Determination of favorable inter-particle interactions for formation of substitutionally ordered solid phases from a binary mixture of oppositely charged colloidal suspensions

The solid phase formed by a binary mixture of oppositely charged colloidal particles can be either substitutionally ordered or substitutionally disordered depending on the nature and strength of interactions among the particles. In this work, we use Monte Carlo molecular simulations along with the Gibbs-Duhem integration technique to map out the favorable inter-particle interactions for the formation of substitutionally ordered crystalline phases from a fluid phase. The inter-particle interactions are modeled using the hard core Yukawa potential but the method can be easily extended to other systems of interest. The study obtains a map of interactions depicting regions indicating the type of the crystalline aggregate that forms upon phase transition.

Simultaneous measurement of mechanical and electrical contact resistances during nanoindentation of NiTi shape memory alloys

The nanoindentation technique can be employed in shape memory alloys (SMAs) to discern the transformation temperatures as well as to characterize their mechanical behavior. In this paper, we use it with simultaneous measurements of the mechanical and the electrical contact resistances (ECR) at room temperature to probe two SMAs: austenite (RTA) and martensite (RTM). Two different types of indenter tips - Berkovich and spherical - are employed to examine the SMAs' indentation responses as a function of the representative strain, epsilon(R). In Berkovich indentation, because of the sharp nature of the tip, and in consequence the high levels of strain imposed, discerning the two SMAs on the basis of the indentation response alone is difficult. In the case of the spherical tip, epsilon(R) is systematically varied and its effect on the depth recovery ratio, eta(d), is examined. Results indicate that RTA has higher eta(d) than RTM, but the difference decreases with increasing epsilon(R) such that eta(d) values for both the alloys would be similar in the fully plastic regime. The experimental trends in eta(d) vs. epsilon(R) for both the alloys could be described well with a eta(d) proportional to (epsilon(R))(-1) type equation, which is developed on the basis of a phenomenological model. This fit, in turn, directs us to the maximum epsilon(R), below which plasticity underneath the indenter would not mask the differences in the two SMAs. It was demonstrated that the ECR measurements complement the mechanical measurements in demarcating the reverse transformation from martensite to austenite during unloading of RTA, wherein a marked increase in the voltage was noted. A correlation between recovery due to reverse transformation during unloading and increase in voltage (and hence the electrical resistance) was found. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The X-C center dot center dot center dot Y (X = O/F, Y = O/S/F/Cl/Br/N/P) `carbon bond' and hydrophobic interactions

While the tetrahedral face of methane has an electron rich centre and can act as a hydrogen bond acceptor, substitution of one of its hydrogens with some electron withdrawing group (such as -F/OH) can make the opposite face electron deficient. Electrostatic potential calculations confirm this and high level quantum calculations show interactions between the positive face of methanol/methyl fluoride and electron rich centers of other molecules such as H2O. Analysis of the wave functions of atoms in molecules shows the presence of an unusual C center dot center dot center dot Y interaction, which could be called `carbon bonding'. NBO analysis and vibrational frequency shifts confirm the presence of this interaction. Given the properties of alkyl groups bonded to electronegative elements in biological molecules, such interactions could play a significant role, which is yet to be recognized. This and similar interactions could give an enthalpic contribution to what is called the `hydrophobic interactions'.

Synthon modularity in Cocrystals of 4-Bromobenzamide with n-Alkanedicarboxylic acids: type I and type ll Halogen center dot center dot center dot Halogen interactions

A Cambridge Structural Database (CSD) analysis on halogen center dot center dot center dot halogen contacts (X...X) in organic crystals has been carried out to review the classification criteria for type I, type II, and quasi type I/II halogen interactions. Trends observed in previous CSD analyses of the phenomenon are reinforced in the present study. The manner in which these interactions are manifested in cocrystals of 4-bromobenzamide and dicarboxylic acid is examined. The design strategy for these cocrystals uses synthon theory and follows from an understanding of the crystal structures of gamma-hydroquinone and a previously studied set of 4-hydroxybenzamide dicarboxylic acid cocrystals, making use of Br/OH isostructurality. All cocrystals are obtained by clean insertion of dicarboxylic acids between 4-bromobenzamide molecules. The strategy is deliberate and the prediction of synthons done well in advance, as evidenced from the robustness of the acid-amide heterosynthons in all nine crystal structures, with no aberrant structures in the crystallization experiments. Formation of the acid-amide synthon in these cocrystals is identified with IR spectroscopy. The packing in these cocrystals can be distinguished in terms of whether the Br...Br interactions are type I or II. Eight sets of dimorphs were retrieved from the CSD, wherein the basis of the polymorphism is that one crystal has a type I Br...Br interaction, while the other has a type II interaction.

Stabilizing effect of electrostatic vs. aromatic interactions in diproline nucleated peptide beta-hairpins

The contribution of Tyr-His vs. Cys-His interacting pairs to the scaffold stability of (D)Pro-(L)Pro nucleated peptide beta-hairpins has been examined. We present direct evidence for the superiority of the Cys-His pairs, mediated by sulphur-imidazole interactions, as added stabilizing agents of the beta-hairpin scaffold.

Steric and Electronic Interactions Controlling the cis/trans Isomer Equilibrium at X-Pro Tertiary Amide Motifs in Solution

A systematic understanding of the noncovalent interactions that influence the structures of the cis conformers and the equilibrium between the cis and the trans conformers, of the X-Pro tertiary amide motifs, is presented based on analyses of H-1-, C-13-NMR and FTIR absorption spectra of two sets of homologous peptides, X-Pro-Aib-OMe and X-Pro-NH-Me (where X is acetyl, propionyl, isobutyryl and pivaloyl), in solvents of varying polarities. First, this work shows that the cis conformers of any X-Pro tertiary amide motif, including Piv-Pro, are accessible in the new motifs X-Pro-Aib-OMe, in solution. These conformers are uniquely observable by FTIR spectroscopy at ambient temperatures and by NMR spectroscopy from temperatures as high as 273 K. This is made possible by the persistent presence of n(i-1i)* interactions at Aib, which also influence the disappearance of steric effects at these cis X-Pro rotamers. Second, contrary to conventional understanding, the energy contribution of steric effects to the cis/trans equilibrium at the X-Pro motifs is found to be nonvariant (0.54 +/- 0.02 kcal/mol) with increase in steric bulk on the X group. Third, the current studies provide direct evidence for the weak intramolecular interactions namely the n(i-1i)*, the N-Pro center dot center dot center dot Hi+1 (C(5)a), and the C-7 hydrogen bond that operate and influence the structures, stabilities, and dynamics between different conformational states of X-Pro tertiary amide motifs. NMR and IR spectral data suggest that the cis conformers of X-Pro motifs are ensembles of short-lived rotamers about the C-X-N-Pro bond. (c) 2013 Wiley Periodicals, Inc. Biopolymers 101: 66-77, 2014.

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.

Employing synergistic interactions between few-layer WS2 and reduced graphene oxide to improve lithium storage, cyclability and rate capability of Li-ion batteries

The aim of the contribution is to introduce a high performance anode alternative to graphite for lithium-ion batteries (LiBs). A simple process was employed to synthesize uniform graphene-like few-layer tungsten sulfide (WS2) supported on reduced graphene oxide (RGO) through a hydrothermal synthesis route. The WS2-RGO (80:20 and 70:30) composites exhibited good enhanced electrochemical performance and excellent rate capability performance when used as anode materials for lithium-ion batteries. The specific capacity of the WS2-RGO composite delivered a capacity of 400-450 mAh g(-1) after 50 cycles when cycled at a current density of 100 mA g(-1). At 4000 mA g(-1), the composites showed a stable capacity of approximately 180-240 mAh g(-1), respectively. The noteworthy electrochemical performance of the composite is not additive, rather it is synergistic in the sense that the electrochemical performance is much superior compared to both WS2 and RGO. As the observed lithiation/delithiation for WS2-RGO is at a voltage 1.0 V (approximate to 0.1 V for graphite, Li* /Li), the lithium-ion battery with WS2-RGO is expected to possess high interface stability, safety and management of electrical energy is expected to be more efficient and economic. (C) 2013 Elsevier Ltd. All rights reserved.

Conformational Diversity in Contryphans from Conus Venom: cis-trans Isomerisation and Aromatic/Proline Interactions in the 23-Membered Ring of a 7-Residue Peptide Disulfide Loop

Conformational diversity or shapeshifting in cyclic peptide natural products can, in principle, confer a single molecular entity with the property of binding to multiple receptors. Conformational equilibria have been probed in the contryphans, which are peptides derived from Conus venom possessing a 23-membered cyclic disulfide moiety. The natural sequences derived from Conus inscriptus, GCV(D)LYPWC* (In936) and Conus loroisii, GCP(D)WDPWC* (Lo959) differ in the number of proline residues within the macrocyclic ring. Structural characterisation of distinct conformational states arising from cis-trans equilibria about Xxx-Pro bonds is reported. Isomerisation about the C2-P3 bond is observed in the case of Lo959 and about the Y5-P6 bond in In936. Evidence is presented for as many as four distinct species in the case of the synthetic analogue V3P In936. The Tyr-Pro-Trp segment in In936 is characterised by distinct sidechain orientations as a consequence of aromatic/proline interactions as evidenced by specific sidechain-sidechain nuclear Overhauser effects and ring current shifted proton chemical shifts. Molecular dynamics simulations suggest that Tyr5 and Trp7 sidechain conformations are correlated and depend on the geometry of the Xxx-Pro bond. Thermodynamic parameters are derived for the cis trans equilibrium for In936. Studies on synthetic analogues provide insights into the role of sequence effects in modulating isomerisation about Xxx-Pro bonds.

Elastic-plastic contact conditions for frictionally constrained bodies under cyclic tangential loading

A Frictionally constrained condition implies dependence of friction force on tangential displacement amplitude. The condition may occur due to chemical, physical, and/or mechanical interaction between the contacting surfaces. The condition, sometimes also referred to as the presliding condition or partial slip condition, is characterized under fretting. Under such conditions, various experimental studies indicate the existence of two distinguishable regions, that is, stick region and slip region. In the present study, frictionally constrained conditions are identified and the evolutions of stick-slip regions are investigated in detail. Investigations have been performed on self-mated stainless steel and chromium carbide coated surfaces mated against stainless steel, under both vacuum and ambient conditions. Contact conditions prevailing at the contact interface were identified based on the mechanical responses and were correlated with the surface damage observed. Surface degradation has been observed in the form of microcracks and material transfer. Detailed numerical analysis has also been performed in order to understand the energy dissipation and the damage mode involved in the surface or subsurface damage. It has been observed that under frictionally constrained conditions, the occurrence of annular slip features are mainly due to the junction growth, resulting from elastic-plastic deformation at the contact interface. Ratcheting has been observed as the governing damage mode under cyclic tangential loading condition.

Computational Study of the Migration of Rhenium from One Enantioface of an Olefin to the Other Facilitated by (C-H)center dot center dot center dot Re Interactions

The migration of a metal atom in a metal olefin complex from one pi face of the olefin to the opposite pi face has been rarely documented. Gladysz and co-workers showed that such a movement is indeed possible in monosubstituted chiral Re olefin complexes, resulting in diastereomerization. Interestingly, this isomerization occurred without dissociation, and on the basis of kinetic isotope effects, the involvement of a trans C-H bond was indicated. Either oxidative addition or an agostic interaction of the vinylic C-H(D) bond with the metal could account for the experimentally observed kinetic isotope effect. In this study we compute the free energy of activation for the migration of Re from one enantioface of the olefin to the other through various pathways. On the basis of DFT calculations at the B3LYP level we show that a trans (C-H)center dot center dot center dot Re interaction and trans C-H oxidative addition provide a nondissociative path for the diastereomerization. The trans (C-H)center dot center dot center dot Re interaction path is computed to be more favorable by 2.3 kcal mol(-1) than the oxidative addition path. While direct experimental evidence was not able to discount the migration of the metal through the formation of a eta(2)-arene complex (conducted tour mechanism), computational results at the B3LYP level show that it is energetically more expensive. Surprisingly, a similar analysis carried out at the M06 level computes a lower energy path for the conducted tour mechanism and is not consistent with the experimental isotope effects observed. Metal-(C-H) interactions and oxidative additions of the metal into C-H bonds are closely separated in energy and might contribute to unusual fluxional processes such as this diastereomerization.

Detailed investigation of contact deformation in ZrN/Zr multiplayer-understanding the role of volume fraction, bilayer spacing, and morphology of interfaces

A systematic study was done to understand the influence of volume fractions and bilayer spacings for metal/nitride multilayer coating using finite element method (FEM). An axisymmetric model was chosen to model the real situation by incorporating metal and substrate plasticity. Combinations of volume fractions and bilayer spacings were chosen for FEM analysis consistent with experimental results. The model was able to predict trends in cracking with respect to layer spacing and volume fraction. Metal layer plasticity is seen to greatly influence the stress field inside nitride. It is seen that the thicker metal induces higher tensile stresses inside nitride and hence leads to lower cracking loads. Thin metal layers < 10 nm were seen to have curved interfaces, and hence, the deformation mode was interfacial delamination in combination with edge cracking. There is an optimum seen with respect to volume fraction similar to 13% and metal layer thickness similar to 30 nm, which give maximum crack resistance.

Energy Loss in the Impact of Elastic Spheres on a Rigid Half-Space in Presence of Adhesion

Adhesion can cause energy losses in asperities or particles coming into dynamic contact resulting in frictional dissipation, even if the deformation occurring is purely elastic. Such losses are of special significance in impact of nanoparticles and friction between surfaces under low contact pressure to hardness ratio. The objective of this work is to study the effect of adhesion during the normal impact of elastic spheres on a rigid half-space, with an emphasis on understanding the mechanism of energy loss. We use finite element method for modeling the impact phenomenon, with the adhesion due to van der Waals force and the short-range repulsion included as body forces distributed over the volume of the sphere. This approach, in contrast with commonly used surface force approximation, helps to model the interactions in a more precise way. We find that the energy loss in impact of elastic spheres is negligible unless there are adhesion-induced instabilities. Significant energy loss through elastic stress waves occurs due to jump-to-contact and jump-out-of-contact instabilities and can even result in capture of the elastic sphere on the half-space.

Interspecies and intraspecies interactions in social amoebae

The stable co-existence of individuals of different genotypes and reproductive division of labour within heterogeneous groups are issues of fundamental interest from the viewpoint of evolution. Cellular slime moulds are convenient organisms in which to address both issues. Strains of a species co-occur, as do different species; social groups are often genetically heterogeneous. Intra- and interspecies 1:1 mixes of wild isolates of Dictyostelium giganteum and D.purpureum form chimaeric aggregates, following which they segregate to varying extents. Intraspecies aggregates develop in concert and give rise to chimaeric fruiting bodies that usually contain more spores (reproductives) of one component than the other. Reproductive skew and variance in the proportion of reproductives are positively correlated. Interspecies aggregates exhibit almost complete sorting; most spores in a fruiting body come from a single species. Between strains, somatic compatibility correlates weakly with sexual compatibility. It is highest within clones, lower between strains of a species and lowest between strains of different species. Trade-offs among fitness-related traits (between compatible strains), sorting out (between incompatible strains) and avoidance (between species) appear to lie behind coexistence.