Bimetallic core-shell nanocomposites using weak reducing agent and their transformation to alloy nanostructures

An in situ seeding growth methodology towards the preparation of core-shell nanoparticles composed of noble metals has been developed by employing trimethylamine borane (TMAB) as the reducing agent. Being a weak reducing agent, TMAB is able to distinguish the smallest reduction potential window of any two metals which renders selective reduction of metal ions thus affording a core-shell architecture of the nanoparticles. A dramatic effect of solvent was noted during the reduction of Ag+ ions: an immediate reduction took place at room temperature when dry THF was used as solvent however, usage of wet THF (THF used directly from the bottle) brings out the reduction only at reflux conditions. In the case of Au and Pd nanoparticles, preparation was found to be independent of the quality of solvent used. Au nanoparticles are realized at room temperature whereas reflux conditions are required in the case of Pd nanoparticles. This difference in behavior of the monometallic nanoparticles was successfully exploited to construct different noble metal nanoparticles with core-shell architectures such as Au@Ag, Ag@Au, and Ag@Pd. Transformation of these core-shell nanoparticles to their thermodynamically stable alloy counterparts is also demonstrated under very mild conditions reported to date.

Quantum phases and phase transitions of frustrated hard-core bosons on a triangular ladder

Kinetically frustrated bosons at half filling in the presence of a competing nearest-neighbor repulsion support a wide supersolid regime on the two-dimensional triangular lattice. We study this model on a two-leg ladder using the finite-size density-matrix renormalization-group method, obtaining a phase diagram which contains three phases: a uniform superfluid (SF), an insulating charge density wave (CDW) crystal, and a bond ordered insulator (BO). We show that the transitions from SF to CDW and SF to BO are continuous in nature, with critical exponents varying continuously along the phase boundaries, while the transition from CDW to BO is found to be first order. The phase diagram is also found to contain an exactly solvable Majumdar Ghosh point, and reentrant SF to CDW phase transitions.

Structural characterization and molecular order of rodlike mesogens with three- and four-ring core by XRD and C-13 NMR spectroscopy

Structural characterizations using XRD and C-13 NMR spectroscopy of two rodlike mesogens consisting of (i) three phenyl ring core with a polar cyano terminal and (ii) four phenyl ring core with flexible dodecyl terminal chain are presented. The three-ring-core mesogen with cyano terminal exhibits enantiotropic smectic A phase while the four-ring mesogen reveals polymesomorphism and shows enantiotropic nematic, smectic C, and tilted hexatic phases. The molecular organization in the three-ring mesogen is found to be partial bilayer smectic Ad type, and the interdigitation of the molecules in the neighboring layers is attributed to the presence of the polar terminal group. For the four-ring mesogen, the XRD results confirm the existence of the smectic C and the tilted hexatic mesophases. A thermal variation of the layer spacing across the smectic C phase followed by a discrete jump at the transition to the tilted hexatic phase is also observed. The tilt angles have been estimated to be about 45 degrees in the smectic C phase and about 40 degrees in tilted hexatic phase. C-13 NMR results indicate that in the mesophase the molecules are aligned parallel to the magnetic field. From the C-13-H-1 dipolar couplings determined from the 2D experiments, the overall order parameter for the three-ring mesogen in its smectic A phase has been estimated to be 0.72 while values ranging from 0.88 to 0.44 have been obtained for the four-ring mesogen as it passes from the tilted hexatic to the nematic phase. The orientations of the different rings of the core unit with respect to each other and also with respect to the long axis of the molecule have also been obtained.

Calibration of etched fiber bragg grating sensor arrays for measurement of molecular surface adsorption

Etched Fiber Bragg Grating (EFBG) sensors are attractive from the point of the inherently high multiplexing ability of fiber based sensors. However, the strong dependence of the sensitivity of EFBG sensors on the fiber diameter requires robust methods for calibration when used for distributed sensing in a large array format. Using experimental data and numerical modelling, we show that knowledge of the wavelength shift during the etch process is necessary for high-fidelity calibration of EFBG arrays. However as this approach requires the monitoring of every element of the sensor array during etching, we also proposed and demonstrated a calibration scheme using data from bulk refractometry measurements conducted post-fabrication without needing any information about the etching process. Although this approach is not as precise as the first one, it may be more practical as there is no requirement to monitor each element of the sensor array. We were able to calibrate the response of the sensors to within 3% with the approach using information acquired during etching and to within 5% using the post-fabrication bulk refractometry approach in spite of the sensitivities of the array element differing by more than a factor of 4. These two approaches present a tradeoff between accuracy and practicality.

Detection limit of etched fiber bragg grating sensors

While Fiber Bragg Grating (FBG) sensors have been extensively used for temperature and strain sensing, clad etched FBGs (EFBGs) have only recently been explored for refractive index sensing. Prior literature in EFBG based refractive index sensing predominantly deals with bulk refractometry only, where the Bragg wavelength shift of the sensor as a function of the bulk refractive index of the sample can be analytically modeled, unlike the situation for adsorption of molecular thin films on the sensor surface. We used a finite element model to calculate the Bragg wavelength change as a function of thickness and refractive index of the adsorbing molecular layer and compared the model with the real-time, in-situ measurement of electrostatic layer-by-layer (LbL) assembly of weak polyelectrolytes on the silica surface of EFBGs. We then used this model to calculate the layer thickness of LbL films and found them to be in agreement with literature. Further, we used this model to arrive at a realistic estimate of the limit of detection of EFBG sensors based on nominal measurement noise levels in current FBG interrogation systems and found that sufficiently thinned EFBGs can provide a competitive platform for real-time measurement of molecular interactions while simultaneously leveraging the high multiplexing capabilities of fiber optics.

The Escherichia coli Phosphotyrosine Proteome Relates to Core Pathways and Virulence

While phosphotyrosine modification is an established regulatory mechanism in eukaryotes, it is less well characterized in bacteria due to low prevalence. To gain insight into the extent and biological importance of tyrosine phosphorylation in Escherichia coli, we used immunoaffinity-based phosphotyrosine peptide enrichment combined with high resolution mass spectrometry analysis to comprehensively identify tyrosine phosphorylated proteins and accurately map phosphotyrosine sites. We identified a total of 512 unique phosphotyrosine sites on 342 proteins in E. coli K12 and the human pathogen enterohemorrhagic E. coli (EHEC) O157:H7, representing the largest phosphotyrosine proteome reported to date in bacteria. This large number of tyrosine phosphorylation sites allowed us to define five phosphotyrosine site motifs. Tyrosine phosphorylated proteins belong to various functional classes such as metabolism, gene expression and virulence. We demonstrate for the first time that proteins of a type III secretion system (T3SS), required for the attaching and effacing (A/E) lesion phenotype characteristic for intestinal colonization by certain EHEC strains, are tyrosine phosphorylated by bacterial kinases. Yet, A/E lesion and metabolic phenotypes were unaffected by the mutation of the two currently known tyrosine kinases, Etk and Wzc. Substantial residual tyrosine phosphorylation present in an etk wzc double mutant strongly indicated the presence of hitherto unknown tyrosine kinases in E. coli. We assess the functional importance of tyrosine phosphorylation and demonstrate that the phosphorylated tyrosine residue of the regulator SspA positively affects expression and secretion of T3SS proteins and formation of A/E lesions. Altogether, our study reveals that tyrosine phosphorylation in bacteria is more prevalent than previously recognized, and suggests the involvement of phosphotyrosine-mediated signaling in a broad range of cellular functions and virulence.

EFFECT OF CORE-SHELL STRUCTURE OF HYDROGEL BEADS ON THE THRESHOLD CONCENTRATION OF WATER FOR SWELLING AND ITS PH SENSITIVITY

In this paper we investigate the effect of core-shell structure of Sodium Alginate based hydrogel beads and their size on certain activation threshold concentration of water for applications in swelling and pH sensing. This type of hydrogel experiences diffusive pressure due to transport of certain free charges across its interface with a solvent or electrolyte. This process is essentially a dynamic equilibrium of the electric force field, stress in the polymeric network with cage like structure and molecular diffusion including phase transformation due to pressure imbalance between the hydrogel and its surroundings. The effect of pH of the solvant on the swelling rate of these beads has been studied experimentally. A mathematical model of the swelling process has been developed by considering Nernst-Planck equation representing the migration of mobile ions and Er ions, Poisson equation representing the equilibrium of the electric field and mechanical field equation representing swelling of the gel. An attempt has been made to predict the experimentally observed phenomena using these numerical simulations. It is observed experimentally that certain minimum concentration called activation threshold concentration of the water molecules must be present in the hydrogel in order to activate the swelling process. For the required activation threshold concentration of water in the beads, the pH induced change in the rate of swelling is also investigated. This effect is analyzed for various different core-shell structures of the beads.

pH Induced switching in hydrogel coated fiber bragg grating sensor

In this paper we report a novel hydrogel functionalized optical Fiber Bragg Grating (FBG) sensor based on chemo-mechanical-optical sensing, and demonstrate its specific application in pH activated process monitoring. The sensing mechanism is based on the stress due to ion diffusion and polymer phase transition which produce strain in the FBG. This results in shift in the Bragg wavelength which is detected by an interrogator system. A simple dip coating method to coat a thin layer of hydrogel on the FBG has been established. The gel consists of sodium alginate and calcium chloride. Gel formation is observed in real-time by continuously monitoring the Bragg wavelength shift. We have demonstrated pH sensing in the range of pH of 2 to 10. Another interesting phenomenon is observed by swelling and deswelling of FBG functionalized with hydrogel by a sequence of alternate dipping between acidic and base solutions. It is observed that the Bragg wavelength undergoes reversible and repeatable pH dependent switching.

Blood pressure evaluation using sphygmomanometry assisted by arterial pulse waveform detection by fiber Bragg grating pulse device

We report a blood pressure evaluation methodology by recording the radial arterial pulse waveform in real time using a fiber Bragg grating pulse device (FBGPD). Here, the pressure responses of the arterial pulse in the form of beat-to-beat pulse amplitude and arterial diametrical variations are monitored. Particularly, the unique signatures of pulse pressure variations have been recorded in the arterial pulse waveform, which indicate the systolic and diastolic blood pressure while the patient is subjected to the sphygmomanometric blood pressure examination. The proposed method of blood pressure evaluation using FBGPD has been validated with the auscultatory method of detecting the acoustic pulses (Korotkoff sounds) by an electronic stethoscope. (C) 2013 Society of Photo-Optical Instrumentation Engineers (SPIE)

Real time monitoring of petroleum leakage detection using etched fiber Bragg grating

Detection of petroleum leakages in pipelines and storage tanks is a very important as it may lead to significant pollution of the environment, accidental hazards, and also it is a very important fuel resource. Petroleum leakage detection sensor based on fiber optics was fabricated by etching the fiber Bragg grating (FBG) to a region where the total internal reflection is affected. The experiment shows that the reflected Bragg's wavelength and intensity goes to zero when etched FBG is in air and recovers Bragg's wavelength and intensity when it is comes in contact with petroleum or any external fluid. This acts as high sensitive, fast response fluid optical switch in liquid level sensing, petroleum leakage detection etc. In this paper we present our results on using this technique in petroleum leakage detection.

Carbon nanotube coated fiber Bragg grating for photomechanical optic modulator

We have demonstrated novel concept of utilizing the photomechanical actuation in carbon nanotubes (CNTs) to tune and reversibly switch the Bragg wavelength. When fiber Bragg grating coated with CNTs (CNT-FBG) is exposed externally to a wide range of optical wavelengths, e. g., ultraviolet to infrared (0.2-200 mu m), a strain is induced in the CNTs which alters the grating pitch and refractive index in the CNT-FBG system resulting in a shift in the Bragg wavelength. This novel approach will find applications in telecommunication, sensors and actuators, and also for real time monitoring of the photomechanical actuation in nanoscale materials. (C) 2013 AIP Publishing LLC.

CUDA-for-clusters: a system for efficient execution of CUDA kernels on multi-core clusters

Rapid advancements in multi-core processor architectures coupled with low-cost, low-latency, high-bandwidth interconnects have made clusters of multi-core machines a common computing resource. Unfortunately, writing good parallel programs that efficiently utilize all the resources in such a cluster is still a major challenge. Various programming languages have been proposed as a solution to this problem, but are yet to be adopted widely to run performance-critical code mainly due to the relatively immature software framework and the effort involved in re-writing existing code in the new language. In this paper, we motivate and describe our initial study in exploring CUDA as a programming language for a cluster of multi-cores. We develop CUDA-For-Clusters (CFC), a framework that transparently orchestrates execution of CUDA kernels on a cluster of multi-core machines. The well-structured nature of a CUDA kernel, the growing popularity, support and stability of the CUDA software stack collectively make CUDA a good candidate to be considered as a programming language for a cluster. CFC uses a mixture of source-to-source compiler transformations, a work distribution runtime and a light-weight software distributed shared memory to manage parallel executions. Initial results on running several standard CUDA benchmark programs achieve impressive speedups of up to 7.5X on a cluster with 8 nodes, thereby opening up an interesting direction of research for further investigation.

Energy Hyperspace for Stacking Interaction in AU/AU Dinucleotide Step: Dispersion-Corrected Density Functional Theory Study

Double helical structures of DNA and RNA are mostly determined by base pair stacking interactions, which give them the base sequence-directed features, such as small roll values for the purine-pyrimidine steps. Earlier attempts to characterize stacking interactions were mostly restricted to calculations on fiber diffraction geometries or optimized structure using ab initio calculations lacking variation in geometry to comment on rather unusual large roll values observed in AU/AU base pair step in crystal structures of RNA double helices. We have generated stacking energy hyperspace by modeling geometries with variations along the important degrees of freedom, roll, and slide, which were chosen via statistical analysis as maximally sequence dependent. Corresponding energy contours were constructed by several quantum chemical methods including dispersion corrections. This analysis established the most suitable methods for stacked base pair systems despite the limitation imparted by number of atom in a base pair step to employ very high level of theory. All the methods predict negative roll value and near-zero slide to be most favorable for the purine-pyrimidine steps, in agreement with Calladine's steric clash based rule. Successive base pairs in RNA are always linked by sugar-phosphate backbone with C3-endo sugars and this demands C1-C1 distance of about 5.4 angstrom along the chains. Consideration of an energy penalty term for deviation of C1-C1 distance from the mean value, to the recent DFT-D functionals, specifically B97X-D appears to predict reliable energy contour for AU/AU step. Such distance-based penalty improves energy contours for the other purine-pyrimidine sequences also. (c) 2013 Wiley Periodicals, Inc. Biopolymers 101: 107-120, 2014.

Engineered spin-valve type magnetoresistance in Fe3O4-CoFe2O4 core-shell nanoparticles

Naturally occurring spin-valve-type magnetoresistance (SVMR), recently observed in Sr2FeMoO6 samples, suggests the possibility of decoupling the maximal resistance from the coercivity of the sample. Here we present the evidence that SVMR can be engineered in specifically designed and fabricated core-shell nanoparticle systems, realized here in terms of soft magnetic Fe3O4 as the core and hard magnetic insulator CoFe2O4 as the shell materials. We show that this provides a magnetically switchable tunnel barrier that controls the magnetoresistance of the system, instead of the magnetic properties of the magnetic grain material, Fe3O4, and thus establishing the feasibility of engineered SVMR structures. (C) 2013 AIP Publishing LLC.

Hard-core bosons in a zig-zag optical superlattice

We study a system of hard-core bosons at half-filling in a one-dimensional optical superlattice. The bosons are allowed to hop to nearest-and next-nearest-neighbor sites. We obtain the ground-state phase diagram as a function of microscopic parameters using the finite-size density-matrix renormalization-group method. Depending on the sign of the next-nearest-neighbor hopping and the strength of the superlattice potential the system exhibits three different phases, namely the bond-order (BO) solid, the superlattice induced Mott insulator (SLMI), and the superfluid (SF) phase. When the signs of both hopping amplitudes are the same (the unfrustratedase), the system undergoes a transition from the SF to the SLMI at a nonzero value of the superlattice potential. On the other hand, when the two amplitudes differ in sign (the frustrated case), the SF is unstable to switching on a superlattice potential and also exists only up to a finite value of the next-nearest-neighbor hopping. This part of the phase diagram is dominated by the BO phase which breaks translation symmetry spontaneously even in the absence of the superlattice potential and can thus be characterized by a bond-order parameter. The transition from BO to SLMI appears to be first order.