Elasticity of DNA and the effect of dendrimer binding

Negatively charged DNA can be compacted by positively charged dendrimers and the degree of compaction is a delicate balance between the strength of the electrostatic interaction and the elasticity of DNA. We report various elastic properties of short double-stranded DNA (dsDNA) and the effect of dendrimer binding using fully atomistic molecular dynamics and numerical simulations. In equilibrium at room temperature, the contour length distribution P(L) and the end-to-end distance distribution P(R) are nearly Gaussian, the former gives an estimate of the stretch modulus gamma(1) of dsDNA in quantitative agreement with the literature value. The bend angle distribution P(.) of the dsDNA also has a Gaussian form and allows to extract a persistence length, L-p of 43 nm. When the dsDNA is compacted by positively charged dendrimer, the stretch modulus stays invariant but the effective bending rigidity estimated from the end-to-end distance distribution decreases dramatically due to backbone charge neutralization of dsDNA by dendrimer. We support our observations with numerical solutions of the worm-like-chain (WLC) model as well as using non-equilibrium dsDNA stretching simulations. These results are helpful in understanding the dsDNA elasticity at short length scales as well as how the elasticity is modulated when dsDNA binds to a charged object such as a dendrimer or protein.

Analysis of size quantization and temperature effects on the threshold voltage of thin silicon film double-gate metal-oxide-semiconductor field-effect transistor (MOSFET)

In this paper, we analyze the combined effects of size quantization and device temperature variations (T = 50K to 400 K) on the intrinsic carrier concentration (n(i)), electron concentration (n) and thereby on the threshold voltage (V-th) for thin silicon film (t(si) = 1 nm to 10 nm) based fully-depleted Double-Gate Silicon-on-Insulator MOSFETs. The threshold voltage (V-th) is defined as the gate voltage (V-g) at which the potential at the center of the channel (Phi(c)) begins to saturate (Phi(c) = Phi(c(sat))). It is shown that in the strong quantum confinement regime (t(si) <= 3nm), the effects of size quantization far over-ride the effects of temperature variations on the total change in band-gap (Delta E-g(eff)), intrinsic carrier concentration (n(i)), electron concentration (n), Phi(c(sat)) and the threshold voltage (V-th). On the other hand, for t(si) >= 4 nm, it is shown that size quantization effects recede with increasing t(si), while the effects of temperature variations become increasingly significant. Through detailed analysis, a physical model for the threshold voltage is presented both for the undoped and doped cases valid over a wide-range of device temperatures, silicon film thicknesses and substrate doping densities. Both in the undoped and doped cases, it is shown that the threshold voltage strongly depends on the channel charge density and that it is independent of incomplete ionization effects, at lower device temperatures. The results are compared with the published work available in literature, and it is shown that the present approach incorporates quantization and temperature effects over the entire temperature range. We also present an analytical model for V-th as a function of device temperature (T). (C) 2013 AIP Publishing LLC.

Synthetic glutathione peroxidase mimics: effect of nucleophilicity of the aryl thiol cofactor on the antioxidant activity

Catalytic activity of a series of potent amide- and amine-based organoselenium compounds are studied in the presence of various aromatic thiols having electron donating and electron withdrawing substituents on the phenyl ring. This study suggests that the antioxidant activities of the synthetic GPx mimics can be significantly increased by the incorporation of a suitable electron donating group on the phenyl ring of an aromatic thiol.

Stabilizing effect of electrostatic vs. aromatic interactions in diproline nucleated peptide beta-hairpins

The contribution of Tyr-His vs. Cys-His interacting pairs to the scaffold stability of (D)Pro-(L)Pro nucleated peptide beta-hairpins has been examined. We present direct evidence for the superiority of the Cys-His pairs, mediated by sulphur-imidazole interactions, as added stabilizing agents of the beta-hairpin scaffold.

Effect of Texture and Grain Size on Bio-Corrosion Response of Ultrafine-Grained Titanium

The bio-corrosion response of ultrafine-grained commercially pure titanium processed by different routes of equal-channel angular pressing has been studied in simulated body fluid. The results indicate that the samples processed through route B-c that involved rotation of the workpiece by 90 deg in the same sense between each pass exhibited higher corrosion resistance compared to the ones processed by other routes of equal-channel angular pressing, as well as the coarse-grained sample. For a similar grain size, the higher corrosion resistance of the samples exhibiting off-basal texture compared to shear texture indicates the major role of texture in corrosion behavior. It is postulated that an optimum combination of microstructure and crystallographic texture can lead to high strength and excellent corrosion resistance.

Performance analysis of adaptive physical layer network coding for wireless two-way Relaying

The analysis of modulation schemes for the physical layer network-coded two way relaying scenario is presented which employs two phases: Multiple access (MA) phase and Broadcast (BC) phase. Depending on the signal set used at the end nodes, the minimum distance of the effective constellation seen at the relay becomes zero for a finite number of channel fade states referred as the singular fade states. The singular fade states fall into the following two classes: (i) the ones which are caused due to channel outage and whose harmful effect cannot be mitigated by adaptive network coding called the non-removable singular fade states and (ii) the ones which occur due to the choice of the signal set and whose harmful effects can be removed called the removable singular fade states. In this paper, we derive an upper bound on the average end-to-end Symbol Error Rate (SER), with and without adaptive network coding at the relay, for a Rician fading scenario. It is shown that without adaptive network coding, at high Signal to Noise Ratio (SNR), the contribution to the end-to-end SER comes from the following error events which fall as SNR-1: the error events associated with the removable and nonremovable singular fade states and the error event during the BC phase. In contrast, for the adaptive network coding scheme, the error events associated with the removable singular fade states fall as SNR-2, thereby providing a coding gain over the case when adaptive network coding is not used. Also, it is shown that for a Rician fading channel, the error during the MA phase dominates over the error during the BC phase. Hence, adaptive network coding, which improves the performance during the MA phase provides more gain in a Rician fading scenario than in a Rayleigh fading scenario. Furthermore, it is shown that for large Rician factors, among those removable singular fade states which have the same magnitude, those which have the least absolute value of the phase - ngle alone contribute dominantly to the end-to-end SER and it is sufficient to remove the effect of only such singular fade states.

Sr2+ and Cd2+ coordination polymers: the effect of the different coordinating behaviour of a newly designed tricarboxylic acid

This article presents the investigation of the coordination behavior of a newly synthesized tricarboxylate ligand, obtained by joining imidazole dicarboxylic acid and 4-carboxybenzyl moieties cbimdaH(3), 1-(4-carboxybenzyl)-1H-imidazole-4,5-dicarboxylic acid]. Two novel coordination polymers were obtained through solvothermal reactions under similar conditions namely Sr(cbimdaH)(H2O)](n) (1) and Cd-2(cbimdaH)(2)(H2O)(6)](n)center dot(DMF)(3n)(H2O)(3n) (2), with the ligand behaving as a dianionic tricarboxylate linker. The single crystal X-ray structures show that while 1 forms a 3D coordination polymer, 2 forms a 1D polymer which is further assembled in three dimensions through supramolecular interactions (H-bonding). Complex 1 consists of Sr2+ ions in a distorted dodecahedral coordination geometry, while 2 consists of Cd2+ ions in distorted pentagonal bipyramidal geometries. A topology study reveals that 1 has a new topology based on the 5,6-coordinated 3D net architecture. The luminescence properties of the complexes in the solid state and their thermal stabilities were studied.

Role of Crystal Field in Mixed Alkali Metal Effect: Electron Paramagnetic Resonance Study of Mixed Alkali Metal Oxyfluoro Vanadate Glasses

The mixed alkali metal effect is a long-standing problem in glasses. Electron paramagnetic resonance (EPR) is used by several researchers to study the mixed alkali metal effect, but a detailed analysis of the nearest neighbor environment of the glass former using spin-Hamiltonian parameters was elusive. In this study we have prepared a series of vanadate glasses having general formula (mol %) 40 V2O5-30BaF(2)-(30 - x)LiF-xRbF with x = 5, 10, 15, 20, 25, and 30. Spin-Hamiltonian parameters of V4+ ions were extracted by simulating and fitting to the experimental spectra using EasySpin. From the analysis of these parameters it is observed that the replacement of lithium ions by rubidium ions follows a ``preferential substitution model''. Using this proposed model, we were able to account for the observed variation in the ratio of the g parameter, which goes through a maximum. This reflects an asymmetric to symmetric changeover of. the alkali metal ion environment around the vanadium site. Further, this model also accounts for the variation in oxidation state of vanadium ion, which was confirmed from the variation in signal intensity of EPR spectra.

Effect of substituent position on optical properties of boron-dipyrromethane isomers

Three isomeric meso-SiMe3C6H4 substituted BODIPYs have been synthesized and their optical properties studied. The constitutional isomers show similar absorption properties but vastly different emissive properties as a result of their different conformational flexibility. Fluorine-19 NMR study is used to unravel the conformational state of the BODIPY isomers at a molecular level. (C) 2013 Elsevier B. V. All rights reserved.

An oxygen evolution Co-Ac catalyst - the synergistic effect of phosphate ions

Formation of an amorphous cobalt based oxygen evolution catalyst called Co-Pi has been recently reported from a neutral phosphate buffer solution containing Co2+. But the concentration of Co2+ is as low as 0.5 mM due to poor solubility of a cobalt salt in phosphate medium. In the present study, a cobalt acetate based oxygen evolution catalyst (Co-Ac) is prepared from a neutral acetate buffer solution, where the solubility of Co2+ is very high (>100 times in comparison with phosphate buffer solution). The Co-Ac possesses better catalytic activity than the Co-Pi with an additional advantage of easy bulk scale preparation. The comparative studies on the oxygen evolution reaction (OER) activity of Co-Ac and Co-Pi in phosphate and acetate buffer electrolytes reveal that the Co-Ac exhibits enhanced synergistic catalytic activity in phosphate solution, probably due to partial substitution of acetate in the catalyst layer by phosphate, resulting in the formation of a Co-Ac-Pi catalyst.

Calibration Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced Breakdown Spectroscopic Analysis

The present article describes a working or combined calibration curve in laser-induced breakdown spectroscopic analysis, which is the cumulative result of the calibration curves obtained from neutral and singly ionized atomic emission spectral lines. This working calibration curve reduces the effect of change in matrix between different zone soils and certified soil samples because it includes both the species' (neutral and singly ionized) concentration of the element of interest. The limit of detection using a working calibration curve is found better as compared to its constituent calibration curves (i.e., individual calibration curves). The quantitative results obtained using the working calibration curve is in better agreement with the result of inductively coupled plasma-atomic emission spectroscopy as compared to the result obtained using its constituent calibration curves.

Effect of quantum nuclear motion on hydrogen bonding

This work considers how the properties of hydrogen bonded complexes, X-H center dot center dot center dot Y, are modified by the quantum motion of the shared proton. Using a simple two-diabatic state model Hamiltonian, the analysis of the symmetric case, where the donor (X) and acceptor (Y) have the same proton affinity, is carried out. For quantitative comparisons, a parametrization specific to the O-H center dot center dot center dot O complexes is used. The vibrational energy levels of the one-dimensional ground state adiabatic potential of the model are used to make quantitative comparisons with a vast body of condensed phase data, spanning a donor-acceptor separation (R) range of about 2.4-3.0 angstrom, i.e., from strong to weak hydrogen bonds. The position of the proton (which determines the X-H bond length) and its longitudinal vibrational frequency, along with the isotope effects in both are described quantitatively. An analysis of the secondary geometric isotope effect, using a simple extension of the two-state model, yields an improved agreement of the predicted variation with R of frequency isotope effects. The role of bending modes is also considered: their quantum effects compete with those of the stretching mode for weak to moderate H-bond strengths. In spite of the economy in the parametrization of the model used, it offers key insights into the defining features of H-bonds, and semi-quantitatively captures several trends. (C) 2014 AIP Publishing LLC.

Process induced electroactive beta-polymorph in PVDF: effect on dielectric and ferroelectric properties

The effects of various processing conditions, like annealing, poling, mechanical rolling and their combinations, on the dielectric and ferroelectric properties of PVDF poly(vinylidene fluoride)] were systematically studied in this work. Further, the effect of processing sequence on the structure and properties was investigated. While all the processing conditions adopted here resulted in phase transformation of the alpha- to electroactive beta-polymorph in PVDF, the fraction of beta-phase developed was observed to be strongly contingent on the adopted process. The transformation of alpha- to electroactive beta-polymorph was determined by X-ray diffraction and FTIR. The neat PVDF showed only beta-phase, whereas mechanically rolled samples exhibited the highest ca. 85% beta-phase in PVDF. Both the permittivity and the loss tangent decreased in the samples which had undergone different processing conditions. The polarization-electric field (P-E) loops for all the samples were evaluated. Interestingly, the energy density, estimated from the electrical displacement-electric field (D-E) loops, was observed to be highest for the poled samples which were initially rolled. The results indicate that various processing conditions can influence the dielectric and the ferroelectric properties differently.

Substituent effect on fluorescence signaling of the cell permeable HSO4- receptors through single point to ratiometric response in green solvent

Two new 2-(2-aminophenyl)benzimidazole-based HSO4- ion selective receptors, 6-(4-nitrophenyl)-5,6-dihydrobenzo4,5]imidazo1,2-c]quinazoline (L1H) and 6-(4-methoxyphenyl)-5,6-dihydrobenzo4,5]imidazo1,2-c] quinazoline (L2H), and their 1 : 1 molecular complexes with HSO4- were prepared in a facile synthetic method and characterized by physicochemical and spectroscopic techniques along with the detailed structural analysis of L1H by single crystal X-ray crystallography. Both receptors (L1H and L2H) behave as highly selective chemosensor for HSO4- ions at biological pH in ethanol-water HEPES buffer (1/5) (v/v) medium over other anions such as F-, Cl-, Br-, I-, AcO-, H2PO4-, N-3(-) and ClO4-. Theoretical and experimental studies showed that the emission efficiency of the receptors (L1H and L2H) was tuned successfully through single point to ratiometric detection by employing the substituent effects. Using 3 sigma method the LOD for HSO4- ions were found to be 18.08 nM and 14.11 nM for L1H and L2H, respectively, within a very short responsive time (15-20 s) in 100 mM HEPES buffer (ethanol-water: 1/5, v/v). Comparison of the utility of the probes (L1H and L2H) as biomarkers for the detection of intracellular HSO4- ions concentrations under a fluorescence microscope has also been included and both probes showed no cytotoxic effect.

Polymer-grafted multiwall carbon nanotubes functionalized by nitrene chemistry: effect on cooperativity and phase miscibility

The demixing of polystyrene (PS) and poly(vinyl methylether) (PVME) was systematically investigated in the presence of surface functionalized multiwall carbon nanotubes (MWNTs) by melt rheology. As PS-PVME blends are weakly interacting blends, the contribution of conformational entropy increases, resulting in thermo-rheological complexity wherein the concentration fluctuation persists even beyond the critical demixing temperature. These phenomenal changes were followed here in the presence of MWNTs with different surface functional groups. Polystyrene was synthesised by atom transfer radical polymerization and was immobilized onto carboxyl acid functionalized multiwall carbon nanotubes (COOH-MWNTs) via nitrene chemistry in order to improve the phase miscibility in PS-PVME blends. Interestingly, blends with 0.25 wt% polystyrene grafted multiwall carbon nanotubes (PS-g-MWNTs) delayed the spinodal decomposition temperature in the blends by similar to 33 degrees C with respect to both control blends and those with COOH-MWNTs. While the localization of COOH-MWNTs in PVME was explained from a thermodynamic point of view, the localization of PS-g-MWNTs was understood to result from favorable PS-PVME contact and the degree of surface coverage of PS on the surface of MWNTs. The length of the cooperative rearranging region (xi) decreased in presence of PS-g-MWNTs, suggesting confinement effects on large scale motions and enhanced interchain concentration fluctuation.