Search results for "Radical"

Die zweifache unterdrückung der polymerisation einiger bis(methacrylsäureester) mittels radikalischer additionsreaktionen

1973

Aus Hydrochinon, Resorcin, Dihydroxydiphenylen und Dihydroxynaphthalinen wurden mit Methacrylsaurechlorid Bis(methacrylsaureester) hergestellt. Setzte man diese in siedendem Benzol mit groser Verdunnung gelosten Ester dem Angriff von Radikalen aus α.α′-Azoisobuttersauredinitril (Primarradikale) aus, dessen Uberschus in Beziehung zum Ester mindestens zwanzigfach molar war, so erhielt man mittels saulenchromatographischer Trennung Verbindungen, bei denen je olefinische Doppelbindung zwei Primarradikale addiert waren (unterdruckte Polymerisation). Die Struktur dieser Produkte wurde mittels Elementaranalyse, Molekulargewichtsbestimmung, IR- und 1H-NMR-Spektren bewiesen. Demnach kann die Polymer…

1993

Several zwitterionic polymers were prepared by radical homopolymerization of surfactant monomers which bear diallyl, diene or vinylcyclopropane moieties. These polymer systems were complemented by alternating copolymers of appropriate zwitterionic vinyl compounds. Thus, polymers with reduced (as compared with simple vinylic homopolymers, or statistical copolymers) and well defined density of surfactant side groups are obtained. The solubilities found for these polymers are dominated by polymer geometry rather than by the balance of hydrophilic and hydrophobic fragments, thus corroborating a “main-chain spacer” model proposed recently. All water-soluble polymers exhibit characteristic featur…

Über polymerisationen mit hilfe von redox-systemen

1951

Bei der durch Eisen-Redox-Systeme ausgelosten Polymerisation von Styrol und von Dimethylbutadien -2.3 wird die peroxydische Komponente (Diacylperoxyd) in die Makromolekule eingebaut. Es wird gezeigt, das bei der Polymerisation des Styrols mit Dibrombenzoylperoxyd-Eisenbenzoat-Benzoin die Zahl der eingebauten, markierten Endgruppen die gleiche ist wie bei der peroxydischen Polymerisation mit Di-Brombenzoylperoxyd. Dies spricht dafur, das auch die peroxydische Polymerisation durch Radikale ausgelost wird, die bei einer Redox-Reaktion zwischen Peroxyd und Monomerem entstehen. Fur das polymere Dimethylbutadien wurde nachgewiesen, das alle markierten Endgruppen, die bei der eisen-redox-katalysie…

Synthesis of Photoreactive Block Copolymers Based on 1-Iminopyridinium Ylides

2010

Two photoreactive pyridinium ylide containing monomers, {[2-(metacryloyloxy)ethoxy]carbonyl}(pyridinium-1-yl)azanide (M1) and pyridinium-1-yl-(4-vinylbenzoyl)azanide (M2), were synthesized. Both monomers were polymerized under controlled radical polymerization conditions, i.e. reversible addition–fragmentation chain transfer polymerization (M1 and M2) and nitroxide-mediated polymerization (M2). Further block copolymers PMMA-b-PM1 and PS-b-PM2 were successfully synthesized and their molecular weight, Mn, and block ratio could be determined by 1H NMR analysis, thereby opening the synthetic possibilities of photoreactive ylides in block copolymer syntheses.

Oxidative DNA Damage Profiles in Mammalian Cells

1997

Reactive oxygen species (ROS) are formed inside cells not only under the influence of exogenous agents (visible light, ionizing radiation, and many oxidants such as peroxides or quinones), but also under normal (physiological) conditions as byproducts of oxygen metabolism and other cellular redox reactions (Pryor 1986; Halliwell and Gutteridge 1986; Sies 1986; Clayson et al. 1994). ROS such as hydroxyl radicals and singlet oxygen are a serious threat to the integrity of the cellular genome, since they efficiently react with DNA to generate many types of DNA modifications, at least some of which are pre- mutagenic (Breimer 1990; Halliwell and Aruoma 1991; Epe 1991; Feig et al. 1994). Steady-…

Glial Swelling and Damage by Arachidonic Acid

1994

Arachidonic acid (AA) is a major constituent of membrane phospholipids in brain tissue. Normally, the free fatty acid is present only in small amounts, but it accumulates under adverse conditions such as ischemia (Kinouchi et al. 1990). The release of free fatty acids involves activation of phospholipases and breakdown of membrane phospholipids. A A in particular is considered to mediate pathological processes. It is a polyunsaturated compound and precursor of prostaglandins, leukotrienes, and oxygen-derived free radicals (Wolfe 1982). In cerebral ischemia concentrations of free AA of up to 0.5mM/kg were found (Kinouchi et al. 1990). But also brain injury and seizures cause increased levels…

Oxygen Radical Scavengers

2010

The myocardium can tolerate only relatively short periods of total myocardial ischemia without myocardial cell death. Following short ischemic periods, ischemic damage is reversible by reperfusion. However, with increasing duration and severity of ischemia, the damage inflicted to cardiomyocytes following reperfusion becomes irreversible. The combined pathologic events in the myocardium that follow a critical period of ischemia and leading to either reversible or irreversible damage to both cardiomyocytes and cardiac microvasculature is known as ischemia-reperfusion injury (Goldhaber and Weiss 1992).

Probing the Folding of Peptide–Polymer Conjugates Using the π-Dimerization of Viologen End-Groups

2020

The synthesis of a foldable viologen-functionalized peptide–polymer conjugate is presented. The ABA-type triblock conjugate with a PEG polymer was capped with a FHFHF pentapeptide sequence and further modified with a viologen building block at both chain ends. The pH-responsive peptide domains fold into an intermediate structure inducing close proximity of the viologen units, which upon a reduction step form π-dimers of the radical cation. Overall the intramolecular folding and intermolecular self-assembly process leads to the formation of supramolecular nanorods. Mixing of viologen-peptide–polymer conjugates with unfunctionalized conjugates leads to crosslinking of the nanorods and hydroge…

Polymerization of methyl and phenyl oxazoline initiated with alkyl chloroformates

2010

It has been shown that alkyl chloroformates are capable of initiating the polymerization of oxazolines. Esters itself initiate rather slowly and the polymerization proceeds via covalent growing species. Exchange of counter ions with triflate or iodide anions leads to faster initiation and higher reaction rates. The polymerization is of living character.

Kinetics of Group Transfer Polymerization

1987

The group transfer polymerization (GTP) of methyl methacrylate (MMA) and tert.-butyl methacrylate (TBMA), catalyzed by bifluoride, is of first order with respect to monomer and catalyst concentrations. A slightly negative order with respect to initiator concentration is observed, indicating an inhibitive function of the initiator. Termination reactions occur at lower catalyst concentrations. They are very pronounced for TBMA and result in incomplete conversions. For MMA, at lower catalyst and higher initiator concentrations, induction periods are observed which increase when lowering the temperature. This is related with the formation of active chains. The Arrhenius plots for the propagatio…