Off-resonance binomial preparatory pulse technique for high sensitivity MRI of H2O17

H2O17 is a freely diffusible tracer and naturally occurring isotope of O16 detectable by MRI and has been shown to be useful for assessing cerebral perfusion in animal studies using direct and indirect MR detection techniques. However, earlier MR techniques are either not sensitive to changes in small concentrations of tissue H2O17 or are not practical for use on clinical scanners. In this work, a novel method for detecting H2O17 with high sensitivity has been proposed that uses a short, intense, binomial preparatory spin lock pulse with resonance offsets for high sensitive rapid, multislice imaging of tissue H2O17. Two sets of phantom experiments were performed on the 1.5 T and repeated on 3.0 T to assess the feasibility of the proposed technique. The phantom was constructed using ovalbumin and doped with 0.4 atom% and 1.0 atom% H2O17. After obtaining initial parameters, the proposed technique was validated in an anesthetized primate model that was injected with 1.8 cc of 40 atom% H2O17. Phantom experiments showed that the proposed technique was able to detect H2O17 with relatively high sensitivity and high B1 amplitude (and small offsets) preparatory pulses produced similar results as low B1 amplitude (and larger offsets). Primate brain study showed a 42.97% difference in mean signal intensity between pre- and post-H2O17 injection. The proposed technique was successfully implemented on a clinical scanner and was able to detect H2O17 with relatively high sensitivity. Primate study has shown that such a technique can be successfully used for human imaging applications to investigate and assess cerebral perfusion.     

Photoelectrochemical performance of bilayered Fe–TiO<Subscript>2</Subscript>/Zn–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films for solar generation of hydrogen

A visible-light sensitive bilayered photoanode of Fe–TiO₂/Zn–Fe₂O₃ has been developed by spray pyrolytically depositing Zn–Fe₂O₃ layers onto predeposited Fe–TiO₂ thin film on ITO substrate. Fe–TiO₂/Zn–Fe₂O₃ photoelectrodes were characterized by XRD, Raman, AFM, UV-vis absorption spectroscopy. Photoelectrochemical properties of bilayered Fe–TiO₂/Zn–Fe₂O₃ photoelectrode were studied by Mott–Schottky curves and I–V characteristics. Bilayered Fe–TiO₂/Zn–Fe₂O₃ photoelectrode was observed to possess much higher separation efficiency of photogenerated charge carriers and could generate nine times better photocurrent density than pure Fe–TiO₂. Solar to hydrogen conversion efficiency exhibited by this electrode was 0.77%.     

Synthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species

A mixture of cyclic gold(I) complexes [Au(2)(μ-cis-dppen)(2)]X(2) (X = OTf 1, PF(6)3) and [Au(cis-dppen)(2)]X (X = OTf 2, PF(6)4) is obtained from the reaction of [Au(tht)(2)]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au(3)(μ-trans-dppen)(3)]X(3) (X = OTf 11, PF(6)12) and tetranuclear [Au(4)(μ-dppa)(4)]X(4) (X = OTf 13, PF(6)14, ClO(4)15) gold complexes, respectively. Recrystallization of 15 from CH(2)Cl(2)/MeOH yielded a crystal of the octanuclear gold cluster [Au(8)Cl(2)(μ-dppa)(4)](ClO(4))(2)16. Attempts to prepare dicationic binuclear gold(II) species from the reaction of a mixture of 3 and 4 with halogens gave a mixture of products, the components of which confirmed to be acyclic binuclear gold(I) [Au(2)X(2)(cis-dppen)] (X = I 5, Br 7) and cyclic mononuclear gold(III) [AuX(2)(cis-dppen)]PF(6) (X = I 6, Br 8) complexes. Complexes 11-14 reveal weak emission in butyronitrile glass at 77 K, but they are non-emissive at room temperature. Ab initio modelling was performed to determine the charge state of the gold atoms involved. Extensive structural comparisons were made to experimental data to benchmark these calculations and rationalize the conformations.     

Isolation of template effects that control the structure and function of nonspherical, biotemplated Pd nanomaterials

Advances in nanotechnology have indicated that the passivant and the inorganic surface play a pivotal role in controlling the structure/function relationship of materials. Beyond standard materials-based methods, bioligands have recently demonstrated the production of unique nanomaterial morphologies for application under ambient conditions for multiple activities, such as catalysis and biosensing. We have recently demonstrated that a biotemplate technique could be employed to produce spherical and linear Pd nanostructures in water using a self-assembling peptide framework. The materials possessed high catalytic reactivity that was controlled by the three-dimensional structure of the composite materials. To investigate the effect of the peptide template on the reactivity of Pd nanostructures, an in depth analysis of the catalytic activity of Pd nanostructures fabricated via truncated templates is presented. The new templates were designed from portions of the original framework, which demonstrated unique synthetic and functionality control. Two different reactions, Stille C-C coupling and 4-nitrophenol reduction, were employed to ascertain the effect of template structure on the reactivity of synthesized Pd nanomaterials via changes in reagent diffusion through the bioscaffold. The results indicate that the peptide framework plays an important role and could be used to tune and optimize the functionality of the final composite materials for the target application.     

A study of the galvanic replacement reaction at surfaces and the role of lateral charge propagation

The galvanic replacement of isolated nanostructures of copper and silver on conducting supports as well as continuous films of copper with gold is reported. The surface morphology was characterized by scanning electron microscopy and the replacement with gold was confirmed by EDX analysis. It was found that lateral charge propagation during the replacement reaction had a significant effect in all cases. For the isolated nanostructures the deposition of gold was observed not only at the sacrificial template but also at the surrounding unmodified areas of the conducting substrate. In the case of copper films the role of lateral charge propagation was also confirmed by connecting it to an ITO electrode through an external circuit upon which gold deposition was also observed to occur. Interestingly, by inhibiting the rate of charge propagation, through the introduction of a series resistor, the morphology of gold on the copper substrate could be changed from discrete surface decoration with cube like nanoparticles to a more porous rough surface.     

Poly(L-Lysine)-pyranine-3 coacervate mediated nanoparticle-assembly: fabrication of dynamic pH-responsive containers

Counter-ion condensation of Poly(L-Lysine) in the presence of pyranine-3 generates spherical coacervates, which then template the assembly of silica nanoparticles to form microcapsule structures that dynamically control the optical ratiometric sensing of both the change in pH and release of the probe molecule.     

Electron beam irradiation induced changes in the dielectric and electro-optical properties of a room temperature nematic display material 4-(trans-4′-n-hexylcyclohexyl) isothiocyanatobenzoate (6CHBT)

Dielectric and electro-optical studies of a pure and electron beam irradiated liquid crystalline compound 4-(trans-4′-n-hexylcyclohexyl) isothiocyanatobenzoate have been carried out. Dielectric anisotropy, relaxation frequency, activation energy and distribution parameter of an observed non-collective mode corresponding to the molecular rotation about the short axes have been determined as a function of temperature and irradiation dose whereas threshold and switching voltages, splay elastic constant are determined as a function of irradiation dose. The relaxation frequencies initially decrease up to an irradiation dose of 40 kGy but thereafter increase due to irradiation. The activation energies are increased up to irradiation dose of 40 kGy but around 60 kGy dose of irradiation, we found decrease in the activation energy. Electro-optical measurements show the lowering of the threshold voltage with sufficient improvement in the steepness of the transmission voltage curves due to irradiation. The observed changes in the dielectric and electro-optical properties are related with the cis–trans isomerization due to electron beam irradiation.     

A finer modeling approach for numerically predicting single track geometry in two dimensions during Laser Rapid Manufacturing

We simulated the temperature distribution and single track geometry in Laser Rapid Manufacturing (LRM) of metal structures using two dimensional FEM with a finer modeling approach. This approach involved the calculation of excessive enthalpies above melting point for all nodal points in the process domain and using those for the computation of local track height at every node along the track width on the substrate. Laser power, laser beam size with its spatial profile, scan speed, powder feed rate and powder stream diameter with its flow distribution were taken as user-defined input parameters to simulate the single track geometry during LRM. The simulated results were experimentally verified. The percentage errors in simulated and corresponding experimental track heights along the normalized track width were calculated and compared with those of other existing models. With our modeling approach, the localized errors in predicting track geometries were found to be the least. This model is capable of dynamically predicting the temperatures and track geometry at various user-defined input parameters.     

Dissociative electron attachment resonances in ammonia: a velocity slice imaging based study

Negative ion resonance states of ammonia are accessed upon capture of electrons with energy 5.5 eV and 10.5 eV, respectively. These resonance states dissociate to produce H(-) and NH(2)(-) fragment anions via different fragmentation channels. Using the velocity slice imaging technique, we measured the angular and kinetic energy distribution of the fragment H(-) and NH(2)(-) anions with full 0-2π angular coverage across the two resonances. The scattered H(-) ions at both resonances show variation in their angular distribution as a function of the kinetic energy indicating geometric rearrangement of NH(3)(-*) ion due to internal excitations and differ from the equilibrium geometry of the neutral molecule. The second resonance at 10.5 eV shows strong forward-backward asymmetry in the scattering of H(-) and NH(2)(-) fragment ions. Based on the angular distributions of the H(-) ions, the symmetry of the resonances at 5.5 eV and 10 .5 eV are determined to be A(1) and E, respectively, within C(3v) geometry.     

Arrest of Opening of Two Circular-Arc Cracks with Coalesced Plastic Zones

The closure of plastic zones developed ahead of the tips of two unequal hairline arc cracks in an unbounded elastic-perfectly plastic plate is studied. The cracks lie along the circumference of one and the same circle. The rims of the cracks are opened in mode I type deformation by biaxial tension applied at infinity, and consequently plastic zones develop ahead of the tips of the cracks. The tension is increased to such an extent that the plastic zones of both cracks, lying adjacent to each other, are coalesced. To prevent the cracks from further opening, the rim of the plastic zone is subjected to a uniform, constant compressive yield-point stress. The problem is solved using the complex variable technique and the principle of superimposition of the stress intensity factors. The Dugdale hypothesis is used to determined the length of the plastic zones developed. The behavior of each of the parameters, viz. the length of the plastic zone, the crack length, and the intercrack distance effecting the crack closure, is investigated and reported graphically.