Preparation of fully cross-linked CNBR/PP-g-GMA and CNBR/PP/PP-g-GMA thermoplastic elastomers and their morphology, structure and properties

Binary CNBR/PP-g-GMA and ternary CNBR/PP/PP-g-GMA thermoplastic elastomers were prepared by reactive blending carboxy nitrile rubber (CNBR) powder with nanometer dimension and polypropylene functionalized with glycidyl methacrylate (PP-g-GMA). Morphology observation by using an atomic force microscope (AFM) and TEM revealed that the size of CNBR dispersed phase in CNBR/PP-g-GMA binary blends was much smaller than that of the corresponding CNBR/PP binary blends. Thermal behavior of CNBR/PP-g-GMA and CNBR/PP blends was studied by DSC. Comparing with the plain PP-g-GMA, T, of PP-g-GMA in CNBR/PP-g-GMA blends increased about 10degreesC. Both thermodynamic and kinetic effects would influence the crystallization behavior of PP-g-GMA in CNBR/PP-g-GMA blends. At a fixed content of CNBR, the apparent viscosity of the blending system increased with increasing the content of PP-g-GMA. FTIR spectrum verified that the improvement of miscibility of CNBR and PP-g-GMA was originated from the reaction between carboxy end groups of CNBR and epoxy groups of GMA grafted onto PP molecular chains. Comparing with CNBR/PP blends, the tensile strength, stress at 100% strain, and elongation at break of CNBR/PP-g-GMA blends were greatly improved.

Structure and identity of 4,4 '-thiobisbenzenethiol self-assembled monolayers

Self-assembled monolayers (SAMs) of 4,4'-thiobisbenzenethiol (TBBT) can be formed on Au surface spontaneously. The structural characteristics and adsorption behavior of TBBT SAMs on Au have been investigated by surface enhanced Raman scattering (SERS), electrochemical cyclic voltammetry (CV), ac impedance spectroscopy (EIS), and atomic force microscopy (AFM). It is demonstrated that TBBT adsorbed on Au by losing a H atom, forming one Au-S bond, and the other mercapto group is free at the surface of the monolayer owing to the presence of the nu(S-H) at 2513 cm(-1) and the delta(C-S-H) at 910 cm(-1) in SERS. The enhancement of the vibration of C-S (1064 cm(-1)), the aromatic C-H vibration (3044 cm(-1)), and the absence of the vibration of S-S illustrate TBBT adsorbed on Au forming a monolayer with one benzene ring tilted with respect to the Au surface. The interpretation of the observed frequencies is aided by ab initio molecular orbital (MO) calculations at the HF/6-31G* level of theory. Electrochemical CV and EIS indicate TBBT monolayers can passivate the Au effectively for its low ratio of pinhole defects (theta = 99.6%). AFM studies give details about the surface morphology. The applications of TBBT SAMs have been extensively investigated by exposure of Cu2+ ion to TBBT SAMs on Au and covalent adsorption of metal nanoparticles.

Boundary effect of relief structure on crystallization of diblock copolymer in thin films

In this Letter, crystal growth of a symmetric crystalline-amorphous diblock copolymer, poly(styrene-b-epsilon-caprolactone) (PS-b-PCL), in thin films was investigated by atomic force microscopy (AFM), Relief structures of holes and islands were formed during annealing the film at the molten state, and the in situ observation of subsequent crystal growth at room temperature indicated that the crystals were preferred to occur at the edge of holes or islands and grew into the interior area. It was concluded that the stretched PCL blocks at the edge of relief structures, caused by material transportation or deformation of the interface, could act as nucleation agents during polymer crystallization. The crystal growth rate of individual lamellae varied both from lamellae to lamellae and in time, but the area occupied by crystals increased constantly with time. At 22 degreesC, the growth rate was 1.2 x 10(-2) mum(2)/min with the scan size 2 x 2 mum(2).

Probing UPD-induced surface atomic rearrangement of polycrystalline gold nanofilms with surface plasmon resonance spectroscopy and cyclic voltammetry

Silver underpotential deposition (UPD)-induced surface atomic rearrangement of polycrystalline gold nanofilms was probed with use of surface plasmon resonance spectroscopy (SPRs) as a novel probe tool in combination with cyclic voltammetry. Interestingly, upon repetitive electrochemical UPD and stripping of Ag, the surface structure of the resulting bare Au film is rearranged due to strong adatom-substrate interactions, which causes a large angle shift of SPR R-theta curves, in a good linear relationship with the number of UPDs, to a lower SPR angle. The n, K values of the surfacial Au monolayers before and after the repetitive Ag UPD and stripping for 27 times are found to be 0.133, 3.60 and 0.565, 9.39, respectively, corresponding to the huge shift of 1.61degrees to the left of the SPR minima. Cyclic voltammetry experiments in 0.10 M H2SO4 are carried out before and after the UPD treatment to examine the quality of the whole electrode surface and confirmed this change. To correlate the angle change in SPRs with the profile change in the cyclic voltammogram, the UPD treatment was also performed on a Au(111) textured thin film. It was therefore confirmed that the resonance position of the SPR spectrum is very sensitive to the surface crystallographic orientation of the bare Au substrates. Some surface atomic rearrangement can cause a pronounced SPR angle shift.

Morphology and structure of nylon-2,14 single crystals from dilute solution

A perfect single crystal of nylon-2,14 was prepared from 0.02% (w/v) 1,4-butanediol solution by a "self-seeding" technique and isothermal crystallization at 120 and 145 degreesC. The morphology and structure features were examined by transmission electron microscopy with both image and diffraction modes, atomic force microscopy, and wide-angle X-ray diffraction (WAXD). The nylon-2,14 single crystal grown from 1,4-butanediol at 145 degreesC inhabited a lathlike shape with a lamellar thickness of about 9 nm. Electron diffraction and WAXD data indicated that nylon-2,14 crystallized in a triclinic system with lattice dimensions a = 0.49 nm, b = 0.51 nm, c = 2.23 nm, alpha = 60.4degrees, beta = 77degrees, and gamma = 59degrees. The crystal structure is different from that of nylon-6,6 but similar to that of other members of nylon-2Y.

Atomic force microscopy imaging of molybdenum oxide film electrodeposited on a carbon electrode

Non-stoichiometric mixed-valent molybdenum(VI, V) oxide film was grown on carbon substrates by the electrodeposition method. Responses of the prepared molybdenum oxide thin films to potential and to different solution acidities were studied by cyclic voltammetry, and the corresponding morphological changes of the film were monitored by atomic force microscopy (AFM). AFM images of the molybdenum oxide film show that the characteristic domed structure on the film surface increased during the transition from the oxidized state to the reduced state without signification change in the KMS surface roughness value. Furthermore, AFM studies show that the solution acidity has great effect on the morphology of the films, and the films undergo a homogenizing process with increasing pH of the solutions. (C) 1999 Elsevier Science S.A. All rights reserved.

In situ electrochemical scanning tunnelling microscopy investigation of structure for horseradish peroxidase and its electrocatalytic property

Immobilization of protein molecules is a fundamental problem for scanning tunnelling microscopy (STM) measurements with high resolution. In this paper, an electrochemical method has been proved to be an effective way to fix native horseradish peroxidase (HRP) as well as inactivated HRP from electrolyte onto a highly oriented pyrolytic graphite (HOPG) surface. This preparation is suitable for both ex situ and in situ electrochemical STM (ECSTM) measurements. In situ STM has been successfully employed to observe totally different structures of HRP in three typical cases: (1) in situ ECSTM reveals an oval-shaped pattern for a single molecule in neutral buffer solution, which is in good agreement with the dimension determined as 6.2 x 4.3 x 1.2. nm(3) by ex situ STM for native HRP; (2) in situ ECSTM shows that the adsorbed HRP molecules on HOPG in a denatured environment exhibit swelling globes at the beginning and then change into a V-shaped pattern after 30 min; (3) in situ ECSTM reveals a black hole in every ellipsoidal sphere for inactivated HRP in strong alkali solution. The cyclic voltammetry results indicate that the adsorbed native HRP can directly catalyse the reduction of hydrogen peroxide, demonstrating that a direct electron transfer reduction occurred between the enzyme and HOPG electrode, whereas the corresponding cyclic voltammograms for denatured HRP and inactivated HRP adsorbed on HOPG electrodes indicate a lack of ability to catalyse H2O2 reduction, which confirms that the HRP molecules lost their biological activity. Obviously, electrochemical results powerfully support in situ STM observations.

HYPERFINE-STRUCTURE OF SOME ODD PARITY LEVELS IN THE THULIUM SPECTRUM

The laser-atomic-beam spectroscopy technique has been used to make measurements of the hyperfine structure in some odd parity levels of thulium by stepwise excitation. With the experimental results the magnetic dipole hyperfine constants A for the four levels in the configurations 4f12 5d6s6p and 4f12 (H-3(5))6s2 6p3/2 and for two intermediate levels have been obtained.

Historical changes in nutrient structure and its influences on phytoplantkon composition in Jiaozhou Bay

Due to the influence of human activities, nutrient concentrations, nutrient ratios and phytoplankton composition have notably changed in Jiaozhou Bay, China since the 1960s. From the 1960s to the 1990s, nutrient concentrations have increased 1.4 times for PO4-P, 4.3 times for NO3-N, 4.1 times for NH4-N and 3.9 times for DIN. The atomic ratio of DIN:PO4-P increased very rapidly from 15.9 +/- 6.3 for the 1960s, to 37.8 +/- 22.9 for the 1990s. SiO3-Si concentration has remained at a very low level from the 1980s to the 1990s. The high ratio of DIN: PO4-P and low ratios of SiO3-Si:PO4-P (7.6 +/- 8.9) and SiO3-Si:DIN (0.19 +/- 0.15) showed the nutrient structure of Jiaozhou Bay has changed from more balanced to unbalanced during the last 40 years. The possibility that DIN and/or PO4-P as limiting factors of Jiaozhou Bay phytoplankton has been lessened or eliminated and that of SiO3-Si limiting has been increased. The changes in nutrient structure may have led to the decrease of large diatoms and a shift of phytoplankton species composition. It is likely that there is a trend from large diatoms to smaller cells in Jiaozhou Bay. (C) 2001 Academic Press.

Internal structure of copper(II)-phthalocyanine thin films on SiO2/Si substrates investigated by grazing incidence x-ray reflectometry

Jenkins, Tudor; Brieva, A.C.; Jones, D.G.; Evans, D.A., (2006) 'Internal structure of copper(II)-phthalocyanine thin films on SiO2/Si substrates investigated by grazing incidence x-ray reflectometry', Journal of Applied Physics 99 pp.73504 RAE2008

Visible Volume: a Robust Measure for Protein Structure Characterization

We propose a new characterization of protein structure based on the natural tetrahedral geometry of the β carbon and a new geometric measure of structural similarity, called visible volume. In our model, the side-chains are replaced by an ideal tetrahedron, the orientation of which is fixed with respect to the backbone and corresponds to the preferred rotamer directions. Visible volume is a measure of the non-occluded empty space surrounding each residue position after the side-chains have been removed. It is a robust, parameter-free, locally-computed quantity that accounts for many of the spatial constraints that are of relevance to the corresponding position in the native structure. When computing visible volume, we ignore the nature of both the residue observed at each site and the ones surrounding it. We focus instead on the space that, together, these residues could occupy. By doing so, we are able to quantify a new kind of invariance beyond the apparent variations in protein families, namely, the conservation of the physical space available at structurally equivalent positions for side-chain packing. Corresponding positions in native structures are likely to be of interest in protein structure prediction, protein design, and homology modeling. Visible volume is related to the degree of exposure of a residue position and to the actual rotamers in native proteins. In this article, we discuss the properties of this new measure, namely, its robustness with respect to both crystallographic uncertainties and naturally occurring variations in atomic coordinates, and the remarkable fact that it is essentially independent of the choice of the parameters used in calculating it. We also show how visible volume can be used to align protein structures, to identify structurally equivalent positions that are conserved in a family of proteins, and to single out positions in a protein that are likely to be of biological interest. These properties qualify visible volume as a powerful tool in a variety of applications, from the detailed analysis of protein structure to homology modeling, protein structural alignment, and the definition of better scoring functions for threading purposes.

Nano-urchin: The formation and structure of high-density spherical clusters of vanadium oxide nanotubes

We report the observation of urchin-like nanostructures consisting of high-density spherical nanotube radial arrays of vanadium oxide nanocomposite, successfully synthesized by a simple chemical route using an ethanolic solution of vanadium tri-isopropoxide and alkyl amine hexadecylamine for 7 days at 180oC. The results show that the growth process of the NanoUrchin occurs in stages, starting with a radial self-organized arrangement of lamina followed by the rolling of the lamina into nanotubes. The longest nanotubes are measured to be several micrometers in length with diameters of ~120 nm and hollow centers typically measured to be ~75 nm. The NanoUrchin have an estimated density of nanotubes of ~40 sr-1. The tube walls comprise layers of vanadium oxide with the organic surfactant intercalated between atomic layers. The interlayer distance is measured to be 2.9 ± 0.1 nm and electron diffraction identified the vanadate phase in the VOx nanocomposite as orthorhombic V2O5. These nanostructures may be used as three-dimensional composite materials and as supports for other materials.

Investigation of numerical atomic orbitals for first-principles calculations of the electronic and transport properties of silicon nanowire structures

This thesis is focused on the application of numerical atomic basis sets in studies of the structural, electronic and transport properties of silicon nanowire structures from first-principles within the framework of Density Functional Theory. First we critically examine the applied methodology and then offer predictions regarding the transport properties and realisation of silicon nanowire devices. The performance of numerical atomic orbitals is benchmarked against calculations performed with plane waves basis sets. After establishing the convergence of total energy and electronic structure calculations with increasing basis size we have shown that their quality greatly improves with the optimisation of the contraction for a fixed basis size. The double zeta polarised basis offers a reasonable approximation to study structural and electronic properties and transferability exists between various nanowire structures. This is most important to reduce the computational cost. The impact of basis sets on transport properties in silicon nanowires with oxygen and dopant impurities have also been studied. It is found that whilst transmission features quantitatively converge with increasing contraction there is a weaker dependence on basis set for the mean free path; the double zeta polarised basis offers a good compromise whereas the single zeta basis set yields qualitatively reasonable results. Studying the transport properties of nanowire-based transistor setups with p+-n-p+ and p+-i-p+ doping profiles it is shown that charge self-consistency affects the I-V characteristics more significantly than the basis set choice. It is predicted that such ultrascaled (3 nm length) transistors would show degraded performance due to relatively high source-drain tunnelling currents. Finally, it is shown the hole mobility of Si nanowires nominally doped with boron decreases monotonically with decreasing width at fixed doping density and increasing dopant concentration. Significant mobility variations are identified which can explain experimental observations.

Atomic layer deposition of copper – study through density functional theory

The wonder of the last century has been the rapid development in technology. One of the sectors that it has touched immensely is the electronic industry. There has been exponential development in the field and scientists are pushing new horizons. There is an increased dependence in technology for every individual from different strata in the society. Atomic Layer Deposition (ALD) is a unique technique for growing thin films. It is widely used in the semiconductor industry. Films as thin as few nanometers can be deposited using this technique. Although this process has been explored for a variety of oxides, sulphides and nitrides, a proper method for deposition of many metals is missing. Metals are often used in the semiconductor industry and hence are of significant importance. A deficiency in understanding the basic chemistry at the nanoscale for possible reactions has delayed the improvement in metal ALD. In this thesis, we study the intrinsic chemistry involved for Cu ALD. This work reports computational study using Density Functional Theory as implemented in TURBOMOLE program. Both the gas phase and surface reactions are studied in most of the cases. The merits and demerits of a promising transmetallation reaction have been evaluated at the beginning of the study. Further improvements in the structure of precursors and coreagent have been proposed. This has led to the proposal of metallocenes as co-reagents and Cu(I) carbene compounds as new set of precursors. A three step process for Cu ALD that generates ligand free Cu layer after every ALD pulse has also been studied. Although the chemistry has been studied under the umbrella of Cu ALD the basic principles hold true for ALD of other metals (e.g. Co, Ni, Fe ) and also for other branches of science like thin film deposition other than ALD, electrochemical reactions, etc.