Efficacious redox-responsive gene delivery in serum by ferrocenylated monomeric and dimeric cationic cholesterols

Herein, we present the design and synthesis of new redox-active monomeric and dimeric (gemini) cationic lipids based on ferrocenylated cholesterol derivatives for gene delivery. The cationic cholesterols are shown to be transfection efficient after being formulated with the neutral helper lipid DOPE in the presence of serum (FBS). The redox activity of the resulting co-liposomes and their lipoplexes could be regulated using the alkanyl ferrocene moiety attached to the ammonium head groups of the cationic cholesterols. Atomic force microscopy (AFM), dynamic light scattering (DLS) and zeta potential measurements were performed to characterize the co-liposomal aggregates and their complexes with pDNA. The transfection efficiency of lipoplexes could be tuned by changing the oxidation state of the ferrocene moiety. The gene transfection capability was assayed in terms of green fluorescence protein (GFP) expression using pEGFP-C3 plasmid DNA in three cell lines of different origins, namely Caco-2, HEK293T and HeLa, in the presence of serum. The vesicles possessing ferrocene in the reduced state induced an efficient transfection, even better than a commercial reagent Lipofectamine 2000 (Lipo 2000) as evidenced by flow cytometry and fluorescence microscopy. All the co-liposomes containing the oxidized ferrocene displayed diminished levels of gene expression. Gene transfection events from the oxidized co-liposomes were further potentiated by introducing ascorbic acid (AA) as a reducing agent during lipoplex incubation with cells, leading to the resumption of transfection activity. Assessment of transfection capability of both reduced and oxidized co-liposomes was also undertaken following cellular internalization of labelled pDNA using confocal microscopy and flow cytometry. Overall, we demonstrate here controlled gene transfection activities using redox-driven, transfection efficient cationic monomeric and dimeric cholesterol lipids. Such systems could be used in gene delivery applications where transfection needs to be performed spatially or temporally.

A spectral element for wave propagation in honeycomb sandwich construction considering core flexibility

Spectral elements are found to be extremely resourceful to study the wave propagation characteristics of structures at high frequencies. Most of the aerospace structures use honeycomb sandwich constructions. The existing spectral elements use single layer theories for a sandwich construction wherein the two face sheets vibrate together and this model is sufficient for low frequency excitations. At high frequencies, the two face sheets vibrate independently. The Extended Higher order SAndwich Plate theory (EHSaPT) is suitable for representing the independent motion of the face sheets. A 1D spectral element based on EHSaPT is developed in this work. The wave number and the wave speed characteristics are obtained using the developed spectral element. It is shown that the developed spectral element is capable of representing independent wave motions of the face sheets. The propagation speeds of a high frequency modulated pulse in the face sheets and the core of a honeycomb sandwich are demonstrated. Responses of a typical honeycomb sandwich beam to high frequency shock loads are obtained using the developed spectral element and the response match very well with the finite element results. It is shown that the developed spectral element is able to represent the flexibility of the core resulting into independent wave motions in the face sheets, for which a finite element method needs huge degrees of freedom. (C) 2015 Elsevier Ltd. All rights reserved.

Growth of TiO2 Films by RF Magnetron Sputtering for MOS Gate Dielectrics: Influence of Substrate Temperature

Titanium dioxide thin films were deposited by RF reactive magnetron sputtering technique on p-type silicon(100) substrates held at temperatures in the range 303-673 K. The influence of substrate temperature on the core level binding energies, chemical bonding configuration, crystallographic structure and dielectric properties was investigated. X-ray photoelectron spectroscopy studies and Fourier transform infrared transmittance data confirmed the formation of stoichiometric films with anatase phase at a substrate temperature of 673 K. The films formed at 303 K were nanocrystalline with amorphous matrix while those deposited at 673 K were transformed in to crystalline phase and growth of grains in pyramidal like structure as confirmed by X-ray diffraction and atomic force microscopy respectively. Metal-oxide-semiconductor capacitors were fabricated with the configuration of Al/TiO2/Si structures. The current voltage, capacitance voltage and conductance voltage characteristics were studied to understand the electrical conduction and dielectric properties of the MOS devices. The leakage current density (at gate voltage of 2 V) decreased from 2.2 x 10(-6) to 1.7 x 10(-7) A/cm(2), the interface trap density decreased from 1.2 x 10(13) to 2.1 x 10(12) cm(-2) eV(-1) and the dielectric constant increased from 14 to 36 with increase of substrate temperature from 303 to 673 K.

Deformability Measurement of Single-Cells at High-Throughput With Imaging Flow Cytometry

Disease conditions like malaria, sickle cell anemia, diabetes mellitus, cancer, etc., are known to significantly alter the deformability of certain types of cells (red blood cells, white blood cells, circulating tumor cells, etc.). To determine the cellular deformability, techniques like micropipette aspiration, atomic force microscopy, optical tweezers, quantitative phase imaging have been developed. Many of these techniques have an advantage of determining the single cell deformability with ultrahigh precision. However, the suitability of these techniques for the realization of a deformability based diagnostic tool is questionable as they are expensive and extremely slow to operate on a huge population of cells. In this paper, we propose a technique for high-throughput (800 cells/s) determination of cellular deformability on a single cell basis. This technique involves capturing the image(s) of cells in flow that have undergone deformation under the influence of shear gradient generated by the fluid flowing through the microfluidic channels. Deformability indices of these cells can be computed by performing morphological operations on these images. We demonstrate the applicability of this technique for examining the deformability index on healthy, diabetic, and sphered red blood cells. We believe that this technique has a strong role to play in the realization of a potential tool that uses deformability as one of the important criteria in disease diagnosis.

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.

Interplay of electrostatics and lipid packing determines the binding of charged polymer coated nanoparticles to model membranes

Understanding of nanoparticle-membrane interactions is useful for various applications of nanoparticles like drug delivery and imaging. Here we report on the studies of interaction between hydrophilic charged polymer coated semiconductor quantum dot nanoparticles with model lipid membranes. Atomic force microscopy and X-ray reflectivity measurements suggest that cationic nanoparticles bind and penetrate bilayers of zwitterionic lipids. Penetration and binding depend on the extent of lipid packing and result in the disruption of the lipid bilayer accompanied by enhanced lipid diffusion. On the other hand, anionic nanoparticles show minimal membrane binding although, curiously, their interaction leads to reduction in lipid diffusivity. It is suggested that the enhanced binding of cationic QDs at higher lipid packing can be understood in terms of the effective surface potential of the bilayers which is tunable through membrane lipid packing. Our results bring forth the subtle interplay of membrane lipid packing and electrostatics which determine nanoparticle binding and penetration of model membranes with further implications for real cell membranes.

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.

Structural and optical characterization of nonpolar (10-10) m-InN/m-GaN epilayers grown by PAMBE

Plasma-assisted molecular beam epitaxy growth of (10-10) m-InN/(10-10) m-GaN was carried out on bare (10-10) m-sapphire substrate. The high resolution X-ray diffraction studies confirmed the orientation of the as-grown films. Nonpolar InN layer was grown at different growth temperatures ranging from 390 degrees C to 440 degrees C and the FWHM of rocking curve revealed good quality film at low temperatures. An in-plane relationship was established for the hetrostructures using phi-scan and a perfect alignment was found for the epilayers. Change of morphology of the films grown at different temperatures was observed using an atomic force microscopy technique showing the smoothest film grown at 400 degrees C. InN optical band gap was found to be vary from 0.79-0.83 eV from absorption spectra. The blue-shift of absorption edge was found to be induced by excess background electron concentration. (C) 2015 Elsevier B.V. All rights reserved.

Solution processible Cu2SnS3 thin films for cost effective photovoltaics: Characterization

Thin films of Cu2SnS3 (CTS) were deposited by the facile solution processed sol-gel route followed by a low-temperature annealing. The Cu-Sn-thiourea complex formation was analysed using Fourier Transform Infrared spectrophotometer (FTIR). The various phase transformations and the deposition temperature range for the initial precursor solution was determined using Thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC). X-Ray Diffraction (XRD) studies revealed the tetragonal phase formation of the CTS annealed films. Raman spectroscopy studies further confirmed the tetragonal phase formation and the absence of any deterioratory secondary phases. The morphological investigations and compositional analysis of the films were determined using Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) respectively. Atomic Force Microscopy (AFM) was used to estimate the surface roughness of 1.3 nm. The absorption coefficient was found to be 10(4) cm(-1) and bandgap 1.3 eV which qualifies CTS to be a potential candidate for photovoltaic applications. The refractive index, extinction coefficient and relative permittivity of the film were measured by Spectroscopic ellipsometry. Hall effect measurements, indicated the p type nature of the films with a hole concentration of 2 x 10(18) cm(-3), electrical conductivity of 9 S/cm and a hole mobility of 29 cm(2)/V. The properties of CTS as deduced from the current study, present CTS as a potential absorber layer material for thin film solar cells. (C) 2015 Elsevier B.V. All rights reserved.

Enhanced UV detection by non-polar epitaxial GaN films

Nonpolar a-GaN (11-20) epilayers were grown on r-plane (1-102) sapphire substrates using plasma assisted molecular beam epitaxy. High resolution x-ray diffractometer confirmed the orientation of the grown film. Effect of the Ga/N ratio on the morphology and strain of a-GaN epilayers was compared and the best condition was obtained for the nitrogen flow of 1 sccm. Atomic force microscopy was used to analyze the surface morphology while the strain in the film was quantitatively measured using Raman spectroscopy and qualitatively analyzed by reciprocal space mapping technique. UV photo response of a-GaN film was measured after fabricating a metal-semiconductor-metal structure over the film with gold metal. The external quantum efficiency of the photodetectors fabricated in the (0002) polar and (11-20) nonpolar growth directions were compared in terms of responsivity and nonpolar GaN showed the best sensitivity at the cost of comparatively slow response time. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

Nickel Electrode for Improving Current Density in Organic Electronic Device

In this work, polymer diode performance was analyzed by using nickel as anode electrode from two kinds of nickel as starting materials, namely nickel wire Ni{B} and nickel nano-particle Ni{N}. Metal electrode surface roughness and grain morphology were investigated by atomic force microscope and scanning electron microscope, respectively. Current-voltage (I-V) and capacitance-voltage (C-V) characteristics were measured for the fabricated device at room temperature. Obtained result from the current-voltage characteristics shows an increment in the current density for nickel nano-particle top electrode device. The increase in the current density could be due to a reduction in built-in voltage at P3HT/Ni{N} interface.