The dorsolateral pre‑frontal cortex bi‑polar error‑related potential in a locked‑in patient implanted with a daily use brain–computer interface

While brain computer interfaces (BCIs) offer the potential of allowing those suffering from loss of muscle control to once again fully engage with their environment by bypassing the affected motor system and decoding user intentions directly from brain activity, they are prone to errors. One possible avenue for BCI performance improvement is to detect when the BCI user perceives the BCI to have made an unintended action and thus take corrective actions. Error-related potentials (ErrPs) are neural correlates of error awareness and as such can provide an indication of when a BCI system is not performing according to the user’s intentions. Here, we investigate the brain signals of an implanted BCI user suffering from locked-in syndrome (LIS) due to late-stage ALS that prevents her from being able to speak or move but not from using her BCI at home on a daily basis to communicate, for the presence of error-related signals. We first establish the presence of an ErrP originating from the dorsolateral pre-frontal cortex (dLPFC) in response to errors made during a discrete feedback task that mimics the click-based spelling software she uses to communicate. Then, we show that this ErrP can also be elicited by cursor movement errors in a continuous BCI cursor control task. This work represents a first step toward detecting ErrPs during the daily home use of a communications BCI.     

ALGAMES: a fast augmented Lagrangian solver for constrained dynamic games

Autonomous Robots - Dynamic games are an effective paradigm for dealing with the control of multiple interacting actors. This paper introduces augmented Lagrangian GAME-theoretic solver (ALGAMES),...     

Crack initiation,propagation, and arrest in sintering powder aggregates

Cracking during sintering is a common problem in powder processing and is usually caused by constraint that prevents the sintering material from shrinking in one or more directions. Different factors influence sintering-induced cracking, including temperature schedule, packing density, and specimen geometry. Here we use the discrete element method to directly observe the stress distribution and sinter-cracking behavior in edge notched panels sintered under a uniaxial restraint. This geometry allows an easy comparison with traditional fracture mechanics parameters, facilitating analysis of sinter-cracking behavior. We find that cracking caused by self-stress during sintering resembles the growth of creep cracks in fully dense materials. By deriving the constrained densification rate from the appropriate constitutive equations, we discover that linear shrinkage transverse to the loading axis is accelerated by a contribution from the effective Poisson's ratio of a sintering solid. Simulation of different notch geometries and initial relative densities reveals conditions that favor densification and minimize crack growth, alluding to design methods for avoiding cracking in actual sintering processes. We combine the far-field stress and crack length to compute the net section stress, finding that it characterizes the stress profile between the notches and correlates with the sinter-crack growth rate, demonstrating its potential to quantitatively describe sinter-cracking.     

Solvent-drop assisted mechanochemical synthesis of the black and green polymorphs of the tetrathiafulvalene–chloranil charge transfer salt

This work describes the synthesis of the green and black polymorphic forms of the tetrathiafulvalene–chloranil (TTF–CA) charge transfer salt as pure phases, by solvent-assisted mechanochemistry. Both materials were characterized using laboratory and high-resolution X-ray powder diffraction (XRPD), elemental analysis and scanning electron microscopy (SEM). The high-resolution XRPD pattern of the TTF–CA black polymorph was indexed with a triclinic lattice a = 10.756(5) Å, b = 11.057(4) Å, c = 6.614(2) Å, α = 101.36(2)°, β = 93.69(3)°, γ = 89.37(3)°, V = 769.6(5) Å³. The chemical stability of these phases upon heating was investigated using thermogravimetric analysis (TGA), elemental analysis and X-ray powder diffraction (XRPD), indicating that both polymorphs undergo chemical decomposition, and ruling out the transition to an air-stable high temperature polymorph.     

Antivirulence Isoquinolone Mannosides: Optimization of the Biaryl Aglycone for FimH Lectin Binding Affinity and Efficacy in the Treatment of Chronic UTI

Uropathogenic E. coli (UPEC) employ the mannose‐binding adhesin FimH to colonize the bladder epithelium during urinary tract infection (UTI). Previously reported FimH antagonists exhibit good potency and efficacy, but low bioavailability and a short half‐life in vivo. In a rational design strategy, we obtained an X‐ray structure of lead mannosides and then designed mannosides with improved drug‐like properties. We show that cyclizing the carboxamide onto the biphenyl B‐ring aglycone of biphenyl mannosides into a fused heterocyclic ring, generates new biaryl mannosides such as isoquinolone 22 (2‐methyl‐4‐(1‐oxo‐1,2‐dihydroisoquinolin‐7‐yl)phenyl α‐d ‐mannopyranoside) with enhanced potency and in vivo efficacy resulting from increased oral bioavailability. N‐Substitution of the isoquinolone aglycone with various functionalities produced a new potent subseries of FimH antagonists. All analogues of the subseries have higher FimH binding affinity than unsubstituted lead 22 , as determined by thermal shift differential scanning fluorimetry assay. Mannosides with pyridyl substitution on the isoquinolone group inhibit bacteria‐mediated hemagglutination and prevent biofilm formation by UPEC with single‐digit nanomolar potency, which is unprecedented for any FimH antagonists or any other antivirulence compounds reported to date.     

Gas permeation in thin films of “high free-volume” glassy perfluoropolymers: Part I. Physical aging

Physical aging of both thick and thin films of “high free-volume” glassy perfluoropolymers was studied by monitoring changes in pure gas permeability of O₂, N₂ and CH₄. All permeability measurements were done at a fixed temperature of 35 °C for more than 1000 h of aging. Two grades of perfluoropolymers, Teflon AF and Hyflon AD, having different comonomer structures but with similar comonomer ratios were studied to understand the effect of comonomer type and content on the aging behavior. The effect of casting process (solution vs. spin coating) and solvent type (vapor pressure and boiling point) had a significant effect on the absolute permeability of both thick and thin films; however, the aging rates were more affected by thickness and solvent type rather than the casting process for similar thicknesses. After 1000 h of aging, the relative permeability for thin films of Teflon AF 2400 was decreased by 27% compared to only 10% for thick films prepared from Novec 7500 solvent. Teflon AF, which has a higher fractional free volume (FFV) than Hyflon AD, is believed to undergo significant aging well before the initial permeability measurement could be made (after ∼ 1 h of aging) and, therefore, Teflon AF materials showed a lower decrease in relative permeability compared to Hyflon AD for the same aging time. The comonomer type and content has a significant effect on the permeability; the initial absolute oxygen permeability for AF 2400 was an order of magnitude higher compared to AD 60. The physical aging of thin films of the various glassy perfluoropolymers was also tracked by recording changes in the refractive index and thickness with time by ellipsometry. The ellipsometry data also confirmed higher aging rates in Hyflon AD compared to Teflon AF materials. The volumetric aging rate, obtained from the change in the refractive index using the Lorentz–Lorenz equation, and the permeability reduction rate from the (P_1000h/P_1h) ratio showed an excellent linear correlation. The (P_1000h/P_1h) ratio also showed a stronger correlation with (T_g−35) °C than with FFV.     

Influence of polyimide precursor synthesis route and ortho-position functional group on thermally rearranged (TR) polymer properties: Conversion and free volume

Thermal rearrangement of polyimides with ortho-position groups to polybenzoxazoles and related structures has been of recent interest for producing gas separation membranes. This study explores the influence of synthesis route and ortho-position functional group on the thermal rearrangement process and the fractional free volume of thermally rearranged (TR) polymers produced from polyimides derived from 3,3′-dihydroxy-4,4′-diamino-biphenyl and 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (HAB–6FDA). Acetate, propanoate, and pivalate ortho-position functional groups were considered. Thermogravimetric analysis (TGA) was used to study thermal rearrangement at temperatures between 350 and 450 °C, and evolved gases from TGA were analyzed via mass spectrometry to characterize the byproducts of thermal rearrangement and thermal degradation. CO₂ was the major byproduct of thermal rearrangement for all samples, and its evolution began well before the onset of thermal degradation. When non-hydroxyl ortho-position groups were present in the polymers, several byproducts other than CO₂ were also observed due to the loss of these ortho-position groups before thermal rearrangement. Free volume generally increased with increasing extent of thermal rearrangement, but precise values of free volume could not be accurately determined for polymers with propanoate and pivalate ortho-position functional groups due to uncertainties in the chemical structure of partially converted materials. For polymers with acetate and hydroxyl ortho-position groups, free volume could be determined within the uncertainty of density measurements. Thermal rearrangement behavior and free volume results for acetate containing polymers synthesized via different routes were very similar. Based on these results, the chemical structure of the ortho-position functional group has a larger impact on TR polymer properties than the polyimide precursor synthesis route.