Search results for "Oxide"

1977

The reaction of ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 3,6-dioxaoctane-1,8-diol (triethylene glycol), poly(ethylene oxide)s with Mn = 300,1000 and 3000, or with poly(propylene oxide)s with Mn = 425 and 2000 in excess with AIBN leads to the corresponding bis(hydroxyalkyl) 2,2′-azodiisobutyrates (1a–i). These initiators are suited to synthesize telechelics. With equimolar amounts of AIBN and 3-oxapentane-1,5-diol (diethylene glycol), poly(ethylene oxide)s with Mn = 300, 1000 and 12000, poly(propylene oxide) with Mn = 425, or with poly(tetrahydrofuran) with Mn = 1000 and 2000 polymeric azoinitiators of structure 2 are formed. Blockcopolymers may be synthesized by means of these polym…

Assembly of iron oxide nanosheets at the air-water interface by leucine-histidine peptides

2021

The fabrication of inorganic nanomaterials is important for a wide range of disciplines. While many purely inorganic synthetic routes have enabled a manifold of nanostructures under well-controlled conditions, organisms have the ability to synthesize structures under ambient conditions. For example, magnetotactic bacteria, can synthesize tiny ‘compass needles’ of magnetite (Fe3O4). Here, we demonstrate the bio-inspired synthesis of extended, self-supporting, nanometer-thin sheets of iron oxide at the water–air interface through self-assembly using small histidine-rich peptides.

Redistribution of total reactive nitrogen in the lowermost Arctic stratosphere during the cold winter 2015/2016

2021

During winter 2015/2016 the Arctic stratosphere was characterized by extraordinarily low temperatures in connection with the occurrence of extensive polar stratospheric clouds. From mid of December 2015 until mid of March 2016 the German research aircraft HALO (High Altitude and Long–Range Research Aircraft) was deployed to probe the lowermost stratosphere in the Arctic region within the POLSTRACC (Polar Stratosphere in a Changing Climate) mission. More than twenty flights have been conducted out of Kiruna/Sweden and Oberpfaffenhofen/Germany, covering the whole winter period. Besides total reactive nitrogen (NOy), observations of nitrous oxide, nitric acid, ozone and water were used f…

Involvement of Peroxynitrite on the Early Loss of P450 in Short-Term Hepatocyte Cultures

2001

The biological chemistry of nitric oxide (NO) in the oxygenated cellular environment is extremely complex. It involves the direct interaction of NO with specific biomolecules and the so-called indirect effects, due to secondary more potent oxidant species derived from NO which are also able to react with DNA, lipids, thiols and transition metals (Wink et al. 1996; Nathan, 1992). In addition to its regulatory role as a signalling molecule (Nathan, 1992; Moncada and Palmer, 1991) it has become evident that NO (or NO-derived species) is a critical factor involved in various toxicological mechanisms (Wink et al. 1996; Wang et al. 1998; Estevez et al. 1999; Wink et al. 1999). Some controversy ex…

An Efficient Method for Controlled Propylene Oxide Polymerization: The Significance of Bimetallic Activation in Aluminum Lewis Acids

2009

Switchable palladium-catalyst reaction of bromomethyl sulfoxides, CO, and N-nucleophiles: aminocarbonylation at Csp3 versus oxidative carbonylation o…

2012

The palladium-catalyzed reaction of α-bromomethyl sulfoxides, carbon monoxide, and N-nucleophiles follows different reaction pathways according to the catalytic system and the reaction conditions. The Pd-xantphos catalyst affords high yields of α-sulfinyl amides by an aminocarbonylation process and is the first example of this type of transformation for a nonbenzylic sp(3)-hybridized carbon. On the other hand, the oxidative carbonylation of amines occurs with α-bromomethyl sulfoxides, carbon monoxide, and catalytic Pd(PPh(3))(4) under aerobic conditions, yielding ureas and oxalamides from either primary or secondary amines. The reaction with ambident nucleophiles such as amino alcohols was …

Der nachweis der primärreaktion bei der autoxydation des tetralins

1964

Die Autoxydation des Tetralins wurde bei kleinen Umsatzen durch polarographische oder kolorimetrische Bestimmung des Peroxidgehaltes verfolgt und eine Anfangsgeschwindigkeit gefunden, die groser ist, als sie nach dem Peroxidgehalt des Tetralins sein sollte. Diese zusatzliche Reaktionsgeschwindigkeit ist die der Primarreaktion der Autoxydation. Dabei bilden sich aus Tetralin und molekularem Sauerstoff Radikale. Diese Primarreaktion ist nur dann beobachtbar, wenn der Peroxidgehalt des Tetralins etwa 10−5 Mol/l betragt oder kleiner ist. The autoxidation of tetraline was measured to a low degree of conversion by polarographic or colorimetric determination of tetraline hydroperoxide. The extrapo…

Mechanism of the oxidation of sulfides by dioxiranes: conformational mobility and transannular interaction in the oxidation of thianthrene 5-oxide.

2004

The detailed study of the oxidation of thianthrene 5-oxide (1) with methyl(trifluoromethyl)dioxirane (5b) in different solvents and in the presence of (18)O isotopic tracers is reported. Thianthrene 5-oxide (1) is a flexible molecule in solution, and this property allows for transannular interaction of the sulfoxide group with the expected zwitterionic 7 and hypervalent 10-S-4 sulfurane 9 intermediates formed in the oxidation and biases the course of the reaction toward the monooxygenation pathway.

Über die photosensibilisierte autoxydation von polyvinylalkohol

1968

Polyvinylalkohol wurde in wasriger Losung bei 30°C unter Belichtung mit einer Quecksilberhochdrucklampe einer mit benzophenn-3.3′-disulfonsaurem Natrium photosensibilisierten Autoxydation unterworfen. Als Reaktionsprodukte wurden Wasserstoffperoxid, Sauren und Kohlendioxid ermittelt. Unter den gewahlten Reaktionsbedingungen werden die Makromolekule statistisch abgebaut. Viskositatsmessungen und analytische Bestimmungen zeigen, das pro Spaltung der polymerkette nur eine Carboxylendgruppe entsteht. Ein Reaktionsmechanismus wird diskutiert. Polyvinylalcohol was oxidized in water solution at 30°C by irradiation with a mercury high pressure lamp and benzophenon-3.3′-disodiumdisulfonate as sensit…

1990

The effect of lithium tert-butoxide (t-BuOLi) on rate constants and equilibrium constants of reactions involved in the initial stage of the anionic polymerization of methyl methacrylate (MMA) in tetrahydrofuran, initiated by methyl α-lithioisobutyrate (P) was investigated at 23 ± 3°C. Addition of t-BuOLi decreases the rate constants of initiation and propagation by one order of magnitude; the rate constants of termination by cyclization decrease by two orders of magnitude. This leads to an overall tenfold higher preference of propagation with respect to termination and explains the favourable effect of alkoxide in the polymerization reported earlier. Within experimental error, the equilibri…