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Nitroxyl-mediated radical

M26. Misra, H. P., Inhibition of superoxide dismutase by nitroprusside and electron spin resonance observations on the formation of a superoxide-mediated nitroprusside nitroxyl free radical. J. [Pg.55]

NMP is another controlled free radical polymerization technique that can be used to polymerize styrene [98-100]. Weimer et al. investigated surface-initiated PS-MMT nanocomposites using MMT modified with a nitroxyl-mediated living... [Pg.351]

More recently, refinements and new approaches for controlling radical polymerization have been described (155). Two of the most studied methods feature either stable counter-radicals, eg, nitroxyl-mediated pol5unerization (NMP), or reversible activation of carbon-halogen bonds by transition-metal species in a... [Pg.3935]

The example described below refers to nitroxide-mediated free radical polymerizations. Initially, a methacrylic monomer carrying an alkoxyamine group is copolymerized at moderate temperature with a comonomer (H2C=CHA) to form the backbone. In a second step the grafts are grown by thermal activation of alkoxyamine groups, which produce, in addition to stable nitroxyl free radicals, reactive free radicals capable of initiating the polymerization of H2C=CHB (see Section 8.5.11 for the mechanism). [Pg.386]

Nitroxyl radicals, stable, 14 298 Nitroxy-mediated polymerization (NMP), 14 297-298... [Pg.628]

Scheme 30 Nitroxyl-radical-mediated selective oxidation of primary alcohols. Scheme 30 Nitroxyl-radical-mediated selective oxidation of primary alcohols.
The last decades have witnessed the emergence of new living Vcontrolled polymerizations based on radical chemistry [81, 82]. Two main approaches have been investigated the first involves mediation of the free radical process by stable nitroxyl radicals, such as TEMPO while the second relies upon a Kharash-type reaction mediated by metal complexes such as copper(I) bromide ligated with 2,2 -bipyridine. In the latter case, the polymerization is initiated by alkyl halides or arenesulfonyl halides. Nitroxide-based initiators are efficient for styrene and styrene derivatives, while the metal-mediated polymerization system, the so called ATRP (Atom Transfer Radical Polymerization) seems the most robust since it can be successfully applied to the living Vcontrolled polymerization of styrenes, acrylates, methacrylates, acrylonitrile, and isobutene. Significantly, both TEMPO and metal-mediated polymerization systems allow molec-... [Pg.32]

The inclusion of stable free radicals such as TEMPO (18, TO ) in free radical polymerizations leads to precise control of chain length by restricting the number of polymerizing chains (equation 96). This process is known as nitroxyl radical mediated polymerization (NRMP). [Pg.39]

Nitroxide mediated polymerization (NMP) [56, 57]. This consists in a thermally reversible termination reaction by a homolytic cleavage of a C-ON bond of an alkoxyamine, giving rise to an initiating alkyl radical (active species) and a nitroxyl radical, which brings control to the reaction [58]. [Pg.12]

Scheme 10.11 shows a PRE-mediated 5-exo-trig radical cyclisation in which the controlled thermal formation of active radicals from the dormant alkoxyamine 2 is facilitated by steric compression of the alkoxyamine C—O bond by the bulky N-alkyl and O-alkyl groups [8]. Intramolecular H-bonding between a —CH2—OH and the nitroxyl oxygen of the incipient nitroxide in a six-membered cyclic transition structure further facilitated the dissociation of 2. After cyclisation, the resultant primary cyclopentylmethyl radical was trapped by the free nitroxide to form the new dormant isomerised alkoxyamine 3, which is more stable than 2 since the O-alkyl is now primary. The same reaction using TEMPO as the nitroxide component did not work presumably because the C—O bond in the alkoxyamine precursor is much stronger. [Pg.274]

Several systems have been proposed to fulfill these conditions. Among them is the one mediated by stable nitroxyl radicals such as 2, 2, 6, 6-tetra-methylpiperidinyl-l-oxy (TEMPO) ... [Pg.57]

A. E. J. De Nooy, A. C. Besemer, and H. van Bekkum, Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans, Carbohydr. Res., 269 (1995) 89-98. [Pg.280]

A. E. J. de Nooy, A. C. Besemer, and H. van Bekkum, Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans, Carbohydr. Res., 269 (1995) 89-98 A. E. J. de Nooy, V. Rori, G. Masci, M. Dentini, and V. Crescenzi, Synthesis and preliminary characterisation of charged derivatives and hydrogels from scleroglucan, ibid., 324 (2000) 116-126. [Pg.364]

Denooy, A. E. J., Besemer, A. C., and Vanbekkum, H., Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous-solution - Kinetics and mechanism. Tetrahedron 1995, 51 (29), 8023-8032. [Pg.1539]

The first demonstration of the chemical existence of free radicals had been made with the isolation of the nitroxyl radical in the form of Fremy s salt (KS03)2N0 in 1845 [5], Surprisingly, it was only in 1987 that nitric oxide release was shown to be associated with the production of an endothelium-derived relaxing factor (EDRF) which is biosynthesized from arginine and released by the vascular system of mammals [6,7]. Nitric oxide has since been shown to serve as a cytotoxic mediator of macrophages against tumor cells, yeasts, mycobacteria and parasites, and it is actually secreted by a variety of mammalian cells [8,9],... [Pg.26]

Halide ions, multiple valence metal ions (transition metal complexes), viologen, triarylamines, nitroxyl radicals, and fused arenes like naphthalene are used as mediators for this method. Mediators very often act as an electrocatalyst. [Pg.92]

The nitroxyls (a.k.a. nitroxides) are remarkably stable free radicals. Nitroxyls have two major resonance structures, one N-centered and one O-centered the lone electron may also be considered to be in the 7T orbital of an N=0 tt bond. Nitroxyls are thermodynamically stable because dimerization would give a very weak N-N, N-O, or 0-0 bond. TEMPO (2,2,6,6-tetramethylgiperidin-l-oxyl), a commercially available nitroxyl, is further stabilized by steric shielding. Other thermodynamically stable free radicals include the small molecules O2 (a 1,2-diradical, best represented as -0-0-) and nitric oxide ( N=0), a messenger molecule in mammals that mediates smooth muscle contraction. [Pg.226]

Free-radical polymerization mediated by stable nitroxyl radicals like TEMPO (2,2,6,6-tetramethylpiperidinyl-l-oxy) (Fig. 6.23) is a simple and robust method to synthesize homopolymers and random and block copolymers with narrow poly-dispersities and/or controlled chain architectures. A key to the success of this polymerization is believed to be the reversible combination of a polymer radical, P , with a stable nitroxyl radical, N, to form an adduct, P-N, which is a dormant species ... [Pg.410]

Alkoxyamine-mediated assembly of indolinones and indolines has been described [57]. This route offered the added benefits of employing tin-free conditions and the possibility of inserting oxygen functionality through trapping with a nitroxyl radical. As such, when unsubstituted or para-substituted anilines were treated with three Tordo-type alkoxyamines, 81a-c, the cyclized indolines were obtained in modest to fair yield. [Pg.250]

Patel NS, Chatterjee PK, Chatterjee BE et al. The stable nitroxyl radical TEMPONE reduces renal dysfunction and injury mediated by oxidative stress in the rat kidney. Free Rad Med Biol 2002 33 1575-1589. [Pg.178]


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Nitroxyl

Nitroxyl radical

Nitroxyl-mediated radical polymerization

Nitroxylation

Nitroxylic radicals

Nitroxyls

Radical mediated

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