Weak interactions involving organic fluorine: analysis of structural motifs in Flunazirine and Haloperidol

The crystal structure of Flunazirine, an anticonvulsant drug, is analyzed in terms of intermolecular interactions involving fluorine. The structure displays motifs formed by only weak interactions C–H⋯F and C–H⋯π. The motifs thus generated show cavities, which could serve as hosts for complexation. The structure of Flunazirine displays cavities formed by C–H⋯F and C–H⋯π interactions. Haloperidol, an antipsychotic drug, shows F⋯F interactions in the crystalline lattice in lieu of Cl⋯Cl interactions. However, strong O–H⋯N interactions dominate packing. The salient features of the two structures in terms of intermolecular interactions reveal, even though organic fluorine has lower tendency to engage in hydrogen bonding and F⋯F interactions, these interactions could play a significant role in the design of molecular assemblies via crystal engineering.

Weak C-H center dot center dot center dot O hydrogen bonds in anisaldehyde, salicylaldehyde and cinnamaldehyde

In situ cryocrystallization has been employed to grow single crystals of 4-methoxybenzaldehyde (anisaldehyde), C(8)H(8)O(2), 2-hydroxybenzaldehyde (salicylaldehyde), C(7)H(6)O(2), and (2E)-3-phenylprop-2-enal (cinnamaldehyde), C(9)H(8)O, all of which are liquids at room temperature. Several weak C-H center dot center dot center dot O interactions of the types C(aryl)-H center dot center dot center dot O, C(formyl)-H center dot center dot center dot O and Csp(3)-H center dot center dot center dot O are present in these related crystal structures.

Evolution of sub-micron grain size and weak texture in magnesium alloy Mg-3Al-0.4Mn by a modified multi-axial forging process

This is the first successful attempt to produce simultaneously ultrafine grain size and weak texture in a single-phase magnesium alloy Mg-3Al-0.4Mn through an optimal choice of processing parameters in a modified multi-axial forging (MAF) process. An average grain size of similar to 0.4 mu m and a weak texture could be achieved. This has led to an increase in the strength as well as room-temperature ductility (55%). The plot of the yield loci shows a decrease in anisotropy after MAF. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Presence of dark energy and dark matter: does cosmic acceleration signifies a weak gravitational collapse?

In this work the collapsing process of a spherically symmetric star, made of dust cloud, in the background of dark energy is studied for two different gravity theories separately, i.e., DGP Brane gravity and Loop Quantum gravity. Two types of dark energy fluids, namely, Modified Chaplygin gas and Generalised Cosmic Chaplygin gas are considered for each model. Graphs are drawn to characterize the nature and the probable outcome of gravitational collapse. A comparative study is done between the collapsing process in the two different gravity theories. It is found that in case of dark matter, there is a great possibility of collapse and consequent formation of Black hole. In case of dark energy possibility of collapse is far lesser compared to the other cases, due to the large negative pressure of dark energy component. There is an increase in mass of the cloud in case of dark matter collapse due to matter accumulation. The mass decreases considerably in case of dark energy due to dark energy accretion on the cloud. In case of collapse with a combination of dark energy and dark matter, it is found that in the absence of interaction there is a far better possibility of formation of black hole in DGP brane model compared to Loop quantum cosmology model.

Cavitation in materials with distributed weak zones: Implications on the origin of brittle fracture in metallic glasses

Several experimental studies have shown that fracture surfaces in brittle metallic glasses (MGs) generally exhibit nanoscale corrugations which may be attributed to the nucleation and coalescence of nanovoids during crack propagation. Recent atomistic simulations suggest that this phenomenon is due to large spatial fluctuations in material properties in a brittle MG, which leads to void nucleation in regions of low atomic density and then catastrophic fracture through void coalescence. To explain this behavior, we propose a model of a heterogeneous solid containing a distribution of weak zones to represent a brittle MG. Plane strain continuum finite element analysis of cavitation in such an elastic-plastic solid is performed with the weak zones idealized as periodically distributed regions having lower yield strength than the background material. It is found that the presence of weak zones can significantly reduce the critical hydrostatic stress for the onset of cavitation which is controlled uniquely by the local yield properties of these zones. Also, the presence of weak zones diminishes the sensitivity of the cavitation stress to the volume fraction of a preexisting void. These results provide plausible explanations for the observations reported in recent atomistic simulations of brittle MGs. An analytical solution for a composite, incompressible elastic-plastic solid with a weak inner core is used to investigate the effect of volume fraction and yield strength of the core on the nature of cavitation bifurcation. It is shown that snap-cavitation may occur, giving rise to sudden formation of voids with finite size, which does not happen in a homogeneous plastic solid. (c) 2012 Elsevier Ltd. All rights reserved.

Bimetallic core-shell nanocomposites using weak reducing agent and their transformation to alloy nanostructures

An in situ seeding growth methodology towards the preparation of core-shell nanoparticles composed of noble metals has been developed by employing trimethylamine borane (TMAB) as the reducing agent. Being a weak reducing agent, TMAB is able to distinguish the smallest reduction potential window of any two metals which renders selective reduction of metal ions thus affording a core-shell architecture of the nanoparticles. A dramatic effect of solvent was noted during the reduction of Ag+ ions: an immediate reduction took place at room temperature when dry THF was used as solvent however, usage of wet THF (THF used directly from the bottle) brings out the reduction only at reflux conditions. In the case of Au and Pd nanoparticles, preparation was found to be independent of the quality of solvent used. Au nanoparticles are realized at room temperature whereas reflux conditions are required in the case of Pd nanoparticles. This difference in behavior of the monometallic nanoparticles was successfully exploited to construct different noble metal nanoparticles with core-shell architectures such as Au@Ag, Ag@Au, and Ag@Pd. Transformation of these core-shell nanoparticles to their thermodynamically stable alloy counterparts is also demonstrated under very mild conditions reported to date.

The Role of Weak Interactions in the Phase Transition and Distinct Mechanical Behavior of Two Structurally Similar Caffeine Co-crystal Polymorphs Studied by Nanoindentation

Although weak interactions, such as C-H center dot center dot center dot O and pi-stacking, are generally considered to be insignificant, it is their reorganization that holds the key for many a solid-state phenomenon, such as phase transitions, plastic deformation, elastic flexibility, and mechanochromic luminescence in solid-state fluorophores. Despite this, the role of weak interactions in these dynamic phenomena is poorly understood. In this study, we investigate two co-crystal polymorphs of caffeine:4-chloro-3-nitrobenzoic acid, which have close structural similarity (2D layered structures), but surprisingly show distinct mechanical behavior. Form I is brittle, but shows shear-induced phase instability and, upon grinding, converts to Form II, which is soft and plastically shearable. This observation is in contrast to those reported in earlier studies on aspirin, wherein the metastable drug forms are softer and convert to stable and harder forms upon stressing To establish a molecular level understanding, have investigated the two co-crystal polymorphs I and II by single crystal X-ray diffraction, nanoindentation to quantify mechanical properties, and theoretical calculations. The lower hardness (from nanoindentation) and smooth potential surfaces (from theoretical studies) for shearing of layers in Form II allowed us to rationalize the role of stronger intralayer (sp(2))C-H center dot center dot center dot O and nonspecific interlayer pi-stacking interactions in the structure of II. Although the Form I also possesses the same type of interactions, its strength is clearly opposite, that is, weaker intralayer (sp(3))C-H center dot center dot center dot O and specific interlayer pi-stacking interactions. Hence, Form I is harder than Form IL Theoretical calculations and indentation on (111) of Form I suggested the low resistance of this face to mechanical stress; thus, Form I converts to II upon mechanical action. Hence, our approach demonstrates the usefulness of multiple techniques for establishing the role of weak noncovalent interactions in solid-state dynamic phenomena, such as stress induced phase transformation, and hence is important in the context of solid-state pharmaceutical chemistry and crystal engineering.

Designing Ternary Co-crystals with Stacking Interactions and Weak Hydrogen Bonds. 4,4 `-Bis-hydroxyazobenzene

Three ternary co-crystals of the title compound are reported. The design strategy hinges on the identification of a robust synthon with O-H center dot center dot center dot N hydrogen bonds in a binary co-crystal. Construction of this module allows the tuning of pi center dot center dot center dot pi stacking interactions and weak hydrogen bonds to incorporate the third component into the crystal structure. Screening of various co-formers showed that a delicate balance of electrostatics is required for stacking to favor the formation of ternaries. A C-H center dot center dot center dot N hydrogen-bonded motif was also found to occur repetitively in the ternary co-crystals. The directional nature of weak hydrogen bonds allows them to be used effectively in this study.

Reversible and irreversible pH induced conformational changes in self-assembled weak polyelectrolyte multilayers probed using etched fiber Bragg grating sensors

Polyelectrolytes are charged polymer species which electrostatically adsorb onto surfaces in a layer by layer fashion leading to the sequential assembly of multilayer structures. It is known that the morphology of weak polyelectrolyte structures is strongly influenced by environmental variables such as pH. We created a weak polyelectrolyte multilayer structure (similar to 100 nm thick) of cationic polymer poly-allylamine hydrochloride (PAH) and an anionic polymer poly-acrylic acid (PAA) on an etched clad fiber Bragg grating (EFBG) to study the pH induced conformational transitions in the polymer multilayers brought about by the variation in charge density of weak polyelectrolyte groups as a function of pH. The conformational changes of the polyelectrolyte multilayer structure lead to changes in optical density of the adsorbed film which reflects in the shift of the Bragg wavelength from the EFBG. Using the EFBG system we were able to probe reversible and irreversible pH induced transitions in the PAH/PAA weak polyelectrolyte system. (C) 2014 Elsevier B.V. All rights reserved.

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.

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.