Spatio-temporal correlations in aqueous systems: computational studies of static and dynamic heterogeneity by 2D-IR spectroscopy

Local heterogeneity is ubiquitous in natural aqueous systems. It can be caused locally by external biomolecular subsystems like proteins, DNA, micelles and reverse micelles, nanoscopic materials etc., but can also be intrinsic to the thermodynamic nature of the aqueous solution itself (like binary mixtures or at the gas-liquid interface). The altered dynamics of water in the presence of such diverse surfaces has attracted considerable attention in recent years. As these interfaces are quite narrow, only a few molecular layers thick, they are hard to study by conventional methods. The recent development of two dimensional infra-red (2D-IR) spectroscopy allows us to estimate length and time scales of such dynamics fairly accurately. In this work, we present a series of interesting studies employing two dimensional infra-red spectroscopy (2D-IR) to investigate (i) the heterogeneous dynamics of water inside reverse micelles of varying sizes, (ii) supercritical water near the Widom line that is known to exhibit pronounced density fluctuations and also study (iii) the collective and local polarization fluctuation of water molecules in the presence of several different proteins. The spatio-temporal correlation of confined water molecules inside reverse micelles of varying sizes is well captured through the spectral diffusion of corresponding 2D-IR spectra. In the case of supercritical water also, we observe a strong signature of dynamic heterogeneity from the elongated nature of the 2D-IR spectra. In this case the relaxation is ultrafast. We find remarkable agreement between the different tools employed to study the relaxation of density heterogeneity. For aqueous protein solutions, we find that the calculated dielectric constant of the respective systems unanimously shows a noticeable increment compared to that of neat water. However, the `effective' dielectric constant for successive layers shows significant variation, with the layer adjacent to the protein having a much lower value. Relaxation is also slowest at the surface. We find that the dielectric constant achieves the bulk value at distances more than 3 nm from the surface of the protein.

Direct measurements of growing amorphous order and non-monotonic dynamic correlations in a colloidal glass-former

The transformation of flowing liquids into rigid glasses is thought to involve increasingly cooperative relaxation dynamics as the temperature approaches that of the glass transition. However, the precise nature of this motion is unclear, and a complete understanding of vitrification thus remains elusive. Of the numerous theoretical perspectives(1-4) devised to explain the process, random first-order theory (RFOT; refs 2,5) is a well-developed thermodynamic approach, which predicts a change in the shape of relaxing regions as the temperature is lowered. However, the existence of an underlying `ideal' glass transition predicted by RFOT remains debatable, largely because the key microscopic predictions concerning the growth of amorphous order and the nature of dynamic correlations lack experimental verification. Here, using holographic optical tweezers, we freeze a wall of particles in a two-dimensional colloidal glass-forming liquid and provide direct evidence for growing amorphous order in the form of a static point-to-set length. We uncover the non-monotonic dependence of dynamic correlations on area fraction and show that this non-monotonicity follows directly from the change in morphology and internal structure of cooperatively rearranging regions(6,7). Our findings support RFOT and thereby constitute a crucial step in distinguishing between competing theories of glass formation.

Dielectric and Raman investigations of structural phase transitions in (C2H5NH3)(2)CdCl4

Temperature-dependent Raman and dielectric measurements have been carried out on (C2H5NH3)(2)CdCl4 single crystals. Raman studies reveal the presence of two structural phase transitions below room temperature at 216 K and 114 K. The phase transitions are marked by anomalies in temperature dependence of wave-number and full width half maximum (FWHM) of several vibrational modes. The transitions are also accompanied by anomalies in dielectric measurements. Raman and dielectric data indicate that the transition at 216 K is order-disorder in nature and is driven by re-orientation of organic ions, while the transition at 114 K is due to coupling between the CdCl6 octahedron and the organic chain. Further high temperature dielectric measurements reveal the presence of one more structural phase transition around 473 K across which dispersion in dielectric parameters is observed. The activation energies and relaxation time obtained for high temperature dielectric phases are characteristic of combined reorientation motions of alkyl ammonium cations.

Unusual Fragility and Cooperativity in Glass-Forming and Crystalline PVDF/PMMA Blends in the Presence of Multiwall Carbon Nanotubes

Poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) are completely miscible below 50 wt % PVDF in the blends. In this work, an attempt was made to understand the fragility/cooperativity relation in glass-forming and crystalline blends of PVDF/PMMA and in the presence of a heteronucleating agent, multiwall carbon nanotubes (CNTs). Hence, three representative blends were chosen: a completely amorphous (10/90 by wt, PVDF/PMMA), on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA), and crystalline (60/40 by wt, PVDF/PMMA) blends. The intermolecular cooperativity/coupling, fragility, and configurational entropy near the glass transition temperature (T-g) were studied using differential scanning calorimetry (DSC) and broadband dielectric relaxation spectroscopy (DRS). It was observed that the blends with higher concentration of PMMA were more fragile (fragility index m = 141) and those with higher concentration of PVDF were more strong (m = 78). Interestingly, the coupling was less in the glass-forming blends (10/90 by wt, PVDF/PMMA) than the crystalline blends as manifested from DRS. This observation was also supported by DSC measurements which reflected that the cooperative rearranging region (CRR) existed over a smaller length scales in fragile blends as compared to strong blends, possibly due to restricted amorphous mobility. This effect was more prominent in the presence of CNTs, in particular for 50/50 (by wt) and 60/40 (by wt) PVDF/PMMA blends. Further, the configurational entropy, as manifested from DRS, decreased significantly in the strong blends in striking contrast to the fragile blends, supported by DSC, which manifested in an increase in the volume of cooperativity in the strong blends. The higher coupling in the crystalline blends can be attributed to good packing of the amorphous regions. While this is understood for crystalline blends (60/40 by wt, PVDF/PMMA), it is envisaged that enhanced dynamic heterogeneity is accountable for increased coupling in the case of blends which are on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA). The latter is also supported by broad relaxations near the T-g in DRS. Interestingly, the intermolecular coupling in the blends in the presence of CNTs has reduced, though the potential energy barrier hindering the rearrangement of CRR is lower than the blends without CNTs. In addition, the amorphous packing is not as effective as the blends without CNTs. This is manifested from reduced volume of cooperativity in particular, for 50/50 (by wt) and 60/40 (by wt) blends.

Effect of Manganese (II) Oxide on microstructure and ionic transport properties of nanostructured cubic zirconia

Effect of MnO addition on microstructure and ionic transport properties of nanocrystalline cubic(c)-ZrO2 is reported. Monoclinic (m) ZrO2 powders with 10-30 mol% MnO powder are mechanically alloyed in a planetary ball mill at room temperature for 10 h and annealed at 550 degrees C for 6 h. In all compositions m-ZrO2 transforms completely to nanocrystalline c-ZrO2 phase and MnO is fully incorporated into c-ZrO2 lattice. Rietveld's refinement technique is employed for detailed microstructure analysis by analyzing XRD patterns. High resolution transmission electron microscopy (HRTEM) analysis confirms the complete formation of c-ZrO2 phase. Presence of stoichiometric Mn in c-ZrO2 powder is confirmed by Electron Probe Microscopy analysis. XPS analysis reveals that Mn is mostly in Mn2+ oxidation state. A correlation between lattice parameter and oxygen vacancy is established. A detailed ionic conductivity measurement in the 250 degrees-575 degrees C temperature range describes the effect of MnO on conductivity of c-ZrO2. The ionic conductivity (s) of 30 mol% MnO alloyed ZrO2 at 550 degrees C is 0.04 s cm(-1). Electrical relaxation studies are carried out by impedance and modulus spectroscopy. Relaxation frequency is found to increase with temperature and MnO mol fraction. Electrical characterization predicts that these compounds have potentials for use as solid oxide fuel cell electrolyte material. (C) 2015 Elsevier Ltd. All rights reserved.

Reduction in DNA topoisomerase I level affects growth, phenotype and nucleoid architecture of Mycobacterium smegmatis

The steady-state negative supercoiling of eubacterial genomes is maintained by the action of DNA topoisomerases. Topoisomerase distribution varies in different species of mycobacteria. While Mycobacterium tuberculosis (Mtb) contains a single type I (Topol) and a single type II (Gyrase) enzyme, Mycobacterium smegmatis (Msm) and other members harbour additional relaxases. Topol is essential for Mtb survival. However, the necessity of Topol or other relaxases in Msm has not been investigated. To recognize the importance of Topol for growth, physiology and gene expression of Msm, we have developed a conditional knock-down strain of Topol in Msm. The Topol-depleted strain exhibited extremely slow growth and drastic changes in phenotypic characteristics. The cessation of growth indicates the essential requirement of the enzyme for the organism in spite of having additional DNA relaxation enzymes in the cell. Notably, the imbalance in Topol level led to the altered expression of topology modulatory proteins, resulting in a diffused nucleoid architecture. Proteomic and transcript analysis of the mutant indicated reduced expression of the genes involved in central metabolic pathways and core DNA transaction processes. RNA polymerase (RNAP) distribution on the transcription units was affected in the Topol-depleted cells, suggesting global alteration in transcription. The study thus highlights the essential requirement of Topol in the maintenance of cellular phenotype, growth characteristics and gene expression in mycobacteria. A decrease in Topol level led to altered RNAP occupancy and impaired transcription elongation, causing severe downstream effects.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl center dot center dot center dot N halogen-bonded clusters following vertical ionization

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation-and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH2, CF3, and COOH substituents) molecules paired with NH3 (referred as ACl:NH3 complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation-and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31+G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl center dot center dot center dot NH3 complex, the hole is predicted to migrate from the NH3-end to the ClCN-end of the NCCl center dot center dot center dot NH3 complex in approximately 0.5 fs on the D-0 cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H2NCl:NH3, F3CCl:NH3, and HOOCCl:NH3, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH3 and HOCl:NH3 complexes do not exhibit any charge migration following vertical ionization to the D-0 cation state, pointing to interesting halogen bond strength-dependent charge migration. (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.

Impedance spectroscopic studies on microwave synthesized NaPO3-V2O5 glasses containing SO42- ions

Impedance spectroscopic studies on modified phospho-vanadate glasses containing SO42- ions have been carried out over wide range of frequency. Modulated DSC studies suggest that the addition of alkali salt makes the glass less rigid and more fragile. The frequency dependent impedance data has been used to calculate d.c conductivity and activation energies. These values are comparable with the other ionic liquids. The conductivity and relaxation phenomenon was rationalized using universal a.c conductivity power law and modulus formalism. The activation energies for relaxation mechanism was also determined using imaginary parts of electrical modulus peaks which were close to those of the d.c conductivity implying the involvement of similar energy barriers in both the processes. Kohlrausch-William-Watts (KWW) stretched exponent beta, is temperature insensitive and power law (s) exponent is temperature dependent. The enhanced conductivity in these glasses is attributed to the depolymerised structure in which migration of Na+ ions proceeds in an expanded network comprising SO42- ions in the interstitials. The effect of structure on activation energy is well supported by abinitio DFT computations. (C) 2015 Elsevier B.V. All rights reserved.

Role of thermal annealing on SiGe thin films fabricated by PECVD

Amorphous Silicon Germanium (a-SiGe) thin films of 500 nm thickness are deposited on silicon substrates using Plasma Enhanced Chemical Vapour Deposition (PECVD). To obtain polycrystalline nature of films, thermal annealing is done at various temperature (450-600 degrees C) and time (1-10 h). The surface morphology of the pre- and post-annealed films is investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The crystallographic structure of the film is obtained by X-ray diffraction method. Raman spectroscopy is carried out to quantify the Ge concentration and the degree of strain relaxation in the film. Nano-indentation is performed to obtain the mechanical properties of the film. It is found that annealing reduces the surface roughness of the film and increases the Ge concentration in the film. The grain size of the film increases with increase in annealing temperature. The grain size is found to decrease with increase in annealing time up to 5 h and then increased. The results show that 550 degrees C for 5 h is the critical annealing condition for variation of structural and mechanical properties of the film. Recrystallization starts at this condition and results in finer grains. An increase in hardness value of 7-8 GPa has been observed. Grain growth occurs above this critical annealing condition and degrades the mechanical properties of the film. The strain in the film is only relaxed to about 55% even for 10 h of annealing at 600 degrees C. Transmission Electron Microscopy (TEM) observations show that the strain relaxation occurs by forming misfit dislocations and these dislocations are confined to the SiGe/Si interface. (C) 2015 Elsevier Ltd. All rights reserved.

ASYMPTOTIC PRESERVING SCHEME FOR A KINETIC MODEL DESCRIBING IN COMPRESSIBLE FLUIDS

The kinetic theory of fluid turbulence modeling developed by Degond and Lemou in 7] is considered for further study, analysis and simulation. Starting with the Boltzmann like equation representation for turbulence modeling, a relaxation type collision term is introduced for isotropic turbulence. In order to describe some important turbulence phenomenology, the relaxation time incorporates a dependency on the turbulent microscopic energy and this makes difficult the construction of efficient numerical methods. To investigate this problem, we focus here on a multi-dimensional prototype model and first propose an appropriate change of frame that makes the numerical study simpler. Then, a numerical strategy to tackle the stiff relaxation source term is introduced in the spirit of Asymptotic Preserving Schemes. Numerical tests are performed in a one-dimensional framework on the basis of the developed strategy to confirm its efficiency.

Ultrafast Chemical Dynamics in Time Domain Through Fluorescence Spectroscopy

While absorption and emission spectroscopy have always been used to detect and characterize molecules and molecular complexes, the availability of ultrashort laser pulses and associated computer-aided optical detection techniques allowed study of chemical processes directly in the time domain at unprecedented time scales, through appearance and disappearance of fluorescence from participating chemical species. Application of such techniques to chemical dynamics in liquids, where many processes occur with picosecond and femtosecond time scales lead to the discovery of a host of new phenomena that in turn led to the development of many new theories. Experiment and theory together provided new and valuable insight into many fundamental chemical processes, like isomerization dynamics, electron and proton transfer reactions, vibrational energy and phase relaxation, photosynthesis, to name just a few. In this article, we shall review a few of such discoveries in attempt to provide a glimpse of the fascinating research employing fluorescence spectroscopy that changed the field of chemical dynamics forever.

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.

Anomalous lifetime statistics of ligand-receptor binding in a tethered polymer system

In this paper, motivated by observations of non-exponential decay times in the stochastic binding and release of ligand-receptor systems, exemplified by the work of Rogers et al on optically trapped DNA-coated colloids (Rogers et al 2013 Soft Matter 9 6412), we explore the general problem of polymer-mediated surface adhesion using a simplified model of the phenomenon in which a single polymer molecule, fixed at one end, binds through a ligand at its opposite end to a flat surface a fixed distance L away and uniformly covered with receptor sites. Working within the Wilemski-Fixman approximation to diffusion-controlled reactions, we show that for a flexible Gaussian chain, the predicted distribution of times f(t) for which the ligand and receptor are bound is given, for times much shorter than the longest relaxation time of the polymer, by a power law of the form t(-1/4). We also show when the effects of chain stiffness are incorporated into this model (approximately), the structure of f(t) is altered to t(-1/2). These results broadly mirror the experimental trends in the work cited above.