Aromaticity on the fly: cyclic transition state stabilization at finite temperature.

We study the transition state of pericyclic reactions at elevated temperature with unbiased ab initio molecular dynamics. We find that the transition state of the intramolecular rearrangements for barbaralane and bullvalene remains aromatic at high temperature despite the significant thermal atomic motions. Structural, magnetic, and electronic properties of the dynamical transition state show the concertedness and aromatic character. Free-energy calculations also support the validity of the transition state theory for the present rearrangement reactions. The calculations demonstrate that cyclic delocalization represents a strong force to synchronize the thermal atomic motions even at high temperatures.

Two problems with variational expectation maximisation for time-series models

Variational methods are a key component of the approximate inference and learning toolbox. These methods fill an important middle ground, retaining distributional information about uncertainty in latent variables, unlike maximum a posteriori methods (MAP), and yet generally requiring less computational time than Monte Carlo Markov Chain methods. In particular the variational Expectation Maximisation (vEM) and variational Bayes algorithms, both involving variational optimisation of a free-energy, are widely used in time-series modelling. Here, we investigate the success of vEM in simple probabilistic time-series models. First we consider the inference step of vEM, and show that a consequence of the well-known compactness property of variational inference is a failure to propagate uncertainty in time, thus limiting the usefulness of the retained distributional information. In particular, the uncertainty may appear to be smallest precisely when the approximation is poorest. Second, we consider parameter learning and analytically reveal systematic biases in the parameters found by vEM. Surprisingly, simpler variational approximations (such a mean-field) can lead to less bias than more complicated structured approximations.

Improved switching uniformity and low-voltage operation in TaO x-based RRAM using Ge reactive layer

Significant improvements in the spatial and temporal uniformities of device switching parameters are successfully demonstrated in Ge/TaOx bilayer-based resistive switching devices, as compared with non-Ge devices. In addition, the reported Ge/TaOx devices also show significant reductions in the operation voltages. Influence of the Ge layer on the resistive switching of TaOx-based resistive random access memory is investigated by X-ray spectroscopy and the theory of Gibbs free energy. Higher uniformity is attributed to the confinement of the filamentary switching process. The presence of a larger number of interface traps, which will create a beneficial electric field to facilitate the drift of oxygen vacancies, is believed to be responsible for the lower operation voltages in the Ge/TaO x devices. © 1980-2012 IEEE.

Novel nanostructured biomaterials: implications for coronary stent thrombosis.

BACKGROUND: Nanomedicine has the potential to revolutionize medicine and help clinicians to treat cardiovascular disease through the improvement of stents. Advanced nanomaterials and tools for monitoring cell-material interactions will aid in inhibiting stent thrombosis. Although titanium boron nitride (TiBN), titanium diboride, and carbon nanotube (CNT) thin films are emerging materials in the biomaterial field, the effect of their surface properties on platelet adhesion is relatively unexplored. OBJECTIVE AND METHODS: In this study, novel nanomaterials made of amorphous carbon, CNTs, titanium diboride, and TiBN were grown by vacuum deposition techniques to assess their role as potential stent coatings. Platelet response towards the nanostructured surfaces of the samples was analyzed in line with their physicochemical properties. As the stent skeleton is formed mainly of stainless steel, this material was used as reference material. Platelet adhesion studies were carried out by atomic force microscopy and scanning electron microscopy observations. A cell viability study was performed to assess the cytocompatibility of all thin film groups for 24 hours with a standard immortalized cell line. RESULTS: The nanotopographic features of material surface, stoichiometry, and wetting properties were found to be significant factors in dictating platelet behavior and cell viability. The TiBN films with higher nitrogen contents were less thrombogenic compared with the biased carbon films and control. The carbon hybridization in carbon films and hydrophilicity, which were strongly dependent on the deposition process and its parameters, affected the thrombogenicity potential. The hydrophobic CNT materials with high nanoroughness exhibited less hemocompatibility in comparison with the other classes of materials. All the thin film groups exhibited good cytocompatibility, with the surface roughness and surface free energy influencing the viability of cells.

Spring-to-Spring Balancing as Energy-Free Adjustment Method in Gravity Equilibrators

Generally, adjustment of gravity equilibrator to a new payload requires energy, e.g. to increase the pre-load of the balancing spring. A novel way of energy-free adjustment of gravity equilibrators is possible by introducing the concept of a storage spring. The storage spring supplies or stores the energy necessary to adjust the balancer spring of the gravity equilibrator. In essence the storage spring mechanism maintains a constant potential energy within the spring mechanism; energy is exchanged between the storage and balancer spring when needed. Various conceptual designs using both zero-free-length springs and regular extension springs are proposed. Two models were manufactured demonstrating the practical embodiments and functionality.

An energy-efficient hopping robot based on free vibration of a curved beam

This paper explores a design strategy of hopping robots, which makes use of free vibration of an elastic curved beam. In this strategy, the leg structure consists of a specifically shaped elastic curved beam and a small rotating mass that induces free vibration of the entire robot body. Although we expect to improve energy efficiency of locomotion by exploiting the mechanical dynamics, it is not trivial to take advantage of the coupled dynamics between actuation and mechanical structures for the purpose of locomotion. From this perspective, this paper explains the basic design principles through modeling, simulation, and experiments of a minimalistic hopping robot platform. More specifically, we show how to design elastic curved beams for stable hopping locomotion and the control method by using unconventional actuation. In addition, we also analyze the proposed design strategy in terms of energy efficiency and discuss how it can be applied to the other forms of legged robot locomotion. © 1996-2012 IEEE.

Density, sp3 content and internal layering of DLC films by X-ray reflectivity and electron energy loss spectroscopy

A variety of hydrogenated and non-hydrogenated amorphous carbon thin films have been characterized by means of grazing-incidence X-ray reflectivity (XRR) to give information about their density, thickness, surface roughness and layering. We used XRR to validate the density of ta-C, ta-C:H and a-C:H films derived from the valence plasmon in electron energy loss spectroscopy measurements, up to 3.26 and 2.39 g/cm3 for ta-C and ta-C:H, respectively. By comparing XRR and electron energy loss spectroscopy (EELS) data, we have been able for the first time to fit a common electron effective mass of m*/me = 0.87 for all amorphous carbons and diamond, validating the `quasi-free' electron approach to density from valence plasmon energy. While hydrogenated films are found to be substantially uniform in density across the film, ta-C films grown by the filtered cathodic vacuum arc (FCVA) show a multilayer structure. However, ta-C films grown with an S-bend filter show a high uniformity and only a slight dependence on the substrate bias of both sp3 and layering.

Energy scattering in weakly non-linear systems.

The Chinese Tam-Tam exhibits non-linear behavior in its vibro-acoustic response. The frequency content of the response during free, unforced vibration smoothly changes, with energy being progressively smeared out over a greater bandwidth with time. This is used as a motivating case for the general study of the phenomenon of energy cascading through weak nonlinearity. Numerical models based upon the Fermi-Pasta-Ulam system of non-linearly coupled oscillators, modified with the addition of damping, have been developed. These were used to study the response of ensembles of systems with randomized natural frequencies. Results from simulations will be presented here. For un-damped systems, individual ensemble members exhibit cyclical energy exchange between linear modes, but the ensemble average displays a steady state. For the ensemble response of damped systems, lightly damped modes can exhibit an effective damping which is higher than predicated by linear theory. The presence of a non-linearity provides a path for energy flow to other modes, increasing the apparent damping spectrum at some frequencies and reducing it at others. The target of this work is a model revealing the governing parameters of a generic system of this type and leading to predictions of the ensemble response.

Carbon nanostructure-based field-effect transistors for label-free chemical/biological sensors.

Over the past decade, electrical detection of chemical and biological species using novel nanostructure-based devices has attracted significant attention for chemical, genomics, biomedical diagnostics, and drug discovery applications. The use of nanostructured devices in chemical/biological sensors in place of conventional sensing technologies has advantages of high sensitivity, low decreased energy consumption and potentially highly miniaturized integration. Owing to their particular structure, excellent electrical properties and high chemical stability, carbon nanotube and graphene based electrical devices have been widely developed for high performance label-free chemical/biological sensors. Here, we review the latest developments of carbon nanostructure-based transistor sensors in ultrasensitive detection of chemical/biological entities, such as poisonous gases, nucleic acids, proteins and cells.

Enzyme-free glucose biosensor based on low density CNT forest grown directly on a Si/SiO2 substrate

A highly sensitive nonenzymatic amperometric glucose sensor was fabricated by using Ni nanoparticles homogeneously dispersed within and on the top of a vertically aligned CNT forest (CNT/Ni nanocomposite sensor), which was directly grown on a Si/SiO2 substrate. The surface morphology and elemental analysis were characterized using scanning electron microscopy and energy dispersive spectroscopy, respectively. Cyclic voltammetry and chronoamperometry were used to evaluate the catalytic activities of CNT/Ni electrode. The CNT/Ni nanocomposite sensor exhibited a great enhancement of anodic peak current after adding 5 mM glucose in alkaline solution. The sensor can also be applied to the quantification of glucose content with a linear range covering from 5 μM to 7 mM, a high sensitivity of 1433 μA mM-1 cm-2, and a low detection limit of 2 μM. The CNT/Ni nanocomposite sensor exhibits good reproducibility and long-term stability, moreover, it was also relatively insensitive to commonly interfering species, such as uric acid, ascorbic acid, acetaminophen, sucrose and d-fructose. © 2013 Elsevier B.V.

Taper-free and vertically oriented Ge nanowires on Ge/Si substrates grown by a two-temperature process

Taper-free and vertically oriented Ge nanowires were grown on Si (111) substrates by chemical vapor deposition with Au nanoparticle catalysts. To achieve vertical nanowire growth on the highly lattice mismatched Si substrate, a thin Ge buffer layer was first deposited, and to achieve taper-free nanowire growth, a two-temperature process was employed. The two-temperature process consisted of a brief initial base growth step at high temperature followed by prolonged growth at lower temperature. Taper-free and defect-free Ge nanowires grew successfully even at 270 °C, which is 90 °C lower than the bulk eutectic temperature. The yield of vertical and taper-free nanowires is over 90%, comparable to that of vertical but tapered nanowires grown by the conventional one-temperature process. This method is of practical importance and can be reliably used to develop novel nanowire-based devices on relatively cheap Si substrates. Additionally, we observed that the activation energy of Ge nanowire growth by the two-temperature process is dependent on Au nanoparticle size. The low activation energy (∼5 kcal/mol) for 30 and 50 nm diameter Au nanoparticles suggests that the decomposition of gaseous species on the catalytic Au surface is a rate-limiting step. A higher activation energy (∼14 kcal/mol) was determined for 100 nm diameter Au nanoparticles which suggests that larger Au nanoparticles are partially solidified and that growth kinetics become the rate-limiting step. © 2011 American Chemical Society.

Multi-objective optimisation of horizontal axis wind turbine structure and energy production using aerofoil and blade properties as design variables

The design of wind turbine blades is a true multi-objective engineering task. The aerodynamic effectiveness of the turbine needs to be balanced with the system loads introduced by the rotor. Moreover the problem is not dependent on a single geometric property, but besides other parameters on a combination of aerofoil family and various blade functions. The aim of this paper is therefore to present a tool which can help designers to get a deeper insight into the complexity of the design space and to find a blade design which is likely to have a low cost of energy. For the research we use a Computational Blade Optimisation and Load Deflation Tool (CoBOLDT) to investigate the three extreme point designs obtained from a multi-objective optimisation of turbine thrust, annual energy production as well as mass for a horizontal axis wind turbine blade. The optimisation algorithm utilised is based on Multi-Objective Tabu Search which constitutes the core of CoBOLDT. The methodology is capable to parametrise the spanning aerofoils with two-dimensional Free Form Deformation and blade functions with two tangentially connected cubic splines. After geometry generation we use a panel code to create aerofoil polars and a stationary Blade Element Momentum code to evaluate turbine performance. Finally, the obtained loads are fed into a structural layout module to estimate the mass and stiffness of the current blade by means of a fully stressed design. For the presented test case we chose post optimisation analysis with parallel coordinates to reveal geometrical features of the extreme point designs and to select a compromise design from the Pareto set. The research revealed that a blade with a feasible laminate layout can be obtained, that can increase the energy capture and lower steady state systems loads. The reduced aerofoil camber and an increased L/. D-ratio could be identified as the main drivers. This statement could not be made with other tools of the research community before. © 2013 Elsevier Ltd.