Singlet Oxygen Photooxygenation of Tricyclo[4.3.0.01,3]nona-6,8-dienes and Bicyclo[4.3.0]nona-1(6),7-dienes: Characterization of the Primary Reaction Products and Subsequent Transformations

1995 ◽  
Vol 60 (7) ◽  
pp. 1952-1958 ◽  
Author(s):  
Axel G. Griesbeck ◽  
Thomas Deufel ◽  
Karl Peters ◽  
Eva-Maria Peters ◽  
Hans Georg von Schnering
Author(s):  
G. Das ◽  
R. E. Omlor

Fiber reinforced titanium alloys hold immense potential for applications in the aerospace industry. However, chemical reaction between the fibers and the titanium alloys at fabrication temperatures leads to the formation of brittle reaction products which limits their development. In the present study, coated SiC fibers have been used to evaluate the effects of surface coating on the reaction zone in the SiC/IMI829 system.IMI829 (Ti-5.5A1-3.5Sn-3.0Zr-0.3Mo-1Nb-0.3Si), a near alpha alloy, in the form of PREP powder (-35 mesh), was used a茸 the matrix. CVD grown AVCO SCS-6 SiC fibers were used as discontinuous reinforcements. These fibers of 142μm diameter contained an overlayer with high Si/C ratio on top of an amorphous carbon layer, the thickness of the coating being ∽ 1μm. SCS-6 fibers, broken into ∽ 2mm lengths, were mixed with IMI829 powder (representing < 0.1vol%) and the mixture was consolidated by HIP'ing at 871°C/0. 28GPa/4h.


Author(s):  
Gyeung Ho Kim ◽  
Mehmet Sarikaya ◽  
D. L. Milius ◽  
I. A. Aksay

Cermets are designed to optimize the mechanical properties of ceramics (hard and strong component) and metals (ductile and tough component) into one system. However, the processing of such systems is a problem in obtaining fully dense composite without deleterious reaction products. In the lightweight (2.65 g/cc) B4C-Al cermet, many of the processing problems have been circumvented. It is now possible to process fully dense B4C-Al cermet with tailored microstructures and achieve unique combination of mechanical properties (fracture strength of over 600 MPa and fracture toughness of 12 MPa-m1/2). In this paper, microstructure and fractography of B4C-Al cermets, tested under dynamic and static loading conditions, are described.The cermet is prepared by infiltration of Al at 1150°C into partially sintered B4C compact under vacuum to full density. Fracture surface replicas were prepared by using cellulose acetate and thin-film carbon deposition. Samples were observed with a Philips 3000 at 100 kV.


TAPPI Journal ◽  
2013 ◽  
Vol 12 (1) ◽  
pp. 37-43 ◽  
Author(s):  
HANNU PAKKANEN ◽  
TEEMU PALOHEIMO ◽  
RAIMO ALÉN

The influence of various cooking parameters, such as effective alkali, cooking temperature, and cooking time on the formation of high molecular mass lignin-derived and low molecular mass carbohydrates-derived (aliphatic carboxylic acids) degradation products, mainly during the initial phase of softwood kraft pulping was studied. In addition, the mass transfer of all of these degradation products was clarified based on their concentrations in the cooking liquor inside and outside of the chips. The results indicated that the degradation of the major hemicellulose component, galactoglucomannan, typically was dependent on temperature, and the maximum degradation amount was about 60%. In addition, about 60 min at 284°F (140°C) was needed for leveling off the concentrations of the characteristic reaction products (3,4-dideoxy-pentonic and glucoisosaccharinic acids) between these cooking liquors. Compared with low molecular mass aliphatic acids, the mass transfer of soluble lignin fragments with much higher molecular masses was clearly slower.


2018 ◽  
Vol 18 (6) ◽  
pp. 784-804 ◽  
Author(s):  
Georg Bauer

Background: Application of cold atmospheric plasma to medium generates “plasma-activated medium” that induces apoptosis selectively in tumor cells and that has an antitumor effect in vivo. The underlying mechanisms are not well understood. Objective: Elucidation of potential chemical interactions within plasma-activated medium and of reactions of medium components with specific target structures of tumor cells should allow to define the active principle in plasma activated medium. Methods: Established knowledge of intercellular apoptosis-inducing reactive oxygen/nitrogen species-dependent signaling and its control by membrane-associated catalase and SOD was reviewed. Model experiments using extracellular singlet oxygen were analyzed with respect to catalase inactivation and their relevance for the antitumor action of cold atmospheric plasma. Potential interactions of this tumor cell-specific control system with components of plasma-activated medium or its reaction products were discussed within the scope of the reviewed signaling principles. Results: None of the long-lived species found in plasma-activated medium, such as nitrite and H2O2, nor OCl- or .NO seemed to have the potential to interfere with catalase-dependent control of apoptosis-inducing signaling of tumor cells when acting alone. However, the combination of H2O2 and nitrite might generate peroxynitrite. The protonation of peroxnitrite to peroxynitrous acid allows for the generation of hydroxyl radicals that react with H2O2, leading to the formation of hydroperoxide radicals. These allow for singlet oxygen generation and inactivation of membrane-associated catalase through an autoamplificatory mechanism, followed by intercellular apoptosis-inducing signaling. Conclusion: Nitrite and H2O2 in plasma-activated medium establish singlet oxygen-dependent interference selectively with the control system of tumor cells.


1993 ◽  
Vol 34 (8) ◽  
pp. 1255-1258 ◽  
Author(s):  
Ihsan Erden ◽  
Jane Drummond ◽  
Roger Alstad ◽  
Fupei Xu

Atmosphere ◽  
2020 ◽  
Vol 11 (4) ◽  
pp. 358 ◽  
Author(s):  
Mengjie Fan ◽  
Shiqing Ma ◽  
Nahin Ferdousi ◽  
Ziwei Dai ◽  
Joseph L. Woo

The proper characterization of aqueous brown carbon (BrC) species, their formation, and their light absorbance properties is critical to understanding the aggregate effect that they have on overall atmospheric aerosol climate forcing. The contribution of dark chemistry secondary organic aerosol (SOA) products from carbonyl-containing organic compounds (CVOCs) to overall aqueous aerosol optical properties is expected to be significant. However, the multiple, parallel pathways that take place within CVOC reaction systems and the differing chromophoricity of individual products complicates the ability to reliably model the chemical kinetics taking place. Here, we proposed an alternative method of representing UV-visible absorbance spectra as a composite of Gaussian lineshape functions to infer kinetic information. Multiple numbers of curves and different CVOC/ammonium reaction systems were compared. A model using three fitted Gaussian curves with magnitudes following first-order kinetics achieved an accuracy within 65.5% in the 205–300-nm range across multiple organic types and solution aging times. Asymmetrical peaks that occurred in low-200-nm wavelengths were decomposed into two overlapping Gaussian curves, which may have been attributable to different functional groups or families of reaction products. Component curves within overall spectra exhibited different dynamics, implying that the utilization of absorbance at a single reference wavelength to infer reaction rate constants may result in misrepresentative kinetics for these systems.


1990 ◽  
Vol 68 (3) ◽  
pp. 492-501 ◽  
Author(s):  
Andrew P. Masters ◽  
Ted S. Sorensen

Reactions of pentacarbonyl manganate anion with 4-halocrotonate esters or 2-halocarboxylate esters result in a complex set of inorganic and organic products, usually including the expected dienolate (or enolate) complexes. The reaction variables include the counterion, solvent, and halo group. The mechanism of the reaction has been investigated by conducting a thorough characterization of the reaction products under various conditions and also by carrying out model reactions. One can rationalize most of the non-organometallic products using either a radical or carbanion mechanism, but the latter seems to fit the available data better. Experimental procedures for optimizing the yield of the organometallic dienolate or enolate complexes have been worked out. Keywords: pentacarbonyl manganate, metalate nucleophilicity, enolate complex, nucleophilic substitution, 55Mn NMR spectroscopy.


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