scotia Arc. This cut replenishment to the northern portion of the krill stock, as evidenced by declining density and swarm frequency. Concomitantly, a new, southern reproduction area developed after the 1990s, reinforcing the range shift despite the lack of surface warming. New spawning hotspots may provide the stepping stones needed for range shifts into polar regions, so planning of climate-ready marine protected areas should include these key areas of future habitat.

Phenological sensitivity to climate across taxa and trophic levels.

Differences in phenological responses to climate change among species can desynchronise ecological interactions and thereby threaten ecosystem function. To assess these threats, we must quantify the relative impact of climate change on species at different trophic levels. Here, we apply a Climate Sensitivity Profile approach to 10,003 terrestrial and aquatic phenological data sets, spatially matched to temperature and precipitation data, to quantify variation in climate sensitivity. The direction, magnitude and timing of climate sensitivity varied markedly among organisms within taxonomic and trophic groups. Despite this variability, we detected systematic variation in the direction and magnitude of phenological climate sensitivity. Secondary consumers showed consistently lower climate sensitivity than other groups. We used mid-century climate change projections to estimate that the timing of phenological events could change more for primary consumers than for species in other trophic levels (6.2 versus 2.5-2.9 days earlier on average), with substantial taxonomic variation (1.1-14.8 days earlier on average).

Performing a shortened version of the Action Research Arm Test in immersive virtual reality to assess post-stroke upper limb activity.

BACKGROUND: To plan treatment and measure post-stroke recovery, frequent and time-bounded functional assessments are recommended. With increasing needs for neurorehabilitation advances, new technology based methods, such as virtual reality (VR) have emerged. Here, we developed an immersive VR version of the Action Research Arm Test (ARAT-VR) to complement neurorehabilitation. OBJECTIVE: This study aimed to assess the validity, usability and test-retest reliability of the ARAT-VR among individuals with stroke, healthcare professionals and healthy control subjects (HCS). METHODS: Among the 19 items of the ARAT, 13 items were selected and developed in immersive VR. 11 healthcare professionals, 30 individuals with stroke, and 25 HCS were recruited. Content validity was assessed by asking healthcare professionals to rate the difficulty of performing each item of the ARAT-VR in comparison to the classical Action Research Arm Test (ARAT-19). Concurrent validity was first measured using correlation (Spearman tests) between the ARAT-VR and ARAT-19 scores for the individuals with stroke, and second through correlation and comparison between the scores of the ARAT-VR and the reduced version of the ARAT (ARAT-13) for both individuals with stroke and HCS (Wilcoxon signed rank tests and Bland-Altman plots). Usability was measured using the System Usability Scale. A part of individuals with stroke and HCS were re-tested following a convenient delay to measure test-retest reliability (Intra-class correlation and Wilcoxon tests). RESULTS: Regarding the content validity, median difficulty of the 13 ARAT-VR items (0[0 to - 1] to 0[0-1]) evaluated by healthcare professionals was rated as equivalent to the classical ARAT for all tasks except those involving the marbles. For these, the difficulty was rated as superior to the real tasks (1[0-1] when pinching with the thumb-index and thumb-middle fingers, and 1[0-2] when pinching with thumb-ring finger). Regarding the concurrent validity, for paretic hand scores, there were strong correlations between the ARAT-VR and ARAT-13 (r = 0.84), and between the ARAT-VR and ARAT-19 (r = 0.83). Usability (SUS = 82.5[75-90]) and test-retest reliability (ICC = 0.99; p < 0.001) were excellent. CONCLUSION: The ARAT-VR is a valid, usable and reliable tool that can be used to assess upper limb activity among individuals with stroke, providing potential to increase assessment frequency, remote evaluation, and improve neurorehabilitation. Trial registration https://clinicaltrials.gov/ct2/show/NCT04694833 ; Unique identifier: NCT04694833, Date of registration: 11/24/2020.

Concurrent validity of an immersive virtual reality version of the Box and Block Test to assess manual dexterity among patients with stroke.

BACKGROUND: After a stroke, experts recommend regular monitoring and kinematic assessments of patients to objectively measure motor recovery. With the rise of new technologies and increasing needs for neurorehabilitation, an interest in virtual reality has emerged. In this context, we have developed an immersive virtual reality version of the Box and Block Test (BBT-VR). The aim of this study was to assess the concurrent validity of the BBT-VR among patients with stroke and healthy participants. METHODS: Twenty-three healthy participants and 22 patients with stroke were asked to perform the classical Box and Block Test (BBT) and BBT-VR three times with both hands. Concurrent validity was assessed through correlations between these two tests and reliability of the BBT-VR through correlation on test-retest. Usability of the BBT-VR was also evaluated with the System Usability Scale. Hand kinematic data extracted from controller's 3D position allowed to compute mean velocity (Vmean), peak velocity (Vpeak) and smoothness (SPARC). RESULTS: Results showed strong correlations between the number of blocks displaced with the BBT and the BBT-VR among patients with stroke for affected (r = 0.89; p < 0.001) and less-affected hands (r = 0.76; p < 0.001) and healthy participants for dominant (r = 0.58; p < 0.01) and non-dominant hands (r = 0.68; p < 0.001). Reliability for test-retest was excellent (ICC > 0.8; p < 0.001) and usability almost excellent (System Usability Scale = 79 ± 12.34%). On average participants moved between 30 and 40% less blocks during the BBT-VR than during the BBT. Healthy participants demonstrated significantly higher kinematic measures (Vmean = 0.22 ± 0.086 ms-1; Vpeak = 0.96 ± 0.341 ms-1; SPARC = - 3.31 ± 0.862) than patients with stroke (Vmean = 0.12 ± 0.052 ms-1; Vpeak = 0.60 ± 0.202 ms-1; SPARC = - 5.04[- 7.050 to - 3.682]). CONCLUSION: The BBT-VR is a usable, valid and reliable test to assess manual dexterity, providing kinematic parameters, in a population of patients with stroke and healthy participants. Trial registration http://www.clinicaltrials.gov ; Unique identifier: NCT04694833, Date of registration: 11/24/2020.

Predictors of mental health in aid workers: meaning, resilience, and psychological flexibility as personal resources for increased well-being and reduced distress.

Aid workers operate in stressful environments and tend to experience high psychological distress, yet not enough is known about their well-being and how to improve their mental health. This research project surveyed 243 aid workers in 77 countries undertaking humanitarian and development work who reported lower well-being and higher psychological distress than the general population. Well-being and distress emerged as two related but distinct mental health outcomes, encouraging further research on well-being in the sector. Better mental health outcomes were predicted by the presence of meaning, psychological flexibility, and resilience. Presence of meaning was the strongest predictor, whereas resilience was the weakest. Meaning was a stronger predictor of good mental health among national workers, whereas psychological flexibility was a stronger predictor among female, older, and international workers. These results can support evidence-based approaches to staff care and mental health interventions for aid workers, expanding the current focus on resilience to include meaning and psychological flexibility.

Mobile EEG reveals functionally dissociable dynamic processes supporting real-world ambulatory obstacle avoidance: Evidence for early proactive control.

The ability to safely negotiate the world on foot takes humans years to develop, reflecting the extensive cognitive demands associated with real-time planning and control of walking. Despite the importance of walking, methodological limitations mean that surprisingly little is known about the neural and cognitive processes that support ambulatory motor control. Here, we report mobile EEG data recorded from 32 healthy young adults during real-world ambulatory obstacle avoidance. Participants walked along a path while stepping over expected and unexpected obstacles projected on the floor, allowing us to capture the dynamic oscillatory response to changes in environmental demands. Compared to obstacle-free walking, time-frequency analysis of the EEG data revealed clear neural markers of proactive and reactive forms of movement control (occurring before and after crossing an obstacle), visible as increases in frontal theta and centro-parietal beta power respectively. Critically, the temporal profile of changes in frontal theta allowed us to arbitrate between early selection and late adaptation mechanisms of proactive control. Our data show that motor plans are updated as soon as an upcoming obstacle appears, rather than when the obstacle is reached. In addition, regardless of whether motor plans required updating, a clear beta rebound was present after obstacles were crossed, reflecting the resetting of the motor system. Overall, mobile EEG recorded during real-world walking provides novel insight into the cognitive and neural basis of dynamic motor control in humans, suggesting new routes to the monitoring and rehabilitation of motor disorders such as dyspraxia and Parkinson's disease.

The Visuo-Spatial Abilities Diagnosis (VSAD) test: Evaluating the potential cognitive difficulties of children with vestibular impairment through a new tablet-based computerized test battery.

Recent data collected on adult patients with vestibular loss (VL) tend to demonstrate possible cognitive impairments in visuospatial working memory, mental rotation, selective attention, and space orientation. However, the neuropsychological profile of children with VL remains largely under-investigated in the scientific literature. Although previous research has shown that children with VL may experience some degree of delayed motor development, it is not yet clear if VL could also lead to specific delayed cognitive development. In this study, we will present the development and validation of a new tablet-based computerized test battery (VSAD) that evaluates visuospatial working memory, mental rotation, selective attention, and space orientation abilities. Thirteen children with VL and 54 average-age matched healthy children performed the VSAD and classical paper-and-pencil neuropsychological tasks twice within a 1-month interval. Our results demonstrated a good concurrent validity with strong correlations between the visuospatial working memory, mental rotation, and space orientation tests of the VSAD and classical tasks. Test-retest reliability was also supported through good intra-class coefficients. However, the test of selective attention showed no concurrent validity with the matched classical task. The discriminant validity of the VSAD was partially supported for visuospatial working memory and mental rotation performance accuracy. The VSAD shows good concurrent validity and reliability for measuring visuospatial working memory, mental rotation, and space orientation in children with VL. Future studies are needed to extend discriminant validity with other populations.

Visualization of Hydrogen Evolution at Individual Platinum Nanoparticles at a Buried Interface.

Electrochemical processes occurring at solid/solid and solid/membrane interfaces govern the behavior of a variety of energy storage devices, including electrocatalytic reactions at electrode/membrane interfaces in fuel cells and ion insertion at electrode/electrolyte interfaces in solid-state batteries. Due to the heterogeneity of these systems, interrogation of interfacial activity at nanometer length scales is desired to understand system performance, yet the buried nature of the interfaces makes localized activity inaccessible to conventional electrochemical techniques. Herein, we demonstrate nanoscale electrochemical imaging of hydrogen evolution at individual Pt nanoparticles (PtNPs) positioned at a buried interface using scanning electrochemical cell microscopy (SECCM). Specifically, we image the hydrogen evolution reaction (HER) at individual carbon-supported PtNP electrocatalysts covered by a 100 to 800 nm thick layer of the proton exchange membrane Nafion. The rate of hydrogen evolution at PtNP at this buried interface is shown to be a function of Nafion thickness, with the highest activity observed for ∼200 nm thick films.

Nitrogen Bubbles at Pt Nanoelectrodes in a Nonaqueous Medium: Oscillating Behavior and Geometry of Critical Nuclei.

Gas bubble evolution is present in many electrochemical and photoelectrochemical processes. We previously reported the formation of individual H2, N2, and O2 nanobubbles generated from electrocatalytic reduction of H+ and oxidation of N2H4 and H2O2, respectively, at Pt nanodisk electrodes in an aqueous solution. All the nanobubbles formed display a dynamic stationary state of a three-phase boundary with an invariant residual current. Here, we test the hypothesis that gas nanobubbles can also be electrogenerated in a nonaqueous medium. Interestingly, we found oscillating bubble behavior corresponding to nucleation, growth, and dissolution in dimethyl sulfoxide and methanol. One possible explanation of the oscillation mechanism is provided by the instable dynamic equilibrium between the gas influx due to supersaturation and outflux due to Laplace pressure. Furthermore, the critical gas concentrations for N2 nanobubble nucleation are estimated to be 148, 386, 200, and 16 times supersaturation and the contact angles of the critical nuclei to be 164°, 151°, 160°, and 174° in water, dimethyl sulfoxide, ethylene glycol, and methanol, respectively. This is the first report on electrochemical nucleation of gas bubbles in nonaqueous solvents. Our electrochemical gas bubble study based on a nanoelectrode platform has proven to be a prototypical example of single-entity electrochemistry.

Applying Statistical Design of Experiments To Understanding the Effect of Growth Medium Components on Cupriavidus necator H16 Growth.

Cupriavidus necator H16 is gaining significant attention as a microbial chassis for range of biotechnological applications. While the bacterium is a major producer of bioplastics, its lithoautotrophic and versatile metabolic capabilities make the bacterium a promising microbial chassis for biofuels and chemicals using renewable resources. It remains necessary to develop appropriate experimental resources to permit controlled bioengineering and system optimization of this microbe. In this study, we employed statistical design of experiments to gain understanding of the impact of components of defined media on C. necator growth and built a model that can predict the bacterium's cell density based on medium components. This highlighted medium components, and interaction between components, having the most effect on growth: fructose, amino acids, trace elements, CaCl2, and Na2HPO4 contributed significantly to growth (t values of <-1.65 or >1.65); copper and histidine were found to interact and must be balanced for robust growth. Our model was experimentally validated and found to correlate well (r2 = 0.85). Model validation at large culture scales showed correlations between our model-predicted growth ranks and experimentally determined ranks at 100 ml in shake flasks (ρ = 0.87) and 1 liter in a bioreactor (ρ = 0.90). Our approach provides valuable and quantifiable insights on the impact of medium components on cell growth and can be applied to model other C. necator responses that are crucial for its deployment as a microbial chassis. This approach can be extended to other nonmodel microbes of medical and industrial biotechnological importance.IMPORTANCE Chemically defined media (CDM) for cultivation of C. necator vary in components and compositions. This lack of consensus makes it difficult to optimize new processes for the bacterium. This study employed statistical design of experiments (DOE) to understand how basic components of defined media affect C. necator growth. Our growth model predicts that C. necator can be cultivated to high cell density with components held at low concentrations, arguing that CDM for large-scale cultivation of the bacterium for industrial purposes will be economically competitive. Although existing CDM for the bacterium are without amino acids, addition of a few amino acids to growth medium shortened lag phase of growth. The interactions highlighted by our growth model show how factors can interact with each other during a process to positively or negatively affect process output. This approach is efficient, relying on few well-structured experimental runs to gain maximum information on a biological process, growth.