Seed-Mediated Growth of Ag@Au Nanodisks with Improved Chemical Stability and Surface-Enhanced Raman Scattering.

Bimetallic Ag@Au nanoparticles (NPs) have received significant research interest because of their unique optical properties and molecular sensing ability through surface-enhanced Raman scattering (SERS). However, the synthesis of Ag@Au core-shell plasmonic nanostructures with precisely controlled size and shape remained a great challenge. Here, we report a simple approach for the synthesis of bimetallic Ag@Au nanodisks of about 13.5 nm thickness and different diameters through a seed-mediated growth process. The synthesis involves the conformal deposition of Au atoms at the corner sites of Ag nanoplate (AgNPL) seeds coupled with site-selective oxidative etching of AgNPL edges to generate Ag@Au nanodisks. The resultant Ag@Au nanodisks manifest significantly improved chemical stability and tunable localized surface plasmon resonance from the visible to the near-infrared spectral range. Moreover, in comparison to AgNPLs, the Ag@Au nanodisks showed greatly enhanced SERS performance with an enhancement factor up to 0.47 × 105, which is nearly 3-fold higher than that of the original AgNPLs (0.18 × 105). Furthermore, the Ag@Au nanodisks show a high sensitivity for detecting probe molecules such as crystal violet of concentration as low as 10-9 M and excellent reproducibility, with the SERS intensity fluctuation less than 12.5%. The synthesis route adapted for the controlled fabrication of Ag@Au nanodisks can be a potential platform for maneuvering other bimetallic plasmonic nanostructures useful for plasmonics and sensing applications.

From Intermolecular Interactions to Texture in Polycrystalline Surfaces of 1,ω-alkanediols (ω = 10-13).

Differences on herringbone molecular arrangement in two forms of long-chain 1,ω-alkanediols (CnH2n+2O2 with n = 10, 11, 12, 13) are explained from the analysis of O-H···O hydrogen-bond sequences in infinite chains and the role of a C-H···O intramolecular hydrogen-bond in stabilization of a gauche defect, as well as the inter-grooving effectiveness on molecular packing. GIXD (Glancing Incidence X-ray Diffraction) experiments were conducted on polycrystalline monophasic samples. Diffracted intensities were treated with the multi-axial March-Dollase method to correlate energetic and geometrical features of molecular interactions with the crystalline morphology and textural pattern of samples. The monoclinic (P21/c, Z = 2) crystals of the even-numbered members (n = 10, 12; DEDOL and DODOL, respectively) are diametrical prisms with combined form {104}/{-104}/{001} and present a two-fold platelet-like preferred orientation, whereas orthorhombic (P212121, Z = 4) odd-numbered members (n = 11, 13; UNDOL and TRDOL, respectively) present a dominant needle-like orientation on direction [101] (fiber texture). We show that crystalline structures of medium complexity and their microstructures can be determined from rapid GIXD experiments from standard radiation, combined with molecular replacement procedure using crystal structures of compounds with higher chain lengths as reference data.

Theoretical Rationale for a Thermodynamic Glass State.

Using a chemical potential route, the square-well (SW) fluid model is solved in a quasichemical approximation (QCSW). At low temperatures, the liquid reaches a limiting density greater than the triple point density of a SW fluid but less than the equilibrium liquid-to-solid transition density for hard spheres. As this unique density is approached with decreasing temperature, the liquid entropy also approaches an asymptotic value, thus averting the "entropy catastrophe". Mean-field models in the van der Waals (VDW) genre fail to predict this type of behavior. In VDW models, attractive force contributions to the equation of state incorrectly diverge with decreasing temperature as 1/T, whereas those for the QCSW model asymptote to a fixed value. The QCSW model posits the intuitively pleasing idea that, at high densities, attractive contributions to the configurational energy begin to saturate well before zero temperature is reached. As a consequence, the force balance between repulsive and attractive forces stabilizes the liquid density, which thereafter becomes effectively independent of temperature. This fixed density in turn fixes all other density-dependent thermodynamic properties. These low-temperature, force-stabilized states are identified as glass states.

New Zeno-Like Liquid States.

A Zeno line is a straight line in a fluid's temperature-density plane where the compressibility factor equals unity and stretches from supercritical to subcritical regimes. A second unexpected linearity also occurs in liquids in their normal liquid range (NLR) where the compressibility factor approaches zero. This Zeno-like line includes liquids as diverse as monatomic and diatomic elements to hydrogen bonding liquids, with water and helium being the only currently known exceptions. Remarkably, this second linearity is also present in polymeric liquids, molten metals, and salts, i.e., it is a generic characteristic of liquids with negligible or low vapor pressures. This observation yields the following new corresponding states principle: Saturated liquid densities are a linear function of temperature in the NLR for molecular, polymeric, inorganic, ionic, and metallic liquids and superpose to form a single master curve. Another Zeno-like linearity in the NLR has also been identified for the configurational energy of many liquids. Extension of this line to zero temperature defines the ground state configurational energy of the hypothetical disordered liquid (glass).

System-size effects in ionic fluids under periodic boundary conditions.

We investigate the system-size dependence of the thermodynamic properties of ionic fluids under periodic boundary conditions. Following an approach previously developed in the context of quantum Monte Carlo simulations of many-electron systems, we show that the leading-order finite-size artifact in the Coulomb energy per particle of a classical fluid of N structureless ions at given density and temperature is simply -kBT(2N)-1. Analytical approximations for the periodicity-induced size dependence of the excess thermodynamic properties of the fluid in the weak-coupling regime are obtained within the linearized Debye-Hückel theory. Theoretical results are compared with published simulations of the one-component plasma and our own simulations of a primitive-model electrolyte solution. Our work is directly relevant to estimating finite-size corrections in simulations of charged fluids comprising structureless ions embedded in continuous media. We outline in the Appendix how some of our formal results may be generalized to molecular fluids with mobile ions; e.g., electrolyte solutions with explicit solvent.

Universal thermodynamics at the liquid-vapor critical point.

For 68 fluids that include hydrogen bonding and quantum fluids, the fugacity coefficient that defines the residual chemical potential adopts a near universal value of 2/3 at the critical point. More precisely, the reciprocal of the fugacity coefficient equals 1.52 ± 0.02 and includes fluids as diverse as helium (1.50), dodecafluoropentane (1.50), and water (1.53). For 65 classical fluids, a dimensionless thermal pressure coefficient and internal pressure attain critical values of 1.88 ± 0.11 and 1.61 ± 0.11, respectively. From equations of state, values of these new critical constants have been calculated and agree favorably with experimental values. Specifically, for the critical fugacity coefficient, the following results were obtained for its reciprocal: van der Waals (1.44), lattice gas (1.43), scaled particle theory (1.46), and the Redlich-Kwong eq (1.50). The semiempirical Redlich-Kwong equation is also the most accurate for the thermal pressure coefficient (1.86) and internal pressure (1.53). Physical interpretations of these results are discussed as well as their implications for other critical phenomena.

Novel gigahertz frequency dielectric relaxations in chitosan films.

Molecular relaxations of chitosan films have been investigated in the wide frequency range of 0.1 to 3 × 10(9) Hz from -10 °C to 110 °C using dielectric spectroscopy. For the first time, two high-frequency relaxation processes (in the range 10(8) to 3 × 10(9) Hz) are reported in addition to the low frequency relaxations α and ß. These two relaxation processes are related to the vibrations of OH and NH2/NH3(+), respectively. The high-frequency relaxations exhibit Arrhenius-type dependencies in the temperature range 10 °C to 54 °C with negative activation energy; this observation is traceable to hydrogen bonding reorientation. At temperatures above the glass transition temperature (54 °C), the activation energy changes from negative to positive values due to breaking of hydrogen bonding and water loss. Upon cooling in a sealed environment, the activation energies of two relaxation processes are nearly zero. FTIR and XRD analyses reveal associated structural changes upon heating and cooling. These two new high-frequency relaxation processes can be attributed to the interaction of bound water with OH and NH2/NH3(+), respectively. A plausible scenario for these high-frequency relaxations is discussed in light of impedance spectroscopy, TGA, FTIR and XRD measurements.

Dimensionless thermodynamics: a new paradigm for liquid state properties.

Equations of state in the van der Waals genre suggest that saturated liquids should adhere to the following corresponding states principle (CSP): saturated liquids at the same reduced density (ρR = ρ/ρc) have comparable dimensionless thermodynamic properties. This CSP is shown to be applicable to a variety of thermodynamic properties that include entropy of vaporization, cohesive energy density, thermal expansion coefficient, isothermal compressibility, thermal pressure coefficient, compressibility factor, temperature coefficient of the vapor pressure, heat capacity difference, and surface tension. For two classes of liquids, all properties rendered dimensionless by the proper choice of scaling variables superpose to form "master curves" that illustrate the CSP. Using scaled particle theory, an improved van der Waals model is developed whose results are compared with existing experimental thermodynamic data in dimensionless form. Properly expressing thermodynamic properties in dimensionless form acts to consolidate and harmonize liquid state properties.

Dynamic void distribution in myoglobin and five mutants.

Globular proteins contain cavities/voids that play specific roles in controlling protein function. Elongated cavities provide migration channels for the transport of ions and small molecules to the active center of a protein or enzyme. Using Monte Carlo and Molecular Dynamics on fully atomistic protein/water models, a new computational methodology is introduced that takes into account the protein's dynamic structure and maps all the cavities in and on the surface. To demonstrate its utility, the methodology is applied to study cavity structure in myoglobin and five of its mutants. Computed cavity and channel size distributions reveal significant differences relative to the wild type myoglobin. Computer visualization of the channels leading to the heme center indicates restricted ligand access for the mutants consistent with the existing interpretations. The new methodology provides a quantitative measure of cavity structure and distributions and can become a valuable tool for the structural characterization of proteins.

Effect of doping in carbon nanotubes on the viability of biomimetic chitosan-carbon nanotubes-hydroxyapatite scaffolds.

This work describes the preparation and characterization of biomimetic chitosan/multiwall carbon nanotubes/nano-hydroxyapatite (CTS/MWCNT/nHAp) scaffolds and their viability for bone tissue engineering applications. The cryogenic process ice segregation-induced self-assembly (ISISA) was used to fabricate 3D biomimetic CTS scaffolds. Proper combination of cryogenics, freeze-drying, nature and molecular ratio of solutes give rise to 3D porous interconnected scaffolds with clusters of nHAp distributed along the scaffold surface. The effect of doping in CNT (e.g. with oxygen and nitrogen atoms) on cell viability was tested. Under the same processing conditions, pore size was in the range of 20-150 µm and irrespective on the type of CNT. Studies on cell viability with scaffolds were carried out using human cells from periosteum biopsy. Prior to cell seeding, the immunophenotype of mesenchymal periosteum or periosteum-derived stem cells (MSCs-PCs) was characterized by flow cytometric analysis using fluorescence-activated and characteristic cell surface markers for MSCs-PCs. The characterized MSCs-PCs maintained their periosteal potential in cell cultures until the 2nd passage from primary cell culture. Thus, the biomimetic CTS/MWCNT/nHAp scaffolds demonstrated good biocompatibility and cell viability in all cases such that it can be considered as promising biomaterials for bone tissue engineering.

New insights into the bactericidal activity of chitosan-Ag bionanocomposite: the role of the electrical conductivity.

The relationship between electrical conductivity, structure and antibacterial properties of chitosan-silver nanoparticles (CS/AgnP) biocomposites has been analyzed. To test the film's antimicrobial activity, Gram-positive and Gram-negative bacteria were studied. The interactions between silver nanoparticles with chitosan suggest the formation of silver ions which plays a major role in nanocomposite's bactericidal potency. In CS/AgnP biocomposites, the bactericide effectiveness increases by increasing AgnP concentrations up to 3 wt%, which is close to the electrical percolation threshold of ca. 3 wt%. As the AgnP concentration increases above this threshold, the bactericidal potency is greatly diminished. The elucidated correlation between electrical conductivity and antibacterial activity could be useful in the design of other nanocomposites that involve polymeric-based matrices.

Frontal polymerizations carried out in Deep-Eutectic mixtures providing both the monomers and the polymerization medium.

Deep Eutectic Solvents (DESs) based upon mixtures of Acrylic Acid (AA) or Methacrylic Acid (MAA) and Choline Chloride (CCl) demonstrated superior performance than regular organic solvents and even ionic liquids for frontal polymerizations (FPs). Full recovering of CCl after FP provided an interesting green character to the process.

On the asymptotic properties of a hard sphere fluid.

An analysis of the expected divergences in thermodynamic properties at the close-pack density (eta(cp) = pi square root(2)/6) along with the known virial coefficients up to 10th order suggests a weak logarithmic singularity in the excess fluid entropy. The corresponding equation of state (EOS) also possesses a singularity at eta(cp). The new EOS accurately describes extant molecular dynamics data up to the fluid-solid transition (eta approximately 0.494) with differences of less than 1 part per thousand. This accuracy is maintained into the metastable fluid regime up to eta approximately 0.52. In terms of accuracy, the new EOS is no better than Pade approximants, but the new EOS, unlike the Pade approximants, diverges at eta(cp). In addition, a new order parameter is defined that enables all system configurations to be classified as either disordered or ordered. Monte Carlo simulations are used to determine this order parameter in the metastable fluid range. Using this new order parameter, evidence is presented to support a thermodynamic glass transition at eta approximately 0.54. With respect to this transition, congruence is found with the traditional ideas espoused by Gibbs and DiMarzio and Adam and Gibbs. It is the rapid disappearance of disordered (random) configurations with increasing density that drives the glass transition and slows the dynamics.

Welding immiscible polymers with a supercritical fluid.

Polymer adhesion between two immiscible polymers is usually poor because there is little interpenetration of one polymer into the other at the interface. Increasing the width of the interfacial zone can enhance adhesion and mechanical properties. In principle, this can be accomplished by exposing heterogeneous polymer materials to a high-pressure fluid. The fluid can act as a common solvent and promote interpenetration. It also increases chain mobility at the interface, which helps to promote "welding" of the two polymers. A combination of the gradient theory of inhomogeneous systems and the Sanchez-Lacombe equation of state was used to investigate this phenomenon, especially the effect of the high compressibility of supercritical (SC) fluid on the compatibilization of two incompatible polymers. We calculate the interfacial density profile, interfacial thickness, and interfacial tension between the two polymers with and without the SC fluid. We find that the interfacial tension is decreased and the interfacial thickness is increased with high-pressure SC fluid for the ternary systems we have investigated. As the critical point is approached and the SC compressibility becomes large, no enhancement or deleterious effects on compatibilization were observed.

Gas diffusion in glasses via a probabilistic molecular dynamics.

A probabilistic protocol which makes possible the calculation of the diffusivity of light gases in amorphous materials from limited Monte Carlo and molecular dynamics data is presented. Diffusion coefficients are calculated for helium and methane in polystyrene, and for helium, neon, and methane in three pairs of polysulfone isomers. Results include diffusion coefficients as small as 10(-9) cm2/s and are in good agreement with results obtained from traditional molecular dynamics and with available experimental data.

Ordering in asymmetric block copolymer films by a compressible fluid.

We examine the morphological structures of asymmetric poly(ethylene oxide)-b-poly(1,1'-dihydroperflurooctyl methacrylate) (PEO-b-PFOMA) thin films upon annealing in a compressible fluid, supercritical CO2 (Sc-CO2). The strong affinity between PFOMA and CO2 is found to induce phase segregation when annealing PEO-b-PFOMA films at the same temperature as compared with vacuum. In vacuum, PEO-b-PFOMA films remain disordered from 80 to 180 degrees C, whereas, in Sc-CO2 at 13.9 MPa, an upper order-disorder transition (UODT) between 116 and 145 degrees C is found. In Sc-CO2, the observed ordered structure is layers of PEO spheres embedded in the matrix of PFOMA, followed by a brush layer, in which PEO wets the substrate. The swelling isotherms of PFOMA and PEO in CO2 are correlated with the Sanchez-Lacombe equation of state (SLEOS) to estimate the interaction parameters, XPFOMA-CO2 and XPEO-CO2. The phase segregation (order) induced by CO2 relative to vacuum at a given temperature is explained in terms of two factors: (1) copolymer volume fraction upon dilution with CO2, phi, and (2) the relative interaction parameter, DeltaX= XPEO-CO2 - XPFOMA-CO2. The latter factor favors order and is dominant at low temperatures over the phi factor, which always favors disorder. At high temperatures (above the T(ODT)), the preferential swelling of PFOMA by CO2 is less pronounced ( DeltaX decreases), and the copolymer is disordered.

Anomalous sorption of supercritical fluids on polymer thin films.

Unusual sorption has been reported in thin polymer films exposed to near-critical CO2. When the supercritical fluid approaches the critical point, the film appears to thicken, but it is not clear whether the film swells or there is an adsorption layer on the film surface. A combination of the gradient theory of inhomogeneous systems and the Sanchez-Lacombe equation of state has been used to investigate this phenomenon. It is shown analytically that surface adsorption on an attractive surface is proportional to the compressibility of the fluid. We have also investigated numerically the sorption of supercritical CO2 on poly(dimethylsiloxane) and polyisobutylene, and supercritical 1,1-difluoroethane on polystyrene. By calculating the Gibbs adsorption and adsorption layer thickness of the supercritical fluids, we found in all cases (different substrates, different supercritical fluids) that maximum adsorption occurs when the supercritical fluid is near its compressibility maximum.

Molecular simulations of physical aging in polymer membrane materials.

Poly(1-trimethylsilyl-1-propyne) (PTMSP), the most permeable polymer known, undergoes rapid physical aging. The permeability of PTMSP to gases and vapors decreases dramatically with physical aging. Cavity size (free volume) distributions were calculated in as-cast and aged PTMSP, using an energetic based cavity-sizing algorithm. The large cavities found in as-cast PTMSP disappear in aged PTMSP, which is consistent with the positron annihilation lifetime spectroscopy (PALS) measurements. We also characterized the connectivity of cavities in both as-cast and aged PTMSP membranes. Cavities are more connected in as-cast PTMSP than in aged PTMSP. The average cavity sizes calculated from computer simulation are in good agreement with PALS measurements. The transport and sorption properties of gases in as-cast and aged PTMSP are also measured by molecular simulation. Computer simulations showed the decrease of permeability and the increase of permeability selectivity in PTMSP membranes with physical aging, which agrees with experimental observations. The reduction in gas permeability with physical aging results mainly from the decrease of diffusion coefficients. Solubility coefficients show no significant changes with physical aging.

Nonequilibrium molecular dynamics of the rheological and structural properties of linear and branched molecules. Simple shear and poiseuille flows; instabilities and slip.

Nonequilibrium molecular-dynamics simulations are performed for linear and branched chain molecules to study their rheological and structural properties under simple shear and Poiseuille flows. Molecules are described by a spring-monomer model with a given intermolecular potential. The equations of motion are solved for shear and Poiseuille flows with Lees and Edward's [A. W. Lees and S. F. Edwards, J. Phys. C 5, 1921 (1972)] periodic boundary conditions. A multiple time-scale algorithm extended to nonequilibrium situations is used as the integration method, and the simulations are performed at constant temperature using Nose-Hoover [S. Nose, J. Chem. Phys. 81, 511 (1984)] dynamics. In simple shear, molecules with flow-induced ellipsoidal shape, having significant segment concentrations along the gradient and neutral directions, exhibit substantial flow resistance. Linear molecules have larger zero-shear-rate viscosity than that of branched molecules, however, this behavior reverses as the shear rate is increased. The relaxation time of the molecules is associated with segment concentrations directed along the gradient and neutral directions, and hence it depends on structure and molecular weight. The results of this study are in qualitative agreement with other simulation studies and with experimental data. The pressure (Poiseuille) flow is induced by an external force F(e) simulated by confining the molecules in the region between surfaces which have attractive forces. Conditions at the boundary strongly influence the type of the slip flow predicted. A parabolic velocity profile with apparent slip on the wall is predicted under weakly attractive wall conditions, independent of molecular structure. In the case of strongly attractive walls, a layer of adhered molecules to the wall produces an abrupt distortion of the velocity profile which leads to slip between fluid layers with magnitude that depends on the molecular structure. Finally, the molecular deformation under flow depends on the attractive force of the wall, in such a way that molecules are highly deformed in the case of strong attracting walls.