Asymmetric reactions of organosilicon compounds and properties of novel optically active organosilanes

Partial reduction of racemic methoxysilanes by 1:1 complexes of lithium aluminium hydride with optically active cinchona and ephedra alkaloids give optically active silanes and methoxysilanes. Optical yields depend on the groups attached to silicon and the alkaloid used but in some cases approach 50%, The method has been used to prepare novel optically active organosilanes, possessing an asymmetric silicon centre, which are either inaccessible by any of the other available routes or would require a time consuming preparation. Such compounds are of use in the study of the mechanism of substitutions at silicon. Attempts have been made to rationalize the results of the asymmetric reductions in terms of differences in sterio and electronic interactions in diastereoisomeric transition states. Circular dichroism and optical rotatory dispersion spectra have been obtained for the optically active products in an attempt to elucidate the absolute configurations of the novel asymmetric organosilanes. The results from these studies provide a useful addition to the data so far accumulated for asymmetrically perturbed aromatic chromophores. Nuclear magnetic resonanoe studies of diastereoisomaric (-)-menthoxysilanes show that these compounds possess resonances extremely useful in the determination of optical purities for asymmetric organosilanes which possess an aromatic group. The effect of variable temperature on the spectra has revealed evidence for the conformational preferences in these compounds. Other diastereoisomeric alkoxysilanes have been prepared and their n.m.r.spectra studied in the hope of establishing trends. Exploratory studies for other asymmetric reactions proceeding at silicon have proved unfruitful.

Study on fatigue and energy-dissipation properties of nanolayered Cu/Nb thin films

Energy dissipation and fatigue properties of nano-layered thin films are less well studied than bulk properties. Existing experimental methods for studying energy dissipation properties, typically using magnetic interaction as a driving force at different frequencies and a laser-based deformation measurement system, are difficult to apply to two-dimensional materials. We propose a novel experimental method to perform dynamic testing on thin-film materials by driving a cantilever specimen at its fixed end with a bimorph piezoelectric actuator and monitoring the displacements of the specimen and the actuator with a fibre-optic system. Upon vibration, the specimen is greatly affected by its inertia, and behaves as a cantilever beam under base excitation in translation. At resonance, this method resembles the vibrating reed method conventionally used in the viscoelasticity community. The loss tangent is obtained from both the width of a resonance peak and a free-decay process. As for fatigue measurement, we implement a control algorithm into LabView to maintain maximum displacement of the specimen during the course of the experiment. The fatigue S-N curves are obtained.

Resonance properties of domain boundaries in quasi-two dimensional antiferromagnets

The so-called "internal modes" localized near the domain boundaries in quasi-two dimensional antiferromagnets are investigated. The possible localized states are classified and their frequency dependences on the system discreteness parameter λ=J/β, which describes the ratio of the magnitudes of the exchange interplane interaction and the magnetic anisotropy, are found. A sudden change in the spectrum of the local internal modes is observed at a critical value of this parameter, λ=λb=3/4, where the domain wall shifts from a collinear to a canted shape. When λ<λb there are one symmetric and two antisymmetric local modes, and when λ>λb the modes are two symmetric, one antisymmetric, and one shear. For discreteness parameters close to the critical value, the frequencies of some of the local modes lie deep inside the gap for the linear AFM magnon spectrum and can be observed experimentally. © 2010 American Institute of Physics.

Mechanical and electrical properties of single-walled carbon nanotubes synthesized by chemical vapor deposition

Despite the tremendous application potentials of carbon nanotubes (CNTs) proposed by researchers in the last two decades, efficient experimental techniques and methods are still in need for controllable production of CNTs in large scale, and for conclusive characterizations of their properties in order to apply CNTs in high accuracy engineering. In this dissertation, horizontally well-aligned high quality single-walled carbon nanotubes (SWCNTs) have been successfully synthesized on St-cut quartz substrate by chemical vapor deposition (CVD). Effective radial moduli (Eradial) of these straight SWCNTs have been measured by using well-calibrated tapping mode and contact mode atomic force microscopy (AFM). It was found that the measured Eradial decreased from 57 to 9 GPa as the diameter of the SWCNTs increased from 0.92 to 1.91 nm. The experimental results were consistent with the recently reported theoretical simulation data. The method used in this mechanical property test can be easily applied to measure the mechanical properties of other low-dimension nanostructures, such as nanowires and nanodots. The characterized sample is also an ideal platform for electrochemical tests. The electrochemical activities of redox probes Fe(CN)63-/4-, Ru(NH3) 63+, Ru(bpy)32+ and protein cytochrome c have been studied on these pristine thin films by using aligned SWCNTs as working electrodes. A simple and high performance electrochemical sensor was fabricated. Flow sensing capability of the device has been tested for detecting neurotransmitter dopamine at physiological conditions with the presence of Bovine serum albumin. Good sensitivity, fast response, high stability and anti-fouling capability were observed. Therefore, the fabricated sensor showed great potential for sensing applications in complicated solution.^

Room temperature ferroelectric and magnetic investigations and detailed phase analysis of Aurivillius phase Bi 5Ti 3Fe 0.7Co 0.3O 15 thin films

Aurivillius phase Bi 5Ti 3Fe 0.7Co 0.3O 15 (BTF7C3O) thin films on α-quartz substrates were fabricated by a chemical solution deposition method and the room temperature ferroelectric and magnetic properties of this candidate multiferroic were compared with those of thin films of Mn 3 substituted, Bi 5Ti 3Fe 0.7Mn 0.3O 15 (BTF7M3O). Vertical and lateral piezoresponse force microscopy (PFM) measurements of the films conclusively demonstrate that BTF7C3O and BTF7M3O thin films are piezoelectric and ferroelectric at room temperature, with the major polarization vector in the lateral plane of the films. No net magnetization was observed for the in-plane superconducting quantum interference device (SQUID) magnetometry measurements of BTF7M3O thin films. In contrast, SQUID measurements of the BTF7C3O films clearly demonstrated ferromagnetic behavior, with a remanent magnetization, B r, of 6.37 emu/cm 3 (or 804 memu/g), remanent moment 4.99 × 10 -5 emu. The BTF7C3O films were scrutinized by x-ray diffraction, high resolution transmission electron microscopy, scanning transmission electron microscopy, and energy dispersive x-ray analysis mapping to assess the prospect of the observed multiferroic properties being intrinsic to the main phase. The results of extensive micro-structural phase analysis demonstrated that the BTF7C3O films comprised of a 3.95 Fe/Co-rich spinel phase, likely CoFe 2 - xTi xO 4, which would account for the observed magnetic moment in the films. Additionally, x-ray magnetic circular dichroism photoemission electron microscopy (XMCD-PEEM) imaging confirmed that the majority of magnetic response arises from the Fe sites of Fe/Co-rich spinel phase inclusions. While the magnetic contribution from the main phase could not be determined by the XMCD-PEEM images, these data however imply that the Bi 5Ti 3Fe 0.7Co 0.3O 15 thin films are likely not single phase multiferroics at room temperature. The PFM results presented demonstrate that the naturally 2D nanostructured Bi 5Ti 3Fe 0.7Co 0.3O 15 phase is a novel ferroelectric and has potential commercial applications in high temperature piezoelectric and ferroelectric memory technologies. The implications for the conclusive demonstration of ferroelectric and ferromagnetic properties in single-phase materials of this type are discussed.

Magnetic extracts of three gravity cores located at the Ceará Rise, the Mid-Atlantic Ridge and the Sierra Leone Rise

The magnetic microparticle and nanoparticle inventories of marine sediments from equatorial Atlantic sites were investigated by scanning and transmission electron microscopy to classify all present detrital and authigenic magnetic mineral species and to investigate their regional distribution, origin, transport, and preservation. This information is used to establish source-to-sink relations and to constrain environmental magnetic proxy interpretations for this area. Magnetic extracts were prepared from sediments of three supralysoclinal open ocean gravity cores located at the Ceará Rise (GeoB 1523-1; 3°49.9'N/41°37.3'W), the Mid-Atlantic Ridge (GeoB 4313-2; 4°02.8'N/33°26.3'W), and the Sierra Leone Rise (GeoB 2910-1; 4°50.7'N/21°03.2'W). Sediments from two depths corresponding to marine isotope stages 4 and 5.5 were processed. This selection represents glacial and interglacial conditions of sedimentation for the western, central, and eastern equatorial Atlantic and avoids interferences from subsurface and anoxic processes. Crystallographic, elemental, morphological, and granulometric data of more than 2000 magnetic particles were collected by scanning and transmission electron microscopy. On basis of these properties, nine particle classes could be defined: detrital magnetite, titanomagnetite (fragmental and euhedral), titanomagnetite-hemoilmentite intergrowths, silicates with magnetic inclusions, microcrystalline hematite, magnetite spherules, bacterial magnetite, goethite needles, and nanoparticle clusters. Each class can be associated with fluvial, eolian, subaeric, and submarine volcanic, biogenic, or chemogenic sources. Large-scale sedimentation patterns are delineated as well: detrital magnetite is typical of Amazon discharge, fragmental titanomagnetite is a submarine weathering product of mid-ocean ridge basalts, and titanomagnetite-hemoilmenite intergrowths are common magnetic particles in West African dust. This clear regionalization underlines that magnetic petrology is an excellent indicator of source-to-sink relations. Hematite encrustations, magnetic spherules, and nanoparticle clusters were found at all investigated sites, while bacterial magnetite and authigenic hematite were only detected at the more oxic western site. At the eastern site, surface pits and crevices were seen on the crystal faces indicating subtle early diagenetic reductive dissolution. It was observed that paleoclimatic signatures of magnetogranulometric parameters such as the ratio of anhysteretic and isothermal remanent magnetizations can be formed either by mixing of multiple sources with separate, relatively narrow grain size ranges (western site) or by variable sorting of a single source with a broad grain size distribution (eastern site). Hematite, goethite, and possibly ferrihydrite nanoparticles occur in all sediment cores studied and have either high-coercive or superparamagnetic properties depending on their partly ultrafine grain sizes. These two magnetic fractions are generally discussed as separate fractions, but we suggest that they could actually be genetically linked.

Investigating the potential magnetic origin of wind variability in OB stars

In this thesis, the origin of large-scale structures in hot star winds, believed to be responsible for the presence of discrete absorption components (DACs) in the absorption troughs of ultraviolet resonance lines, is constrained using both observations and numerical simulations. These structures are understood as arising from bright regions on the stellar surface, although their physical cause remains unknown. First, we use high quality circular spectropolarimetric observations of 13 well-studied OB stars to evaluate the potential role of dipolar magnetic fields in producing DACs. We perform longitudinal field measurements and place limits on the field strength using Bayesian inference, assuming that it is dipolar. No magnetic field was detected within this sample. The derived constraints statistically refute any significant dynamical influence from a magnetic dipole on the wind for all of these stars, ruling out such fields as a cause for DACs. Second, we perform numerical simulations using bright spots constrained by broadband optical photometric observations. We calculate hydrodynamical wind models using three sets of spot sizes and strengths. Co-rotating interaction regions are yielded in each model, and radiative transfer shows that the properties of the variations in the UV resonance lines synthesized from these models are consistent with those found in observed UV spectra, establishing the first consistent link between UV spectroscopic line profile variability and photometric variations and thus supporting the bright spot paradigm (BSP). Finally, we develop and apply a phenomenological model to quantify the measurable effects co-rotating bright spots would have on broadband optical photometry and on the profiles of photopheric lines in optical spectra. This model can be used to evaluate the existence of these spots, and, in the event of their detection, characterize them. Furthermore, a tentative spot evolution model is presented. A preliminary analysis of its output, compared to the observed photometric variations of xi Persei, suggests the possible existence of “active longitudes” on the surface of this star. Future work will expand the range of observational diagnostics that can be interpreted within the BSP, and link phenomenology (bright spots) to physical processes (magnetic spots or non-radial pulsations).

Photoconductivity and electrical properties of diamond films grown by MPCVD

The electrical and photoconductive features of as-grown microwave-plasma-assisted chemical-vapour deposition (MPCVD) diamond films are studied in correlation with magnetic results obtained from electron paramagnetic resonance (EPR). Also, the morphology is analysed by atomic force microscopy (AFM) showing [111] crystals with a good uniformity of the deposit. The photoresponse as well the current-voltage features observed show an efficient photogeneration of carriers while the optoelectronic characteristics of the metal-diamond junction have an ideality factor of 1.6 together with a rectification ratio of about 10(4) at +/-2.5 V. The nature of the mechanisms responsible for the conduction is discussed. (C) 1998 Elsevier Science S.A.

Structural and mechanical properties of La0.6Sr0.4M0.1Fe0.9O3-δ (M: Co, Ni and Cu) perovskites

La0.6Sr0.4M0.1Fe0.9O3-δ (M: Co, Ni and Cu) perovskite nanostructures were synthesized using low frequency ultrasound assisted synthesis technique and effect of substitution of Fe by Co, Ni and Cu on crystal structure and mechanical properties in La0.6Sr0.4FeO3-δ perovskite were studied. The HRTEM and Rietveld refinement analyses revealed the uniform equi-axial shape of the obtained nanostructures with the existence of La0.6Sr0.4M0.1Fe0.9O3−δ with mixed rhombohedral and orthorhombic structures. Substitution of Cu decreases the melting point of La0.6Sr0.4FeO3-δ. The results of mechanical characterizations show that La0.6Sr0.4Co0.1Fe0.9O3−δ and La0.6Sr0.4Ni0.1Fe0.9O3−δ have ferroelastic behavior and comparable elastic moduli, however, subtitution of Ni shows higher hardness and lower fracture toughness than Co in Bsite doping

Photoconductivity and electrical properties of diamond films grown by MPCVD

The electrical and photoconductive features of as-grown microwave-plasma-assisted chemical-vapour deposition (MPCVD) diamond films are studied in correlation with magnetic results obtained from electron paramagnetic resonance (EPR). Also, the morphology is analysed by atomic force microscopy (AFM) showing [111] crystals with a good uniformity of the deposit. The photoresponse as well the current-voltage features observed show an efficient photogeneration of carriers while the optoelectronic characteristics of the metal-diamond junction have an ideality factor of 1.6 together with a rectification ratio of about 10(4) at +/-2.5 V. The nature of the mechanisms responsible for the conduction is discussed. (C) 1998 Elsevier Science S.A.