Enhanced Gas Adsorption on Graphitic Substrates via Defects and Local Curvature: A Density Functional Theory Study

Using van-der-Waals-corrected density functional theory calculations, we explore the possibility of engineering the local structure and morphology of high-surface-area graphene-derived materials to improve the uptake of methane and carbon dioxide for gas storage and sensing. We test the sensitivity of the gas adsorption energy to the introduction of native point defects, curvature, and the application of strain. The binding energy at topological point defect sites is inversely correlated with the number of missing carbon atoms, causing Stone-Wales defects to show the largest enhancement with respect to pristine graphene (similar to 20%). Improvements of similar magnitude are observed at concavely curved surfaces in buckled graphene sheets under compressive strain, whereas tensile strain tends to weaken gas binding. Trends for CO2 and CH4 are, similar, although CO2 binding is generally stronger by similar to 4 to 5 kJ mol(-1). However, the differential between the adsorption of CO2 and CH4 is much higher on folded graphene sheets and at concave curvatures; this could possibly be leveraged for CH4/CO2 flow separation and gasselective sensors.

Anomalous power law decay in solvation dynamics of DNA: a mode coupling theory analysis of ion contribution

Several time dependent fluorescence Stokes shift (TDFSS) experiments have reported a slow power law decay in the hydration dynamics of a DNA molecule. Such a power law has neither been observed in computer simulations nor in some other TDFSS experiments. Here we observe that a slow decay may originate from collective ion contribution because in experiments DNA is immersed in a buffer solution, and also from groove bound water and lastly from DNA dynamics itself. In this work we first express the solvation time correlation function in terms of dynamic structure factors of the solution. We use mode coupling theory to calculate analytically the time dependence of collective ionic contribution. A power law decay in seen to originate from an interplay between long-range probe-ion direct correlation function and ion-ion dynamic structure factor. Although the power law decay is reminiscent of Debye-Falkenhagen effect, yet solvation dynamics is dominated by ion atmosphere relaxation times at longer length scales (small wave number) than in electrolyte friction. We further discuss why this power law may not originate from water motions which have been computed by molecular dynamics simulations. Finally, we propose several experiments to check the prediction of the present theoretical work.

Spectral finite element based on an efficient layerwise theory for wave propagation analysis of composite and sandwich beams

In this paper, we present a spectral finite element model (SFEM) using an efficient and accurate layerwise (zigzag) theory, which is applicable for wave propagation analysis of highly inhomogeneous laminated composite and sandwich beams. The theory assumes a layerwise linear variation superimposed with a global third-order variation across the thickness for the axial displacement. The conditions of zero transverse shear stress at the top and bottom and its continuity at the layer interfaces are subsequently enforced to make the number of primary unknowns independent of the number of layers, thereby making the theory as efficient as the first-order shear deformation theory (FSDT). The spectral element developed is validated by comparing the present results with those available in the literature. A comparison of the natural frequencies of simply supported composite and sandwich beams obtained by the present spectral element with the exact two-dimensional elasticity and FSDT solutions reveals that the FSDT yields highly inaccurate results for the inhomogeneous sandwich beams and thick composite beams, whereas the present element based on the zigzag theory agrees very well with the exact elasticity solution for both thick and thin, composite and sandwich beams. A significant deviation in the dispersion relations obtained using the accurate zigzag theory and the FSDT is also observed for composite beams at high frequencies. It is shown that the pure shear rotation mode remains always evanescent, contrary to what has been reported earlier. The SFEM is subsequently used to study wavenumber dispersion, free vibration and wave propagation time history in soft-core sandwich beams with composite faces for the first time in the literature. (C) 2014 Elsevier Ltd. All rights reserved.

Emergent properties of the interferon-signalling network may underlie the success of hepatitis C treatment

Current interferon alpha-based treatment of hepatitis C virus (HCV) infection fails to cure a sizeable fraction of patients treated. The cause of this treatment failure remains unknown. Here using mathematical modelling, we predict treatment failure to be a consequence of the emergent properties of the interferon-signalling network. HCV induces bistability in the network, creating a new steady state where it can persist. Cells that admit the new steady state alone are refractory to interferon. Using a model of viral kinetics, we show that when the fraction of cells refractory to interferon in a patient exceeds a critical value, treatment fails. Direct-acting antivirals that suppress HCV replication can eliminate the new steady state, restoring interferon sensitivity and improving treatment response. Our study thus presents a new conceptual basis of HCV persistence and treatment response, elucidates the origin of the synergy between interferon and direct-acting antivirals, and facilitates rational treatment optimization.

Cu-II-Azide Polynuclear Complexes of Three Different Building Clusters with the Same Schiff-Base Ligand: Synthesis, Structures, Magnetic Behavior, and Density Functional Theory Studies

Three copper-azido complexes Cu-4(N-3)(8)(L-1)(2)(MeOH)(2)](n) (1), Cu-4(N-3)(8)(L-1)(2)] (2), and Cu-5(N-3)(10)(L-1)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with 2-(2-pyridyl)ethylamine] have been synthesized using lower molar equivalents of the Schiff base ligand with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of the complexes 1 and 2 contains Cu-4(II) building blocks; however, they have distinct basic and overall structures due to a small change in the bridging mode of the peripheral pair of copper atoms in the linear tetranudear structures. Interestingly, these changes are the result of changing the solvent system (MeOH/H2O to EtOH/H2O) used for the synthesis, without changing the proportions of the components (metal to ligand ratio 2:1). Using even lower proportions of the ligand, another unique complex was isolated with Cu-5(II) building units, forming a two-dimensional complex (3). Magnetic susceptibility measurements over a wide range of temperature exhibit the presence of both antiferromagnetic (very weak) and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional, and two different basis sets) have been performed on the complexes 1 and 2 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Silent katydid females are at higher risk of bat predation than acoustically signalling katydid males

Males that produce conspicuous mate attraction signals are often at high risk of predation from eavesdropping predators. Females of such species typically search for signalling males and their higher motility may also place them at risk. The relative predation risk faced by males and females in the context of mate-finding using long-distance signals has rarely been investigated. In this study, we show, using a combination of diet analysis and behavioural experiments, that katydid females, who do not produce acoustic signals, are at higher risk of predation from a major bat predator, Megaderma spasma, than calling males. Female katydids were represented in much higher numbers than males in the culled remains beneath roosts of M. spasma. Playback experiments using katydid calls revealed that male calls were approached in only about one-third of the trials overall, whereas tethered, flying katydids were always approached and attacked. Our results question the idea that necessary costs of mate-finding, including risk of predation, are higher in signalling males than in searching females.

Monopoles, Dirac operator, and index theory for fuzzy SU(3) / (U(1) x U(1))

The intersection of the ten-dimensional fuzzy conifold Y-F(10) with S-F(5) x S-F(5) is the compact eight-dimensional fuzzy space X-F(8). We show that X-F(8) is (the analogue of) a principal U(1) x U(1) bundle over fuzzy SU(3) / U(1) x U(1)) ( M-F(6)). We construct M-F(6) using the Gell-Mann matrices by adapting Schwinger's construction. The space M-F(6) is of relevance in higher dimensional quantum Hall effect and matrix models of D-branes. Further we show that the sections of the monopole bundle can be expressed in the basis of SU(3) eigenvectors. We construct the Dirac operator on M-F(6) from the Ginsparg-Wilson algebra on this space. Finally, we show that the index of the Dirac operator correctly reproduces the known results in the continuum.

Ecology of acoustic signalling and the problem of masking interference in insects

The efficiency of long-distance acoustic signalling of insects in their natural habitat is constrained in several ways. Acoustic signals are not only subjected to changes imposed by the physical structure of the habitat such as attenuation and degradation but also to masking interference from co-occurring signals of other acoustically communicating species. Masking interference is likely to be a ubiquitous problem in multi-species assemblages, but successful communication in natural environments under noisy conditions suggests powerful strategies to deal with the detection and recognition of relevant signals. In this review we present recent work on the role of the habitat as a driving force in shaping insect signal structures. In the context of acoustic masking interference, we discuss the ecological niche concept and examine the role of acoustic resource partitioning in the temporal, spatial and spectral domains as sender strategies to counter masking. We then examine the efficacy of different receiver strategies: physiological mechanisms such as frequency tuning, spatial release from masking and gain control as useful strategies to counteract acoustic masking. We also review recent work on the effects of anthropogenic noise on insect acoustic communication and the importance of insect sounds as indicators of biodiversity and ecosystem health.

Anisotropic isometric fluctuation relations in experiment and theory on a self-propelled rod

The isometric fluctuation relation (IFR) P. I. Hurtado et al., Proc. Natl. Acad. Sci. USA 108, 7704 (2011)] relates the relative probability of current fluctuations of fixed magnitude in different spatial directions. We test its validity in an experiment on a tapered rod, rendered motile by vertical vibration and immersed in a sea of spherical beads. We analyze the statistics of the velocity vector of the rod and show that they depart significantly from the IFR of Hurtado et al. Aided by a Langevin-equation model we show that our measurements are largely described by an anisotropic generalization of the IFR R. Villavicencio et al., Europhys. Lett. 105, 30009 (2014)], with no fitting parameters, but with a discrepancy in the prefactor whose origin may lie in the detailed statistics of the microscopic noise. The experimentally determined large-deviation function of the velocity vector has a kink on a curve in the plane.

Kinetic theory for sheared granular flows

Rapid granular flows are far-from-equilibrium-driven dissipative systems where the interaction between the particles dissipates energy, and so a continuous supply of energy is required to agitate the particles and facilitate the rearrangement required for the flow. This is in contrast to flows of molecular fluids, which are usually close to equilibrium, where the molecules are agitated by thermal fluctuations. Sheared granular flows form a class of flows where the energy required for agitating the particles in the flowing state is provided by the mean shear. These flows have been studied using the methods of kinetic theory of gases, where the particles are treated in a manner similar to molecules in a molecular gas, and the interactions between particles are treated as instantaneous energy-dissipating binary collisions. The validity of the assumptions underlying kinetic theory, and their applicability to the idealistic case of dilute sheared granular flows are first discussed. The successes and challenges for applying kinetic theory for realistic dense sheared granular flows are then summarised. (C) 2014 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

A micropolar peridynamic theory in linear elasticity

A state-based micropolar peridynamic theory for linear elastic solids is proposed. The main motivation is to introduce additional micro-rotational degrees of freedom to each material point and thus naturally bring in the physically relevant material length scale parameters into peridynamics. Non-ordinary type modeling via constitutive correspondence is adopted here to define the micropolar peridynamic material. Along with a general three dimensional model, homogenized one dimensional Timoshenko type beam models for both the proposed micropolar and the standard non-polar peridynamic variants are derived. The efficacy of the proposed models in analyzing continua with length scale effects is established via numerical simulations of a few beam and plane-stress problems. (C) 2015 Elsevier Ltd. All rights reserved.

Markov chains, R-trivial monoids and representation theory

We develop a general theory of Markov chains realizable as random walks on R-trivial monoids. It provides explicit and simple formulas for the eigenvalues of the transition matrix, for multiplicities of the eigenvalues via Mobius inversion along a lattice, a condition for diagonalizability of the transition matrix and some techniques for bounding the mixing time. In addition, we discuss several examples, such as Toom-Tsetlin models, an exchange walk for finite Coxeter groups, as well as examples previously studied by the authors, such as nonabelian sandpile models and the promotion Markov chain on posets. Many of these examples can be viewed as random walks on quotients of free tree monoids, a new class of monoids whose combinatorics we develop.

Mode coupling theory analysis of electrolyte solutions: Time dependent diffusion, intermediate scattering function, and ion solvation dynamics

A self-consistent mode coupling theory (MCT) with microscopic inputs of equilibrium pair correlation functions is developed to analyze electrolyte dynamics. We apply the theory to calculate concentration dependence of (i) time dependent ion diffusion, (ii) intermediate scattering function of the constituent ions, and (iii) ion solvation dynamics in electrolyte solution. Brownian dynamics with implicit water molecules and molecular dynamics method with explicit water are used to check the theoretical predictions. The time dependence of ionic self-diffusion coefficient and the corresponding intermediate scattering function evaluated from our MCT approach show quantitative agreement with early experimental and present Brownian dynamic simulation results. With increasing concentration, the dispersion of electrolyte friction is found to occur at increasingly higher frequency, due to the faster relaxation of the ion atmosphere. The wave number dependence of intermediate scattering function, F(k, t), exhibits markedly different relaxation dynamics at different length scales. At small wave numbers, we find the emergence of a step-like relaxation, indicating the presence of both fast and slow time scales in the system. Such behavior allows an intriguing analogy with temperature dependent relaxation dynamics of supercooled liquids. We find that solvation dynamics of a tagged ion exhibits a power law decay at long times-the decay can also be fitted to a stretched exponential form. The emergence of the power law in solvation dynamics has been tested by carrying out long Brownian dynamics simulations with varying ionic concentrations. The solvation time correlation and ion-ion intermediate scattering function indeed exhibit highly interesting, non-trivial dynamical behavior at intermediate to longer times that require further experimental and theoretical studies. (c) 2015 AIP Publishing LLC.

THEORY OF NEWFORMS OF HALF-INTEGRAL WEIGHT

We set up the theory of newforms of half-integral weight on Gamma(0)(8N) and Gamma(0)(16N), where N is odd and squarefree. Further, we extend the definition of the Kohnen plus space in general for trivial character and also study the theory of newforms in the plus spaces on Gamma(0)(8N), Gamma(0)(16N), where N is odd and squarefree. Finally, we show that the Atkin-Lehner W-operator W-4 acts as the identity operator on S-2k(new)(4N), where N is odd and squarefree. This proves that S-2k(-)(4) = S-2k(4).