Weinerodgaard0025

Interestingly, these hybrid particles exhibit modulating catalytic activity with variation in pH. The reduction kinetics decreases with increasing pH and the corresponding apparent rate constant exhibits two linear regimes with one at pH below pKa and another at pH above pKa of acrylic acid. This pH-modulated catalytic behavior of PNIPAM-co-PAA@AgAu hybrids is discussed based on pH-induced swelling/deswelling transition, the core-shell nature of microgel particles, and its intrinsic interplay with the diffusion of nitrophenols within the microgel network. Finally, our results are compared and discussed in the context of previously studied catalytic activities in different polymer-metal hybrids.Graphane is formed by bonding hydrogen (and deuterium) atoms to carbon atoms in the graphene mesh, with modification from the pure planar sp2 bonding towards an sp3 configuration. Atomic hydrogen (H) and deuterium (D) bonding with C atoms in fully free-standing nano porous graphene (NPG) is achieved, by exploiting low-energy proton (or deuteron) non-destructive irradiation, with unprecedented minimal introduction of defects, as determined by Raman spectroscopy and by the C 1s core level lineshape analysis. Evidence of the H- (or D-) NPG bond formation is obtained by bringing to light the emergence of a H- (or D-) related sp3-distorted component in the C 1s core level, clear fingerprint of H-C (or D-C) covalent bonding. The H (or D) bonding with the C atoms of free-standing graphene reaches more than 1/4 (or 1/3) at% coverage. This non-destructive H-NPG (or D-NPG) chemisorption is very stable at high temperatures up to about 800 K, as monitored by Raman and x-ray photoelectron spectroscopy, with complete healing and restoring of clean graphene above 920 K. The excellent chemical and temperature stability of H- (and D-) NPG opens the way not only towards the formation of semiconducting graphane on large-scale samples, but also to stable graphene functionalisation enabling futuristic applications in advanced detectors for the β-spectrum analysis.The Schrödinger equation in a square or rectangle with hard walls is solved in every introductory quantum mechanics course. Solutions for other polygonal enclosures only exist in a very restricted class of polygons, and are all based on a result obtained by Lamé in 1852. Any enclosure can, of course, be addressed by finite element methods for partial differential equations. In this paper, we present a variational method to approximate the low-energy spectrum and wave-functions for arbitrary convex polygonal enclosures, developed initially for the study of vibrational modes of plates. In view of the recent interest in the spectrum of quantum dots of two dimensional materials, described by effective models with massless electrons, we extend the method to the Dirac-Weyl equation for a spin-1/2 fermion confined in a quantum billiard of polygonal shape, with different types of boundary conditions. We illustrate the method's convergence in cases where the spectrum is known exactly and apply it to cases where no exact solution exists.An appropriate treatment of electronic correlation effects plays an important role in accurate descriptions of physical and chemical properties of real materials. The recently proposed Correlation Matrix Renormalization theory with Sum Rule correction (CMR) for studying correlated electron materails has shown good performance in molecular systems and a periodic Hydrogen chain in comparison with various quantum chemistry and quantum Monte Carlo calculations. This work gives a detailed formulation and computational code implementation of CMR in multi-band periodic lattice systems. This lattice CMR ab initio theory is highly efficient, has no material specific adjustable parameters, and has no double counting issues faced by the hybrid approaches like LDA+U, DFT+DMFT and DFT+GA type theories. Benchmark studies on materials with s and p orbitals in this study show that CMR in its current implementation consistently performs well for these systems as the electron correlation increases from the bonding region to the bond breaking region.Positronium formation at 4H SiC(0001) surfaces were investigated upon the removal of natural oxide layers by hydrofluoric acid etching and heat treatment at 1000 K in ultra-high vacuum. Two types of positronium were observed in the positronium time-of-flight (PsTOF) measurements irrespective of conduction type and surface polarity. One type formed the major part of the PsTOF spectrum with a maximum energy of 4.7 ± 0.3 eV. This energy exceeded the theoretical positronium work function calculated with valence electrons. The PsTOF spectrum shape was different from those of metal surfaces, suggesting that the surface state electrons or conduction electrons need to be considered as the positronium source. Another positronium appeared at 1000 K in the tail of the PsTOF spectrum with a maximum energy of 0.2-0.5 eV. This thermally-assisted athermal positronium may be formed via the surface state positrons and electrons.Graphene-based nano-porous materials (GNM) are potentially useful for all those applications needing a large specific surface area (SSA), typical of the bidimensional graphene, yet realized in the bulk dimensionality. Such applications include for instance gas storage and sorting, catalysis and electrochemical energy storage. While a reasonable control of the structure is achieved in micro-porous materials by using nano-micro particles as templates, the controlled production or even characterization of GNMs with porosity strictly at the nano-scale still raises issues. These are usually produced using dispersion of nano-flakes as precursors resulting in little control on the final structure, which in turn reflects in problems in the structural model building for computer simulations. In this work, we describe a strategy to build models for these materials with predetermined structural properties (SSA, density, porosity), which exploits molecular dynamics simulations, Monte Carlo methods and machine learning algorithms. Our strategy is inspired by the real synthesis process starting from randomly distributed flakes, we include defects, perforation, structure deformation and edge saturation on the fly, and, after structural refinement, we obtain realistic models, with given structural features. We find relationships between the structural characteristics and size distributions of the starting flake suspension and the final structure, which can give indications for more efficient synthesis routes. We subsequently give a full characterization of the models versus H2 adsorption, from which we extract quantitative relationship between the structural parameters and the gravimetric density. Our results quantitatively clarify the role of surfaces and edges relative amount in determining the H2 adsorption, and suggest strategies to overcome the inherent physical limitations of these materials as adsorbers. We implemented the model building and analysis procedures in software tools, freely available upon request.Microbial electrosynthesis (MES) is an emerging technology that can convert carbon dioxide (CO2) into value-added organic carbon compounds using electrons supplied from a cathode. However, MES is affected by low product formation due to limited extracellular electron uptake by microbes. Herein, a novel cathode was developed from chemically synthesized magnetite nanoparticles and reduced graphene oxide nanocomposite (rGO-MNPs). This nanocomposite was electrochemically deposited on carbon felt (CF/rGO-MNPs), and the modified material was used as a cathode for MES production. The bioplastic, polyhydroxybutyrate (PHB) produced by Rhodopseudomonas palustris TIE-1 (TIE-1), was measured from reactors with modified and unmodified cathodes. Results demonstrate that the magnetite nanoparticle anchored graphene cathode (CF/rGO-MNPs) exhibited higher PHB production (91.31 ± 0.9 mg l-1). This is ∼4.2 times higher than unmodified carbon felt (CF), and 20 times higher than previously reported using graphite. This modified cathode enhanced electron uptake to -11.7 ± 0.1 μA cm-2, ∼5 times higher than CF cathode (-2.3 ± 0.08 μA cm-2). The faradaic efficiency of the modified cathode was ∼2 times higher than the unmodified cathode. Electrochemical analysis and scanning electron microscopy suggest that rGO-MNPs facilitated electron uptake and improved PHB production by TIE-1. Overall, the nanocomposite (rGO-MNPs) cathode modification enhances MES efficiency.We investigate the radiation of energy and angular momentum from 2D topological systems with broken inversion symmetry and time reversal symmetry. A general theory of far-field radiation is developed using the linear response of 2D materials to the thermal fluctuation of electric currents. Applying the theory to the Haldane model, we verify that the heat radiation complies with Planck's law only at low temperature and deviates from it as temperature becomes high. In contrast to normal metals, angular momentum radiation is possible for this system and exhibits saturation as temperature increases. Parameters crucial to the radiation are investigated and optimized. This research enlightens the possibility of transposing the quantum information to the angular momentum degree of freedom.We illustrate how the tensorial kernel support vector machine (TK-SVM) can probe the hidden multipolar orders and emergent local constraint in the classical kagome Heisenberg antiferromagnet. We show that TK-SVM learns the finite-temperature phase diagram in an unsupervised way. Moreover, in virtue of its strong interpretability, it identifies the tensorial quadrupolar and octupolar orders, which define a biaxial $D_3h$ spin nematic, and the local constraint that underlies the selection of coplanar states. We then discuss the disorder hierarchy of the phases, which can be inferred from both the analytical order parameters and a SVM bias parameter. For completeness we mention that the machine also picks up the leading $\sqrt3 \times \sqrt3$ correlations in the dipolar channel at very low temperature, which are however weak compared to the quadrupolar and octupolar orders. Our work shows how TK-SVM can facilitate and speed up the analysis of classical frustrated magnets.

Time of day has been shown to impact athletic performance, with improved performance observed in the late afternoon-early evening. Diurnal variations in physiological factors may contribute to variations in pacing selection; however, research investigating time-of-day influence on pacing is limited.

To investigate the influence of time-of-day on pacing selection in a 4-km cycling time trial (TT).

Nineteen trained male cyclists (mean [SD] age 39.0 [10.7]y, height 1.8 [0.1]m, body mass 78.0 [9.4]kg, VO2max 62.1 [8.7]mL·kg-1·min-1) completed a 4-km TT on 5 separate occasions at 0830, 1130, 1430, 1730, and 2030. All TTs were completed in a randomized order, separated by a minimum of 2d and maximum of 7d.

No time-of-day effects were observed in pacing as demonstrated by similar power outputs over 0.5-km intervals (P = .78) or overall mean power output (333.0 [38.9], 339.8 [37.2], 335.5 [31.2], 336.7 [35.2], and 334.9 [35.7]W; P = .45) when TTs were performed at 0830, 1130, 1430, 1730, and 2030. Preexercise tympanic temperature demonstrated a time-of-day effect (P < .