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This paper reviews results from research conducted at the University of Oklahoma on the development of new IV-VI semiconductor (lead salt) epitaxial growth and laser fabrication procedures that can ultimately lead to dramatic increases in mid-IR laser operating temperatures. Work has focused on growth of IV-VI semiconductor laser structures on silicon substrates using buffer layers that contain BaF2. Recent experiments show that it is possible to obtain high crystalline quality IV-VI semiconductor layer structures on (111)-oriented silicon substrates using molecular beam epitaxy (MBE) or on (100)-oriented silicon using a combination of MBE and liquid phase epitaxy (LPE). Experimental data for IV-VI semiconductor layer structures grown on silicon substrates including crystalline quality information as determined by high resolution X-ray diffraction (HRXRD) measurements and absorption edge information as determined by Fourier transform infrared (FTIR) transmission measurements are presented. Results show that these materials can be used to fabricate lasers that cover the 3 microns (3333 cm-1) to 16 microns (625 cm-1) spectral range. Removal of IV-VI semiconductor laser structures from the silicon growth substrate by dissolving BaF2 buffer layers with water is also demonstrated. This allows epitaxially-grown laser structures to be sandwiched between two heat sinks with a minimum of thermally resistive IV-VI semiconductor material. Theoretical modeling predicts that IV-VI lasers fabricated this way will have maximum continuous wave (cw) operating temperatures at least 60 degrees higher than those of IV-VI lasers fabricated on PbSe or PbTe substrates.
Spectrochim Acta A Mol Biomol Spectrosc 1999 Sep 01
PMID:IV-VI semiconductor growth on silicon substrates and new mid-infrared laser fabrication methods 1064 75

Silicosis is a serious occupational lung disease associated with irreversible pulmonary fibrosis. The interaction between inhaled crystalline silica and the alveolar macrophage (AM) is thought to be a key event in the development of silicosis and fibrosis. Silica can cause direct injury to AMs and can induce AMs to release various inflammatory mediators. Acute silicosis is also characterized by a marked elevation in surfactant apoprotein A (SP-A); however, the role of SP-A in silicosis is unknown. We investigated whether SP-A directly affects the response of AMs to silica. In this study, the degree of silica toxicity to cultured rat AMs as assessed by a (51)Cr cytotoxicity assay was shown to be dependent on the time of exposure and the concentration and size of the silica particles. Silica directly injured rat AMs as evidenced by a cytotoxic index of 32.9 +/- 2.5, whereas the addition of rat SP-A (5 microg/ml) significantly reduced the cytotoxic index to 16.6 +/- 1.2 (P < 0. 001). This effect was reversed when SP-A was incubated with either polyclonal rabbit anti-rat SP-A antibody or D-mannose. These data indicate that SP-A mitigates the effect of silica on AM viability, and this effect may involve the carbohydrate recognition domain of SP-A. The elevation of SP-A in acute silicosis may serve as a normal host response to prevent lung cell injury after exposure to silica.
Am J Physiol Lung Cell Mol Physiol 2000 Apr
PMID:Surfactant protein A prevents silica-mediated toxicity to rat alveolar macrophages. 1074 48

Anomalous diffraction with soft X-ray synchrotron radiation opens new possibilities in protein crystallography and materials science. Low-Z elements like silicon, phosphorus, sulfur and chlorine become accessible as new labels in structural studies. Some of the heavy elements like uranium exhibit an unusually strong dispersion at their M(V) absorption edge (lambdaMV = 3.497 A, E(MV) = 3545 eV) and so does thorium. Two different test experiments are reported here showing the feasibility of anomalous X-ray diffraction at long wavelengths with a protein containing uranium and with a salt containing chlorine atoms. With 110 electrons the anomalous scattering amplitude of uranium exceeds by a factor of 4 the resonance scattering of other strong anomalous scatterers like that of the lanthanides at their L(III) edge. The resulting exceptional phasing power of uranium is most attractive in protein crystallography using the multi-wavelength anomalous diffraction (MAD) method. The anomalous dispersion of an uranium derivative of asparaginyl-tRNA synthetase (hexagonal unit cell; a = 123.4 A, c = 124.4 A) has been measured for the first time at 4 wavelengths near the M(V) edge using the beamline ID1 of ESRF (Grenoble, France). The present set up allowed to measure only 30% of the possible reflections at a resolution of 4 A, mainly because of the low sensitivity of the CCD detector. In the second experiment, the dispersion of the intensity of 5 X-ray diffraction peaks from pentakismethylammonium undecachlorodibismuthate (PMACB, orthorhombic unit cell; a = 13.003 A, b = 14.038 A, c = 15.450 A) has been measured at 30 wavelengths near the K absorption edge of chlorine (lambdaK = 4.397 A, EK= 2819.6 eV). All reflections within the resolution range from 6.4 A to 3.4 A expected in the 20 degree scan were observed. The chemical state varies between different chlorine atoms of PMACB, and so does the dispersion of different Bragg peaks near the K-edge of chlorine. The results reflect the performance of the beamline ID1 of ESRF at wavelengths beyond 3 A at the end of 1998. A gain by a factor 100 for diffraction experiments with 4.4 A photons was achieved in Autumn 1999 when two focusing mirrors had been added to the X-ray optics. Further progress is expected from area detectors more sensitive to soft X-rays. Both CCD detectors and image plates would provide a gain of two orders of measured intensity. Image plates would have the additional advantage that they can be bent cylindrically and thus cover a larger solid angle in reciprocal space. In many cases, samples need to be cooled: closed and open systems are presented. A comparison with the state of art of soft X-ray diffraction, as it had been reached at HASYLAB (Hamburg, Germany), and as it is developing at the Brookhaven National Laboratory (USA), is given.
Cell Mol Biol (Noisy-le-grand) 2000 Jul
PMID:Anomalous X-ray diffraction with soft X-ray synchrotron radiation. 1097 74

Thirty-nine patients with fibromyalgia syndrome (FMS) according to American College of Rheumatology criteria were studied for cell-mediated sensitivity to environmental chemicals. Lymphocytes were tested by standard [(3)H]thymidine incorporation in vitro for T cell memory to 11 chemical substances. Concanavalin A (Con A) was used to demonstrate T cell proliferation. Controls were 25 contemporaneous healthy adults and 252 other concurrent standard controls without any aspect of FMS. Significantly higher (P < 0.01) stimulation indexes (SI) were found in FMS for aluminum, lead, and platinum; borderline higher (0.05 > P > 0.02) SI were found for cadmium and silicon. FMS patients showed sporadic responses to the specific substances tested, with no high-frequency result (>50%) and no obvious pattern. Mitogenic responses to Con A indicated some suppression of T cell functionality in FMS. Possible links between mitogenicity and immunogenic T cell proliferation, certain electrochemical specifics of granuloma formation, maintenance of connective tissue, and the fundamental nature of FMS are considered.
Exp Mol Pathol 2000 Oct
PMID:Environmental immunogens and T-cell-mediated responses in fibromyalgia: evidence for immune dysregulation and determinants of granuloma formation. 1100 60

Alveolar macrophages (AMs) are the principal target cells of silica and occupy a key position in the pathogenesis of silica-related diseases. Silica has been found to induce apoptosis in AMs, whereas its underlying mechanisms involving the initiation and execution of apoptosis are largely unknown. The main objective of the present study was to examine the form of cell death caused by silica and the mechanisms involved. Silica-induced apoptosis in AMs was evaluated by terminal deoxynucleotidyltransferase-mediated dUTP nick end-labeling assay and cell cycle/DNA content analysis. The elevated level of reactive oxygen species (ROS), caspase-9 and caspase-3 activation, and poly(ADP-ribose) polymerase (PARP) cleavage in silica-treated AMs were also determined. The results showed that there was a temporal pattern of apoptotic events in silica-treated AMs, starting with ROS formation and followed by caspase-9 and caspase-3 activation, PARP cleavage, and DNA fragmentation. Silica-induced apoptosis was significantly attenuated by a caspase-3 inhibitor, N-acetyl-Asp-Glu-Val-Asp aldehyde, and ebselen, a potent antioxidant. These findings suggest that apoptosis is an important form of cell death caused by silica exposure in which the elevated ROS level that results from silica exposure may act as an initiator, leading to caspase activation and PARP cleavage to execute the apoptotic process.
Am J Physiol Lung Cell Mol Physiol 2001 Jan
PMID:Reactive oxygen species and caspase activation mediate silica-induced apoptosis in alveolar macrophages. 1113 90

DFT(B3LYP) and MP2 calculations with the 6-311G(2d, 2p)-type basis set have been carried out for the prediction of molecular parameters (bond distances, bond angles, rotational constants, and dipole moments) and vibrational Raman and infrared spectra (harmonic wavenumbers, absolute intensities, Raman scattering activities, and depolarization ratios) of bromochlorofluoromethane (HCBrCIF) and its silicon and germanium analogs (HSiBrClF and HGeBrCIF). The predicted geometry and vibrational Raman and infrared spectra of HCBrClF agree well with the available experimental data for this molecule and their deuterated derivatives. This agreement allows one to believe that the predicted molecular parameters and vibrational spectra of HSiBrClF, HGeBrClF, and their deuterated derivatives will guide their future experimental studies.
Spectrochim Acta A Mol Biomol Spectrosc 2000 Dec
PMID:Molecular structure and vibrational raman and infrared spectra of bromochlorofluoromethane and its silicon and germanium analogs: quantum-mechanical DFT and MP2 calculations. 1114 32

Carbon nanoparticles synthesised by laser pyrolysis of small hydrocarbons are deposited at low energy on a silicon substrate. Infrared spectroscopy of the as-formed films are studied as a function of the synthesis parameters and post-treatments, such as annealing and heavy ion irradiation. Correlation between infrared spectroscopy and multiscale organisation of the samples is made through transmission electron microscopy, including image analysis. Changes in infrared spectra are analysed in terms of the carbon network building. The relevance of the results to model the structure and spectroscopy of carbon dust in the carbon-rich circumstellar media is discussed.
Spectrochim Acta A Mol Biomol Spectrosc 2001 Mar 15
PMID:Optical properties of synthetic carbon nanoparticles as model of cosmic dust. 1134 55

We review the evidence for carbides in space both from infrared spectroscopy and direct measurements on presolar grains extracted from primitive meteorites. The paper includes a discussion of the structural properties of silicon carbide and metal carbides and their formation routes from the gas phase. In addition, we present spectroscopic data in the infrared, which are required for a better understanding of astronomical spectra.
Spectrochim Acta A Mol Biomol Spectrosc 2001 Mar 15
PMID:Formation and spectroscopy of carbides. 1134 56

Ever since scientists discovered that conventional silicon-based computers have an upper limit in terms of speed, they have been searching for alternative media with which to solve computational problems. That search has led them, among other places, to DNA.
Nat Rev Mol Cell Biol 2000 10
PMID:The past, present and future of molecular computing. 1141 91

Atomic force microscopy (AFM) has great potential as a tool for structural biology, a field in which there is increasing demand to characterize larger and more complex biomolecular systems. However, the poorly characterized silicon and silicon nitride probe tips currently employed in AFM limit its biological applications. Carbon nanotubes represent ideal AFM tip materials due to their small diameter, high aspect ratio, large Young's modulus, mechanical robustness, well-defined structure, and unique chemical properties. Nanotube probes were first fabricated by manual assembly, but more recent methods based on chemical vapor deposition provide higher resolution probes and are geared towards mass production, including recent developments that enable quantitative preparation of individual single-walled carbon nanotube tips [J. Phys. Chem. B 105 (2001) 743]. The high-resolution imaging capabilities of these nanotube AFM probes have been demonstrated on gold nanoparticles and well-characterized biomolecules such as IgG and GroES. Using the nanotube probes, new biological structures have been investigated in the areas of amyloid-beta protein aggregation and chromatin remodeling, and new biotechnologies have been developed such as AFM-based haplotyping. In addition to measuring topography, chemically functionalized AFM probes can measure the spatial arrangement of chemical functional groups in a sample. However, standard silicon and silicon nitride tips, once functionalized, do not yield sufficient resolution to allow combined structural and functional imaging of biomolecules. The unique end-group chemistry of carbon nanotubes, which can be arbitrarily modified by established chemical methods, has been exploited for chemical force microscopy, allowing single-molecule measurements with well-defined functionalized tips.
Prog Biophys Mol Biol 2001
PMID:Structural and functional imaging with carbon nanotube AFM probes. 1147 87


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