Rigid and flexible region in lysozyme and the invariant features in its hydration shell

Water-mediated transformations provide a useful handle for exploring the flexibility in protein molecules and the invariant features in their hydration shells. Low-humidity monoclinic hen egg white lysozyme, resulting from such a transformation, has perhaps the lowest solvent content observed in any protein crystal so far and has a well-ordered structure. A detailed comparison involving this structure, low-humidity tetragonal lysozyme, and the other available refined crystal structures of the enzyme permits the delineation of the relatively rigid, moderately flexible and highly flexible regions of the molecule. The relatively rigid region forms a contiguous structural unit close to the molecular centroid and encompasses parts of of the main beta-structure and three alpha-helices. The hydration shell of the protein contains 30 invariant water molecules. Many of them are involved in holding different parts of the molecule together or in stabilizing local structure. Five of the six invariant water molecules attached to the substrate-binding region form part of a water cluster contiguous with the side-chains of the catalytic residues Glu-35 and Asp-52.

Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-delta solid solution

The structure and chemical environment of Cu in Cu/CeO2 catalysts synthesized by the solution combustion method have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and extended X-ray fine structure (EXAFS) spectroscopy. High-resolution XRD studies of 3 and 5 atom % Cu/CeO2 do not show CuO lines in their respective patterns. The structure could be refined for the composition Ce1-xCuxO2-delta (x = 0.03 and 0.05; delta similar to 0.13 and 0.16) in the fluorite structure with 5-8% oxide ion vacancy. High-resolution TEM did not show CuO particles in 5 atom % Cu/CeO2. EPR as well as XPS studies confirm the presence of Cu2+ species in the CeO2 matrix. Redox potentials of Cu species in the CeO2 matrix are lower than those in CuO. EXAFS investigations of these catalysts show an average coordination number of 3 around the Cu2+ ion in the first shell at a distance of 1.96 Angstrom, indicating the O2- ion vacancy around the Cu2+ ion. The Cu-O bond length also decreases compared to that in CuO. The second and third shell around the Cu2+ ion in the catalysts are attributed to -Cu2+-O2--Cu2+ - at 2.92 Angstrom and -Cu2+-O2--Ce4+- at the distance of 3.15 Angstrom, respectively. The present results provide direct evidence for the formation of a Ce1-xCuxO2-delta type of solid solution phase having -square-Cu2+-O-Ce4+- kind of linkages.

Suspended core-shell Pt-PtOx nanostructure for ultrasensitive hydrogen gas sensor

High sensitivity gas sensors are typically realized using metal catalysts and nanostructured materials, utilizing non-conventional synthesis and processing techniques, incompatible with on-chip integration of sensor arrays. In this work, we report a new device architecture, suspended core-shell Pt-PtOx nanostructure that is fully CMOS-compatible. The device consists of a metal gate core, embedded within a partially suspended semiconductor shell with source and drain contacts in the anchored region. The reduced work function in suspended region, coupled with builtin electric field of metal-semiconductor junction, enables the modulation of drain current, due to room temperature Redox reactions on exposure to gas. The device architecture is validated using Pt-PtO2 suspended nanostructure for sensing H-2 down to 200 ppb under room temperature. By exploiting catalytic activity of PtO2, in conjunction with its p-type semiconducting behavior, we demonstrate about two orders of magnitude improvement in sensitivity and limit of detection, compared to the sensors reported in recent literature. Pt thin film, deposited on SiO2, is lithographically patterned and converted into suspended Pt-PtO2 sensor, in a single step isotropic SiO2 etching. An optimum design space for the sensor is elucidated with the initial Pt film thickness ranging between 10 nm and 30 nm, for low power (< 5 mu W), room temperature operation. (C) 2015 AIP Publishing LLC.

Static analysis of infinite laminated cylindrical shell panel

This paper presents an approximate three-dimensional elasticity solution for an infinitely long, cross-ply laminated circular cylindrical shell panel with simply supported boundary conditions, subjected to an arbitrary discontinuous transverse loading. The solution is based on the principal assumption that the ratio of the thickness of the lamina to its middle surface radius is negligible compared to unity. The validity of this assumption and the range of application of this approximate solution have been established through a comparison with an exact solution. Results of classical and first-order shear deformation shell theories have been compared with the results of the present solution to bring out the accuracy of these theories. It is also shown that for very shallow shell panels the definition of a thin shell should be based on the ratio of thickness to chord width rather than the ratio of thickness to mean radius.

Structural and optical investigation of semiconductor CdSe/CdS core-shell quantum dot thin films

Highly luminescent CdSe/CdS core-shell nanocrystals have been assembled on indium tin oxide (ITO) coated glass substrates using a wet synthesis route. The physical properties of the quantum dots (QD) have been investigated using X-ray diffraction, transmission electron microscopy and optical absorption spectroscopy techniques. These quantum dots showed a strong enhancement in the near band edge absorption. The in situ luminescence behavior has been interpreted in the light of the quantum confinement effect and induced strain in the core-shell structure.

Simplified dispersion curves for circular cylindrical shells using shallow shell theory.

An alternative derivation of the dispersion relation for the transverse vibration of a circular cylindrical shell is presented. The use of the shallow shell theory model leads to a simpler derivation of the same result. Further, the applicability of the dispersion relation is extended to the axisymmetric mode and the high frequency beam mode.

Analysis of laminated shells with laminated stiffeners using rectangular shell finite elements

A finite element analysis of laminated shells reinforced with laminated stiffeners is described in this paper. A rectangular laminated anisotropic shallow thin shell finite element of 48 d.o.f. is used in conjunction with a laminated anisotropic curved beam and shell stiffening finite element having 16 d.o.f. Compatibility between the shell and the stiffener is maintained all along their junction line. Some problems of symmetrically stiff ened isotropic plates and shells have been solved to evaluate the performance of the present method. Behaviour of an eccentrically stiffened laminated cantilever cylindrical shell has been predicted to show the ability of the present program. General shells amenable to rectangular meshes can also be solved in a similar manner.

Analysis of EXAFS data of multiphasic heterogeneous catalysts

Cu K-edge EXAFS spectra of Cu-Ni/Al2O3 and Cu-ZnO catalysts, both of which contain more than one Cu species, have been analysed making use of an additive relation for the EXAFS function. The analysis, which also makes use of residual spectra for identifying the species, shows good agreement between experimental and calculated spectra.

Noble Metal Ionic Catalysts

Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NOx, and unburned hydrocarbons-need to be fully converted to CO2, N-2, and H2O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al2O3 or SiO2 promoted by CeO2. However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce1-xMxO2-delta and Ce1-x-yTiyMxO2-delta (M = Pt, Pd, Rh; x = 0,01-0.02, delta approximate to x, y = 0.15-0.25) oxides in fluorite structure, In these oxide catalysts, pt(2+), Pd2+, or Rh3+ ions are substituted only to the extent of 1-2% of Ce4+ ion. Lower-valent noble metal ion substitution in CeO2 creates oxygen vacancies. Reducing molecules (CO, H-2, NH3) are adsorbed onto electron-deficient noble metal ions, while oxidizing (02, NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NOx reduction (with >80% N-2 selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO2 or Ce1-xTixO2 were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the more expensive Pt and Rh metals are not necessary in exhaust catalysts. We have also grown these nanocrystalline ionic catalysts on ceramic cordierite and have reproduced the results we observed in powder material on the honeycomb catalytic converter. Oxygen in a CeO2 lattice is activated by the substitution of Ti ion, as well as noble metal ions. Because this substitution creates longer Ti-O and M-O bonds relative to the average Ce-O bond within the lattice, the materials facilitate high oxygen storage and release. The interaction among M-0/Mn+, Ce4+/Ce3+, and Ti4+/Ti3+ redox couples leads to the promoting action of CeO2, activation of lattice oxygen and high oxygen storage capacity, metal support interaction, and high rates of catalytic activity in exhaust catalysis.

Analysis of laminated shells with laminated stiffeners using rectangular shell finite elementsstar

A finite element analysis of laminated shells reinforced with laminated stiffeners is described in this paper. A rectangular laminated anisotropic shallow thin shell finite element of 48 d.o.f. is used in conjunction with a laminated anisotropic curved beam and shell stiffening finite element having 16 d.o.f. Compatibility between the shell and the stiffener is maintained all along their junction line. Some problems of symmetrically stiffened isotropic plates and shells have been solved to evaluate the performance of the present method. Behaviour of an eccentrically stiffened laminated cantilever cylindrical shell has been predicted to show the ability of the present program. General shells amenable to rectangular meshes can also be solved in a similar manner.

The effect of some catalysts on the curing of oxiranes with p-phenylenediamine

The effect of some alcohols, acetylacetonates of transition metals, and manganese stearate and naphthenate on the curing reaction of a diglycidyl ether of ether of bisphenol-A with p-phenylenediamine is studied. Maximum catalytic activity is shown by the manganese compounds and triethanolamine.

Comparison of Elasticity, Shell Core, and Sandwich Shell Theories

The problem of an infinite circular sandwich shell subjected to an a\isymmetric radial line load is investigated using three-dimensional elasticity theory, shell core method, and sandwich shell theory due to Fulton and Schmidt. A comparison of the stresses and displacements with an exact elasticity solution is carried out for various shell parameters in order to clearly bring out the limitations of sandwich shell theories of Fulton and Schmidt as well as the shell core solution.

Transversely isotropic infinite cylindrical shell subjected to a radial axisymmetric line load

The problem of an infinite transversely isotropic circular cylindrical shell subjected to an axisymmetric radial external line load is investigated using elasticity theory, classical shell theory and shear deformation theory. The results obtained by these methods are compared for two ratios of inner to outer shell radius and for varying degrees of anisotropy. Some typical results are given here to show the effect of anisotropy and the thickness of the shell on the distribution of stresses and displacements.

Elasticity solution for a long circular sandwich cylindrical shell subjected to axisymmetric load

An elasticity solution has been obtained for a long circular sandwich cylindrical shell subjected to axisymmetric radial ring load using Love's stress function approach. Numerical results are presented for different ratios of modulus of elasticity of the layers. The results obtained from this analysis have been compared with those obtained from sandwich shell theory due to Fulton.