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.

Efficient Low Complexity Power Allocation Policies for Wireless Communication Systems Guaranteeing QoS

We consider near-optimal policies for a single user transmitting on a wireless channel which minimize average queue length under average power constraint. The power is consumed in transmission of data only. We consider the case when the power used in transmission is a linear function of the data transmitted. The transmission channel may experience multipath fading. Later, we also extend these results to the multiuser case. We show that our policies can be used in a system with energy harvesting sources at the transmitter. Next we consider data users which require minimum rate guarantees. Finally we consider the system which has both data and real time users. Our policies have low computational complexity, closed form expression for mean delays and require only the mean arrival rate with no queue length information.

Secure Communication in Amplify-and-Forward Networks with Multiple Eavesdroppers: Decoding with SNR Thresholds

The problem of secure unicast communication over a two hop Amplify-and-Forward wireless relay network with multiple eavesdroppers is considered. Assuming that a receiver (destination or eavesdropper) can decode a message only if the received SNR is above a predefined threshold, we consider this problem in two scenarios. In the first scenario, we maximize the SNR at the legitimate destination, subject to the condition that the received SNR at each eavesdropper is below the target threshold. Due to the non-convex nature of the objective function and eavesdroppers' constraints, we transform variables and obtain a quadratically constrained quadratic program (QCQP) with convex constraints, which can be solved efficiently. When the constraints are not convex, we consider a semidefinite relaxation (SDR) to obtain computationally efficient approximate solution. In the second scenario, we minimize the total power consumed by all relay nodes, subject to the condition that the received SNR at the legitimate destination is above the threshold and at every eavesdropper, it is below the corresponding threshold. We propose a semidefinite relaxation of the problem in this scenario and also provide an analytical lower bound.

Efficient Protocol for Authenticated Email Search

Executing authenticated computation on outsourced data is currently an area of major interest in cryptology. Large databases are being outsourced to untrusted servers without appreciable verification mechanisms. As adversarial server could produce erroneous output, clients should not trust the server's response blindly. Primitive set operations like union, set difference, intersection etc. can be invoked on outsourced data in different concrete settings and should be verifiable by the client. One such interesting adaptation is to authenticate email search result where the untrusted mail server has to provide a proof along with the search result. Recently Ohrimenko et al. proposed a scheme for authenticating email search. We suggest significant improvements over their proposal in terms of client computation and communication resources by properly recasting it in two-party settings. In contrast to Ohrimenko et al. we are able to make the number of bilinear pairing evaluation, the costliest operation in verification procedure, independent of the result set cardinality for union operation. We also provide an analytical comparison of our scheme with their proposal which is further corroborated through experiments.

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.

A comparative phase 1 clinical trial to identify anti-infective mechanisms of vitamin D in people with HIV infection

Objectives:To determine if there is a biological mechanism that explains the association between HIV disease progression and increased mortality with low circulating vitamin D levels; specifically, to determine if restoring vitamin D levels induced T-cell functional changes important for antiviral immunity.Design:This was a pilot, open-label, three-arm prospective phase 1 study.Methods:We recruited 28 patients with low plasma vitamin D (<50nmol/l 25-hydroxyvitamin D3), comprising 17 HIV+ patients (11 on HAART, six treatment-naive) and 11 healthy controls, who received a single dose of 200000IU oral cholecalciferol. Advanced T-cell flow cytometry methods measured CD4(+) T-cell function associated with viral control in blood samples at baseline and 1-month after vitamin D supplementation.Results:One month of vitamin D supplementation restored plasma levels to sufficiency (>75nmol/l) in 27 of 28 patients, with no safety issues. The most striking change was in HIV+ HAART+ patients, where increased frequencies of antigen-specific T cells expressing macrophage inflammatory protein (MIP)-1 - an important anti-HIV blocking chemokine - were observed, with a concomitant increase in plasma MIP-1, both of which correlated significantly with vitamin D levels. In addition, plasma cathelicidin - a vitamin D response gene with broad antimicrobial activity - was enhanced.Conclusion:Vitamin D supplementation modulates disease-relevant T-cell functions in HIV-infected patients, and may represent a useful adjunct to HAART therapy. Copyright (C) 2015 Wolters Kluwer Health, Inc. All rights reserved.

High frequency millimetre wave absorbers derived from polymeric nanocomposites

The world has dominated by automation, wireless communication and various electronic equipments, which has led to the most undesirable offshoots like electromagnetic (EM) pollution. The rationale is environmental concern and the necessity to develop EM absorbing materials. This paper reviews the state of the art of designing polymer based nanocomposites containing nanoscopic particles with high electrical conductivity and complex microwave properties for enhanced EM attenuation. Given the brevity of this review article, herein we have summarized the high frequency millimetre wave absorbing properties of polymer nanocomposites consisting of various nanoparticles that either reflect or absorb microwave radiation like electrically conducting carbon nanotubes (CNTs) and graphene nanosheets (GNs), high dielectric constant ceramic nanoparticles that show relaxation loss in the microwave frequency and magnetic metal and ferrite nanoparticles that absorb microwave radiation through natural resonance, eddy current and hysteresis losses. Furthermore, we have stressed the necessity and impact of hybrid nanoparticles consisting of magnetic and dielectric nanoparticles along with conducting inclusions like CNT and GNs in this review. Electromagnetic interference (EMI) theory and necessary criterion for attenuation has been briefly discussed. The emphasis is made on various mechanisms towards EM attenuation controlled by these nanoparticles. Various structures developed using polymer nanocomposites like bulk, foam and layered structures and their effect on EM attenuation has been elaborately discussed. In addition, various covalent/non-covalent modifications on nanoparticles have been juxtaposed in context to EM attenuation. In addition, we have highlighted important facets and direction for enhancing the microwave attenuation. (C) 2016 Elsevier Ltd. All rights reserved.

Three-dimensional warping in strip-based composite four-bar mechanisms

This work intends to demonstrate the effect of geometrically non-linear cross-sectional analysis of certain composite beam-based four-bar mechanisms in predicting the three-dimensional warping of the cross-section. The only restriction in the present analysis is that the strains within each elastic body remain small (i.e., this work does not deal with materials exhibiting non-linear constitutive laws at the 3-D level). Here, all component bars of the mechanism are made of fiber-reinforced laminates. They could, in general, be pre-twisted and/or possess initial curvature, either by design or by defect. Each component of the mechanism is modeled as a beam based on geometrically non-linear 3-D elasticity theory. The component problems are thus split into 2-D analyses of reference beam cross-sections and non-linear 1-D analyses along the three beam reference curves. The splitting of the three-dimensional beam problem into two- and one-dimensional parts, called dimensional reduction, results in a tremendous savings of computational effort relative to the cost of three-dimensional finite element analysis, the only alternative for realistic beams. The analysis of beam-like structures made of laminated composite materials requires a much more complicated methodology. Hence, the analysis procedure based on Variational Asymptotic Method (VAM), a tool to carry out the dimensional reduction, is used here. The representative cross-sections of all component bars are analyzed using two different approaches: (1) Numerical Model and (2) Analytical Model. Four-bar mechanisms are analyzed using the above two approaches for Omega = 20 rad/s and Omega = pi rad/s and observed the same behavior in both cases. The noticeable snap-shots of the deformation shapes of the mechanism about 1000 frames are also reported using commercial software (I-DEAS + NASTRAN + ADAMS). The maximum out-of-plane warping of the cross-section is observed at the mid-span of bar-1, bar-2 and bar-3 are 1.5 mm, 250 mm and 1.0 mm, respectively, for t = 0:5 s. (C) 2015 Elsevier Ltd. All rights reserved.

AN INVESTIGATION OF CUTTING MECHANISMS AND STRAIN FIELDS DURING ORTHOGONAL CUTTING IN CFRPs

Fiber-reinforced plastics (FRPs) are typically difficult to machine due to their highly heterogeneous and anisotropic nature and the presence of two phases (fiber and matrix) with vastly different strengths and stiffnesses. Typical machining damage mechanisms in FRPs include series of brittle fractures (especially for thermosets) due to shearing and cracking of matrix material, fiber pull-outs, burring, fuzzing, fiber-matrix debonding, etc. With the aim of understanding the influence of the pronounced heterogeneity and anisotropy observed in FRPs, ``Idealized'' Carbon FRP (I-CFRP) plates were prepared using epoxy resin with embedded equispaced tows of carbon fibers. Orthogonal cutting of these I-CFRPs was carried out, and the chip formation characteristics, cutting force signals and strain distributions obtained during machining were analyzed using the Digital Image Correlation (DIC) technique. In addition, the same procedure was repeated on Uni-Directional CFRPs (UD-CFRPs). Chip formation mechanisms in FRPs were found to depend on the depth of cut and fiber orientation with pure epoxy showing a pronounced ``size effect.'' Experimental results indicate that in-situ full field strain measurements from DIC coupled with force measurements using dynamometry provide an adequate measure of anisotropy and heterogeneity during orthogonal cutting.