The role of the surfaces in the photon absorption in Ge nanoclusters embedded in silica.

The usage of semiconductor nanostructures is highly promising for boosting the energy conversion efficiency in photovoltaics technology, but still some of the underlying mechanisms are not well understood at the nanoscale length. Ge quantum dots (QDs) should have a larger absorption and a more efficient quantum confinement effect than Si ones, thus they are good candidate for third-generation solar cells. In this work, Ge QDs embedded in silica matrix have been synthesized through magnetron sputtering deposition and annealing up to 800°C. The thermal evolution of the QD size (2 to 10 nm) has been followed by transmission electron microscopy and X-ray diffraction techniques, evidencing an Ostwald ripening mechanism with a concomitant amorphous-crystalline transition. The optical absorption of Ge nanoclusters has been measured by spectrophotometry analyses, evidencing an optical bandgap of 1.6 eV, unexpectedly independent of the QDs size or of the solid phase (amorphous or crystalline). A simple modeling, based on the Tauc law, shows that the photon absorption has a much larger extent in smaller Ge QDs, being related to the surface extent rather than to the volume. These data are presented and discussed also considering the outcomes for application of Ge nanostructures in photovoltaics.PACS: 81.07.Ta; 78.67.Hc; 68.65.-k.

Engineering of micro- and nanostructured surfaces with anisotropic geometries and properties

Widespread approaches to fabricate surfaces with robust micro- and nanostructured topographies have been stimulated by opportunities to enhance interface performance by combining physical and chemical effects. In particular, arrays of asymmetric surface features, such as arrays of grooves, inclined pillars, and helical protrusions, have been shown to impart unique anisotropy in properties including wetting, adhesion, thermal and/or electrical conductivity, optical activity, and capability to direct cell growth. These properties are of wide interest for applications including energy conversion, microelectronics, chemical and biological sensing, and bioengineering. However, fabrication of asymmetric surface features often pushes the limits of traditional etching and deposition techniques, making it challenging to produce the desired surfaces in a scalable and cost-effective manner. We review and classify approaches to fabricate arrays of asymmetric 2D and 3D surface features, in polymers, metals, and ceramics. Analytical and empirical relationships among geometries, materials, and surface properties are discussed, especially in the context of the applications mentioned above. Further, opportunities for new fabrication methods that combine lithography with principles of self-assembly are identified, aiming to establish design principles for fabrication of arbitrary 3D surface textures over large areas. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local Frustration Determines Molecular and Macroscopic Helix Structures

The effect of displaying cytochromes from an amyloid fibre is modelled as perturbation of -strands in a bilayer of helical -sheets, thereby explaining the spiral morphology of decorated amyloid and the dynamic response of morphology to cytochrome conformation. The morphology of the modelled fibre, which consists of minimal energy assemblies of rigid building blocks containing two anisotropic interacting units, depends primarily on the rigid constraints between units rather than the soft interactions between them. The framework is a discrete version of the bilayered frustration principle that drives morphology in Bauhinia seedpods. We show that self-assembly of frustrated long range structures can occur if the building blocks themselves are internally frustrated, e.g. amyloid morphology is governed by the conformation of the misfolded protein nucleating the fibre. Our model supports the idea that any peptide sequence can form amyloid if bilayers can form first, albeit stabilised by additional material such as chaperones or cytochromes. Analysis of experimentally derived amyloid structures supports our conclusions and suggests a range of frustration effects, which natural amyloid fibres may exploit. From this viewpoint, amyloid appears as a molecular example of a more general universal bilayered frustration principle, which may have profound implications for materials design using fibrous systems. Our model provides quantitative guidance for such applications. The relevance to longer length scales was proved by designing the morphology of a series of macroscopic magnetic stacks. Finally, this work leads to the idea of mixing controlled morphologically defined species to generate higher-order assembly and complex functional behaviour. The systematic kinking of decorated fibres and the nested frustration of the Bauhinia seed pod are two outstanding examples.

Consensus under general convexity

A method is proposed to characterize contraction of a set through orthogonal projections. For discrete-time multi-agent systems, quantitative estimates of convergence (to a consensus) rate are provided by means of contracting convex sets. Required convexity for the sets that should include the values that the transition maps of agents take is considered in a more general sense than that of Euclidean geometry. © 2007 IEEE.

Direct numerical simulation of turbulent flows over superhydrophobic surfaces with gas pockets using linearized boundary conditions

Superhydrophobic surfaces are shown to be effective for surface drag reduction under laminar regime by both experiments and simulations (see for example, Ou and Rothstein, Phys. Fluids 17:103606, 2005). However, such drag reduction for fully developed turbulent flow maintaining the Cassie-Baxter state remains an open problem due to high shear rates and flow unsteadiness of turbulent boundary layer. Our work aims to develop an understanding of mechanisms leading to interface breaking and loss of gas pockets due to interactions with turbulent boundary layers. We take advantage of direct numerical simulation of turbulence with slip and no-slip patterned boundary conditions mimicking the superhydrophobic surface. In addition, we capture the dynamics of gas-water interface, by deriving a proper linearized boundary condition taking into account the surface tension of the interface and kinematic matching of interface deformation and normal velocity conditions on the wall. We will show results from our simulations predicting the dynamical behavior of gas pocket interfaces over a wide range of dimensionless surface tensions.

Differentiated adipose-derived stem cells act synergistically with RGD-modified surfaces to improve neurite outgrowth in a co-culture model.

Peripheral nerve damage is a problem encountered after trauma and during surgery and the development of synthetic polymer conduits may offer a promising alternative to autografts. In order to improve the performance of the polymer to be used for nerve conduits, poly-ε-caprolactone (PCL) films were chemically functionalized with RGD moieties, using a chemical reaction previously developed. In vitro cultures of dissociated dorsal root ganglion (DRG) neurons provide a valid model to study different factors affecting axonal growth. In this work, DRG neurons were cultured on RGD-functionalized PCL films. Adult adipose-derived stem cells differentiated to Schwann cells (dASCs) were initially cultured on the functionalized PCL films, resulting in improved attachment and proliferation. dASCs were also co-cultured with DRG neurons on treated and untreated PCL to assess stimulation by dASCs on neurite outgrowth. Neuron response was generally poor on untreated PCL films, but long neurites were observed in the presence of dASCs or RGD moieties. A combination of the two factors enhanced even further neurite outgrowth, acting synergistically. Finally, in order to better understand the extracellular matrix (ECM)-cell interaction, a β1 integrin blocking experiment was carried out. Neurite outgrowth was not affected by the specific antibody blocking, showing that β1 integrin function can be compensated by other molecules present on the cell membrane. Copyright © 2013 John Wiley & Sons, Ltd.

The interaction of riblets with wall-bounded turbulence

The purpose of this thesis is to give answer to the question: why do riblets stop working for a certain size? Riblets are small surface grooves aligned in the mean direction of an overlying turbulent flow, designed specifically to reduce the friction between the flow and the surface. They were inspired by biological surfaces, like the oriented denticles in the skin of fastswimming sharks, and were the focus of a significant amount of research in the late eighties and nineties. Although it was found that the drag reduction depends on the riblet size scaled in wall units, the physical mechanisms implicated have not been completely understood up to now. It has been explained how riblets of vanishing size interact with the turbulent flow, producing a change in the drag proportional to their size, but that is not the regime of practical interest. The optimum performance is achieved for larger sizes, once that linear behavior has broken down, but before riblets begin adopting the character of regular roughness and increasing drag. This regime, which is the most relevant from a technological perspective, was precisely the less understood, so we have focused on it. Our efforts have followed three basic directions. First, we have re-assessed the available experimental data, seeking to identify common characteristics in the optimum regime across the different existing riblet geometries. This study has led to the proposal of a new length scale, the square root of the groove crosssection, to substitute the traditional peak-to-peak spacing. Scaling the riblet dimension with this length, the size of breakdown of the linear behavior becomes roughly universal. This suggests that the onset of the breakdown is related to a certain, fixed value of the cross-section of the groove. Second, we have conducted a set of direct numerical simulations of the turbulent flow over riblets, for sizes spanning the full drag reduction range. We have thus been able to reproduce the gradual transition between the different regimes. The spectral analysis of the flows has proven particularly fruitful, since it has made possible to identify spanwise rollers immediately above the riblets, which begin to appear when the riblet size is close to the optimum. This is a quite surprising feature of the flow, not because of the uniqueness of the phenomenon, which had been reported before for other types of complex and porous surfaces, but because most previous studies had focused on the detail of the flow above each riblet as a unit. Our novel approach has provided the adequate tools to capture coherent structures with an extended spanwise support, which interact with the riblets not individually, but collectively. We have also proven that those spanwise structures are responsible for the increase in drag past the viscous breakdown. Finally, we have analyzed the stability of the flow with a simplified model that connects the appearance of rollers to a Kelvin–Helmholtz-like instability, as is the case also for the flow over plant canopies and porous surfaces. In spite of the model emulating the presence of riblets only in an averaged, general fashion, it succeeds to capture the essential attributes of the breakdown, and provides a theoretical justification for the scaling with the groove cross-section.