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Nitroxide Radicals (nitroxide + radical)

Distribution by Scientific Domains

Chemistry	53%
Polymers and Materials Science	33%
Life Sciences	13%

Kinds of Nitroxide Radicals

nitronyl nitroxide radical

Selected Abstracts

Crystal Structures and Magnetic Properties of Nitronyl Nitroxide Radicals

HELVETICA CHIMICA ACTA, Issue 4 2003
Alexander Zakrassov
The crystal structures and magnetic properties of the nitronyl nitroxide radicals 4,5-dihydro-4,4,5,5-tetramethyl-3-oxido(1H -imidazol-1-yloxyl) (1), 4,5-dihydro-2,4,4,5,5-pentamethyl-3-oxido(1H -imidazol-1-yloxyl) (2), 2-(4-chlorophenyl)-4,5-dihydro-4,4,5,5-tetramethyl-3-oxido(1H -imidazol-1-yloxyl) (3), and 4,5-dihydro-2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-3-oxido(1H -imidazol-1-yloxyl) (4) are reported. Compound 1 has two polymorphic forms: the , phase is monoclinic (P21/n space group), with a single molecule in the asymmetric unit, and the , phase is monoclinic (P21/c space group), with four molecules in the asymmetric unit. In the two polymorphs, the molecules are arranged in dimers formed by hydrogen bonds of the type CH,,,ON. The crystal structure of 3 contains layers of antiparallel ribbons of molecules. Compound 4 crystallizes with solvent molecules, and an intramolecular hydrogen bond is formed between the 2-OH group of the phenyl ring and the nitroxide O-atom. Compound 4 also loses the two O-atoms of the nitroxide moiety upon heating to 90°. Magnetic measurements showed that both , and , polymorphs of 1 exhibit antiferromagnetic coupling. The best fit to the experimental data was obtained using BleanyBower's singlet-triplet model (H=,2JSaSb): J=,11.2,K for the , phase and J=,15.0,K for the , phase. Compounds 3 and 4 show no evidence for spin coupling. [source]

ChemInform Abstract: Synthesis of ,,,,-Asymmetric Nitroxide Radicals by C- or O-Acylation of Radical-Enolate Intermediates Generated by Reduction of Homoallylic Nitro Enones with Samarium(II) Iodide.

CHEMINFORM, Issue 23 2001
Rui Tamura
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

ChemInform Abstract: Synthesis of 2-Substituted Pyrrolidine Nitroxide Radicals.

CHEMINFORM, Issue 13 2001
Szilvia Gadanyi
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Formation of Inorganic/Organic Nanocomposites by Nitroxide-Mediated Polymerization in Bulk Using a Bimolecular System

MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 10 2004
Julien Parvole
Abstract Summary: A series of organic-inorganic nanoparticles were synthesized by nitroxide-mediated polymerization (NMP) of butyl acrylate initiated by a self-assembled monolayer of an azo initiator. The azo initiator was immobilized on silica particles in the presence of a stable nitroxide radical, SG1 (an acyclic , -phosphonylated nitroxide, N - tert -butyl- N -(1-diethylphosphono-2,2-dimethyl)propyl nitroxide). After preliminary qualitative characterization by X-ray spectroscopy (XPS) and Fourier-transform infrared (FTIR) measurements, the nanoparticles were studied by thermogravimetric analysis (TGA) to determine the polymer grafting density and to permit a comparison with corresponding values of the initiator monolayer. It was demonstrated that the grafting from polymerization exhibits a controlled character with a low polydispersity (,<,1.2) in a large range of molecular weights of the grafted chains (from 4,000 up to 145,000 g,·,mol,1) under the conditions when the stable radical SG1, acting as chain growth moderator tethered to the inorganic core, was used. [source]

Dual Chromophore-Nitroxides: Novel Molecular Probes, Photochemical and Photophysical Models and Magnetic Materials

PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2007
Gertz I. Likhtenstein
Over the last decades scientists have faced growing requirements in novel methods of fast and sensitive analysis of antioxidant status of biological systems, spin redox probing and spin trapping, investigation of molecular dynamics, and of convenient models for studies of photophysical and photochemical processes. In approaching this problem, methods based upon the use of dual chromophore-nitroxide (CN) compounds have been suggested and developed. A CN consists of two molecular sub-functionality (a chromophore and a stable nitroxide radical) tethered together by spacers. In the dual compound the nitroxide is a strong intramolecular quencher of the fluorescence from the chromophore fragment. Reduction to hydroxylamine, oxidation of the nitroxide fragment or addition of an active radical yield the fluorescence increase and the parallel decay of the fragment electron spin resonance (ESR) signal. At certain conditions the dual molecules undergo photomagnetic switching and form excited state multi-spin systems. These unique properties of CN were intensively exploited as the basis for several methodologies, which include molecular probing, modeling intramolecular photochemical and photophysical processes, and construction of new magnetic materials. [source]

The study of the miscibility and morphology of poly(styrene-co-4-vinylphenol)/poly(propylene carbonate) blends

POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 8 2004
Furong Qiu
Abstract Blends of poly(propylene carbonate) (PPC) with copolymer poly(styrene-co-4-vinyl phenol) (STVPh) have been studied by electron spin resonance (ESR) spin probe method and Raman spectroscopy. The ESR results indicated that the nitroxide radical existed in a PPC-rich and an STVPh-rich micro domain in the blends, corresponding to the fast-motion and slow-motion component in the ESR spectra, respectively. And in the temperature dependence composite spectra, the fast-motion fraction increased with increasing the hydroxyl group content in copolymer STVPh. Moreover, the ESR parameter T5mT, rotational correlation times (,c) and activation energies (Ea) showed similar dependence on the hydroxyl group content as the fast-motion fraction. It resulted from the enhancement of the hydrogen-bonding interaction between the hydroxyl groups in STVPh and the carboxyl groups and ether oxygen in PPC. However, the distinct band shift and intensity change among the Raman spectra of pure polymer components and those of the blends were observed. In the carboxyl-stretching region, the band shifted to lower frequency with increasing the hydroxyl groups. Furthermore, the phase morphologies of the blends were obtained by optical microscopy. All could be concluded that the hydrogen-bonding interaction between the two components was progressively favorable to the mixing process and was the driving force for the miscibility enhancement in the blends. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Hybrid Magnetic Materials Based on Nitroxide Free Radicals and Extended Oxalato-Bridged Bimetallic Networks

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2005
Antonio Alberola
Abstract A series of hybrid organic-inorganic magnets of formula p -rad[MIICr(ox)3] [M = Mn (1), Co (2), Ni (3), Zn (4)] and m -rad[MIICr(ox)3] [M = Mn (5), Co (6)], in which N -methylpyridinium cations bearing a nitronyl nitroxide moiety in positions 3 (m -rad) or 4 (p -rad) of the pyridine ring coexist with the 2D honeycomb-like oxalato-bridged bimetallic lattice, has been prepared and studied by AC and DC magnetic susceptibility measurements and EPR spectroscopy. In general, the physical properties of these magnets are not altered significantly by the insertion of the nitronyl nitroxide radicals although these paramagnetic molecules seem to interact weakly with the inorganic network as demonstrated by EPR spectroscopy. Some differences can also be observed between the p -rad and m -rad series, i.e. m -rad derivatives have smaller values for the critical temperatures and coercive fields. We also report on the X-ray crystal structures and magnetic properties of p -rad[Mn(H2O)Cr(ox)3]·2H2O (7) and m -rad[Mn(H2O)2Cr(ox)3]·2H2O (8), two extended oxalato-bridged compounds with new topologies. Compound 7 is antiferromagnetic and its structure is a 3D achiral lattice in which zigzag ferromagnetic MnCr chains (J/k = +0.8 K) are interconnected to form hellicoidal hexagonal channels with the cationic free radicals residing in the free space. Compound 8, however, exhibits a ladder-like structural pattern with competing magnetic interactions and paramagnetic behaviour down to low temperatures. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

The Reaction of Peroxynitrite with Morpholine (Secondary Amines) Revisited: The Overlooked Hydroxylamine Formation

HELVETICA CHIMICA ACTA, Issue 10 2006
Michael Kirsch
Abstract The reaction of peroxynitrite/peroxynitrous acid with morpholine as a model compound for secondary amines is reinvestigated in the absence and presence of carbon dioxide. The concentration- and pH-dependent formation of N -nitrosomorpholine and N -nitromorpholine as reported in three previous papers ([25],[26],[14]) is basically confirmed. However, 13C-NMR spectroscopic product analysis shows that, in the absence of CO2, N -hydroxymorpholine is, at pH,,,7, the major product of this reaction, even under anaerobic conditions. The formation of N -hydroxymorpholine has been overlooked in the three cited papers. Additional (ring-opened) oxidation products of morpholine are also detected. The data account for radical pathways for the formation of these products via intermediate morpholine-derived aminyl and , -aminoalkyl radicals. This is further supported by EPR-spectrometric detection of morpholine-derived nitroxide radicals, i.e., morpholin-4-yloxy radicals. N -Nitrosomorpholine, however, is very likely formed by electrophilic attack of peroxynitrite-derived N2O4. 15N-CIDNP Experiments establish that, in the presence of CO2, N -nitro- and C -nitromorpholine are generated by radical recombination. The present results are in full accord with a fractional (28,±,2%) homolytic decay of peroxynitrite/peroxynitrous acid with release of free hydroxyl and nitrogen dioxide radicals. [source]

Crystal Structures and Magnetic Properties of Nitronyl Nitroxide Radicals

Clinical significance of a highly sensitive enzyme immunoassay of hepatitis B surface antigen using a novel electron spin resonance technique

JOURNAL OF MEDICAL VIROLOGY, Issue 2 2002
Masanori Aoki
Abstract We developed a highly sensitive enzyme immunoassay (EIA), the p-AP/HHTIO method, that detects serum hepatitis B surface antigen (HBsAg) by measuring stabilized nitroxide radicals using a novel electron spin resonance technique [Matsuo et al. (1998) Free Radic Biol Med 25:929,935]. To demonstrate the clinical significance of this method and to reveal occult hepatitis B virus (HBV) infection in patients, we used the method to analyze serum samples of 30 patients with acute or fulminant hepatitis who were negative for HBsAg by standard EIA, and those of seven chronic HBV carriers who became negative for HBsAg during a follow-up period by standard EIA. We also examined serum HBV DNA by amplification of the HBV S gene, using the polymerase chain reaction (PCR) technique. The p-AP/HHTIO method showed that 9 of 20 (45%) patients with acute hepatitis and 2 of 10 (20%) with fulminant hepatitis were positive for HBsAg; PCR detected HBV DNA in these HBsAg-positive patients. Antibody against hepatitis B core antigen was detected in one patient with fulminant hepatitis. The p-AP/HHTIO method demonstrated prolonged seropositivity of HBsAg even after standard EIA showed a loss of HBsAg in all seven HBV carriers. Our p-AP/HHTIO method is useful for screening and diagnosing HBV infection in patients with liver diseases who are negative for conventional HBV-related serological markers. J. Med. Virol. 66:166,170, 2002. © 2002 Wiley-Liss, Inc. [source]

One-pot synthesis of heterograft copolymers via "graft onto" by atom transfer nitroxide radical coupling chemistry

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2008
Qiang Fu
Abstract Heterograft copolymers poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl- co - ethylene oxide)- graft -polystyrene and poly(tert -butyl acrylate) (poly (GTEMPO- co -EO)- g -PS/PtBA) were synthesized in one-pot by atom transfer nitroxide radical coupling (ATNRC) reaction via "graft onto." The main chain was prepared by the anionic ring-opening copolymerization of ethylene oxide (EO) and 4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (GTEMPO) first, then the polystyrene and poly (tert -butyl acrylate) with bromine end (PS-Br, PtBA-Br) were prepared by atom transfer radical polymerization (ATRP). When three of them were mixed each other in the presence of CuBr/N,N,N,,N,,N,-pentamethyldiethylenetriamine (PMDETA) at 90 °C, the formed secondary carbon radicals at the PS and PtBA chain ends were quickly trapped by nitroxide radicals on poly(GTEMPO- co -EO). The heterograft copolymers were well defined by 1H NMR, size exclusion chromatography, fourier transform infrared, and differential scanning calorimetry in detail. It was found that the density of GTEMPO groups on main chain poly(GTEMPO- co -EO), the molecular weights of PS/PtBA side chains, and the structure of macroradicals can exert the great effects on the graft efficiency. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6770,6779, 2008 [source]

Incubation period in the 2,2,4,4-tetramethyl-1-piperidinyloxy-mediated thermal autopolymerization of styrene: Kinetics and simulations

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2006
Enrique Saldívar-Guerra
Abstract Mechanisms and simulations of the induction period and the initial polymerization stages in the nitroxide-mediated autopolymerization of styrene are discussed. At 120,125 °C and moderate 2,2,4,4-tetramethyl-1-piperidinyloxy (TEMPO) concentrations (0.02,0.08 M), the main source of radicals is the hydrogen abstraction of the Mayo dimer by TEMPO [with the kinetic constant of hydrogen abstraction (kh)]. At higher TEMPO concentrations ([N,] > 0.1 M), this reaction is still dominant, but radical generation by the direct attack against styrene by TEMPO, with kinetic constant of addition kad, also becomes relevant. From previous experimental data and simulations, initial estimates of kh , 1 and kad , 6 × 10,7 L mol,1 s,1 are obtained at 125 °C. From the induction period to the polymerization regime, there is an abrupt change in the dominant mechanism generating radicals because of the sudden decrease in the nitroxide radicals. Under induction-period conditions, the simulations confirm the validity of the quasi-steady-state assumption (QSSA) for the Mayo dimer in this regime; however, after the induction period, the QSSA for the dimer is not valid, and this brings into question the scientific basis of the well-known expression kth[M]3 (where [M] is the monomer concentration and kth is the kinetic constant of autoinitiation) for the autoinitiation rate in styrene polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6962-6979, 2006 [source]

On the Nitroxide Quasi-Equilibrium in the Alkoxyamine-Mediated Radical Polymerization of Styrene

MACROMOLECULAR THEORY AND SIMULATIONS, Issue 2 2006
Enrique Saldívar-Guerra
Abstract Summary: The range of validity of two popular versions of the nitroxide quasi-equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, kc[P][N],=,kd[PN], where P, N and PN are living, nitroxide radicals and dormant species respectively, with kinetic constants kc and kd, is found valid only for small values of the equilibrium constant K (10,11,10,12 mol,·,L,1) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, kc[P][N],=,kd[PN]0 was found to be remarkably good up to values of K around 10,8 mol,·,L,1. This upper bound is numerically found to be 2,3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico-chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested. Validity of the rigorous nitroxide quasi-equilibrium assumption as a function of the nitroxide equilibrium constant. [source]

Functionalization of PAMAM dendrimers with nitronyl nitroxide radicals as models for the outer-sphere relaxation in dentritic potential MRI contrast agents

MAGNETIC RESONANCE IN CHEMISTRY, Issue 2 2003
Giancarlo Francese
Abstract PAMAM dendrimers functionalized with nitronyl nitroxide radicals were characterized. Quantitative determination of substitution with radicals was performed using EPR and electrochemical methods. The study of the 1H NMR relaxation of the surrounding water showed how the outer-sphere contribution to the relaxivity may be limited by the presence of the dendrimer core. Copyright © 2003 John Wiley & Sons, Ltd. [source]