Optically transparent polymer devices for in situ assessment of cell electroporation

In order to study cell electroporation in situ, polymer devices have been fabricated from poly-dimethyl siloxane with transparent indium tin oxide parallel plate electrodes in horizontal geometry. This geometry with cells located on a single focal plane at the interface of the bottom electrode allows a longer observation time in both transmitted bright-field and reflected fluorescence microscopy modes. Using propidium iodide (PI) as a marker dye, the number of electroporated cells in a typical culture volume of 10-100 mu l was quantified in situ as a function of applied voltage from 10 to 90 V in a series of 2-ms pulses across 0.5-mm electrode spacing. The electric field at the interface and device current was calculated using a model that takes into account bulk screening of the transient pulse. The voltage dependence of the number of electroporated cells could be explained using a stochastic model for the electroporation kinetics, and the free energy for pore formation was found to be kT at room temperature. With this device, the optimum electroporation conditions can be quickly determined by monitoring the uptake of PI marker dye in situ under the application of millisecond voltage pulses. The electroporation efficiency was also quantified using an ex situ fluorescence-assisted cell sorter, and the morphology of cultured cells was evaluated after the pulsing experiment. Importantly, the efficacy of the developed device was tested independently using two cell lines (C2C12 mouse myoblast cells and yeast cells) as well as in three different electroporation buffers (phosphate buffer saline, electroporation buffer and 10 % glycerol).

Kinetics of dispersion of nanoparticles in thin polymer films at high temperature

We report the first detailed study of the kinetics of dispersion of nanoparticles in thin polymer films using temperature dependent in situ X-ray scattering measurements. We show a comparably enhanced dispersion at higher temperatures for systems which are otherwise phase segregated at room temperature. Detailed analysis of the time dependent X-ray reflectivity and diffuse scattering data allows us to explore the out-of-plane and in-plane mobility of the nanoparticles in the polymer films. While the out-of-plane motion is diffusive with a diffusion coefficient almost two orders of magnitude lower than that expected in bulk polymer, the in-plane one is found to be super-diffusive resulting in significantly larger in-plane displacement at similar time scales. We discuss the origin of the observed highly anisotropic motion of nanoparticles due to their slaved motion with respect to the anisotropic chain orientation and consequent diffusivity anisotropy of matrix chains. We also suggest strategies to utilize these observations to kinetically improve dispersion in otherwise thermodynamically segregated polymer nanocomposite films.

Performance Analysis of Heat Sinks With Phase-Change Materials Subjected to Transient and Cyclic Heating

Phase-change cooling technique is a suitable method for thermal management of electronic equipment subjected to transient or cyclic heat loads. The thermal performance of a phase-change based heat sink under cyclic heat load depends on several design parameters, namely, applied heat flux, cooling heat transfer coefficient, thermophysical properties of phase-change materials (PCMs), and physical dimensions of phase-change storage system during melting and freezing processes. A one-dimensional conduction heat transfer model is formulated to evaluate the effectiveness of preliminary design of practical PCM-based energy storage units. In this model, the phase-change process of the PCM is divided into melting and solidification subprocesses, for which separate equations are written. The equations are solved sequentially and an explicit closed-form solution is obtained. The efficacy of analytical model is estimated by comparing with a finite-volume-based numerical solution for both transient and cyclic heat loads.

Analyzing the kinetic response of tin oxide-carbon and tin oxide-CNT composites gas sensors for alcohols detection

Tin oxide nanoparticles are synthesized using solution combustion technique and tin oxide - carbon composite thick films are fabricated with amorphous carbon as well as carbon nanotubes (CNTs). The x-ray diffraction, Raman spectroscopy and porosity measurements show that the as-synthesized nanoparticles are having rutile phase with average crystallite size similar to 7 nm and similar to 95 m(2)/g surface area. The difference between morphologies of the carbon doped and CNT doped SnO2 thick films, are characterized using scanning electron microscopy and transmission electron microscopy. The adsorption-desorption kinetics and transient response curves are analyzed using Langmuir isotherm curve fittings and modeled using power law of semiconductor gas sensors. (C) 2015 Author(s).

Observation of photobleaching and intensity dependent kinetics in Ge22As22Se56 thin films under sub-bandgap light illumination

We experimentally demonstrate photobleaching (PB) in Ge22As22Se56 thin films, when illuminated with a diode pumped solid state laser (DPSSL) of wavelength 671 nm, which is far below the optical bandgap of the sample. Interestingly, we found that PB is a slow process and occurs even at moderate pump beam intensity of 0.2 W/cm(2), however the kinetics remain rather different.

Kinetics of CO oxidation on palladium using microkinetics coupled with reaction route analysis

A plausible microkinetic model has been proposed for the CO oxidation reaction catalysed by palladium (Pd) with the kinetic parameters obtained from the literature. A robust rate expression using the reaction route analysis has been developed for the presented microkinetic scheme and the obtained rate expressions have been validated against the experimental data presented in the literature. A wide range of experimental conditions ranging from single Pd crystals under ultra-high vacuum conditions and impregnated Pd used for fixed bed experiments under atmospheric pressure has been used to validate the reaction mechanism. (C) 2015 Elsevier Ltd. All rights reserved.

Mapping the intriguing transient morphologies and the demixing behavior in PS/PVME blends in the presence of rod-like nanoparticles

The demixing behavior, transient morphologies and mechanism of phase separation in PS/PVME blends were greatly altered in the presence of a very low concentration of rod-like particles (multiwall carbon nanotubes, MWNTs). This phenomenon is due to the specific interaction of one of the phases (PVME) with the anisotropic MWNTs, which creates a heterogeneous environment in the blend. This specific interaction alters the chain dynamics in the interfacial region as against the bulk. A comprehensive analysis using isochronal temperature sweep was performed to understand the demixing temperature in the blends. The evolution of phase morphology as a function of time and temperature was assessed by polarizing optical microscopy (POM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The addition of MWNTs increased the rheological demixing temperature and the spinodal temperature in almost all the compositions. The intriguing transient morphologies were mapped, which varied from nucleation and growth to coalescence-induced viscoelastic phase separation (C-VPS) in PVME-rich blends, to spinodal decomposition in the near-critical compositions, to transient gel-induced VPS (T-VPS) in the PS-rich compositions. Mapping of the morphology development displayed two types of fracture mechanisms: ductile fracture for near-critical compositions and brittle fracture for off-critical composition. The change in the phase separation mechanism in the presence of MWNTs was due to the variation in dynamic asymmetry brought about by these anisotropic particles. All these observations were correlated by POM, SEM and AFM studies. The length of the cooperatively rearranging region (CRR), as evaluated using modulated differential scanning calorimetry (MDSC) measurements, was found to be composition-independent. The observed variation of effective glass transition of PVME (low T-g component) on blending with PS (high Tg component) and by the addition of MWNTs accounts for the dynamic heterogeneity introduced by MWNTs in the system.

Origin of nonlinearity and plausible turbulence by hydromagnetic transient growth in accretion disks: Faster growth rate than magnetorotational instability

We investigate the evolution of hydromagnetic perturbations in a small section of accretion disks. It is known that molecular viscosity is negligible in accretion disks. Hence, it has been argued that a mechanism, known as magnetorotational instability (MRI), is responsible for transporting matter in the presence of a weak magnetic field. However, there are some shortcomings, which question the effectiveness of MRI. Now the question arises, whether other hydromagnetic effects, e.g., transient growth (TG), can play an important role in bringing nonlinearity into the system, even at weak magnetic fields. In addition, it should be determined whether MRI or TG is primarily responsible for revealing nonlinearity in order to make the flow turbulent. Our results prove explicitly that the flows with a high Reynolds number (Re), which is the case for realistic astrophysical accretion disks, exhibit nonlinearity via TG of perturbation modes faster than that by modes producing MRI. For a fixed wave vector, MRI dominates over transient effects only at low Re, lower than the value expected to be in astrophysical accretion disks, and low magnetic fields. This calls into serious question the (overall) persuasiveness of MRI in astrophysical accretion disks.

Effective Degradation of Aqueous Nitrobenzene Using the SrFeO3-delta Photocatalyst under UV Illumination and Its Kinetics and Mechanistic Studies

In this article, the SrFeO3-delta photocatalyst was synthesized by a solution combustion method and applied for the photocatalytic degradation of aqueous nitrobenzene in the presence and absence of H2O2. The SrFeO3-delta photocatalyst was characterized by XRD, FT-IR, FE-SEM, TEM, TG-DTG, XPS, and UV visible spectroscopy. The band gap energy of SrFeO3-delta was found to be 3.75 eV which lies in the UV region. The XPS results indicate that the oxidation state of Sr and Fe in SrFeO3-delta was 2+ and 3+, respectively, and the surface atomic ratio of Sr and Fe is 0.995. The photocatalytic activity reveals that the degradation of nitrobenzene over the SrFeO3-delta catalyst itself (UV/SFO) is superior compared to SrFeO3-delta in the presence of H2O2 (UV/SFO/H2O2) with a degradation efficiency of 99-96%. The degradation of nitrobenzene obeys first-order kinetics in both UV/SFO and UV/SFO/H2O2 processes. The decrease in degradation efficiency with UV/SFO/H2O2 was attributed due to the formation of strontium carbonate on the photocatalyst surface.

Universal buckling kinetics in drying nanoparticle-laden droplets on a hydrophobic substrate

We provide a comprehensive physical description of the vaporization, self-assembly, agglomeration, and buckling kinetics of sessile nanofluid droplets pinned on a hydrophobic substrate. We have deciphered five distinct regimes of the droplet life cycle. Regimes I-III consists of evaporation-induced preferential agglomeration that leads to the formation of a unique dome-shaped inhomogeneous shell with a stratified varying-density liquid core. Regime IV involves capillary-pressure-initiated shell buckling and stress-induced shell rupture. Regime V marks rupture-induced cavity inception and growth. We demonstrate through scaling arguments that the growth of the cavity (which controls the final morphology or structure) can be described by a universal function.

Weak conservation of structural features in the interfaces of homologous transient protein-protein complexes

Residue types at the interface of protein-protein complexes (PPCs) are known to be reasonably well conserved. However, we show, using a dataset of known 3-D structures of homologous transient PPCs, that the 3-D location of interfacial residues and their interaction patterns are only moderately and poorly conserved, respectively. Another surprising observation is that a residue at the interface that is conserved is not necessarily in the interface in the homolog. Such differences in homologous complexes are manifested by substitution of the residues that are spatially proximal to the conserved residue and structural differences at the interfaces as well as differences in spatial orientations of the interacting proteins. Conservation of interface location and the interaction pattern at the core of the interfaces is higher than at the periphery of the interface patch. Extents of variability of various structural features reported here for homologous transient PPCs are higher than the variation in homologous permanent homomers. Our findings suggest that straightforward extrapolation of interfacial nature and inter-residue interaction patterns from template to target could lead to serious errors in the modeled complex structure. Understanding the evolution of interfaces provides insights to improve comparative modeling of PPC structures.

Controlled release kinetics of p-aminosalicylic acid from biodegradable crosslinked polyesters for enhanced anti-mycobacterial activity

Unlike conventional polymeric drug delivery systems, where drugs are entrapped in polymers, this study focuses on the incorporation of the drug into the polymer backbone to achieve higher loading and sustained release. Crosslinked, biodegradable, xylitol based polyesters have been synthesized in this study. The bioactive drug moiety, p-aminosalicylic acid (PAS), was incorporated in xylitol based polyesters to impart its anti-mycobacterial activity. To understand the influence of the monomer chemistry on the incorporation of PAS and its subsequent release from the polymer, different diacids have been used. Controlled release profiles of the drug from these polyesters were studied under normal physiological conditions. The degradation of the polyesters varied from 48% to 76% and the release of PAS ranged from 54% to 65% of its initial loading in 7 days. A new model was developed to explain the release kinetics of PAS from the polymer that accounted for the polymer degradation and drug concentration. The thermal, mechanical, drug release and cytocompatibility properties of the polymers indicate their suitability in biomedical applications. The released products from these polymers were observed to be pharmacologically active against Mycobacteria. The high drug loading and sustained release also ensured enhanced efficacy. These polymers form biocompatible, biodegradable polyesters where the sustained release of PAS may be tailored for potential treatment of mycobacterial infections. Statement of significance In the present work, we report on novel polyesters with p-aminosalicylic acid (PAS) incorporated in the polymer backbone. The current work aims to achieve controlled release of PAS and ensures the delivered PAS is stable and pharmacologically active. The novelty of this work primarily involves the synthetic chemistry of polymerization and detailed analysis and efficacy of active PAS delivery. A new kinetic model has been developed to explain the PAS release profiles. These polymers are biodegradable, cytocompatible and anti-mycobacterial in nature. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Fast and slow climate responses to CO2 and solar forcing: A linear multivariate regression model characterizing transient climate change

Climate change in response to a change in external forcing can be understood in terms of fast response to the imposed forcing and slow feedback associated with surface temperature change. Previous studies have investigated the characteristics of fast response and slow feedback for different forcing agents. Here we examine to what extent that fast response and slow feedback derived from time-mean results of climate model simulations can be used to infer total climate change. To achieve this goal, we develop a multivariate regression model of climate change, in which the change in a climate variable is represented by a linear combination of its sensitivity to CO2 forcing, solar forcing, and change in global mean surface temperature. We derive the parameters of the regression model using time-mean results from a set of HadCM3L climate model step-forcing simulations, and then use the regression model to emulate HadCM3L-simulated transient climate change. Our results show that the regression model emulates well HadCM3L-simulated temporal evolution and spatial distribution of climate change, including surface temperature, precipitation, runoff, soil moisture, cloudiness, and radiative fluxes under transient CO2 and/or solar forcing scenarios. Our findings suggest that temporal and spatial patterns of total change for the climate variables considered here can be represented well by the sum of fast response and slow feedback. Furthermore, by using a simple 1-D heat-diffusion climate model, we show that the temporal and spatial characteristics of climate change under transient forcing scenarios can be emulated well using information from step-forcing simulations alone.

On variant distribution and coarsening behavior of the a phase in a metastable beta titanium alloy

The stereology, variant distribution and coarsening behavior of semicoherent alpha(hcp) precipitates in a beta(bcc) matrix of a Ti5553 alloy has been analyzed, and a dominant 3-variant cluster has been observed in which the variants are related to each other by an axis-angle pair <<11(2)over bar> 0 >/60 degrees. Shape and spatial distribution independent elastic self and interaction energies for all pairwise and triplet combinations of a have been calculated and it is found that the 3-cluster combination that is experimentally observed most frequently has the lowest energy for the semicoherent state. The coarsening behavior of the delta distribution follows LSW kinetics after an initial transient, and has been modeled by phase field methods. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.