Computational Study of the Formation of Short Centrosymmetric N-center dot center dot center dot S Supramolecular Synthon and Related Weak Interactions in Crystalline 1,2,4-Triazoles

A comprehensive analysis of the crystal packing and the energetic features of a series of four biologically active molecules belonging to the family of substituted 4-(benzylideneamino)-3-(4-fluoro-3-phenoxyphenyl)-1H-1,2,4-triazole-5-(4 H)-thione derivatives have been performed based on the molecular conformation and the supramolecular packing. This involves the formation of a short centrosymmetric R-2(2)(8) NH...S supramolecular synthon in the solid state, including the presence of CH...S, CH...O, CH...N, CH...F, CH...Cl, CF...FC, CCl...ClC, and CH...pi intermolecular interactions along with pp stacking to evaluate the role of noncovalent interactions in the crystal. The presence of such synthons has a substantial contribution toward the interaction energy (-18 to -20 kcal/mol) as obtained from the PIXEL calculation, wherein the Coulombic and polarization contribution are more significant than the dispersion contribution. The geometrical characteristics of such synthons favor short distance, and the population of related molecules having these geometries is rare as has been obtained from the Cambridge Structural Database (CSD). Furthermore, their interaction energies have been compared with those present in our molecules in the solid state. The topological characteristics of the NH...S supramolecular synthon, in addition to related weak interactions, CH...N, CH...Cl, CF...FC, and CCl...ClC, have been estimated using the quantum theory of atoms in molecules (QTAIM). In addition, an analysis of the Hirshfeld surface and associated fingerprint plots of these four molecules also have provided a platform for the evaluation of the contribution of different atom...atom contacts, which contribute toward the packing of the molecules in solids.

Cavitation in brittle metallic glasses - Effects of stress state and distributed weak zones

Experimental studies and atomistic simulations have shown that brittle metallic glasses fail by a cavitation mechanism whose origin has been traced to the presence of intrinsic atomic density fluctuations which give rise to weak zones with reduced yield strength. It has been shown recently through continuum analysis that the presence of these zones can lower the cavitation stress considerably under equibiaxial loading. The objective of the present work is to study the effect of the applied stress state on the cavitation behavior of such a heterogeneous plastic solid with distributed weak zones. To this end, 2D plane strain finite element simulations are performed by subjecting a unit cell containing a weak zone to different (biaxiality) stress ratios. The volume fraction and yield strength of the weak zone are varied over a wide range. The results show that unlike in a homogeneous plastic solid, the cavitation stress of the heterogeneous aggregate does not reduce appreciably as the stress ratio decreases from unity when the yield strength of the weak zone is low. It is found that a non-dimensional parameter characterizing the stress state prevailing in the weak zone and its yield properties uniquely control the cavitation stress. The nature of cavitation bifurcation may change from unstable bifurcation to the left at sufficiently low stress ratio to one involving snap cavitation at high stress ratio. (C) 2014 Elsevier Ltd. All rights reserved.

Dissociation Constants of Weak Acids from ab Initio Molecular Dynamics Using Metadynamics: Influence of the Inductive Effect and Hydrogen Bonding on pK(a) Values

The theoretical estimation of the dissociation constant, or pK(a), of weak acids continues to be a challenging field. Here, we show that ab initio CarParrinello molecular dynamics simulations in conjunction with metadynamics calculations of the free-energy profile of the dissociation reaction provide reasonable estimates of the pK(a) value. Water molecules, sufficient to complete the three hydration shells surrounding the acid molecule, were included explicitly in the computation procedure. The free-energy profiles exhibit two distinct minima corresponding to the dissociated and neutral states of the acid, and the difference in their values provides the estimate for pK(a). We show for a series of organic acids that CPMD simulations in conjunction with metadynamics can provide reasonable estimates of pK(a) values. The acids investigated were aliphatic carboxylic acids, chlorine-substituted carboxylic acids, cis- and trans-butenedioic acid, and the isomers of hydroxybenzoic acid. These systems were chosen to highlight that the procedure could correctly account for the influence of the inductive effect as well as hydrogen bonding on pK(a) values of weak organic acids. In both situations, the CPMD metadynamics procedure faithfully reproduces the experimentally observed trend and the magnitudes of the pK(a) values.

Secure Transmission in Cooperative Networks with Weak Eavesdroppers

In this letter, we propose a scheme to improve the secrecy rate of cooperative networks using Analog Network Coding (ANC). ANC mixes the signals in the air; the desired signal is then separated out, from the mixed signals, at the legitimate receiver using techniques like self interference subtraction and signal nulling, thereby achieving better secrecy rates. Assuming global channel state information, memoryless adversaries and the decode-and-forward strategy, we seek to maximize the average secrecy rate between the source and the destination, subject to an overall power budget. Then, exploiting the structure of the optimization problem, we compute its optimal solution. Finally, we use numerical evaluations to compare our scheme with the conventional approaches.

Spin-reorientation and weak ferromagnetism in antiferromagnetic TbMn0.5Fe0.5O3

Orthorhombic single crystals of TbMn0.5Fe0.5O3 are found to exhibit spin-reorientation, magnetization reversal, and weak ferromagnetism. Strong anisotropy effects are evident in the temperature dependent magnetization measurements along the three crystallographic axes a, b, and c. A broad magnetic transition is visible at T-N(Fe/Mn) = 286K due to paramagnetic to A(x)G(y)C(z) ordering. A sharp transition is observed at T-SR(Fe/Mn) = 28 K, which is pronounced along c axis in the form of a sharp jump in magnetization where the spins reorient to G(x)A(y)F(z) configuration. The negative magnetization observed below T-SR(Fe/Mn) along c axis is explained in terms of domain wall pinning. A component of weak ferromagnetism is observed in field-scans along c-axis but below 28 K. Field-induced steps-like transitions are observed in hysteresis measurement along b axis below 28 K. It is noted that no sign of Tb-order is discernible down to 2K. TbMn0.5Fe0.5O3 could be highlighted as a potential candidate to evaluate its magneto-dielectric effects across the magnetic transitions. (C) 2015 AIP Publishing LLC.

Pressure-induced structural phase transitions and phonon anomalies in ReO3: Raman and first-principles study

We report high-pressure Raman-scattering studies on single-crystal ReO3 up to 26.9 GPa at room temperature, complemented by first-principles density functional calculations to assign the modes and to develop understanding of the subtle features of the low-pressure phase transition. The pressure (P) dependence of phonon frequencies (omega) reveals three phase transitions at 0.6, 3, and 12.5 GPa with characteristic splitting and changes in the slope of omega(P). Our first-principles theoretical analysis confirms the role of the rotational modes of ReO6, M-3, to the lowest pressure structural transition, and shows that the transition from the Pm3m to the Im3 structure is a weak first-order transition, originating from the strong anharmonic coupling of the M-3 modes with the acoustic modes (strain).

An ultrastable conjugate of silver nanoparticles and protein formed through weak interactions

In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s(-1) implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 mu M and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems.

Origin of room temperature weak-ferromagnetism in antiferromagnetic Pb(Fe2/3W1/3)O-3 ceramic

We report the origin of room temperature weak ferromagnetic behavior of polycrystalline Pb(Fe2/3W1/3)O-3 (PFW) powder. The structure and magnetic properties of the ceramic powder prepared by a Columbite method were characterized by X-ray and neutron diffraction, Mossbauer spectroscopy and magnetization measurements. Rietveld analysis of diffraction data confirm the formation of single phase PFW, without traces of any parasitic pyrochlore phase. PFW was found to crystallize in the cubic structure at room temperature. The Rietveld refinement of neutron diffraction data measured at room temperature confirmed the G-type antiferromagnetic structure of PFW in our sample. However, along with the antiferromagnetic (AFM) ordering of the Fe spins, we have observed the existence of weak ferromagnetism at room temperature through: (i) a clear opening of hysteresis (M-H) loop, (ii) bifurcation of the field cooled and zero-field cooled susceptibility; supported by Mossbauer spectroscopy results. The P-E loop measurements showed a non-linear slim hysteresis loop at room temperature due to the electronic conduction through the local inhomogeneities in the PFW crystallites and the inter-particle regions. By corroborating all the magnetic measurements, especially the spin glass nature of the sample, with the conduction behavior of the sample, we report here that the observed ferromagnetism originates at these local inhomogeneous regions in the sample, where the Fe-spins are not perfectly aligned antiferromagnetically due to the compositional disordering. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Wear Behavior of Cooling Slope Rheocast A356 Al Alloy

In the present study, the dry sliding wear behavior of rheocast A356 Al alloys, cast using a cooling slope, as well as gravity cast A356 Al alloy have been investigated at a low sliding speed of 1ms(-1), against a hardened EN 31 disk at different loads. The wear mechanism involves microcutting-abrasion and adhesion at lower load for all of the alloys studied in the present work. On the other hand, at higher load, mainly adhesive wear along with oxide formation is observed for gravity cast A356 Al alloy and rheocast A356 Al alloy, cast using a 45 degrees slope angle. Unlike other alloys, 60 degrees slope rheocast A356 Al alloy is found to undergo mainly abrasive wear at higher load. Accordingly, the rheocast sample, cast using a 60 degrees cooling slope, exhibits a remarkably lower wear rate at higher load compared to gravity cast and 45 degrees slope rheocast samples. This is attributed to the dominance of abrasive wear at higher load in the case of rheocast A356 Al alloy cast using a 60 degrees slope. The presence of finer and more spherical primary Al grain morphology is found to resist adhesive wear in case of 60 degrees cooling slope processed rheocast alloy and thereby delay the transition of the wear regime from normal wear to severe wear.

Weak conservation of structural features in the interfaces of homologous transient protein-protein complexes

Residue types at the interface of protein-protein complexes (PPCs) are known to be reasonably well conserved. However, we show, using a dataset of known 3-D structures of homologous transient PPCs, that the 3-D location of interfacial residues and their interaction patterns are only moderately and poorly conserved, respectively. Another surprising observation is that a residue at the interface that is conserved is not necessarily in the interface in the homolog. Such differences in homologous complexes are manifested by substitution of the residues that are spatially proximal to the conserved residue and structural differences at the interfaces as well as differences in spatial orientations of the interacting proteins. Conservation of interface location and the interaction pattern at the core of the interfaces is higher than at the periphery of the interface patch. Extents of variability of various structural features reported here for homologous transient PPCs are higher than the variation in homologous permanent homomers. Our findings suggest that straightforward extrapolation of interfacial nature and inter-residue interaction patterns from template to target could lead to serious errors in the modeled complex structure. Understanding the evolution of interfaces provides insights to improve comparative modeling of PPC structures.

Stimuli-responsive weak polyelectrolyte multilayer films: A thin film platform for self triggered multi-drug delivery

Polyelectrolyte multilayer (PEM) thin film composed of weak polyelectrolytes was designed by layer-by-layer (LbL) assembly of poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) for multi-drug delivery applications. Environmental stimuli such as pH and ionic strength showed significant influence in changing the film morphology from pore-free smooth structure to porous structure and favored triggered release of loaded molecules. The film was successfully loaded with bovine serum albumin (BSA) and ciprofloxacin hydrochloride (CH) by modulating the porous polymeric network of the film. Release studies showed that the amount of release could be easily controlled by changing the environmental conditions such as pH and ionic strength. Sustained release of loaded molecules was observed up to 8 h. The fabricated films were found to be biocompatible with epithelial cells during in-vitro cell culture studies. PEM film reported here not only has the potential to be used as self-responding thin film platform for transdermal drug delivery, but also has the potential for further development in antimicrobial or anti-inflammatory coatings on implants and drug-releasing coatings for stents. (C) 2015 Elsevier B.V. All rights reserved.

A novel index for identification of weak nodes for reactive compensation to improve voltage stability

In this study, a new reactive power loss index (RPLI) is proposed for identification of weak buses in the system. This index is further used for determining the optimal locations for placement of reactive compensation devices in the power system for additional voltage support. The new index is computed from the reactive power support and loss allocation algorithm using Y-bus method for the system under intact condition and as well as critical/severe network contingencies cases. Fuzzy logic approach is used to select the important and critical/severe line contingencies from the contingency list. The inherent characteristics of the reactive power in system operation is properly addressed while determining the reactive power loss allocation to load buses. The proposed index is tested on sample 10-bus equivalent system and 72-bus practical equivalent system of Indian southern region power grid. The validation of the weak buses identification from the proposed index with that from other existing methods in the literature is carried out to demonstrate the effectiveness of the proposed index. Simulation results show that the identification of weak buses in the system from the new RPLI is completely non-iterative, thus requires minimal computational efforts as compared with other existing methods in the literature.

An evolutionary formalism for weak quantum measurements

Unitary evolution and projective measurement are fundamental axioms of quantum mechanics. Even though projective measurement yields one of the eigenstates of the measured operator as the outcome, there is no theory that predicts which eigenstate will be observed in which experimental run. There exists only an ensemble description, which predicts probabilities of various outcomes over many experimental runs. We propose a dynamical evolution equation for the projective collapse of the quantum state in individual experimental runs, which is consistent with the well-established framework of quantum mechanics. In case of gradual weak measurements, its predictions for ensemble evolution are different from those of the Born rule. It is an open question whether or not suitably designed experiments can observe this alternate evolution.

Anomalous transport at weak coupling

We evaluate the contribution of chiral fermions in d = 2, 4, 6, chiral bosons, a chiral gravitino like theory in d = 2 and chiral gravitinos in d = 6 to all the leading parity odd transport coefficients at one loop. This is done by using finite temperature field theory to evaluate the relevant Kubo formulae. For chiral fermions and chiral bosons the relation between the parity odd transport coefficient and the microscopic anomalies including gravitational anomalies agree with that found by using the general methods of hydrodynamics and the argument involving the consistency of the Euclidean vacuum. For the gravitino like theory in d = 2 and chiral gravitinos in d = 6, we show that relation between the pure gravitational anomaly and parity odd transport breaks down. From the perturbative calculation we clearly identify the terms that contribute to the anomaly polynomial, but not to the transport coefficient for gravitinos. We also develop a simple method for evaluating the angular integrals in the one loop diagrams involved in the Kubo formulae. Finally we show that charge diffusion mode of an ideal 2 dimensional Weyl gas in the presence of a finite chemical potential acquires a speed, which is equal to half the speed of light.

Continuum in the X-Z-Y Weak Bonds: Z= Main Group Elements

The Continuum in the variation of the X-Z bond length change from blue-shifting to red-shifting through zero-shifting in the X-Z---Y complex is inevitable. This has been analyzed by ab-initio molecular orbital calculations using Z= Hydrogen, Halogens, Chalcogens, and Pnicogens as prototypical examples. Our analysis revealed that, the competition between negative hyperconjugation within the donor (X-Z) molecule and Charge Transfer (CT) from the acceptor (Y) molecule is the primary reason for the X-Z bond length change. Here, we report that, the proper tuning of X-and Y-group for a particular Z-can change the blue-shifting nature of X-Z bond to zero-shifting and further to red-shifting. This observation led to the proposal of a continuum in the variation of the X-Z bond length during the formation of X-Z---Y complex. The varying number of orbitals and electrons available around the Z-atom differentiates various classes of weak interactions and leads to interactions dramatically different from the H-Bond. Our explanations based on the model of anti-bonding orbitals can be transferred from one class of weak interactions to another. We further take the idea of continuum to the nature of chemical bonding in general. (C) 2015 Wiley Periodicals, Inc.