Thomas E. Weirich

Light‐Mediated Heterogeneous Cross Dehydrogenative Coupling Reactions: Metal Oxides as Efficient, Recyclable, Photoredox Catalysts in CC Bond‐Forming Reactions

Let there be light: A heterogeneous photocatalytic system based on easily recyclable TiO(2) or ZnO allows cross dehydrogenative coupling reactions of tertiary amines. The newly developed protocols have successfully been applied to various C-C and C-P bond-forming reactions to provide nitro amines as well as amino ketones, nitriles and phosphonates.

Ultrastructural Analysis of Vascular Calcifications in Uremia

Accelerated intimal and medial calcification and sclerosis accompany the increased cardiovascular mortality of dialysis patients, but the pathomechanisms initiating microcalcifications of the media are largely unknown. In this study, we systematically investigated the ultrastructural properties of medial calcifications from patients with uremia. We collected iliac artery segments from 30 dialysis patients before kidney transplantation and studied them by radiography, microcomputed tomography, light microscopy, and transmission electron microscopy including electron energy loss spectrometry, energy dispersive spectroscopy, and electron diffraction. In addition, we performed synchrotron x-ray analyses and immunogold labeling to detect inhibitors of calcification. Von Kossa staining revealed calcification of 53% of the arteries. The diameter of these microcalcifications ranged from 20 to 500 nm, with a core-shell structure consisting of up to three layers (subshells). Many of the calcifications consisted of 2- to 10-nm nanocrystals and showed a hydroxyapatite and whitlockite crystalline structure and mineral phase. Immunogold labeling of calcification foci revealed the calcification inhibitors fetuin-A, osteopontin, and matrix gla protein. These observations suggest that uremic microcalcifications originate from nanocrystals, are chemically diverse, and intimately associate with proteinaceous inhibitors of calcification. Furthermore, considering the core-shell structure of the calcifications, apoptotic bodies or matrix vesicles may serve as a calcification nidus.

Quasiregular quantum-dot-like structure formation with postgrowth thermal annealing of InGaN'GaN quantum wells

Postgrowth thermal annealing of an InGaN/GaN quantum-well sample with a medium level of nominal indium content (19%) was conducted. From the analyses of high-resolution transmission electron microscopy and energy filter transmission electron microscopy, it was found that thermal annealing at 900 °C led to a quasiregular quantum-dot-like structure. However, such a structure was destroyed when the annealing temperature was raised to 950 °C. Temperature-dependent photoluminescence (PL) measurements showed quite consistent results. Blueshift of the PL peak position and narrowing of the PL spectral width after thermal annealing were observed.

Effect of Si-doping on InAs nanowire transport and morphology

The effect of Si-doping on the morphology, structure, and transport properties of nanowires was investigated. The nanowires were deposited by selective-area metal organic vapor phase epitaxy in an N2 ambient. It is observed that doping systematically affects the nanowire morphology but not the structure of the nanowires. However, the transport properties of the wires are greatly affected. Room-temperature four-terminal measurements show that with an increasing dopant supply the conductivity monotonously increases. For the highest doping level the conductivity is higher by a factor of 25 compared to only intrinsically doped reference nanowires. By means of back-gate field-effect transistor measurements it was confirmed that the doping results in an increased carrier concentration. Temperature dependent resistance measurements reveal, for lower doping concentrations, a thermally activated semiconductor-type increase of the conductivity. In contrast, the nanowires with the highest doping concentration show a...

Structure of nanocrystalline anatase solved and refined from electron powder data

Energy-filtered Debye-Scherrer electron powder data have been successfully employed to determine the structure of nanocrystalline anatase (TiO2). The performed structure analysis includes determining the unit cell, space group, solving the structure via direct methods from extracted intensities and refining the structure using the Rietveld technique. The refined structural parameters for space group I4(1)/amd are a = 3.872 (2), c = 9.616 (5) A with titanium at 0.5,0.75,0.375 and oxygen at 0.5,0.75,0.1618 (6). The obtained structure indicates low internal stress as judged from the almost regular geometry of the TiO6 building blocks. Striking resemblance with the anatase structure determined previously by Burdett, Hughbanks, Miller, Richardson & Smith [J. Am. Chem. Soc. (1987). 109, 3639-3646] from neutron diffraction on coarse-grained material gives strong support for the correctness of the structure determined here. The result of the present study shows that the methods originally developed for determining structures from X-ray powder data work equally well with data from electron powder diffraction. This may open the window for structural investigations on the vast number of nanocrystalline materials and thin films whose structures are difficult to determine by X-ray diffraction since they are frequently only available in small quantities.

Effects of post-growth thermal annealing on the indium aggregated structures in InGaN/GaN quantum wells

Abstract Size and distribution of indium-rich quantum dots (QDs) are important parameters for improving photon emission efficiency of InGaN/GaN quantum well (QW) structures. Our results showed that post-growth thermal annealing of such a sample with temperature ranging from 800°C to 900°C led to a better confinement of indium-rich clusters near InGaN QW layers. Transmission electron microcopy (TEM) and energy filter TEM results manifested that the sizes of indium-rich QDs were reduced with increasing annealing temperature. Also, the size homogeneity was improved. Quasi-regular arrays of indium-rich QDs embedded in InGaN QWs were observed in the sample of 900°C annealing. X-ray diffraction also showed the enhancement of InN relative intensity. Photoluminescence measurements revealed blue shifts of photon emission spectral peak, indicating stronger quantum confinement after thermal annealing. However, such a process of regular QD formation disappeared when annealing temperature was increased to 950°C. In this situation, coarsening of indium-rich clusters occurred and their distribution became irregular.

Structural investigations of Pt/TiOx electrode stacks for ferroelectric thin film devices

Effects of the thermal treatment and the fabrication process of Pb(Zr0.3Ti0.7)O3 (PZT) thin films using chemical solution deposition on Pt∕TiOx electrode stacks were investigated using complementary analytical techniques including atomic force microscopy (AFM), x-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and grazing incidence x-ray reflectivity of synchrotron radiation. The surface and interface structures of the Pt∕TiOx electrode stacks with different thermal treatments, and the PZT∕Pt∕TiOx sample were examined. The propagation of Pt hillocks on the bare Pt∕TiOx electrode stacks upon the annealing was observed. AFM observations also revealed that the upper surface of the Pt bottom electrode under PZT thin film became rougher than that of the bare Pt electrode with the same thermal history. Global structural information including the density, surface or interface root-mean-square roughness, and thickness of each constituent layer in the samples were determined using...

Analysis of Calcifications in Patients with Coral Reef Aorta

BACKGROUND Coral reef aorta is a rare vascular disease with intraluminal calcifications of the dorsal part of the visceral aorta. The pathogenesis of this disease with its topographic and morphologic characteristics is unknown. The aim of our study was to investigate calcification inhibitors and the ultrastructure of calcifications in patients with coral reef aorta. METHODS Ten patients with coral reef aorta were examined. Calcified specimens were investigated by immunohistochemical techniques for the expression of the calcification inhibitors matrix gla protein (MGP) and fetuin-A. Vessel walls were also assessed by electron microscopic techniques including electron energy-lost spectroscopy, electron dispersive spectroscopy, and electron diffraction. Sera of patients were analyzed for fetuin-A, uncarboxylated MGP (ucMGP), and osteoprotegerin. RESULTS As assessed by immunohistochemistry, most MGP was detected in the vicinity of calcified regions. Serum levels of the calcification inhibitors ucMGP, fetuin-A, and osteoprotegerin were 370+/-107 nmol/L, 0.57+/-0.03 g/L, and 5.64+/-0.79 pmol/L, respectively. Ultrastructural analysis of calcified specimens showed a core-shell structure with multiple calcification nuclei. Calcifications displayed a fine-crystalline character, and elemental analysis revealed hydroxyl apatite as the chemical compound. CONCLUSION The coral reef aorta represents an extreme exophytic growth of vascular calcification with multiple nuclei which resemble typical media calcification. Positive vascular immunostaining and low serum levels of both fetuin-A and ucMGP suggest a pathophysiologic role of these calcification inhibitors in the development of coral reef aorta.

Application of EDM Hole-Drilling Method to the Measurement of Residual Stress in Tool and Carbon Steels

This study adopts the application of the electrodischarge machining (EDM) hole-drilling method to the measurement of residual stress in AISI D2 cold work tool steel, AISI H13 hot work tool steel, and AISI 1045 medium carbon steel. A calibration procedure based on the thermal conductivity of the material is conducted to compensate for the additional compressive stress induced in the workpiece by the EDM hole-drilling operation. Since the formation of this white layer influences the magnitude of the induced stress, the scanning electron microscopy, transmission electron microscopy, and nanoindentation techniques are used to examine the microstructure and hardness of the white layer resolidified on the EDMed surface. The experimental results reveal that combination of the hole-drilling strain-gage method (ASTM standard E837) with an EDM drilling process provides the effective means of determining the residual stress in materials with high hardness and good wear resistance.

Probing fatigue in ferroelectric thin films with subnanometer depth resolution

The authors report the study of polarization fatigue in Pb(Zr,Ti)O3 (PZT) ferroelectric thin films using in situ high-resolution grazing incidence x-ray specular reflectivity of synchrotron radiation. The results demonstrate that there is no formation of a region of different electron densities in the film growth direction with subnanometer depth resolution during fatigue. The upper bounds on the theoretically predicted interfacial accumulation of oxygen vacancies at the interfaces between PZT and Pt electrodes are determined by the comparison of experimental results and theoretical simulations.