Altering the ordering and disordering of a triangular nanographene at room temperature

Molecular self-organization has the potential to serve as an efficient and versatile tool for the spontaneous creation of low-dimensional nanostructures on surfaces. We demonstrate how the subtle balance between intermolecular interactions and molecule-surface interactions can be altered by modifying the environment or through manipulation by means of the tip in a scanning tunnelling microscope (STM) at room temperature. We show how this leads to the distinctive ordering and disordering of a triangular nanographene molecule, the trizigzag-hexa-peri-hexabenzocoronenes-phenyl-6 (trizigzagHBC-Ph6), on two different surfaces: graphite and Au(111). The assembly of submonolayer films on graphite reveals a sixfold packing symmetry under UHV conditions, whereas at the graphite-phenyloctane interface, they reorganize into a fourfold packing symmetry, mediated by the solvent molecules. On Au(111) under UHV conditions in the multilayer films we investigated, although disorder prevails with the molecules being randomly distributed, their packing behaviour can be altered by the scanning motion of the tip. The asymmetric diode-like current-voltage characteristics of the molecules are retained when deposited on both substrates. This paper highlights the importance of the surrounding medium and any external stimulus in influencing the molecular organization process, and offers a unique approach for controlling the assembly of molecules at a desired location on a substrate.     

Robust imposition of Dirichlet boundary conditions on embedded surfaces

We develop both stable and stabilized methods for imposing Dirichlet constraints on embedded, three‐dimensional surfaces in finite elements. The stable method makes use of the vital vertex algorithm to develop a stable space for the Lagrange multipliers together with a novel discontinuous set of basis functions for the multiplier field. The stabilized method, on the other hand, follows a Nitsche type variational approach for three‐dimensional surfaces. Algorithmic and implementational details of both methods are provided. Several three‐dimensional benchmark problems are studied to compare and contrast the accuracy of the two approaches. The results indicate that both methods yield optimal rates of convergence in various quantities of interest, with the primary differences being in the surface flux. The utility of the domain integral for extracting accurate surface fluxes is demonstrated for both techniques. Copyright © 2011 John Wiley & Sons, Ltd.     

Modelling cell motility and chemotaxis with evolving surface finite elements

We present a mathematical and a computational framework for the modelling of cell motility. The cell membrane is represented by an evolving surface, with the movement of the cell determined by the interaction of various forces that act normal to the surface. We consider external forces such as those that may arise owing to inhomogeneities in the medium and a pressure that constrains the enclosed volume, as well as internal forces that arise from the reaction of the cells'' surface to stretching and bending. We also consider a protrusive force associated with a reaction–diffusion system (RDS) posed on the cell membrane, with cell polarization modelled by this surface RDS. The computational method is based on an evolving surface finite-element method. The general method can account for the large deformations that arise in cell motility and allows the simulation of cell migration in three dimensions. We illustrate applications of the proposed modelling framework and numerical method by reporting on numerical simulations of a model for eukaryotic chemotaxis and a model for the persistent movement of keratocytes in two and three space dimensions. Movies of the simulated cells can be obtained from http://homepages.warwick.ac.uk/∼maskae/CV_Warwick/Chemotaxis.html.     

Pathological Gait Detection Based on Multiple Regression Models Using Unobtrusive Sensing Technology

Journal of Signal Processing Systems - Analysis of human gait to detect walking abnormality has recently gained growing interest. It carries profound impact in medical diagnosis and rehabilitation...     

Material parameter optimization for interior and exterior fluid-structure acoustic problems

We present an efficient adjoint-based framework for computing sensitivities of quantities of interest with respect to material parameters for coupled fluid-structural acoustic systems with explicit interface coupling. The fluid is modeled using the Helmholtz equation and the structure is modeled using the Navier-Cauchy equations. Sensitivities are used to drive a gradient based optimization algorithm to solve important problems in structural acoustics, viz noise minimization and vibration isolation. For each problem, we consider two different priors: one where the optimal solution has a smooth variation and another with a bimaterial distribution. These priors are imposed with the help of suitable regularization terms. The effectiveness of this approach is demonstrated on both interior and exterior structural acoustic problems.     

Importance of Cr2O3 layer for growth of carbon nanotubes on superalloys

We present a detailed investigation of the formation of stable catalyst particles on Inconel substrates, an important step in the growth mechanism of carbon nanotubes on these substrates. The chemical nature of the interaction of catalyst and substrate was investigated using XPS, high-resolution cross-sectional TEM, and EDS studies. The results indicate that Cr₂O₃, an electrically conductive oxide, plays an important role in stabilizing nanoclusters of Fe catalyst under typical growth conditions. The nature of growth on a number of other superalloys is also presented and is examined with respect to their chemical composition.     

Photoinducible Oncometabolite Detection

Dysregulated metabolism can fuel cancer by altering the production of bioenergetic building blocks and directly stimulating oncogenic gene-expression programs. However, relatively few optical methods for the direct study of metabolites in cells exist. To address this need and facilitate new approaches to cancer treatment and diagnosis, herein we report an optimized chemical approach to detect the oncometabolite fumarate. Our strategy employs diaryl tetrazoles as cell-permeable photoinducible precursors to nitrileimines. Uncaging these species in cells and cell extracts enables them to undergo 1,3-dipolar cycloadditions with endogenous dipolarophile metabolites such as fumarate to form pyrazoline cycloadducts that can be readily detected by their intrinsic fluorescence. The ability to photolytically uncage diaryl tetrazoles provides greatly improved sensitivity relative to previous methods, and enables the facile detection of dysregulated fumarate metabolism through biochemical activity assays, intracellular imaging, and flow cytometry. Our studies showcase an intersection of bioorthogonal chemistry and metabolite reactivity that can be applied for biological profiling, imaging, and diagnostics.     

Dimensionless Empirical Model to Correlate Pharmaceutical Compound Solubility in Supercritical Carbon Dioxide

The accurate experimental determination of pharmaceutical compound solubilities at various temperature and pressure ranges in supercritical carbon dioxide (ScCO₂) is a challenging and time‐consuming task. Therefore, prediction or correlations of solute solubilities are essential for implementation of ScCO₂ technologies to pharmaceutical industries. Solubilities of 41 pharmaceutical compounds in ScCO₂ are correlated by an empirical model, which is developed based on the degree of freedom analysis. Its correlating ability is compared with existing solubility models elaborated by other authors and evaluated in terms of global mean absolute relative deviation, sum of squares due to error, root mean square deviation, R², and Adj. R². The proposed model is found to correlate better than existing models.     

Improved tire tread compounds using functionalized styrene butadiene rubber-silica filler/hybrid filler systems

Automotive industry is currently looking for an eco-friendly tire with low rolling resistance coefficient (RRc), better traction, wear resistance, and fatigue properties. Presently, solution styrene-butadiene rubber (SSBR)-silica systems are pursued for balancing between traction and RRc. However, the interaction between SSBR and silica is not enough to give satisfactory results. Functionalized-SSBR (FSSBR) leads to better rubber-silica interaction due to introduction of polar groups in the polymer chain. The present study investigates the influence of FSSBR, highly dispersible (HD) silica, and its hybrid filler systems with organically modified nanoclay (ONC) and exfoliated graphene nanoplatelet (xGnP). Both M_H, and Δtorque were higher for the FSSBR-HD silica compound (S1) with the lowest change in storage modulus (∆G') value, due to higher polymer-filler interaction. S1 exhibited 16% ice traction and 12% wet traction improvement with 29% lower rolling resistance over SSBR-silica compound. S1 showed the best wet traction rating and wear resistance. Replacing small portion of silica by ONC and xGnP improved the properties further. At 5 phr of nanofiller, TEM images revealed well-dispersed nanofillers in the FSSBR matrix. The xGnP compound showed the least crack growth. For both the cases, abradability decreased with higher nanofiller amount, due to better reinforcement of the rubber.