Energy transfer efficiency distributions in polymers in solution during folding and unfolding

Distribution of fluorescence resonance energy transfer (FRET) efficiency between the two ends of a Lennard-Jones polymer chain both at equilibrium and during folding and unfolding has been calculated, for the first time, by Brownian dynamics simulations. The distribution of FRET efficiency becomes bimodal during folding of the extended state subsequent to a temperature quench, with the width of the distribution for the extended state broader than that for the folded state. The reverse process of unfolding subsequent to a upward temperature jump shows different characteristics. The distributions show significant viscosity dependence which can be tested against experiments.

Thermally induced phase separation in P alpha MSAN/PMMA blends in presence of functionalized multiwall carbon nanotubes: Rheology, morphology and electrical conductivity

The focus of this work is the evaluation and analysis of the state of dispersion of functionalized multiwall carbon nanotubes (CNTs), within different morphologies formed, in a model LCST blend (poly[(alpha-methylstyrene)-co-(acrylonitrile)]/poly(methyl-methacryla te), P alpha MSAN/PMMA). Blend compositions that are expected to yield droplet-matrix (85/15 P alpha MSAN/PMMA and 15/85 P alpha MSAN/PMMA, wt/wt) and co-continuous morphologies (60/40 P alpha MSAN/PMMA, wt/wt) upon phase separation have been combined with two types of CNTs; carboxylic acid functionalized (CNTCOOH) and polyethylene modified (CNTPE) up to 2 wt%. Thermally induced phase separation in the blends has been studied in-situ by rheology and dielectric (conductivity) spectroscopy in terms of morphological evolution and CNT percolation. The state of dispersion of CNTs has been evaluated by transmission electron microscopy. The experimental results indicate that the final blend morphology and the surface functionalization of CNT are the main factors that govern percolation. In presence of either of the CNTs, 60/40 P alpha MSAN/PMMA blends yield a droplet-matrix morphology rather than co-continuous and do not show any percolation. On the other hand, both 85/15 P alpha MSAN/PMMA and 15/85 P alpha MSAN/PMMA blends containing CNTPEs show percolation in the rheological and electrical properties. Interestingly, the conductivity spectroscopy measurements demonstrate that the 15/85 P alpha MSAN/PMMA blends with CNTPEs that show insulating properties at room temperature for the miscible blends reveal highly conducting properties in the phase separated blends (melt state) as a result of phase separation. By quenching this morphology, the conductivity can be retained in the blends even in the solid state. (C) 2011 Elsevier Ltd. All rights reserved.

Synthesis, X-ray crystal structure, DNA binding, antioxidant and cytotoxicity studies of Ni(II) and Pd(II) thiosemicarbazone complexes

New complexes, [Ni(HL)(PPh3)]Cl (1), [Pd(L)(PPh3)](2), and [Pd(L)(AsPh3)](3), were synthesized from the reactions of 4-chloro-5-methyl-salicylaldehyde thiosemicarbazone [H2L] with [NiCl2(PPh3)(2)], [PdCl2(PPh3)(2)] and [PdCl2(AsPh3)(2)]. They were characterized by IR, electronic, H-1-NMR spectral data. Further, the structures of the complexes have been determined by single crystal X-ray diffraction. While the thiosemicarbazone coordinated as binegative tridentate (ONS) in complexes 2 and 3, it is coordinated as mono negative tridentate (ONS) in 1. The interactions of the new complexes with calf thymus DNA was examined by absorption and emission spectra, and viscosity measurements. Moreover, the antioxidant properties of the new complexes have also been tested against DPPH radical in which complex 1 exhibited better activity than that of the other two complexes 2 and 3. The in vitro cytotoxicity of complexes 1-3 against A549 and HepG2 cell lines was assayed, and the new complexes exhibited higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations.

Particle image velocimetry and infrared thermography in a levitated droplet with nanosilica suspensions

Preferential accumulation and agglomeration kinetics of nanoparticles suspended in an acoustically levitated water droplet under radiative heating has been studied. Particle image velocimetry performed to map the internal flow field shows a single cell recirculation with increasing strength for decreasing viscosities. Infrared thermography and high speed imaging show details of the heating process for various concentrations of nanosilica droplets. Initial stage of heating is marked by fast vaporization of liquid and sharp temperature rise. Following this stage, aggregation of nanoparticles is seen resulting in various structure formations. At low concentrations, a bowl structure of the droplet is dominant, maintained at a constant temperature. At high concentrations, viscosity of the solution increases, leading to rotation about the levitator axis due to the dominance of centrifugal motion. Such complex fluid motion inside the droplet due to acoustic streaming eventually results in the formation of a ring structure. This horizontal ring eventually reorients itself due to an imbalance of acoustic forces on the ring, exposing larger area for laser absorption and subsequent sharp temperature rise.

Implications of a viscosity bound on black hole accretion

Motivated by the viscosity bound in gauge/gravity duality, we consider the ratio of shear viscosity (eta) to entropy density (s) in black hole accretion flows. We use both an ideal gas equation of state and the QCD equation of state obtained from lattice for the fluid accreting onto a Kerr black hole. The QCD equation of state is considered since the temperature of accreting matter is expected to approach 10(12) K in certain hot flows. We find that in both the cases eta/s is small only for primordial black holes and several orders of magnitude larger than any known fluid for stellar and supermassive black holes. We show that a lower bound on the mass of primordial black holes leads to a lower bound on eta/s and vice versa. Finally we speculate that the Shakura-Sunyaev viscosity parameter should decrease with increasing density and/or temperatures. (C) 2012 Elsevier B.V. All rights reserved.

Composites of Graphene and Other Nanocarbons with Organogelators Assembled through Supramolecular Interactions

Carbon nanomaterials (CNMs), such as exfoliated graphene (EG), long-chain functionalized EG, single-walled carbon nanotubes (SWNTs), and fullerene (C-60), have been investigated for their interaction with two structurally different gelators based on all-trans tri-p-phenylenevinylene bis-aldoxime (1) and n-lauroyl-L-alanine (2) both in solution and in supramolecular organogels. Gelation occurs in toluene through hydrogen bonding and van der Waals interactions for 1 and 2 in addition to pp stacking specifically in the case of 1. These nanocomposites provide a thorough understanding in terms of molecular-level interactions of dimensionally different CNMs with structurally different gelators. The presence of densely wrapped CNMs encapsulated fibrous network in the resulting composites is evident from various spectroscopic and microscopic studies, indicating the presence of supramolecular interactions. Concentration- and temperature-dependent UV/Vis and fluorescence spectra show that CNMs promote aggregation of the gelator molecules, leading to hypochromism and quenching of the fluorescence intensity. Thermotropic mesophases of 1 are altered by the inclusion of a small amount of CNMs. The gelCNM composites show increased electrical conductivity compared with that of the native organogel. Rheological studies of the composites demonstrate the formation of rigid and viscoelastic solidlike assembly due to reinforced aggregation of the gelators on CNMs. Synergistic behavior is observed in case of the composite gel of 1, containing a mixture of EG and SWNT, when compared with other mixtures of CNMs in all combinations with EG. This affords new nanocomposites with interesting optical, thermal, electrical, and mechanical properties.

Photo, thermal, and ultrasonic degradation of EGDMA-crosslinked poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Superabsorbent polymers (SAPs) based on acrylic acid (AA), sodium acrylate (SA), and acrylamide (AM) were synthesized by inverse suspension polymerization using ethylene glycol dimethacrylate as the crosslinking agent. The equilibrium swelling capacities and the rates of swelling of SAPs varied with the AM content and followed first-order kinetics. The photodegradation of SAPs in their equilibrium swollen state was carried out by monitoring their swelling capacity and the residual weight fraction. The SAPs degraded in two stages, wherein the swelling capacity increased to a maximum and then subsequently decreased. Thermogravimetric analysis of the SAPs indicated that the copolymeric superabsorbents had intermediate thermal stability between the homopolymeric superabsorbents. The activation energies of SAPs with 0, 20, and 100 mol % AM content were determined by Kissinger method and were found to be 299, 248, and 147 kJ mol-1, respectively. The ultrasonic degradation of the superabsorbents was carried out in their equilibrium swollen state, and the change in the viscosity with ultrasonication time was used to quantify the degradation. The ultrasonic degradation of AA/SA superabsorbent was also investigated at various ultrasound intensities. The degradation rate coefficients were found to increase with the intensity of ultrasound. The ultrasonic degradation of AA/SA/AM (20% AM) was also carried out, and degradation rate was found to be more than that of the AA/SA superabsorbent. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Evaluation of DNA binding, antioxidant and cytotoxic activity of mononuclear Co(III) complexes of 2-oxo-1,2-dihydrobenzoh]quinoline-3-carbaldehyde thiosemicarbazones

Four new 2-oxo-1,2-dihydrobenzoh]quinoline-3-carbaldehyde N-substituted thiosemicarbazone ligands (H-2-LR, where R = H, Me, Et or Ph) and their corresponding new cobalt(III) complexes have been synthesized and characterized. The structures of the complexes 2 and 3 were determined by single crystal X-ray diffraction analysis. The interactions of the new complexes with DNA were investigated by absorption, emission and viscosity studies which indicated that the complexes bind to DNA via intercalation. Antioxidant studies of the new complexes showed that the significant antioxidant activity against DPPH radical. In addition, the in vitro cytotoxicity of complexes 1-4 against A549 cell line was assayed which showed higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations. (C) 2012 Elsevier Masson SAS. All rights reserved.

Electrochemical, phosphate hydrolysis, DNA binding and DNA cleavage properties of new polyaza macrobicyclic dinickel(II) complexes

A new class of macrobicyclic dinickel(II) complexes Ni2L1,2 B](ClO4)(4) (1-6), where L-1,L-2 are polyaza macrobicyclic binucleating ligands, and B is a N,N-donor heterocyclic base (viz. 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)) are synthesized and characterized. The redox, catalytic, DNA binding and DNA cleavage properties were studied. They exhibit two irreversible waves in the cathodic region around E-pc = -0.95 V and E-pa = -0.85 V vs. Ag/Ag+ in CH3CN-0.1 M TBAP, respectively. The first order rate constants for the hydrolysis of 4-nitrophenylphosphate to 4-nitrophenolate by the dinickel(II) complexes 1-6 are in the range from 3.36 x 10(-5) to 10.83 x 10(-5) Ms-1. The complexes 3 and 6 show good binding propensity to calf thymus DNA giving binding constant values (K-b) in the range from 3.08 x 10(5) to 5.37 x 10(5) M-1. The binding site sizes and viscosity data suggest the DNA intercalative and/or groove binding nature of the complexes. The complexes display significant hydrolytic cleavage of supercoiled pBR322DNA at pH 7.2 and 37 degrees C. The hydrolytic cleavage of DNA by the complexes is supported by the evidence from free radical quenching and T4 ligase ligation. The pseudo Michaelis-Menten kinetic parameters k(cat) = 5.44 x 10(-2) h(-1) and K-M = 6.23 x 10(-3) M for complex 3 were obtained. Complex 3 also shows an enormous enhancement of the cleavage rate, of 1.5 x 10(6), in comparison to the uncatalysed hydrolysis rate (k = 3.6 x 10(-8) h(-1)) of ds-DNA.

Stabilized SPH-based simulations of impact dynamics using acceleration-corrected artificial viscosity

Artificial viscosity in SPH-based computations of impact dynamics is a numerical artifice that helps stabilize spurious oscillations near the shock fronts and requires certain user-defined parameters. Improper choice of these parameters may lead to spurious entropy generation within the discretized system and make it over-dissipative. This is of particular concern in impact mechanics problems wherein the transient structural response may depend sensitively on the transfer of momentum and kinetic energy due to impact. In order to address this difficulty, an acceleration correction algorithm was proposed in Shaw and Reid (''Heuristic acceleration correction algorithm for use in SPH computations in impact mechanics'', Comput. Methods Appl. Mech. Engrg., 198, 3962-3974) and further rationalized in Shaw et al. (An Optimally Corrected Form of Acceleration Correction Algorithm within SPH-based Simulations of Solid Mechanics, submitted to Comput. Methods Appl. Mech. Engrg). It was shown that the acceleration correction algorithm removes spurious high frequency oscillations in the computed response whilst retaining the stabilizing characteristics of the artificial viscosity in the presence of shocks and layers with sharp gradients. In this paper, we aim at gathering further insights into the acceleration correction algorithm by further exploring its application to problems related to impact dynamics. The numerical evidence in this work thus establishes that, together with the acceleration correction algorithm, SPH can be used as an accurate and efficient tool in dynamic, inelastic structural mechanics. (C) 2011 Elsevier Ltd. All rights reserved.

Ionic conductivity of bis(2-cyanoethyl) ether-lithium salt and poly(propylether imine)-lithium salt liquid electrolytes

We report here a multiple-nitrile based lithium-salt liquid electrolyte. The ionic conductivity of poly (propyl ether imine) (abbreviated as PETIM) lithium salt dendrimer liquid electrolyte was observed to be a function of dendrimer generation number, n=0 (monomer)-3. While the highest room temperature ionic conductivity value (similar to 10(-1) Sm-1) was recorded for the bis-2cyanoethyl ether monomer (i.e. zeroth generation; G(0)-CN), conductivity decreased progressively to lower values (similar to 10(-3) Sm-1) with increase in generation number (G(1)-CN -> G(3)-CN). The G(0)-CN and higher dendrimer generations showed high thermal stability (approximate to 150 to 200 degrees C), low moisture sensitivity and tunable viscosity (similar to 10(-2) (G(0)-CN) to 3 (G(3)-CN) Pa s). The linker ether group was found to be crucial for ion transport and also eliminated a large number of detrimental features, chiefly moisture sensitivity, chemical instability associated typically with prevalent molecular liquid solvents. Based on the combination of several beneficial physicochemical properties, we presently envisage that the PETIM dendrimers especially the G(0)-CN electrolytes hold promise as electrolytes in electrochemical devices such as lithium-ion batteries.

Spreading and atomization of droplets on a vibrating surface in a standing pressure field

We report the first observation and analytical model of deformation and spreading of droplets on a vibrating surface under the influence of an ultrasonic standing pressure field. The standing wave allows the droplet to spread, and the spreading rate varies inversely with viscosity. In low viscosity droplets, the synergistic effect of radial acoustic force and the transducer surface acceleration also leads to capillary waves. These unstable capillary modes grow to cause ultimate disintegration into daughter droplets. We find that using nanosuspensions, spreading and disintegration can be prevented by suppressing the development of capillary modes and subsequent break-up. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4757567]

Velocity and rotation measurements in acoustically levitated droplets

The velocity scale inside an acoustically levitated droplet depends on the levitator and liquid properties. Using Particle Imaging Velocimetry (PIV), detailed velocity measurements have been made in a levitated droplet of different diameters and viscosity. The maximum velocity and rotation are normalized using frequency and amplitude of acoustic levitator, and droplet viscosity. The non-dimensional data are fitted for micrometer- and millimeter-sized droplets levitated in different levitators for different viscosity fluids. It is also shown that the rotational speed of nanosilica droplets at an advanced stage of vaporization compares well with that predicted by exponentially fitted parameters. (C) 2012 Elsevier B.V. All rights reserved.

Cobalt(II), Nickel(II) and Copper(II) complexes of a tetradentate Schiff base as photosensitizers: Quantum yield of O-1(2) generation and its promising role in anti-tumor activity

In the present investigation, a Schiff base N'(1),N'(3)-bis(E)-(5-bromo-2-hydroxyphenyl)methylidene]benzene-1,3-d icarbohydrazide and its metal complexes have been synthesized and characterized. The DNA-binding studies were performed using absorption spectroscopy, emission spectra, viscosity measurements and thermal denatuaration studies. The experimental evidence indicated that, the Co(II), Ni(II) and Cu(II) complexes interact with calf thymus DNA through intercalation with an intrinsic binding constant K-b of 2.6 x 10(4) M-1, 5.7 x 10(4) M-1 and 4.5 x 10(4) M-1, respectively and they exhibited potent photo-damage abilities on pUC19 DNA, through singlet oxygen generation with quantum yields of 0.32, 0.27 and 0.30 respectively. The cytotoxic activity of the complexes resulted that they act as a potent photosensitizers for photochemical reactions. (C) 2012 Elsevier B.V. All rights reserved.