Preferred Orientation of a Physisorbed Molecular Catalyst and Implications for Selectivity
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Introducing chirality into organic/inorganic hybrid materials can impart chiroptical properties such as circular dichroism. The ability to tune chiroptical properties in self-assembled materials can have important implications for spintronic and optoelectronic applications. Here, a chiral organic cation, (R/S)-4-methoxy-a-methylbenzylammonium, is incorporated to synthesize the bismuth-based hybrid organic-inorganic metal halide semiconductor, (R/S-MeOMePMA)BiI4. Thin films of this Bi-based compound demonstrate large chiroptical responses, with circular dichroism anisotropy (gCD) values up to ˜0.1, close to the highest value observed in another chiral metal-halide semiconductor, (R-MBA2CuCl4). Detailed investigation reveals that this large gCD in (R/S-MeOMePMA)BiI4 is caused by the apparent CD effect. Careful selection of deposition conditions and the concomitant thin-film orientation enables the control of gCD, with maximum value observed when its thin film has a well-crystallized preferred (001) orientation parallel to the substrate. The results support a growing body of evidence that low symmetry plays an important role in achieving unusually large gCD in these chiral metal-halide materials and provides design rules for achieving large chiroptical response via morphology control.
Preferred orientation has been examined in extruded, drawn, and swaged nickel, nickel-20% chromium, and nickel-20% chromium-10% tungsten, with and without a dispersion of 2 vol % of thoria particles. Duplex 100 (in carets) + 111 (in carets) fiber textures were observed in most cases. The 100 (in carets) component was stabilized by the presence of particles and also by the application of intermediate anneals during deformation. These results and the stability of the deformed state in thoriated nickel are attributed largely to the action of the particles in generating homogeneous deformation.
A plotting of inverse pole figures is used to characterize the preferred orientations in both powder-extruded and cast-and-extruded NiAl, FeAl, and Ni3Al; the preferred 111 orientation has been noted along the extrusion direction in both powder-extruded and cast-and-extruded NiAl. While powder-extruded FeAl also had a 111 preferred orientation in the as-extruded condition, 110 was observed upon casting and extrusion; this was in turn replaced by a 211 orientation preference upon annealing, although annealing did not change the preferred orientation in either NiAl or in powder-extruded FeAl.
Preferred orientation of pyrolytic carbons, noting relationships and equivalence of parameters
Nano/micro-indentation has been extensively used to examine elastic properties and creep of cement-based materials. However, there have been inconsistencies in the measured elastic moduli and debate on the creep mechanism of calcium (alumino) silicate hydrates (C-(A-)S-H). To bring new insights, we examined the deviatoric stress-induced preferred orientation of calcium aluminosilicate hydrate (C-A-S-H), portlandite, and ettringite compacts, using synchrotron-based X-ray diffraction. Intense preferred orientations were observed in C-A-S-H compacts, and the c-axis of unit cells is highly aligned with the compression direction; weaker c-axis related fiber-type texture formed in portlandite and ettringite. Higher humidity, greater compacting pressure, and/or increased duration of the pressure intensified the C-A-S-H preferred orientation, which is facilitated by gel-pore water lubrication. This pressure-induced time-dependent preferential re-orientation of crystallites can contribute to the creep of cement-based materials, and it may cause overrepresentation of the soft c-axis of C-(A-)S-H unit-cell in nanoindentation experiments and underestimation of Young's modulus.
It is pointed out that in principle all of the preferred-orientation information for the direction normal to a surface will be contained in the intensity differences between X-ray diffraction peaks for a sample with a preferred orientation and one with a fully random crystallite orientation. An experimental investigation is discussed along with questions regarding the procedure used in the evaluation process.
X ray transmission technique to study preferred orientation in recrystallized hot pressed MgO
Automatic device built around a goniometer examines characteristics of polycrystalline materials and determines preferred orientations of crystallites. It is automatically rotatable in each of two planes and has circuit regulated sequential rotation. A fixed X ray source in conjunction with a detector examines the material.
The His-tag is a widely used affinity tag that facilitates purification by means of affinity chromatography of recombinant proteins for functional and structural studies. We show here that His-tag presence affects how coproheme decarboxylase interacts with the air-water interface during grid preparation for cryoEM. Depending on His-tag presence or absence, we observe significant changes in patterns of preferred orientation. Our analysis of particle orientations suggests that His-tag presence can mask the hydrophobic and hydrophilic patches on a protein’s surface that mediate the interactions with the air-water interface, while the hydrophobic linker between a His-tag and the coding sequence of the protein may enhance other interactions with the air-water interface. Our observations suggest that tagging, including rational design of the linkers between an affinity tag and a protein of interest, offer a promising approach to modulating interactions with the air-water interface.
Creep due to ice flow is generally thought to be the main cause for the formation of crystallographic preferred orientations (CPOs) in polycrystalline anisotropic ice. However, linking the development of CPOs to the ice flow history requires a proper understanding of the ice aggregate's microstructural response to flow transitions. In this contribution the influence of ice deformation history on the CPO development is investigated by means of full-field numerical simulations at the microscale. We simulate the CPO evolution of polycrystalline ice under combinations of two consecutive deformation events up to high strain, using the code VPFFT (visco-plastic fast Fourier transform algorithm) within ELLE. A volume of ice is first deformed under coaxial boundary conditions, which results in a CPO. The sample is then subjected to different boundary conditions (coaxial or non-coaxial) in order to observe how the deformation regime switch impacts the CPO. The model results indicate that the second flow event tends to destroy the first, inherited fabric with a range of transitional fabrics. However, the transition is slow when crystallographic axes are critically oriented with respect to the second imposed regime. Therefore, interpretations of past deformation events from observed CPOs must be carried out with caution, particularly in areas with complex deformation histories.
Preferred crystal orientations and vacuum work functions of planar tungsten deposits formed by hydrogen reduction of tungsten chloride
Techniques representing the angular distribution of a particular direction in a crystallographic reference frame or analytical methods were developed. The data required by these techniques for displaying preferred orientation is obtained by measuring the orientation of a large number of crystallites. This may be done visually using etch-pit or Laue techniques which, experimentally, are both tedious and difficult. The intensities of X ray diffraction maxima are proportional to the number of crystallites whose crystallographic plane normals bisect the incident and diffracted beams. Parameters used in calculating powder patterns are also presented.
The spatial organization and interactions of constituent components influence cell growth and determine physical and chemical properties of the cell wall, including its rigidity, flexibility, and degradability. Elucidating the interactions between cell wall polysaccharides is crucial for advancing our knowledge of how cell walls are assembled and for designing approaches to efficiently break down cell walls to produce renewable energy and biomaterials. Here, we investigated the effect of defects in the biosynthesis of cell wall components on the nanoscale organization of cellulose in primary cell walls through grazing incidence wide angle X-ray scattering (GIWAXS) measurements of hypocotyls of wild type Arabidopsis thaliana and of cellulose, pectin, and xyloglucan (hemicellulose) deficient mutants. GIWAXS reveals changes in lattice spacings, coherence lengths, and relative crystalline content for cellulose between wild type and mutant plants. In addition, X-ray pole figures constructed using GIWAXS and X-ray diffraction (XRD) rocking scans quantify an emerging measure of cellulose organization, the degree of preferred orientation (texture) of cellulose crystals with respect to the cell wall plane. Comparing X-ray pole figures from pectin-deficient and xyloglucan-deficient mutants to that of wild type plants reveals that cellulose texture is disrupted in pectin-deficient mutants, but not in xyloglucan mutants. Furthermore, our results indicate that a deficiency of pectin during cell wall biosynthesis alters cellulose organization in plant cell walls.
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Friction characteristics and interfacial recrystallization of single-crystal and polycrystalline copper sliding on aluminum oxide