Excited electronic state decomposition mechanisms of clusters of dimethylnitramine and aluminum

In this report, electronically non-adiabatic decomposition pathways of clusters of dimethylnitramine and aluminum (DMNA-Al and DMNA-Al-2) are discussed in comparison to isolated dimethylnitramine (DMNA). Electronically excited state processes of DMNA-Al and DMNA-Al-2 are explored using the complete active space self-consistent field (CASSCF) and the restricted active space self-consistent field (RASSCF) theories, respectively. Similar to the nitro-nitrite isomerization reaction pathway of DMNA, DMNA-Al-n clusters also exhibit isomerization pathway. However, it involves several other steps, such as, first Al-O bond dissociation, then N-N bond dissociation followed by isomerization and finally NO elimination. Furthermore, DMNA-Al-n clusters exhibit overall exothermic decomposition reaction pathway and isolated DMNA shows overall endothermic reaction channel.

Fracture in metallic glasses: mechanics and mechanisms

Significant progress in understanding the mechanical behavior of metallic glasses (MGs) was made over the past decade, particularly on mechanisms of plastic deformation. However, recent research thrust has been on exploring the mechanics and physics of fracture. MGs can be very brittle with K-Ic values similar to silicate glasses and ceramics or very tough with K-Ic akin to high toughness crystalline metals. Even the tough MGs can become brittle with structural relaxation following annealing at temperatures close to glass transition temperature (T-g). Detailed experimental studies coupled with complementary numerical simulations of the recent past have provided insights on the micromechanisms of failure as well as nature of crack tip fields, and established the governing fracture criteria for ductile and brittle glasses. In this paper, the above advances are reviewed and outstanding issues in the context of fracture of amorphous alloys that need to be resolved are identified.

Restoration Mechanisms During the Friction Stir Processing of Aluminum Alloys

In the current study, correlation of microstructure evolution with bulk crystallographic texture formation during friction stir processing (FSP) of commercial aluminum alloys has been attempted. Electron back-scattered diffraction and X-ray diffraction techniques were employed for characterizing the nugget zone of optimum friction stir processed samples. Volume fraction of measured texture components revealed that the texture formation in aluminum alloys is similar irrespective of the alloy composition. Recrystallization behavior during FSP was more of a composition dependent phenomenon.

Micro-scale composite compliant mechanisms for evaluating the bulk stiffness of MCF-7 cells

Biomechanical assays offer a good alternative to biochemical assays in diagnosing disease states and assessing the efficacy of drugs. In view of this, we have developed a miniature compliant tool to estimate the bulk stiffness of cells, particularly MCF-7 (Michigan Cancer Foundation) cells whose diameter is 12-15 mu m in suspension. The compliant tool comprises a gripper and a displacement-amplifying compliant mechanism (DaCM), where the former helps in grasping the cell and the latter enables vision-based force-sensing. A DaCM is necessary because the microscope's field of view at the required magnification is not sufficient to simultaneously observe the cell and the movement of a point on the gripper, in order to estimate the force. Therefore, a DaCMis strategically embedded within an existing gripper design leading to a composite compliant mechanism. The DaCM is designed using the kinetoelastostatic map technique to achieve a 42 nN resolution of the force. The gripper, microfabricated with SU-8 using photolithography, is within the footprint of about 10 mm by 10 mm with the smallest feature size of about 5 mu m. The experiments with MCF-7 cells suggest that the bulk stiffness of these is in the range of 8090 mN/m. The details of design, prototyping and testing comprise the paper. (C) 2015 Elsevier Ltd. All rights reserved.

MODELING AND SIMULATION OF A THREE-WHEELED MOBILE ROBOT ON UNEVEN TERRAINS WITH TWO-DEGREE-OF-FREEDOM SUSPENSION MECHANISMS

A wheeled mobile robot (WMR) will move on an uneven terrain without slip if its torus-shaped wheels tilt in a lateral direction. An independent two degree-of-freedom (DOF) suspension is required to maintain contact with uneven terrain and for lateral tilting. This article deals with the modeling and simulation of a three-wheeled mobile robot with torus-shaped wheels and four novel two-DOF suspension mechanism concepts. Simulations are performed on an uneven terrain for three representative pathsa straight line, a circular, and an S'-shaped path. Simulations show that a novel concept using double four-bar mechanism performs better than the other three concepts.

Damage mechanisms in stainless steel and chromium carbide coatings under controlled environment fretting conditions

Fretting is of a serious concern in many industrial components, specifically, in nuclear industry for the safe and reliable operation of various component and/or system. Under fretting condition small amplitude oscillations induce surface degradation in the form of surface cracks and/or surface wear. Comprehensive experimental studies have been carried out simulating different fretting regimes under ambient and vacuum (10(-9) MPa) conditions and, temperature up to 400 degrees C. Studies have been carried out with stainless steel spheres on stainless steel flats, and stainless steel spheres against chromium carbide, with 25% nickel chrome binder coatings. Mechanical responses are correlated with the damage observed. It has been observed that adhesion plays a vital role in material degradation process, and its effectiveness depends on mechanical variables such as normal load, interfacial tangential displacement, characteristics of the contacting bodies and most importantly on the environment conditions. Material degradation mechanism for ductile materials involved severe plastic deformation, which results in the initiation or nucleation of cracks. Ratcheting has been observed as the governing damage mode for crack nucleation under cyclic tangential loading condition. Further, propagation of the cracks has been observed under fatigue and their orientation has been observed to be governed by the contact conditions prevailing at the contact interface. Coated surfaces show damage in the form of brittle fracture and spalling of the coatings. Existence of stick slip has been observed under high normal load and low displacement amplitude. It has also been observed that adhesion at the contact interface and instantaneous cohesive strength of the contacting bodies dictates the occurrence of material transfer. The paper discusses the mechanics and mechanisms involved in fretting damage under controlled environment conditions. (C) 2015 Elsevier B.V. All rights reserved.

Multifarious facets of sugar-derived molecular gels: molecular features, mechanisms of self-assembly and emerging applications

The remarkable capability of nature to design and create excellent self-assembled nano-structures, especially in the biological world, has motivated chemists to mimic such systems with synthetic molecular and supramolecular systems. The hierarchically organized self-assembly of low molecular weight gelators (LMWGs) based on non-covalent interactions has been proven to be a useful tool in the development of well-defined nanostructures. Among these, the self-assembly of sugar-derived LMWGs has received immense attention because of their propensity to furnish biocompatible, hierarchical, supramolecular architectures that are macroscopically expressed in gel formation. This review sheds light on various aspects of sugar-derived LMWGs, uncovering their mechanisms of gelation, structural analysis, and tailorable properties, and their diverse applications such as stimuli-responsiveness, sensing, self-healing, environmental problems, and nano and biomaterials synthesis.

Coupled Mechanisms of Precipitation and Atomization in Burning Nanofluid Fuel Droplets

Understanding the combustion characteristics of fuel droplets laden with energetic nanoparticles (NP) is pivotal for lowering ignition delay, reducing pollutant emissions and increasing the combustion efficiency in next generation combustors. In this study, first we elucidate the feedback coupling between two key interacting mechanisms, namely, secondary atomization and particle agglomeration; that govern the effective mass fraction of NPs within the droplet. Second, we show how the initial NP concentration modulates their relative dominance leading to a masterslave configuration. Secondary atomization of novel nanofuels is a crucial process since it enables an effective transport of dispersed NPs to the flame (a pre-requisite condition for NPs to burn). Contrarily, NP agglomeration at the droplet surface leads to shell formation thereby retaining NPs inside the droplet. In particular, we show that at dense concentrations shell formation (master process) dominates over secondary atomization (slave) while at dilute particle loading it is the high frequency bubble ejections (master) that disrupt shell formation (slave) through its rupture and continuous outflux of NPs. This results in distinct combustion residues at dilute and dense concentrations, thereby providing a method of manufacturing flame synthesized microstructures with distinct morphologies.

Mycobacterium tuberculosis RecG Protein but Not RuvAB or RecA Protein Is Efficient at Remodeling the Stalled Replication Forks IMPLICATIONS FOR MULTIPLE MECHANISMS OF REPLICATION RESTART IN MYCOBACTERIA

Aberrant DNA replication, defects in the protection, and restart of stalled replication forks are major causes of genome instability in all organisms. Replication fork reversal is emerging as an evolutionarily conserved physiological response for restart of stalled forks. Escherichia coli RecG, RuvAB, and RecA proteins have been shown to reverse the model replication fork structures in vitro. However, the pathways and the mechanisms by which Mycobacterium tuberculosis, a slow growing human pathogen, responds to different types of replication stress and DNA damage are unclear. Here, we show that M. tuberculosis RecG rescues E. coli Delta recG cells from replicative stress. The purified M. tuberculosis RecG (MtRecG) and RuvAB(MtRuvAB) proteins catalyze fork reversal of model replication fork structures with and without a leading strand single-stranded DNA gap. Interestingly, single-stranded DNA-binding protein suppresses the MtRecG- and MtRuvAB-mediated fork reversal with substrates that contain lagging strand gap. Notably, our comparative studies with fork structures containing template damage and template switching mechanism of lesion bypass reveal that MtRecG but not MtRuvAB or MtRecA is proficient in driving the fork reversal. Finally, unlike MtRuvAB, we find that MtRecG drives efficient reversal of forks when fork structures are tightly bound by protein. These results provide direct evidence and valuable insights into the underlying mechanism of MtRecG-catalyzed replication fork remodeling and restart pathways in vivo.

COMPOSITE AND MULTI-SCALE COMPLIANT MECHANISMS FOR MANIPULATION AND MECHANICAL CHARACTERIZATION

In this paper, we integrate two or more compliant mechanisms to get enhanced functionality for manipulating and mechanically characterizing the grasped objects of varied size (cm to sub-mm), stiffness (1e5 to 10 N/m), and materials (cement to biological cells). The concepts of spring-lever (SL) model, stiffness maps, and non-dimensional kinetoelastostatic maps are used to design composite and multi-scale compliant mechanisms. Composite compliant mechanisms comprise two or more different mechanisms within a single elastic continuum while multi-scale ones possess the additional feature of substantial difference in the sizes of the mechanisms that are combined into one. We present three applications: (i) a composite compliant device to measure the failure load of the cement samples; (ii) a composite multi-scale compliant gripper to measure the bulk stiffness of zebrafish embryos; and (iii) a compliant gripper combined with a negative-stiffness element to reduce the overall stiffness. The prototypes of all three devices are made and tested. The cement sample needed a breaking force of 22.5 N; the zebrafish embryo is found to have bulk stiffness of about 10 N/m; and the stiffness of a compliant gripper was reduced by 99.8 % to 0.2 N/m.

NON-DIMENSIONAL KINETOELASTOSTATIC MAPS FOR COMPLIANT MECHANISMS

How do we assess the capability of a compliant mechanism of given topology and shape? The kinetoelastostatic maps proposed in this paper help answer this question. These maps are drawn in 2D using two non-dimensional quantities, one capturing the nonlinear static response and the other the geometry, material, and applied forces. Geometrically nonlinear finite element analysis is used to create the maps for compliant mechanisms consisting of slender beams. In addition to the topology and shape, the overall proportions and the proportions of the cross-sections of the beam segments are kept fixed for a map. The finite region of the map is parameterized using a non-dimensional quantity defined as the slenderness ratio. The shape and size of the map and the parameterized curves inside it indicate the complete kinetoelastostatic capability of the corresponding compliant mechanism of given topology, shape, and fixed proportions. Static responses considered in this paper include input/output displacement, geometric amplification, mechanical advantage, maximum stress, etc. The maps can be used to compare mechanisms, to choose a suitable mechanism for an application, or re-design as may be needed. The usefulness of the non-dimensional maps is presented with multiple applications of different variety. Non-dimensional portrayal of snap-through mechanisms is one such example. The effect of the shape of the cross-section of the beam segments and the role of different segments in the mechanism as well as extension to 3D compliant mechanisms, the cases of multiple inputs and outputs, and moment loads are also explained. The effects of disproportionate changes on the maps are also analyzed.

Tungsten-based nanomaterials (WO3 & Bi2WO6): Modifications related to charge carrier transfer mechanisms and photocatalytic applications

Heterogeneous photocatalysis is an ideal green energy technology for the purification of wastewater. Although titania dominates as the reference photocatalyst, its wide band gap is a bottleneck for extended utility. Thus, search for non-TiO2 based nanomaterials has become an active area of research in recent years. In this regard, visible light absorbing polycrystalline WO3 (2.4-2.8 eV) and Bi2WO6 (2.8 eV) with versatile structure-electronic properties has gained considerable interest to promote the photocatalytic reactions. These materials are also explored in selective functional group transformation in organic reactions, because of low reduction and oxidation potential of WO3 CB and Bi2WO6 VB, respectively. In this focused review, various strategies such as foreign ion doping, noble metal deposition and heterostructuring with other semiconductors designed for efficient photocatalysis is discussed. These modifications not only extend the optical response to longer wavelengths, but also prolong the life-time of the charge carriers and strengthen the photocatalyst stability. The changes in the surface-bulk properties and the charge carrier transfer dynamics associated with each modification correlating to the high activity are emphasized. The presence of oxidizing agents, surface modification with Cu2+ ions and synthesis of exposed facets to promote the degradation rate is highlighted. In depth study on these nanomaterials is likely to sustain interest in wastewater remediation and envisaged to signify in various green energy applications. (C) 2015 Elsevier B.V. All rights reserved.

Role of different scattering mechanisms on the temperature dependence of transport in graphene

Detailed experimental and theoretical studies of the temperature dependence of the effect of different scattering mechanisms on electrical transport properties of graphene devices are presented. We find that for high mobility devices the transport properties are mainly governed by completely screened short range impurity scattering. On the other hand, for the low mobility devices transport properties are determined by both types of scattering potentials - long range due to ionized impurities and short range due to completely screened charged impurities. The results could be explained in the framework of Boltzmann transport equations involving the two independent scattering mechanisms.

Prediction of electronically nonadiabatic decomposition mechanisms of isolated gas phase nitrogen-rich energetic salt: Guanidium-triazolate

Electronically nonadiabatic decomposition pathways of guanidium triazolate are explored theoretically. Nonadiabatically coupled potential energy surfaces are explored at the complete active space self-consistent field (CASSCF) level of theory. For better estimation of energies complete active space second order perturbation theories (CASPT2 and CASMP2) are also employed. Density functional theory (DFT) with B3LYP functional and MP2 level of theory are used to explore subsequent ground state decomposition pathways. In comparison with all possible stable decomposition products (such as, N-2, NH3, HNC, HCN, NH2CN and CH3NC), only NH3 (with NH2CN) and N-2 are predicted to be energetically most accessible initial decomposition products. Furthermore, different conical intersections between the S-1 and S-0 surfaces, which are computed at the CASSCF(14,10)/6-31G(d) level of theory, are found to play an essential role in the excited state deactivation process of guanidium triazolate. This is the first report on the electronically nonadiabatic decomposition mechanisms of isolated guanidium triazolate salt. (C) 2015 Elsevier B.V. All rights reserved.