Polymer melt dynamics: Microscopic roots of fractional viscoelasticity

The rheological properties of polymer melts and other complex macromolecular fluids are often successfully modeled by phenomenological constitutive equations containing fractional differential operators. We suggest a molecular basis for such fractional equations in terms of the generalized Langevin equation (GLE) that underlies the renormalized Rouse model developed by Schweizer [J. Chem. Phys. 91, 5802 (1989)]. The GLE describes the dynamics of the segments of a tagged chain under the action of random forces originating in the fast fluctuations of the surrounding polymer matrix. By representing these random forces as fractional Gaussian noise, and transforming the GLE into an equivalent diffusion equation for the density of the tagged chain segments, we obtain an analytical expression for the dynamic shear relaxation modulus G(t), which we then show decays as a power law in time. This power-law relaxation is the root of fractional viscoelastic behavior.

Folding a Polymer via Two-Point Interaction with an External Folding Agent: Use of H-Bonding and Charge-Transfer Interactions

A polymer containing electron-rich aromatic donors (1,5-dialkoxynaphthalene (DAN)) was coerced into a folded state by an external folding agent that contained an electron-deficient aromatic acceptor (pyromellitic diimide (PM)) unit. The donor-containing polymer was designed to carry a tertiary amine moiety in the linking segment, which served as an H-bonding site for reinforcing the interaction with the acceptor containing folding agent that also bore a carboxylic acid group. The H-bonding interaction of the carboxylic acid and the tertiary amine brings the PDI unit between two adjacent DAN units along the polymer backbone to induce charge-transfer (C-T) interactions, and this in turn causes the polymer chain to form a pleated structure. Evidence for the formation of such a pleated structure was obtained from NMR titration studies and also by monitoring the C-T band in their UV-visible spectra. By varying the length of the segment that links the PDI acceptor to the carboxylic acid group, we showed that the most effective folding agent was the one that had a single carbon spacer, as evident from the highest value of the association constant. Control experiments with propionic acid clearly demonstrated the importance of the additional C-T interactions for venerating the folded structures. Further, solution viscosity measurements in the presence of varying amounts of the folding agent revealed a gradual stiffening of the chain in the case of the PDI carrying carboxylic acid, whereas no such affect was seen in the case of simple propionic acid. These observations were supported by D FT calculations of the interactions of a dimeric model of the polymer with the various folding agents; here too the stability of the complex was seen to be highest in the case of the single carbon spacer.

Terahertz Spectroscopy of Single-Walled Carbon Nanotubes in a Polymer Film: Observation of Low-Frequency Phonons

We investigate the dielectric response of single-walled carbon nanotubes dispersed in poly(vinyl alcohol) matrix by using terahertz time domain spectroscopy. Frequency-dependent real and imaginary parts of the complex dielectric function are measured experimentally in the terahertz regime. The low-frequency phonons of carbon nanotubes, though predicted theoretically, are directly observed for the first time at frequencies 0.26, 0.60, and 0.85 THz. Further, a broad resonance is observed at 1.15 THz associated with the longitudinal acoustic mode of vibration of straight-chain segments of the long polymeric molecules in the film. The latter is observed at 1.24 THz for a pristine polymer film and has been used to derive the size of crystalline lamellae in the film.

Communication: Evidence of dynamic heterogeneity in glassy polymer monolayers from interface microrheology measurements

We have developed a novel nanoparticle tracking based interface microrheology technique to perform in situ studies on confined complex fluids. To demonstrate the power of this technique, we show, for the first time, how in situ glass formation in polymers confined at air-water interface can be directly probed by monitoring variation of the mean square displacement of embedded nanoparticles as a function of surface density. We have further quantified the appearance of dynamic heterogeneity and hence vitrification in polymethyl methacrylate monolayers above a certain surface density, through the variation of non-Gaussian parameter of the probes. (C) 2010 American Institute of Physics. [doi:10.1063/1.3471584].

Complex Permittivity Characteristics of Epoxy Nanocomposites at Low Frequencies

The complex permittivity characteristics of epoxy nanocomposite systems were examined and an attempt has been made to understand the underlying physics governing some of the unique macroscopic dielectric behaviors. The experimental investigations were performed using two different nanocomposite systems with low filler concentrations over the frequency range of 10(-2)-400 Hz, but for some cases, the data has been reported upto 10(6) Hz for a better understanding of the behaviors. Results demonstrate that nanocomposites do possess unique permittivity behaviors as compared to those already known for unfilled polymer and microcomposite systems. The nanocomposite real permittivity and tan delta values are found to be lower than that of unfilled epoxy. In addition, results show that interfacial polarization and charge carrier mobilities are suppressed in epoxy nanocomposite systems. The complex permittivity spectra coupled with the ac conductivity characteristics with respect to frequency was found to be sufficient to identify several of the nanocomposite characteristics like the reduction in permittivity values, reduction in the interfacial polarization mechanisms and the electrical conduction behaviors. Analysis of the results are also performed using electric modulus formalisms and it has been seen that the nanocomposite dielectric behaviors at low frequencies can also be explained clearly using this formalism.

Synthetic, spectroscopic, magnetic, and x-ray structural studies on a vitamin B6-amino acid Schiff base complex, aqua(5'-phosphopyridoxylidenetyrosinato)copper(II) tetrahydrate

A Schiff base metal complex, [Cu(II)(PLP-DL-tyrosinato)(H2O)].4H2O (PLP = pyridoxal phosphate), with the molecular formula CuC17O13N2H27P has been prepared and characterized by magnetic, spectral, and X-ray structural studies. The compound crystallizes in the triclinic space group P1BAR with a = 8.616 (2) angstrom, b = 11.843 (3) angstrom, c = 12.177 (3) angstrom, alpha = 103.40 (2)degrees, beta = 112.32 (2)degrees, gamma = 76.50 (1)degrees, and Z = 2. The structure was solved by the heavy-atom method and refined by least-squares techniques to a final R value of 0.057 for 3132 independent reflections. The coordination geometry around Cu(II) is distorted square pyramidal with phenolic oxygen, imino nitrogen, and carboxylate oxygen from the Schiff base ligand and water oxygen as basal donor atoms. The axial site is occupied by a phosphate oxygen from a neighboring molecule, thus resulting in a one-dimensional polymer. The structure reveals pi-pi interaction of the aromatic side chain of the amino acid with the pyridoxal pi system. A comparative study is made of this complex with similar Schiff base complexes. The variable-temperature magnetic behavior of this compound shows a weak antiferromagnetic interaction.

Lanthanide Luminescent Coordination Polymer Constructed from Unsymmetrical Dinuclear Building Blocks Based on 4-((1H-Benzod]imidazol-1-yl)methyl)benzoic Acid

Lanthanide coordination polymers of the general formula Ln(2)(L)(5)(NO3)(H2O)(4)](n) (Ln = Eu (1), Tb (2), Gd (3)) supported by a novel aromatic carboxylate ligand 4-((1H-benzod]imidazol-1-yl)methyl)benzoic acid (HL) have been synthesized, characterized, and their photoluminescence behavior is examined. The powder X-ray diffraction patterns of complexes 1-3 showed that 1-3 are isostructural; thus, 1 has been chosen as an example to discuss in detail about the molecular structure by single-crystal X-ray diffraction. Complex 1 is a one-dimensional (1D) helical chain-like coordination polymer consisting of unique unsymmetrical dinuclear lanthanide building blocks. The 1D chains are further linked by the significant intermolecular hydrogen-bonding interactions to form a two-dimensional supramolecular network. The Tb3+ complex exhibits bright green luminescence efficiency in the solid state with a quantum yield of 15%. On the other hand, poor luminescence efficiency has been noted for Eu3+-benzoate complex.

Enhanced lithium-ion transport in PEG-based composite polymer electrolyte with Mn0.03Zn0.97Al2O4 nanoparticles

The ion conduction and thermal properties of composite solid polymer electrolyte (SPE) comprising Poly(ethylene) Glycol (PEG, mol wt. 2000), lithium perchlorate (LiClO4) and insulating Mn0.03Zn0.97Al2O4 nanoparticle fillers were studied by complex impedance analysis and DSC techniques. The average size of the nanoparticles was determined by powder X-ray diffraction (XRD) using Scherrer's equation and was found to be similar to 8 nm. The same was also determined by TEM imaging and found to be similar to 12 nm. The glass transition temperature T, as measured by differential scanning calorimeter (DSC), showed a minimum at 5 mol% of narroparticles. Fractional crystallinity was determined using DSC. NMR was used to deter-mine crystallinity of a pure PEG sample, which was then used as the standard. Fractional crystallinity X. was the lowest for 5 mol% and beyond. The ionic conductivity of the composite polymer electrolyte containing 5 mol% Mn0.03Zn0.97Al2O4 nanoparticles was found to be 1.82 x 10(-5) S/cm, while for the pristine one, it was 7.27 x 10(-7) S/cm at room temperature. As a function of nanoparticle content, conductivity was observed to go through two maxima, one at around 5 mol% and another shallower one at around 12 mol%. The temperature dependence of conductivity could be divided into two regions, one consistent with Arrhenius behaviour and the other with VTF. We conclude that the enhancement of ionic conductivity on the addition of Mn0.03Zn0.97Al2O4 nanoparticles is a result of reduction in both the T, and the crystallinity. (C) 2002 Elsevier Science B.V. All rights reserved.

Electroluminescence from GaN-polymer heterojunction

Inorganic and organic semiconductor devices are generally viewed as distinct and separate technologies. Herein we report a hybrid inorganic-organic light-emitting device employing the use of an air stable polymer, Poly (9,9-dioctylfluorene-alt-benzothiadiazole) as a p-type layer to create a heterojunction, avoiding the use of p-type GaN, which is difficult to grow, being prone to the complex and expensive fabrication techniques that characterises it. I-V characteristics of the GaN-polymer heterojunction fabricated by us exhibits excellent rectification. The luminescence onset voltage is typically about 8-10 V. The device emits yellowish white electroluminescence with CIE coordinates (0.42, 0.44). (C) 2011 Elsevier B.V. All rights reserved.

Subdiffusion as a model of transport through the nuclear pore complex

Cargo transport through the nuclear pore complex continues to be a subject of considerable interest to experimentalists and theorists alike. Several recent studies have revealed details of the process that have still to be fully understood, among them the apparent nonlinearity between cargo size and the pore crossing time, the skewed, asymmetric nature of the distribution of such crossing times, and the non-exponentiality in the decay profile of the dynamic autocorrelation function of cargo positions. In this paper, we show that a model of pore transport based on subdiffusive particle motion is in qualitative agreement with many of these observations. The model corresponds to a process of stochastic binding and release of the particle as it moves through the channel. It suggests that the phenylalanine-glycine repeat units that form an entangled polymer mesh across the channel may be involved in translocation, since these units have the potential to intermittently bind to hydrophobic receptor sites on the transporter protein. (C) 2011 American Institute of Physics. [doi:10.1063/1.3651100]

1-D Hydrogen bonded water in Cu(II)-picolinate coordination polymer: synthesis, crystal structure, and thermogravimetric analysis

A new Cu(II)-picolinate complex was synthesized and characterized by single crystal X-ray crystallography. The complex crystallizes in the centrosymmetric triclinic space group P (1) over bar (no. 2). Picolinate in the complex extends the neutral unit into a 1-D chain through mu(2)-bridging carboxylate. The complex has a hydrogen bonding acceptor in the second coordination sphere allowing lattice water to assemble neighboring chains. Water self-assembles to form a zig-zag 1-D chain. The adjacent chains are assembled by C-H center dot center dot center dot O interactions result in the formation 2-D hydrogen bonded network. The overall hydrogen bonding between water chain and Cu-picolinate network yields a 3-D hydrogen bonded coordination network. X-ray structural analysis, FTIR and thermal analysis have been used to characterize the reported compound in the solid state.

Fish inspired biomimetic ionic polymer metal composite pectoral fins using labriform propulsion

Ionic polymer metal composites (IPMC) are a new class of smart materials that have attractive characteristics such as muscle like softness, low voltage and power consumption, and good performance in aqueous environments. Thus, IPMC’s provide promising application for biomimetic fish like propulsion systems. In this paper, we design and analyze IPMC underwater propulsor inspired from swimming of Labriform fishes. Different fish species in nature are source of inspiration for different biomimetic flapping IPMC fin design. Here, three fish species with high performance flapping pectoral fin locomotion is chosen and performance analysis of each fin design is done to discover the better configurations for engineering applications. In order to describe the behavior of an active IPMC fin actuator in water, a complex hydrodynamic function is used and structural model of the IPMC fin is obtained by modifying the classical dynamic equation for a slender beam. A quasi-steady blade element model that accounts for unsteady phenomena such as added mass effects, dynamic stall, and the cumulative Wagner effect is used to estimate the hydrodynamic performance of the flapping rectangular shape fin. Dynamic characteristics of IPMC actuated flapping fins having the same size as the actual fins of three different fish species, Gomphosus varius, Scarus frenatus and Sthethojulis trilineata, are analyzed with numerical simulations. Finally, a comparative study is performed to analyze the performance of three different biomimetic IPMC flapping pectoral fins.

Role of silica nanoparticles in conductivity enhancement of nanocomposite solid polymer electrolytes: (PEG(x) NaBr): ySiO(2)

Nanocomposite solid polymer electrolytes (NCSPEs) with conducting species other than Li ions are being investigated for solid-state battery applications. Pristine solid polymer electrolytes (SPEs) do not show ionic conductivity suitable for batteries. Addition of inert fillers to SPEs is known to enhance the ionic conductivity. In this paper, we present the role of silica nanoparticles in enhancing the ionic conductivity in NCSPEs with sodium as conducting species. Sodium bromide is complexed with the host polyethylene glycol polymer by solution cast method and silica nanoparticles (SiO2, average particle size 7 nm) are incorporated into the complex in small amounts. The composites are characterized by powder XRD and IR spectroscopy. Conductivity measurements are undertaken as a function of concentration of salt and also as a function of temperature using impedance spectroscopy. Addition of silica nanoparticles shows an enhancement in conductivity by 1-2 orders of magnitude. The results are discussed in terms of interaction of nanoparticles with the nonconducting anions.

D-A-D-structured conducting polymer-modified electrodes for detection of lead(II) ions in water

Donor-acceptor-donor-structured thiophene derivative-based conducting polymer poly(7,9-dithiophene-2yl-8H-cyclopentaa]acenaphthalene-8-one) was chemically synthesized. This polymer was used to modify both glassy-carbon and carbon-paste electrode, which was used to detect lead(II) ions present in water in the range of 1 mM to 0.1 mu M. Cyclic voltammetry confirms the formation of the co-ordination complex between the soft segment of polymer and the dissolved lead ion. Anodic stripping voltammetry was carried out by the modified electrode to determine the lower limit of detection of dissolved lead(II) species in the solution. Differential adsorptive stripping and impedance measurements were also conducted to find the lowest possible response of the as-synthesized polymer to lead(II) ion in water. The electrochemical performance of the modified electrodes at different pH (4, 7 and 9) environments was carried out by stripping voltammetry, to get optimum sensitivity and stability under these conditions. Finally, interference analysis was carried out to detect the modified electrode's sensitivity towards lead ion affinity in water.

Diffusion in an elastic medium: A model for macromolecule transport across the nuclear pore complex

Nuclear pore complexes (NPCs) are very selective filters that sit on the membrane of the nucleus and monitor the transport between the cytoplasm and the nucleoplasm. For the central plug of NPC two models have been suggested in the literature. The first suggests that the plug is a reversible hydrogel while the other suggests that it is a polymer brush. Here we propose a model for the transport of a protein through the plug, which is general enough to cover both the models. The protein stretches the plug and creates a local deformation, which together with the protein, we refer to as the bubble. We start with the free energy for creation of the bubble and consider its motion within the plug. The relevant coordinate is the center of the bubble which executes random walk. We find that for faster relaxation of the gel, the diffusion of the bubble is greater. (C) 2014 Elsevier-B.V. All rights reserved.