Synthesis and Structures of Titanosiloxane Cage Compounds

Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl₃) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {[Ph₃CSiO(OH)]₃(Ph₃CSiO_3/2)(CpTiO_3/2)₄} (2) and cube type (Ph₃CSiO_3/2CpTiO_3/2)₄ (3). The 1:1 reaction of 1 and CpTiCl₃ in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl₃ under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of ¹H, ¹³C, ²⁹Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl₃ > hexane THF.     

Anomalies in the asymmetric hydroboration of olefins with the 11 adduct of (+)-α-pinene and BH3 · THF

The hydroboration of cis-2-butene and cis-3-hexene with pure diisopinocampheylborane (IPC₂BH) and monoisopinocampheylborane (IPCBH₂), both prepared from (+)-α-pinene, were studied. In contrast to IPC₂BH, which yielded R-(?)-2-butanol and R-(?)-3-hexanol in 98.4 and 94.5% optical purities, IPCBH₂ yielded S-(+)-2-butanol and S-(+)-3-hexanol in 23.6 and 19.7% optical purifies respectively. PMR examination of the methanolyzed products were utilized to establish the species present in the freshly prepared and aged $\text{1}\text{1}$ adduct from (+)-α-pinene and BH₃ · THF. The results confirm the interpretation previously advanced for the major differences realized in asymmetric hydroboration with the fresh and aged $\text{1}\text{1}$ adducts.     

A boundary element method for molecular electrostatics with electrolyte effects

A boundary element method is developed to compute the electrostatic potential inside and around molecules in an electrolyte solution. A set of boundary integral equations are derived based on the integral formulations of the Poisson equation and the linearized Poisson-Boltzmann equation. The boundary integral equations are then solved numerically after discretizing the molecular surface into a number of flat triangular elements. The method is applied to a spherical molecule for which analytical solutions are available. Use is made of both constant and linearly varying unknowns over the boundary elements, and the method is tested for various values of parameters such as the dielectric constant of the molecule, ionic strength, and the location of the interior point charge. The use of the boundary integral method incorporating the nonlinear Poisson-Boltzmann equation is also briefly discussed.     

Synthesis and Characterization of Fluoro- and Chloro- bimetallic Alkoxides as Precursors for Luminescent Metal Oxide Materials via Sol-Gel Technique

Heterobimetallic alkoxides are broadly recognized as versatile precursors for luminescence materials, and efforts are being made to develop novel routes by applying the concept of geometrical molecular design, for their synthesis and to design a single source precursor suited to photoluminescent materials. Novel and new series of bimetallic alkoxides has been prepared by metathesis route. They exhibit a lower sensitivity towards hydrolysis and so they are easier to handle as compared to other alkoxides. All the compounds were characterized by elemental analysis, FT-IR and multinuclear NMR spectroscopies. FT-IR revealed that the molecular structure of these metal alkoxides was retained to a large extent in 4 ： 1 halogenated alcohol-benzene solution. The heteronuclear NMR spectroscopy provided useful information about chemical shifts for better understanding the likely structure based on interactions with their coordinate metals. The mass spectra show similar types of fragmentation pattern. SEM-EDS analyses showed consistency with the formulation. XRD patterns show an enhanced homogeneity at high temperature. TGA measurements show that thermal decomposition occured in steps that depended entirely on the chemical compositions and the synthesis routes. SEM observation reveals that the morphology and particle size strongly depend on synthesis routes for their precursors.     

Controlled peak wavelength shift of Ca1−xSrx(SySe1−y):Eu phosphor for LED application

The highly efficient red-orange-yellow-emitting phosphor (Ca_1−xSr_x)(S_1−ySe_y):Eu²⁺ in combination with commercial green phosphor SrGa₂S₄:Eu²⁺ and blue LED are proposed for a three-band white LED. The luminescence mechanism and optimization parameters are discussed on the basis of proposed peak wavelength diagram.     

Mesoscopic structure and properties of liquid crystalline mesophase pitch and its transformation into carbon fiber

The history and present state of the art in the chemistry of mesophase pitch, which is an important precursor for carbon fiber and other high-performance industrial carbons, are reviewed relative to their structural properties. The structural concepts in both microscopic and macroscopic views are summarized in terms of the sp(2) carbon hexagonal plane as a basic unit common to graphitic materials, its planar stacking in clusters, and cluster assembly into microdomains and domains, the latter of which reflect the isochromatic unit of optical anisotropy. Such a series of structural units is described in a semiquantitative manner corresponding to the same units of graphitic materials, although the size and stacking height of the hexagonal planes (graphitic sheets) are very different. Mesophase pitch is a liquid crystal material whose basic structural concepts are maintained in the temperature range of 250 to 350 degrees C. The melt flow and thermal properties are related to its micro- and mesoscopic structure. The structure of mesophase-pitch-based carbon fiber of high tensile strength, modulus, and thermal conductivity has been formed through spinning, and has inherited the same structural concepts of mesophase pitch. Stabilization settles the structure in successive heat treatments up to 3000 degrees C. Carbonization and graphitization enable growth of the hexagonal planes and their stacking into units of graphite. Such growth is governed and controlled by the alignment of micro- and mesoscopic structures in the mesophase pitch, which define the derived carbon materials as nanostructural materials. Their properties are controlled by the nanoscopic units that are expected to behave as nanomaterials when appropriately isolated or handled.     

Electrolytic reduction of spent oxide fuel in a molten LiCl-Li2O system

Summary The Advanced Spent Conditioning Process (ACP) developed by the KAERI is based on pyrometallurgy and the electrolytic reduction plays a central role in transforming spent oxide fuels into metals. The constituents of the spent fuels are distributed between a salt and a reduced metal phase during electrolysis. Lithium metal is produced in a molten LiCl-Li₂O cell and then it reacts with the metal oxides of the spent fuel producing Li₂O and reduced metals. By focusing on the activity of Li₂O and the electric potential, the electrolytic reduction process of the ACP is discussed. Thermodynamic considerations are defined and operation conditions are proposed including Li₂O activity and cell potential.     

Effect of photothermal therapy on breast tumor vascular contents: noninvasive monitoring by near-infrared spectroscopy

The goal of this study was to investigate the effect of photothermal laser irradiation on rat breast tumor (DMBA-4) vascular contents. An 805-nm diode laser was used in our experiment with a power density ranging from 0.32 to 1.27 W/cm2. The dynamic changes of oxygenated hemoglobin and total hemoglobin concentrations, delta[HbO2] and delta[Hb]total, in rat tumors during photothermal irradiation were noninvasively monitored by a near-infrared spectroscopy system. A multichannel thermal detection system was also used simultaneously to record temperatures at different locations within the tumors. Our experimental results showed that: (1) photoirradiation did have the ability to induce hyperthermic effects inside the rat breast tumors in a single exponential trend; (2) the significant changes (P < 0.005) of delta[HbO2] and delta[Hb]total in response to a low dosage of laser irradiation (0.32 W/cm2) have a single exponential increasing trend, similar to that seen in the tumor interior temperature; and (3) the increase in magnitude of delta[HbO2] is nearly two times greater than that of delta[Hb]total, suggesting that photoirradiation may enhance tumor vascular oxygenation. The last observation may be important to reveal the hidden mechanism of photoirradiation on tumors, leading to improvement of tumor treatment efficiency.