Directing role of functional groups in selective generation of C-H center dot center dot center dot pi interactions: In situ cryo-crystallographic studies on benzyl derivatives

The in situ cryo-crystallization study of benzyl derivatives reveals that the molecular packing in these compounds is either through methylene (sp(3)) C-H center dot center dot center dot pi or aromatic (sp(2)) C-H center dot center dot center dot pi interactions depending on the level of acidity of the benzyl proton. These studies of low melting compounds bring out the subtle features of such weak interactions and point to the directional preferences depending on the nature (electron withdrawing, polarizability) of the neighbouring functional group.

An early in-situ stress signature of the AlN-Si pre-growth interface for successful integration of nitrides with (111) Si

The integration of Metal Organic Chemical Vapor Deposition (MOCVD) grown group III-A nitride device stacks on Si (111) substrates is critically dependent on the quality of the first AlN buffer layer grown. A Si surface that is both oxide-free and smooth is a primary requirement for nucleating such layers. A single parameter, the AlN layer growth stress, is shown to be an early (within 50 nm), clear (<0.5 GPa versus > 1GPa), and fail-safe indicator of the pre-growth surface, and the AlN quality required for successful epitaxy. Grain coalescence model for stress generation is used to correlate growth stress, the AlN-Si interface, and crystal quality. (C) 2013 AIP Publishing LLC.

In situ transmission electron microscopy study of deformation of an aluminum alloy tribolayer

Nanoscale deformation in the tribolayer of an Al–Mg alloy is studied using an in situ mechanical probe in a transmission electron microscope. The sample is strained locally at room temperature and the deformation is observed in real time. It is observed that when the tungsten probe comes into contact with the tribolayer, the material exhibits further hardening followed by material removal.

Study of Ion Transport in Lithium Perchlorate-Succinonitrile Plastic Crystalline Electrolyte via Ionic Conductivity and in Situ Cryo-Crystallography

Ion transport mechanism in lithium perchlorate (LiClO4)-succinonitrile (SN), a prototype of plastic crystalline soft matter electrolyte is discussed in the context of solvent configurational isomerism and ion solvation. Contributions of both solvent configurational isomerism and ion solvation are reflected in the activation energy for ion conduction in 0-1 M LiClO4-SN samples. Activation energy due to solvent configurational changes, that is, trans-gauche isomerism is observed to be a function of salt content and decreases in presence of salt (except at high salt concentrations, e.g. 1 M LiClO4-SN). The remnant contribution to activation energy is attributed to ion-association. The X-ray diffraction of single crystals obtained using in situ cryo-crystallography confirms directly the observations of the ionic conductivity measurements. Fourier transform infrared spectroscopy and NMR line width measurements provide additional support to our proposition of ion transport in the prototype plastic crystalline electrolyte.

Electrochemical Reduction of Oriented Graphene Oxide Films: An in Situ Raman Spectroelectrochemical Study

Graphene oxide (GO) is assembled on a gold substrate by a layer-by-layer technique using a self-assembled cystamine monolayer. The negatively charged GO platelets are attached to the positively charged cystamine monolayer through electrostatic interactions. Subsequently, it is shown that the GO can be reduced electrochemically using applied DC bias by scanning the potential from 0 to -1 V vs a saturated calomel electrode in an aqueous electrolyte. The GO and reduced graphene oxide (RGO) are characterized by Raman spectroscopy and atomic force microscopy (AFM). A clear shift of the G band from 1610 cm-1 of GO to 1585 cm-1 of RGO is observed. The electrochemical reduction is followed in situ by micro Raman spectroscopy by carrying out Raman spectroscopic studies during the application of DC bias. The GO and RGO films have been characterized by conductive AFM that shows an increase in the current flow by at least 3 orders of magnitude after reduction. The electrochemical method of reducing GO may open up another way of controlling the reduction of GO and the extent of reduction to obtain highly conducting graphene on electrode materials.

The formation of carbon nanostructures by in situ TEM mechanical nanoscale fatigue and fracture of carbon thin films

A technique to quantify in real time the microstructural changes occurring during mechanical nanoscale fatigue of ultrathin surface coatings has been developed. Cyclic nanoscale loading, with amplitudes less than 100 nm, is achieved with a mechanical probe miniaturized to fit inside a transmission electron microscope (TEM). The TEM tribological probe can be used for nanofriction and nanofatigue testing, with 3D control of the loading direction and simultaneous TEM imaging of the nano-objects. It is demonstrated that fracture of 10-20 nm thick amorphous carbon films on sharp gold asperities, by a single nanoscale shear impact, results in the formation of < 10 nm diameter amorphous carbon filaments. Failure of the same carbon films after cyclic nanofatigue, however, results in the formation of carbon nanostructures with a significant degree of graphitic ordering, including a carbon onion.

Structural origin of set-reset processes in Ge15Te83Si2 glass investigated using in situ Raman scattering and transmission electron microscopy

We report here that the structural origin of an easily reversible Ge15Te83Si2 glass can be a promising candidate for phase change random access memories. In situ Raman scattering studies on Ge15Te83Si2 sample, undertaken during the amorphous set and reset processes, indicate that the degree of disorder in the glass is reduced from off to set state. It is also found that the local structure of the sample under reset condition is similar to that in the amorphous off state. Electron microscopic studies on switched samples indicate the formation of nanometric sized particles of c-SiTe2 structure. ©2009 American Institute of Physics

In Situ Phase Separation Following Dehydration in Bimetallic Sulfates: A Variable-Temperature X-Ray Diffraction Study

Phase separation resulting in a single-crystal-single-crystal transition accompanied by a polycrystalline phase following the dehydration of hydrated bimetallic sulfates [Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O and K4Cd3-(SO4)(5)center dot 3H(2)O] has been investigated by in situ variable-temperature single-crystal X-ray diffraction. With two examples, we illustrate the possibility of generating structural frameworks following dehydration in bimetallic sulfates, which refer to the possible precursor phases at that temperature leading to the mineral formation. The room-temperature structure of Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O is trigonal, space group R (3) over bar. On heating the crystal in situ on the diffractometer, the diffraction images display spherical spots and concentric rings suggesting phase separation, with the spherical spots getting indexed in a monoclinic space group, C2/c. The structure determination based on this data suggests the formation of Na2Mn(SO4)(2). However, the diffraction images from concentric rings could not be indexed. In the second example, the room-temperature structure is determined to be K4Cd3(SO4)(5)center dot 3H(2)O, crystallizing in a monoclinic space group, P2(1)/n. On heating the crystal in situ, the diffraction images collected also have both spherical spots and diffuse rings. The spherical spots could be indexed to a cubic crystal system, space group P2(1)3, and the structure is K4Cd3(SO4)(3). The possible mechanism for the phase transition in the dehydration regime resulting in this remarkable single-crystal to single-crystal transition with the appearance of a surrogate polycrystalline phase is proposed.

Rapid in situ processing for real-time holographic interferometry

Experiments are described which show that a monobath can be used for rapid in situ processing in a liquid gate for real-time holographic interferometry. This also permits utilization of a very simple solution handling system. Changes in emulsion thickness are reduced to an acceptable level and problems of matching refractive indices are eliminated by exposing and viewing the holograms in water. Excellent null patterns are obtained and real-time holographic interferometry can be carried out over long periods of time.

In situ pump probe optical absorption studies on Sb/As2S3 nanomultilayered film

We report the in situ optical transmission change in the complete visible region of the electromagnetic spectrum to asses the kinetics of photo induced interdiffusion in Sb/As2S3 nanomultilayered film. The interdiffusion of Sb into As2S3 matrix results in the formation of Sb-As2S3 ternary solid solutions which is explained by the change in optical band gap, absorption coefficients and Tauc parameter (B-1/2) with evolution of time. The wavelength dependence of the time constants provides a better description of photo induced effects. The time evolution of the absorption coefficients and optical band gap are significantly faster in this process. (C) 2009 Elsevier B.V. All rights reserved.

In situ cryocrystallization of low melting chloro and bromo substituted anilines

In situ cryocrystallographic Studies of chloro and bromo substituted anilines have been performed to evaluate the role of halogen...halogen interactions and the subsequent formation of supramolecular assemblies in the solid state. Ortho Cl/Br substituted anilines are isostructural and belong to the trigonal P3(1) space group. Halogen...halogen intermolecular contacts along with stronger N-H center dot center dot center dot N hydrogen bonds generate helical motifs along the crystallographic c-axis. (C) 2009 Elsevier B.V. All rights reserved.

In situ synthesis and characterization of polyaniline-CaCu3Ti4O12 nanocrystal composites

High dielectric constant (ca. 2.4 x 10(6) at 1 kHz) nanocomposite of polyaniline (PANI)/CaCu3Ti4O12 (CCTO) was synthesized using a simple procedure involving in situ polymerization of aniline in dil. HCl. The PANI and the composite were subjected to X-ray diffraction, Fourier transform infrared, thermo gravimetric, scanning electron microscopy and transmission electron microscopy analyses. The presence of the nanocrystallites of CCTO embedded in the nanofibers of PANI matrix was established by TEM. Frequency dependent characteristics of the dielectric constant. dielectric loss and AC conductivity were studied for the PANI and the composites. The dielectric constant increased as the CCTO content increased in PANI but decreased with increasing frequency (100 Hz-1 MHz) of measurement. The dielectric loss was two times less than the value obtained for pure PANI around 100 Hz. The AC conductivity increased slightly up to 2 kHz as the CCTO content increased in the PANI which was attributed to the polarization of the charge carriers.

Electrical switching and in situ Raman scattering studies on the set-reset processes in Ge-Te-Si glass

Bulk Ge15Te83Si2 glass has been found to exhibit memory-type switching for 1 mA current with a threshold electric field of 7.3 kV/cm. The electrical set and reset processes have been achieved with triangular and rectangular pulses, respectively, of 1 mA amplitude. In situ Raman scattering studies indicate that the degree of disorder in Ge15Te83Si2 glass is reduced from off to set state. The local structure of the sample under reset condition is similar to that in the off state. The Raman results are consistent with the switching results which indicate that the Ge15Te83Si2 glass can be set and reset easily. (C) 2007 American Institute of Physics.

OFDM-MAC algorithms and their impact on TCP performance in next generation mobile networks

Next generation wireless systems employ Orthogonal frequency division multiplexing (OFDM) physical layer owing to the high data rate transmissions that are possible without increase in bandwidth. While TCP performance has been extensively studied for interaction with link layer ARQ, little attention has been given to the interaction of TCP with MAC layer. In this work, we explore cross-layer interactions in an OFDM based wireless system, specifically focusing on channel-aware resource allocation strategies at the MAC layer and its impact on TCP congestion control. Both efficiency and fairness oriented MAC resource allocation strategies were designed for evaluating the performance of TCP. The former schemes try to exploit the channel diversity to maximize the system throughput, while the latter schemes try to provide a fair resource allocation over sufficiently long time duration. From a TCP goodput standpoint, we show that the class of MAC algorithms that incorporate a fairness metric and consider the backlog outperform the channel diversity exploiting schemes.

Visualization of in situ intracellular aggregation of two cataract-associated human gamma-crystallin mutants: Lose a tail, lose transparency

PURPOSE. To understand the molecular features underlying autosomal dominant congenital cataracts caused by the deletion mutations W156X in human gamma D-crystallin and W157X in human gamma C-crystallin. METHODS. Normal and mutant cDNAs (with the enhanced green fluorescent protein [EGFP] tag in the front) were cloned into the pEGFP-C1 vector, transfected into various cell lines, and observed under a confocal microscope for EGFP fluorescence. Normal and W156X gamma D cDNAs were also cloned into the pET21a(+) vector, and the recombinant proteins were overexpressed in the BL-21(DE3) pLysS strain of Escherichia coli, purified, and isolated. The conformational features, structural stability, and solubility in aqueous solution of the mutant protein were compared with those of the wild type using spectroscopic methods. Comparative molecular modeling was performed to provide additional structural information. RESULTS. Transfection of the EGFP-tagged mutant cDNAs into several cell lines led to the visualization of aggregates, whereas that of wild-type cDNAs did not. Turning to the properties of the expressed proteins, the mutant molecules show remarkable reduction in solubility. They also seem to have a greater degree of surface hydrophobicity than the wild-type molecules, most likely accounting for self-aggregation. Molecular modeling studies support these features. CONCLUSIONS. The deletion of C-terminal 18 residues of human gamma C-and gamma D-crystallins exposes the side chains of several hydrophobic residues in the sequence to the solvent, causing the molecule to self-aggregate. This feature appears to be reflected in situ on the introduction of the mutants in human lens epithelial cells.