Polymerization of propylene catalyzed over highly active and stereospecific catalysts synthesized with Mg(OEt)2/benzoyl chloride/TiCl4

A series of monoester catalysts has been studied, each catalyst prepared by the reaction of magnesium diethoxide with benzoyl chloride [BzCOCl, to produce ethyl benzoate (EB) in situ] in the presence of excess titanium tetrachloride. Solid product and catalysts obtained by subsequent treatments with titanium tetrachloride were characterized by elemental analysis, IR spectroscopy, x-ray diffraction, BET measurement, and thermal gravimetric analysis. The catalysts yielded very high activity (above 20 kg polymer/g Ti h atm) for the polymerization of propylene in slurry reactions. From the results of polymerization as well as catalyst characterization, the effects of internal and external Lewis bases on the isospecificity and stability of catalysts are discussed in detail. © 1992 John Wiley & Sons, Inc.     

Superhydrophobic CFx coating via in-line atmospheric RF plasma of He-CF4-H2

Stable superhydrophobic coatings on various substrates are attained with an in-line atmospheric rf plasma process using CF4, H2, and He. The coating layer is composed of CFx nanoparticulates and has an average roughness of approximately 10 nm. This roughness is much smaller than other surfaces reported for superhydrophobicity in the literature. The superhydrophobic coatings are produced on both metallic and insulating substrates without any need of separate microroughening or vacuum lines.     

Dependence of the closed-shell repulsive interaction on the overlap of the electron densities

The relationship between the closed-shell repulsive interactions and overlap of the electron densities is investigated. It is found that the repulsive interactions vary in almost direct proportion to the absolute size of the density overlaps.     

Active control of the depletion boundary layers in microfluidic electrochemical reactors

In this paper, we describe three methods to improve the performance of pressure-driven laminar flow-based microreactors by manipulating reaction-depletion boundary layers to overcome mass transfer limitations at reactive surfaces on the walls, such as electrodes. The transport rate of the reactants to the reactive surfaces is enhanced by (i) removing the depleted zone through multiple periodically-placed outlets; (ii) adding fresh reactants through multiple periodically-placed inlets along the reactive surface; or (iii) producing a spiraling, transverse flow through the integration of herringbone ridges along the channel walls. For approaches (i) and (ii), the network of microfluidic channels needs to be designed such that under the operating conditions used the right amount of boundary layer at each outlet or inlet is removed or replenished, respectively. Here, we report a set of design rules, derived with the help of a fluidic resistance circuit model, to aid in the design of appropriate microfluidic networks. Also, the actual enhancement of the performance of the electrochemical microreactor, i.e. chemical conversion efficiency, using multiple inlets, multiple outlets, or herringbone ridges is reported.     

In vivo high‐resolution synchrotron radiation imaging of collagen‐induced arthritis in a rodent model

In vivo microstructures of the affected feet of collagen‐induced arthritic (CIA) mice were examined using a high‐resolution synchrotron radiation (SR) X‐ray refraction technique with a polychromatic beam issued from a bending magnet. The CIA models were obtained from six‐week‐old DBA/1J mice that were immunized with bovine type II collagen and grouped as grades 0–3 according to a clinical scoring for the severity of arthritis. An X‐ray shadow of a specimen was converted into a visual image on the surface of a CdWO₄ scintillator that was magnified using a microscopic objective lens before being captured with a digital charge‐coupled‐device camera. Various changes in the joint microstructure, including cartilage destruction, periosteal born formation, articular bone thinning and erosion, marrow invasion by pannus progression, and widening joint space, were clearly identified at each level of arthritis severity with an equivalent pixel size of 2.7 µm. These high‐resolution features of destruction in the CIA models have not previously been available from any other conventional imaging modalities except histological light microscopy. However, thickening of the synovial membrane was not resolved in composite images by the SR refraction imaging method. In conclusion, in vivo SR X‐ray microscopic imaging may have potential as a diagnostic tool in small animals that does not require a histochemical preparation stage in examining microstructural changes in joints affected with arthritis. The findings from the SR images are comparable with standard histopathology findings.     

Inverses and eigenpairs of tridiagonal Toeplitz matrix with opposite-bordered rows

In this paper, tridiagonal Toeplitz matrix (type I, type II) with opposite-bordered rows are introduced. Main attention is paid to calculate the determinants, the inverses and the eigenpairs of these matrices. Specifically, the determinants of an $n\times n$ tridiagonal Toeplitz matrix with opposite-bordered rows can be explicitly expressed by using the $(n-1)$th Fibonacci number, the inversion of the tridiagonal Toeplitz matrix with opposite-bordered rows can also be explicitly expressed by using the Fibonacci numbers and unknown entries from the new matrix. Besides, we give the expression of eigenvalues and eigenvectors of the tridiagonal Toeplitz matrix with opposite-bordered rows. In addition, some algorithms are presented based on these theoretical results. Numerical results show that the new algorithms have much better computing efficiency than some existing algorithms studied recently.     

In situ FT-IR studies on the mechanism of selective catalytic reduction of NOx by propene over SnO2/Al2O3 catalyst

The mechanism of the selective catalytic reduction (SCR) of NOx by propene over SnO2/Al2O3 catalyst in the presence of oxygen has been investigated using in situ Fourier transform infrared (FT-IR) spectroscopy. In situ IR measurements indicate that acetate and formate, which are the derivatives of the partial oxidation of propene, play a crucial role in the formation of NCO by reacting with the reactive monodentate nitrate species. The resulting NCO species subsequently reacts with NOx to form N2. The presence of oxygen substantially contributes to the partial oxidation of propene and thus shows a promoting effect for the NOx reduction.     

An L‐shaped nanoprobe for scanning electrochemical microscopy–atomic force microscopy

We present an L‐shaped nanoprobe for scanning electrochemical microscopy–atomic force microscopy (SECM–AFM) capable of imaging the surface topography and the electrochemical activity of nanostructures of interest. Owing to the geometry of the protrusive peak in the L‐shaped probe, the distance between the probe electrode and the substrate is maintained precisely at ～100 nm during surface scanning. The reduction in electrode‐to‐substrate distance significantly improves the positive feedback current on top of the electrochemically active nanomaterials. The L‐shaped nanoprobe successfully acquired simultaneous a topographical image and an electrochemical current image of individual carbon nanotubes (CNTs) in a two‐dimensional (2D) CNT network.

     

Solid state water motions revealed by deuterium relaxation in 2H2O-synthesized kanemite and 2H2O-hydrated Na+-zeolite A

Deuterium NMR relaxation experiments, low temperature deuterium NMR lineshape analysis, and FTIR spectra are consistent with a new model for solid state jump dynamics of water in (2)H(2)O-synthesized kanemite and (2)H(2)O-hydrated Na(+)-Zeolite A. Exchange occurs between two populations of water: one in which water molecules are directly coordinated to sodium ions and experience C(2) symmetry jumps of their OH bonds, and a population of interstitial water molecules outside the sodium ion coordination sphere that experience tetrahedral jumps of their OH bonds. For both samples the C(2) jump rate is much faster than the tetrahedral jump rate. (2)H NMR relaxation experiments match well with the fast exchange regime of the model over a wide range of temperatures, including room temperature and above. For hydrated Zeolite A, the kinetic activation parameters for the tetrahedral and C(2) symmetry jumps are Delta H tet++=+17 kJ/mol, Delta S tet++=-109 J/(mol K), Delta H C2++=+19 kJ/mol, and Delta S C2++=-20 J/(mol K). For kanemite, Delta H tet++ =+23 kJ/mol, Delta S tet++=-69 J/(mol K), Delta H C2++ =+23 kJ/mol, and Delta S C2++ =-11 J/(mol K).