Allosteric Transition Induced by Mg2+ Ion in a Transactivator Monitored by SERS

We demonstrate the utility of the surface-enhanced Raman spectroscopy (SERS) to monitor conformational transitions in protein upon ligand binding. The changes in protein's secondary and tertiary structures were monitored using amide and aliphatic/aromatic side chain vibrations. Changes in these bands are suggestive of the stabilization of the secondary and tertiary structure of transcription activator protein C in the presence of Mg2+ ion, whereas the spectral fingerprint remained unaltered in the case of a mutant protein, defective in Mg2+ binding. The importance of the acidic residues in Mg2+ binding, which triggers an overall allosteric transition in the protein, is visualized in the molecular model. The present study thus opens up avenues toward the application of SERS as a potential tool for gaining structural insights into the changes occurring during conformational transitions in proteins.

Transition in vortex breakdown modes in a coaxial isothermal unconfined swirling jet

This paper reports first observations of transition in recirculation pattern from an open-bubble type axisymmetric vortex breakdown to partially open bubble mode through an intermediate, critical regime of conical sheet formation in an unconfined, co-axial isothermal swirling flow. This time-mean transition is studied for two distinct flow modes which are characterized based on the modified Rossby number (Ro(m)), i.e., Ro(m) <= 1 and Ro(m) > 1. Flow modes with Ro(m) <= 1 are observed to first undergo cone-type breakdown and then to partially open bubble state as the geometric swirl number (S-G) is increased by similar to 20% and similar to 40%, respectively, from the baseline open-bubble state. However, the flow modes with Ro(m) > 1 fail to undergo such sequential transition. This distinct behavior is explained based on the physical significance associated with Ro(m) and the swirl momentum factor (xi). In essence, xi represents the ratio of angular momentum distributed across the flow structure to that distributed from central axis to the edge of the vortex core. It is observed that xi increases by similar to 100% in the critical swirl number band where conical breakdown occurs as compared to its magnitude in the S-G regime where open bubble state is seen. This results from the fact that flow modes with Ro(m) <= 1 are dominated by radial pressure gradient due to swirl/rotational effect when compared to radial pressure deficit arising from entrainment (due to the presence of co-stream). Consequently, the imparted swirl tends to penetrate easily towards the central axis causing it to spread laterally and finally undergo conical sheet breakdown. However, the flow modes with Ro(m) > 1 are dominated by pressure deficit due to entrainment effect. This blocks the radial inward penetration of imparted angular momentum thus preventing the lateral spread of these flow modes. As such these structures fail to undergo cone mode of vortex breakdown which is substantiated by a mere 30%-40% rise in xi in the critical swirl number range. (C) 2014 AIP Publishing LLC.

Fluctuating micro-heterogeneity in water-tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with x(TBA) approximate to 0.03-0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at x(TBA) approximate to 0.05. We note that ``islands'' of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak nonlinearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, x(TBA) approximate to 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level. (C) 2014 AIP Publishing LLC.

Film thickness mediated transition in the kinetics of electric current induced flow of thin liquid metal films

Application of high electric-field between two points in a thin metallic film results in liquefaction and subsequent flow of the liquid-film from one electrode to another in a radially symmetric fashion. Here, we report the transition of the flow kinetics driven by the liquid film thickness varying from 3 to 100 nm. The mechanism of the flow behavior is observed to be independent of the film thickness; however, the kinetics of the flow depends on the film thickness and the applied voltage. An analytical model, incorporating viscosity and varying electrical resistivity with film thickness, is developed to explain the experimental observations. (C) 2014 AIP Publishing LLC.

Pressure-induced semiconducting to metallic transition in multilayered molybdenum disulphide

Molybdenum disulphide is a layered transition metal dichalcogenide that has recently raised considerable interest due to its unique semiconducting and opto-electronic properties. Although several theoretical studies have suggested an electronic phase transition in molybdenum disulphide, there has been a lack of experimental evidence. Here we report comprehensive studies on the pressure-dependent electronic, vibrational, optical and structural properties of multilayered molybdenum disulphide up to 35 GPa. Our experimental results reveal a structural lattice distortion followed by an electronic transition from a semiconducting to metallic state at similar to 19 GPa, which is confirmed by ab initio calculations. The metallization arises from the overlap of the valance and conduction bands owing to sulphur-sulphur interactions as the interlayer spacing reduces. The electronic transition affords modulation of the opto-electronic gain in molybdenum disulphide. This pressure-tuned behaviour can enable the development of novel devices with multiple phenomena involving the strong coupling of the mechanical, electrical and optical properties of layered nanomaterials.

Texture transition in cold-rolled nickel-40 wt.% cobalt alloy

The micromechanical aspects of rolling texture development in Ni-40 wt.% Co alloy during very large reductions (up to epsilon(t) = 3.9) have been studied. The alloy showed a typical Cu-type texture up to a true strain of epsilon(t) = 3; however, the texture undergoes an abrupt transition to Bs-type on further rolling to epsilon(t) approximate to 4. (The Bs-type texture, here, comprises almost equal fractions of Goss and Bs components.) Microstructural observations, at early stages, show that deformation is accommodated entirely by slip, and very little presence of deformation twinning is observed to explain the texture transition. However, at much higher reduction levels, micrographs show a high fraction of Cu-type shear bands. These bands are predominantly found in Cu-oriented grains and the crystallites inside the shear bands are preferentially oriented towards Goss, which could explain the final texture evolution. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Experimental signatures of a nonequilibrium phase transition governing the yielding of a soft glass

We present direct experimental signatures of a nonequilibrium phase transition associated with the yield point of a prototypical soft solid-a binary colloidal glass. By simultaneously quantifying single-particle dynamics and bulk mechanical response, we identified the threshold for the onset of irreversibility with the yield strain. We extracted the relaxation time from the transient behavior of the loss modulus and found that it diverges in the vicinity of the yield strain. This critical slowing down is accompanied by a growing correlation length associated with the size of regions of high Debye-Waller factor, which are precursors to yield events in glasses. Our results affirm that the paradigm of nonequilibrium critical phenomena is instrumental in achieving a holistic understanding of yielding in soft solids.

Rainbow Emission from an Atomic Transition in Doped Quantum Dots

Although semiconductor quantum dots are promising materials for displays and lighting due to their tunable emissions, these materials also suffer from the serious disadvantage of self-absorption of emitted light. The reabsorption of emitted light is a serious loss mechanism in practical situations because most phosphors exhibit subunity quantum yields. Manganese-based phosphors that also exhibit high stability and quantum efficiency do not suffer from this problem but in turn lack emission tunability, seriously affecting their practical utility. Here, we present a class of manganese-doped quantum dot materials, where strain is used to tune the wavelength of the dopant emission, extending the otherwise limited emission tunability over the yellow-orange range for manganese ions to almost the entire visible spectrum covering all colors from blue to red. These new materials thus combine the advantages of both quantum dots and conventional doped phosphors, thereby opening new possibilities for a wide range of applications in the future.

Pressure Dependence of Glass Transition in As2Te3 Glass

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (T-g). Generally, application of high pressure increases the T-g and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As2Te3 glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at T-g. The T-g estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 degrees C/kbar for a linear fit and -2.99 degrees C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As2Se3, and As30Se30Te40 show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As2Te3 glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Delta k/Delta alpha will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between T-g and the optical band gap (E-g for covalent semiconducting glasses when they are grouped according to their average coordination number. The electrical band gap (Delta E) of As2Te3 glass decreases with pressure. The optical and electrical band gaps are related as Delta E-g = 2 Delta E; thus, a negative dT(g)/dP is expected when As2Te3 glass is subjected to high pressures. In this sense, As2Te3 is a unique glass where its variation of T-g with pressure can be understood by both electronic and thermodynamic models.

Orientation, Size, and Temperature Dependent Ductile Brittle Transition in NiAl Nanowire under Tensile Loading - A Molecular Dynamics Study

In the present paper, thermo-mechanical response of B2-NiAl nanowire along the < 100 >, < 110 >, and < 111 > orientations has been studied using molecular dynamics simulations. Nanowire with cross-sectional dimensions of similar to 20x20 angstrom(2), similar to 25x25 angstrom(2), and similar to 30x30 angstrom(2) and temperature range of 10 K-900 K has been considered. A Combined effect of size, orientation, and temperature on the stress-strain behavior under uniaxial tensile loading has been presented. It has been observed that < 111 > oriented NiAl nanowire that is energetically most stable gives highest yield stress which further reduces with < 110 > and < 100 > orientations. A remarkable ductile brittle transition (DBT) with an increase in temperature has also been reported for all the orientations considered in the present study. The DBT observed for the nanowire has also been compared with the reported DBT of bulk B2-NiAl obtained from experiments. Alternate technique has also been proposed to increase the toughness of a given material especially at lower temperature regions, i.e. below DBT.

Conductivity noise study of the insulator-metal transition and phase coexistence in epitaxial samarium nickelate thin films

Interaction between the lattice and the orbital degrees of freedom not only makes rare-earth nickelates unusually ``bad metal,'' but also introduces a temperature-driven insulator-metal phase transition. Here we investigate this insulator-metal phase transition in thin films of SmNiO3 using the slow time-dependent fluctuations (noise) in resistivity. The normalized magnitude of noise is found to be extremely large, being nearly eight orders of magnitude higher than thin films of common disordered metallic systems, and indicates electrical conduction via classical percolation in a spatially inhomogeneous medium. The higher-order statistics of the fluctuations indicate a strong non-Gaussian component of noise close to the transition, attributing the inhomogeneity to the coexistence of the metallic and insulating phases. Our experiment offers insight into the impact of lattice-orbital coupling on the microscopic mechanism of electron transport in the rare-earth nickelates.

Growing dynamical facilitation on approaching the random pinning colloidal glass transition

Despite decades of research, it remains to be established whether the transformation of a liquid into a glass is fundamentally thermodynamic or dynamic in origin. Although observations of growing length scales are consistent with thermodynamic perspectives, the purely dynamic approach of the Dynamical Facilitation (DF) theory lacks experimental support. Further, for vitrification induced by randomly freezing a subset of particles in the liquid phase, simulations support the existence of an underlying thermodynamic phase transition, whereas the DF theory remains unexplored. Here, using video microscopy and holographic optical tweezers, we show that DF in a colloidal glass-forming liquid grows with density as well as the fraction of pinned particles. In addition, we observe that heterogeneous dynamics in the form of string-like cooperative motion emerges naturally within the framework of facilitation. Our findings suggest that a deeper understanding of the glass transition necessitates an amalgamation of existing theoretical approaches.

Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process

Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The nonaqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.

Temperature-Induced Reversible First-Order Single Crystal to Single Crystal Phase Transition in Boc-gamma(4)(R)Val-Val-OH: Interplay of Enthalpy and Entropy

Crystals of Boc-gamma y(4)(R)Val-Val-OH undergo a reversible first-order single crystal to single crystal phase transition at T-c approximate to 205 K from the orthorhombic space group P22(1)2(1) (Z' = 1) to the monoclinic space group P2(1) (Z' = 2) with a hysteresis of similar to 2.1 K. The low-temperature monoclinic form is best described as a nonmerohedral twin with similar to 50% contributions from its two components. The thermal behavior of the dipeptide crystals was characterized by differential scanning calorimetry experiments. Visual changes in birefringence of the sample during heating and cooling cycles on a hot-stage microscope with polarized light supported the phase transition. Variable-temperature unit cell check measurements from 300 to 100 K showed discontinuity in the volume and cell parameters near the transition temperature, supporting the first-order behavior. A detailed comparison of the room-temperature orthorhombic form with the low-temperature (100 K) monoclinic form revealed that the strong hydrogen-bonding motif is retained in both crystal systems, whereas the non-covalent interactions involving side chains of the dipeptide differ significantly, leading to a small change in molecular conformation in the monoclinic form as well as a small reorientation of the molecules along the ac plane. A rigid-body thermal motion analysis (translation, libration, screw; correlation of translation and libration) was performed to study the crystal entropy. The reversible nature of the phase transition is probably the result of an interplay between enthalpy and entropy: the low-temperature monoclinic form is enthalpically favored, whereas the room-temperature orthorhombic form is entropically favored.

Bmi1 regulates self-renewal and epithelial to mesenchymal transition in breast cancer cells through Nanog

Background: The Bmi1 polycomb ring finger oncogene, a transcriptional repressor belonging to the Polycomb group of proteins plays an important role in the regulation of stem cell self-renewal and is elevated in several cancers. In the current study, we have explored the role of Bmi1 in regulating the stemness and drug resistance of breast cancer cells. Methods: Using real time PCR and immunohistochemistry primary breast tissues were analyzed. Retro-and lentiviruses were utilized to overexpress and knockdown Bmi1, RT-PCR and Western blot was performed to evaluate mRNA and protein expression. Stemness properties were analyzed by flow cytometry and sphere-formation and tumor formation was determined by mouse xenograft experiments. Dual luciferase assay was employed to assess promoter activity and MTT assay was used to analyze drug response. Results: We found Bmi1 overexpression in 64% of grade III invasive ductal breast adenocarcinomas compared to normal breast tissues. Bmi1 overexpression in immortalized and transformed breast epithelial cells increased their sphere-forming efficiency, induced epithelial to mesenchymal transition ( EMT) with an increase in the expression of stemness-related genes. Knockdown of Bmi1 in tumorigenic breast cells induced epithelial morphology, reduced expression of stemness-related genes, decreased the IC50 values of doxorubicin and abrogated tumor-formation. Bmi1-high tumors showed elevated Nanog expression whereas the tumors with lower Bmi1 showed reduced Nanog levels. Overexpression of Bmi1 increased Nanog levels whereas knockdown of Bmi1 reduced its expression. Dual luciferase promoter-reporter assay revealed Bmi1 positively regulated the Nanog and NF kappa B promoter activity. RT-PCR analysis showed that Bmi1 overexpression activated the NF kappa B pathway whereas Bmi1 knockdown reduced the expression of NF kappa B target genes, suggesting that Bmi1 might regulate Nanog expression through the NF kappa B pathway. Conclusions: Our study showed that Bmi1 is overexpressed in several high-grade, invasive ductal breast adenocarcinomas, thus supporting its role as a prognostic marker. While Bmi1 overexpression increased self-renewal and promoted EMT, its knockdown reversed EMT, reduced stemness, and rendered cells drug sensitive, thus highlighting a crucial role for Bmi1 in regulating the stemness and drug response of breast cancer cells. Bmi1 may control self-renewal through the regulation of Nanog expression via the NF kappa B pathway.