Spin-polarization and ferromagnetism of graphitic carbon nitride materials

Polymeric graphitic carbon nitride materials have attracted increasing attention in recent years owning to their potential applications in energy conversion, environment protection, and so on. Here, from first-principles calculations, we report the electronic structure modification of graphitic carbon nitride (g-C3N4) in response to carbon doping. We showed that each dopant atom can induce a local magnetic moment of 1.0 μB in non-magnetic g-C3N4. At the doping concentration of 1/14, the local magnetic moments of the most stable doping configuration which has the dopant atom at the center of heptazine unit prefer to align in a parallel way leading to long-range ferromagnetic (FM) ordering. When the joint N atom is replaced by C atom, the system favors an antiferromagnetic (AFM) ordering at unstrained state, but can be tuned to ferromagnetism (FM) by applying biaxial tensile strain. More interestingly, the FM state of the strained system is half-metallic with abundant states at the Fermi level in one spin channel and a band gap of 1.82 eV in another spin channel. The Curie temperature (Tc) was also evaluated using a mean-field theory and Monte Carlo simulations within the Ising model. Such tunable electron spin-polarization and ferromagnetism are quite promising for the applications of graphitic carbon nitride in spintronics.

Spin-coated carbon

We describe a novel and facile approach to covalently graft molecules containing stable free radicals onto carbon surfaces including graphene, carbon nanotubes, glassy carbon and carbon fibres. The new technique employs a stable aryl nitroxide radical diazonium tetrafluoroborate salt. The salt may be isolated and added to carbon surfaces in solution, suspension or electrochemically and represents a convenient, versatile and highly efficient means to adorn graphitic materials with large numbers of free radical spin systems

Treating the whole not the hole : necessary coupling of technologies for diabetic foot ulcer treatment

Highlights • Diabetic foot ulcers (DFUs) are a major complication of diabetes. • We describe the development of next-generation technologies for DFU repair. • We highlight the modest success of growth factor-, scaffold-, and cell-based DFU therapies. • We rationalize that combination therapies will be necessary to enable effective and reliable DFU repair.

Multiscale coupling and multiphysics approaches in earth sciences : theory

Measuring Earth material behaviour on time scales of millions of years transcends our current capability in the laboratory. We review an alternative path considering multiscale and multiphysics approaches with quantitative structure-property relationships. This approach allows a sound basis to incorporate physical principles such as chemistry, thermodynamics, diffusion and geometry-energy relations into simulations and data assimilation on the vast range of length and time scales encountered in the Earth. We identify key length scales for Earth systems processes and find a substantial scale separation between chemical, hydrous and thermal diffusion. We propose that this allows a simplified two-scale analysis where the outputs from the micro-scale model can be used as inputs for meso-scale simulations, which then in turn becomes the micro-model for the next scale up. We present two fundamental theoretical approaches to link the scales through asymptotic homogenisation from a macroscopic thermodynamic view and percolation renormalisation from a microscopic, statistical mechanics view.

Entropic bounds for multi-scale and multi-physics coupling in earth sciences

The ability to understand and predict how thermal, hydrological,mechanical and chemical (THMC) processes interact is fundamental to many research initiatives and industrial applications. We present (1) a new Thermal– Hydrological–Mechanical–Chemical (THMC) coupling formulation, based on non-equilibrium thermodynamics; (2) show how THMC feedback is incorporated in the thermodynamic approach; (3) suggest a unifying thermodynamic framework for multi-scaling; and (4) formulate a new rationale for assessing upper and lower bounds of dissipation for THMC processes. The technique is based on deducing time and length scales suitable for separating processes using a macroscopic finite time thermodynamic approach. We show that if the time and length scales are suitably chosen, the calculation of entropic bounds can be used to describe three different types of material and process uncertainties: geometric uncertainties,stemming from the microstructure; process uncertainty, stemming from the correct derivation of the constitutive behavior; and uncertainties in time evolution, stemming from the path dependence of the time integration of the irreversible entropy production. Although the approach is specifically formulated here for THMC coupling we suggest that it has a much broader applicability. In a general sense it consists of finding the entropic bounds of the dissipation defined by the product of thermodynamic force times thermodynamic flux which in material sciences corresponds to generalized stress and generalized strain rates, respectively.

Multiscale coupling and multiphysics approaches in earth sciences : applications

Geoscientists are confronted with the challenge of assessing nonlinear phenomena that result from multiphysics coupling across multiple scales from the quantum level to the scale of the earth and from femtoseconds to the 4.5 Ga of history of our planet. We neglect in this review electromagnetic modelling of the processes in the Earth’s core, and focus on four types of couplings that underpin fundamental instabilities in the Earth. These are thermal (T), hydraulic (H), mechanical (M) and chemical (C) processes which are driven and controlled by the transfer of heat to the Earth’s surface. Instabilities appear as faults, folds, compaction bands, shear/fault zones, plate boundaries and convective patterns. Convective patterns emerge from buoyancy overcoming viscous drag at a critical Rayleigh number. All other processes emerge from non-conservative thermodynamic forces with a critical critical dissipative source term, which can be characterised by the modified Gruntfest number Gr. These dissipative processes reach a quasi-steady state when, at maximum dissipation, THMC diffusion (Fourier, Darcy, Biot, Fick) balance the source term. The emerging steady state dissipative patterns are defined by the respective diffusion length scales. These length scales provide a fundamental thermodynamic yardstick for measuring instabilities in the Earth. The implementation of a fully coupled THMC multiscale theoretical framework into an applied workflow is still in its early stages. This is largely owing to the four fundamentally different lengths of the THMC diffusion yardsticks spanning micro-metre to tens of kilometres compounded by the additional necessity to consider microstructure information in the formulation of enriched continua for THMC feedback simulations (i.e., micro-structure enriched continuum formulation). Another challenge is to consider the important factor time which implies that the geomaterial often is very far away from initial yield and flowing on a time scale that cannot be accessed in the laboratory. This leads to the requirement of adopting a thermodynamic framework in conjunction with flow theories of plasticity. This framework allows, unlike consistency plasticity, the description of both solid mechanical and fluid dynamic instabilities. In the applications we show the similarity of THMC feedback patterns across scales such as brittle and ductile folds and faults. A particular interesting case is discussed in detail, where out of the fluid dynamic solution, ductile compaction bands appear which are akin and can be confused with their brittle siblings. The main difference is that they require the factor time and also a much lower driving forces to emerge. These low stress solutions cannot be obtained on short laboratory time scales and they are therefore much more likely to appear in nature than in the laboratory. We finish with a multiscale description of a seminal structure in the Swiss Alps, the Glarus thrust, which puzzled geologists for more than 100 years. Along the Glarus thrust, a km-scale package of rocks (nappe) has been pushed 40 km over its footwall as a solid rock body. The thrust itself is a m-wide ductile shear zone, while in turn the centre of the thrust shows a mm-cm wide central slip zone experiencing periodic extreme deformation akin to a stick-slip event. The m-wide creeping zone is consistent with the THM feedback length scale of solid mechanics, while the ultralocalised central slip zones is most likely a fluid dynamic instability.

Optical coupling of Au nanoparticles on vertical graphenes to maximize SERS response

Gold particle interaction with few-layer graphenes is of interest for the development of numerous optical nanodevices. The results of numerical studies of the coupling of gold nanoparticles with few-layer vertical graphene sheets are presented. The field strengths are computed and the optimum nanoparticle configurations for the formation of SERS hotpots are obtained. The nanoparticles are modeled as 8 nm diameter spheres atop 1.5 nm (5 layers) graphene sheet. The vertical orientation is of particular interest as it is possible to use both sides of the graphene structure and potentially double the number of particles in the system. Our results show that with the addition of an opposing particle a much stronger signal can be obtained as well as the particle separation can be controlled by the number of atomic carbon layers. These results provide further insights and contribute to the development of next-generation plasmonic devices based on nanostructures with hybrid dimensionality.

Semantic context and visual feature effects in object naming : an fMRI study using arterial spin labeling

Previous behavioral studies reported a robust effect of increased naming latencies when objects to be named were blocked within semantic category, compared to items blocked between category. This semantic context effect has been attributed to various mechanisms including inhibition or excitation of lexico-semantic representations and incremental learning of associations between semantic features and names, and is hypothesized to increase demands on verbal self-monitoring during speech production. Objects within categories also share many visual structural features, introducing a potential confound when interpreting the level at which the context effect might occur. Consistent with previous findings, we report a significant increase in response latencies when naming categorically related objects within blocks, an effect associated with increased perfusion fMRI signal bilaterally in the hippocampus and in the left middle to posterior superior temporal cortex. No perfusion changes were observed in the middle section of the left middle temporal cortex, a region associated with retrieval of lexical-semantic information in previous object naming studies. Although a manipulation of visual feature similarity did not influence naming latencies, we observed perfusion increases in the perirhinal cortex for naming objects with similar visual features that interacted with the semantic context in which objects were named. These results provide support for the view that the semantic context effect in object naming occurs due to an incremental learning mechanism, and involves increased demands on verbal self-monitoring.

One-step macroscopic alignment of conjugated polymer systems by epitaxial crystallization during spin-coating

The one-step preparation of highly anisotropic polymer semiconductor thin films directly from solution is demonstrated. The conjugated polymer poly(3-hexylthiophene) (P3HT) as well as P3HT:fullerene bulk-heterojunction blends can be spin-coated from a mixture of the crystallizable solvent 1,3,5-trichlorobenzene (TCB) and a second carrier solvent such as chlorobenzene. Solidification is initiated by growth of macroscopic TCB spherulites followed by epitaxial crystallization of P3HT on TCB crystals. Subsequent sublimation of TCB leaves behind a replica of the original TCB spherulites. Thus, highly ordered thin films are obtained, which feature square-centimeter-sized domains that are composed of one spherulite-like structure each. A combination of optical microscopy and polarized photoluminescence spectroscopy reveals radial alignment of the polymer backbone in case of P3HT, whereas P3HT:fullerene blends display a tangential orientation with respect to the center of spherulite-like structures. Moreover, grazing-incidence wide-angle X-ray scattering reveals an increased relative degree of crystallinity and predominantly flat-on conformation of P3HT crystallites in the blend. The use of other processing methods such as dip-coating is also feasible and offers uniaxial orientation of the macromolecule. Finally, the applicability of this method to a variety of other semi-crystalline conjugated polymer systems is established. Those include other poly(3-alkylthiophene)s, two polyfluorenes, the low band-gap polymer PCPDTBT, a diketopyrrolopyrrole (DPP) small molecule as well as a number of polymer:fullerene and polymer:polymer blends. Macroscopic spherulite-like structures of the conjugated polymer poly(3-hexylthiophene) (P3HT) grow directly during spin-coating. This is achieved by processing P3HT or P3HT:fullerene bulk heterojunction blends from a mixture of the crystallizable solvent 1,3,5-trichlorobenzene and a second carrier solvent such as chlorobenzene. Epitaxial growth of the polymer on solidified solvent crystals gives rise to circular-symmetric, spherulite-like structures that feature a high degree of anisotropy.

Iron(II) spin transition complexes with dendritic ligands, Part I

The ligands G1- and G2-oligo (benzyl ether) (PBE) dendrons and their iron(II) complexes [Fe(Gn-PBE)3]A2·xH2O (with n = 1, 2 and A = triflate, tosylate) were prepared. The magnetic properties of the complexes were investigated by a SQUID magnetometer. All complexes exhibit gradual spin transition below room temperature. At very low temperatures the magnetic behaviour reflects zero-field splitting (ZFS) effects. 57Fe-Mössbauer spectroscopy was performed to distinguish between ZFS of high spin species and spin state conversion into the low spin state. Further characterisation was carried out by thermogravimetric analysis (TGA) and FT-IR spectroscopy. Structural features have been determined by powder XRD measurements.

Pyridine-incorporated dihexylquaterthiophene : a novel blue emitter for organic light emitting diodes (OLEDs)

The synthesis and characterisation of 2,5-bis(5′-hexyl-[2,2′- bithiophen]-5-yl)pyridine (Th4PY) and its use as a blue emitter in organic light emitting diodes (OLEDs) is reported. Th4PY was synthesised in high yield using a straightforward Suzuki coupling route with commercially available starting materials. As Th4PY is both soluble and has low molecular weight, blue OLEDs were fabricated using both spin-coating and vacuum deposition thin film processing techniques to study the effect of processing on device performance. OLED devices using a spin-coated layer consisting of 4′,4′′- tris(N-carbazolyl)triphenylamine (TCTA) and 2-(4-biphenylyl)-5-(4-tert- butylphenyl)-1,3,4-oxadiazole (PBD) as a host matrix together with Th4PY as emitter exhibited highly efficient sky-blue emission with a low turn-on voltage of 3V, a maximum brightness close to 15000cdm-2 at 8V, and a maximum luminous efficiency of 7.4cdA -1 (6.3lmW -1) with CIE coordinates of x≤0.212, y≤0.320. The device performance characteristics are compared using various matrices and processing techniques. The promising sky-blue OLED performance, solution processability, and ambient stability make Th4PY a promising blue emitter for application in OLEDs.

Iron(II) spin-transition complexes with dendritic ligands, part II

The dendritic triazole-based complexes \[Fe(G1-BOC)3](triflate) 2·xH2O (1; G1-BOC = tert-butyl {3-\[3-(3-tert- butoxycarbonylaminopropyl)-5-(\[1,2,4]triazol-4-ylcarbamoyl)-phenyl]propyl} carbamate, triflate = CF3SO3-), \[Fe(G1-BOC) 3]-(tosylate)2·xH2O(2;tosylate = p-CH3PhSO3-),\[Fe(G1-DPBE)3]-(triflate) 2·xH2O {3; G1-DPBE = 3,5-bis(3,5- didodecaoxybenzyloxy)-N-\[1,2,4]triazol-4-ylbenzamide}, \[Fe(G1-DPBE) 3]-(tosylate)2·xH2O (4) and \[Fe(G1-DPBE)3](BF4)2·xH2O (5) were designed and synthesized. Magnetic and thermal properties of these novel complexes were characterized by magnetic susceptibility measurements, 57Fe Mössbauer spectroscopy and thermogravimetric analysis or differential scanning calorimetry, respectively. All dendritic complexes under study show different spin-transition behaviour with respect to the nature of different dendritic ligands and counteranions. Complexes 1 and 2 have pronounced effects of a spin-state change during the first heating process and gradual spintransition properties for further temperature treatments, whereas 3 and 4 exhibited a very sharp spin-state change in the first heating procedures. Complex 5 showed a gradual spin-transition curve. In this paper, we report how the magnetic properties of these complexes are correlated with noncoordinated water molecules and their effects on spin states.

Spin polarized DFT calculations of metal borides

The metal borides, in particular the diborides and hexaborides, contain stoichiometric forms that include insulators, semiconductors and superconductors. In addition, their end-member structures have high symmetry and two atoms although, in general, substitution(s) of multi-valent ions into the metal site occurs consistent with Vegard’s law. These characteristics allow for fundamental comparison of important physical properties such as superconductivity and insulation within a relatively simple structure type. Our early work1,2 has demonstrated this for the hexaborides and this work compares similar attributes across a broader suite of boride structures. In all cases, theoretical calculations are referenced to structures determined via high resolution neutron or X-ray diffraction experiments.

The pattern of coupling dynamics between postural motion, isotonic hand movements and physiological tremor

This study was designed to examine differences in the coupling dynamics between upper limb motion, physiological tremor and whole body postural sway in young healthy adults. Acceleration of the hand and fingers, forearm EMG activity and postural sway data were recorded. Estimation of the degree of bilateral and limb motion-postural sway coupling was determined by cross correlation, coherence and Cross-ApEn analyses. The results of the analysis revealed that, under postural tremor conditions, there was no significant coupling between limbs, muscles or sway across all metrics of coupling. In contrast, performing a rapid alternating flexion/extension movement about the wrist joint (with one or both limbs) resulted in stronger coupling between limb motion and postural sway. These results support the view that, for physiological tremor responses, the control of postural sway is maintained independent to tremor in the upper limb. However, increasing the level of movement about a distal segment of one arm (or both) leads to increased coupling throughout the body. The basis for this increased coupling would appear to be related to the enhanced neural drive to task-specific muscles within the upper limb.