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Radical Form (radical + form)
Selected AbstractsParacetamol (Acetaminophen): mechanisms of actionPEDIATRIC ANESTHESIA, Issue 10 2008BRIAN J. ANDERSON PhD FANZCA FJFICM Summary Paracetamol has a central analgesic effect that is mediated through activation of descending serotonergic pathways. Debate exists about its primary site of action, which may be inhibition of prostaglandin (PG) synthesis or through an active metabolite influencing cannabinoid receptors. Prostaglandin H2 synthetase (PGHS) is the enzyme responsible for metabolism of arachidonic acid to the unstable PGH2. The two major forms of this enzyme are the constitutive PGHS-1 and the inducible PGHS-2. PGHS comprises of two sites: a cyclooxygenase (COX) site and a peroxidase (POX) site. The conversion of arachidonic acid to PGG2 is dependent on a tyrosine-385 radical at the COX site. Formation of a ferryl protoporphyrin IX radical cation from the reducing agent Fe3+ at the POX site is essential for conversion of tyrosine-385 to its radical form. Paracetamol acts as a reducing cosubstrate on the POX site and lessens availability of the ferryl protoporphyrin IX radical cation. This effect can be reduced in the presence of hydroperoxide-generating lipoxygenase enzymes within the cell (peroxide tone) or by swamping the POX site with substrate such as PGG2. Peroxide tone and swamping explain lack of peripheral analgesic effect, platelet effect, and anti-inflammatory effect by paracetamol. Alternatively, paracetamol effects may be mediated by an active metabolite (p -aminophenol). p -Aminophenol is conjugated with arachidonic acid by fatty acid amide hydrolase to form AM404. AM404 exerts effect through cannabinoid receptors. It may also work through PGHS, particularly in areas of the brain with high concentrations of fatty acid amide hydrolase. [source] Involvement of Electron Transfer in the Photoreaction of Zebrafish Cryptochrome-DASH,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2008Kazunori Zikihara Photoreaction of a blue-light photoreceptor Cryptochrome-DASH (Cry-DASH), a new member of the Cryptochrome family, from zebrafish was studied by UV,visible absorption spectroscopy in aqueous solutions at 293 K. Zebrafish Cry-DASH binds two chromophores, a flavin adenine dinucleotide (FAD) and a N5,N10-methenyl-5,6,7,8-tetrahydrofolate (MTHF) noncovalently. The bound FAD exists in the oxidized form (FADox) in the dark. Blue light converts FADox to the neutral radical form (FADH?). Formed FADH? is transformed to the fully reduced form FADH2 (or FADH,) by successive light irradiation, or reverts to FADox. FADH2 (or FADH,) reverts to FADH? or possibly to FADox directly. The effect of dithiothreitol suggests a possible electron transfer between FAD in zebrafish Cry-DASH and reductants in the external medium. This is the first report on the photoreaction pathway and kinetics of a vertebrate Cry-DASH family protein. [source] Inscrutable Evil and ScepticismTHE HEYTHROP JOURNAL, Issue 3 2000John Beaudoin Philosophical theologians have in recent years revived and cast in sophisticated form a non-theodical approach to defeating probabilistic arguments from evil. In this article I consider and reject the claim that their emphasis on the epistemic gap separating us from God entails a radical form of scepticism. I then argue, however, that proponents of this view cannot escape and unattractive theological scepticism. [source] DEFEATERS AND HIGHER-LEVEL REQUIREMENTSTHE PHILOSOPHICAL QUARTERLY, Issue 220 2005Michael Bergmann Internalists tend to impose on justification higher-level requirements, according to which a belief is justified only if the subject has a higher-level belief (i.e., a belief about the epistemic credentials of a belief). I offer an error theory that explains the appeal of this requirement: analytically, a belief is not justified if we have a defeater for it, but contingently, it is often the case that to avoid having defeaters, our belief must satisfy a higher-level requirement. I respond to the objection that externalists who endorse this error theory will be forced to accept a radical form of scepticism. [source] A Rigid Molecular Scaffold Affixing a (Polypyridine)ruthenium(II)- and a Nickel(II)-Containing Complex: Spectroscopic Evidence for a Weakly Coupled Bichromophoric SystemEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2003Yann Pellegrin Abstract The synthesis of DppztBuSalH2 (7), a rigid conjugated ditopic ligand containing a Dppz (dipyrido[3,2- a:2,,3,- c]phenazine) skeleton and a salophen-type chelate, is reported. The complexes DppztBuSalNi (10), [Ru(bpy)2(DppztBuSalH2)]2+ (11), and [Ru(bpy)2(DppztBuSalNi)]2+ (12) have been prepared and characterised using common spectroscopic methods. Electrochemical, UV/Vis spectroelectrochemical and EPR studies were conducted on compounds 7, 10, 11, and 12. The singly reduced radical forms of 7 and 10 can be generated electrochemically, with the lone electron located on the low-lying phenazine ,*-molecular orbital. Complexes 11 and 12 show several reduction waves and electronic and EPR data obtained for the electrogenerated singly reduced species show them to be closely related to the radical species 7·, and 10·,, respectively. The presence of nickel(II) in compound 12 renders the addition of the second electron on the phenazine group reversible. Both 11 and 12 show common features on the cathodic side of their cyclic voltammograms, with reversible one-electron ruthenium-centred oxidation. An additional low-potential reversible-oxidation wave is observed for 12, and this is ascribed to oxidation of the nickel(II) ion. The combined spectroscopic data best describe the ruthenium-containing complexes as weakly coupled bichromophoric systems. Photophysical studies attest to the formation of a charge-separated state for 11, whereas a strong quenching is detected for 12. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Civic Governmentality: The Politics of Inclusion in Beirut and MumbaiANTIPODE, Issue 1 2009Ananya Roy Abstract:, This article is concerned with the politics of inclusion. It analyzes the institutionalization of participatory citizenship as the formation of regimes of "civic governmentality". Through the study of key civil society organizations such as SPARC and Hezbollah, it studies three dimensions of civic governmentality: an infrastructure of populist mediation; technologies of governing (for example, knowledge production); and norms of self-rule (for example, concepts of civility and civicness). However, such regimes of civic governmentality operate within frontiers of urban renewal and indeed often facilitate and manage such types of development. The article examines the limits and contradictions of the politics of inclusion in the context of the bourgeois city and also studies radical forms of citizenship that emerge to challenge these limits. [source] Mechanisms and Factors for Edible Oil OxidationCOMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY, Issue 4 2006Eunok Choe ABSTRACT:,Edible oil is oxidized during processing and storage via autoxidation and photosensitized oxidation, in which triplet oxygen (3O2) and singlet oxygen (1O2) react with the oil, respectively. Autoxidation of oils requires radical forms of acylglycerols, whereas photosensitized oxidation does not require lipid radicals since 1O2 reacts directly with double bonds. Lipid hydroperoxides formed by 3O2 are conjugated dienes, whereas 1O2 produces both conjugated and nonconjugated dienes. The hydroperoxides are decomposed to produce off-flavor compounds and the oil quality decreases. Autoxidation of oil is accelerated by the presence of free fatty acids, mono- and diacylglycerols, metals such as iron, and thermally oxidized compounds. Chlorophylls and phenolic compounds decrease the autoxidation of oil in the dark, and carotenoids, tocopherols, and phospholipids demonstrate both antioxidant and prooxidant activity depending on the oil system. In photosensitized oxidation chlorophyll acts as a photosensitizer for the formation of 1O2; however, carotenoids and tocopherols decrease the oxidation through 1O2 quenching. Temperature, light, oxygen concentration, oil processing, and fatty acid composition also affect the oxidative stability of edible oil. [source] |