Search results for "Radical"
showing 10 items of 1401 documents
Spin Trapping of Carbon-Centered Ferrocenyl Radicals with Nitrosobenzene
2015
In contrast to metal centered 17 valence electron radicals, such as [Mn(CO)5]•, ferrocenium ions [Fe(C5H5)2]+ (1+), [Fe(C5Me5)2]+ (2+), [Fe(C5H5)(C5H4Et)]+ (3+), [Fe(C5H5)(C5H4NHC(O)Me)]+ (4+), and [Fe(C5H5)(C5H4NHC(S)Me)]+ (5+) do not add to nitrosobenzene PhNO to give metal-coordinated stable nitroxyl radicals. In the presence of the strong and oxidatively stable phosphazene base tert-butylimino-tris(dimethylamino)phosphorane, the quite acidic ferrocenium ions 1+–5+ are deprotonated to give a pool of transient and persistent radicals with different deprotonation sites [1–Hx]•–[5–Hx]•. One rather persistent iron-centered radical [4–HN]•, deprotonated at the nitrogen atom, has been detected…
A new procedure for the Antioxidant capacity dpph assessment in small samples.
2018
The antioxidant capacity of a substance is its ability to prevent or slow down oxidation. This reaction is a transfer of electrons. The molecule catching electrons is the oxidative agent and the molecule giving electrons is the reducing agent. Oxidative stress is toxic for the cells, and it can be limited by different pathways: the inhibition of enzymes responsible of the production of oxidative species, the synthesis, activation or stabilization of antioxidant enzymes, and finally by direct scavenging of radical species. In living organisms, especially in association to the respiration process, free radicals are commonly produced. Antioxidant are naturally present to prevent damages, and t…
A POLYCARBOXYLIC/AMINO FUNCTIONALIZED HYALURONIC ACID DERIVATIVE FOR THE PRODUCTION OF pH SENSIBLE HYDROGELS IN THE PREVENTION OF BACTERIAL ADHESION …
2014
A graft copolymer derivative of hyaluronic acid bearing pendant amino and short polymethacrylate portions (HA-EDA-BMP-MANa) has been employed for the production of a pH sensible vancomycin releasing hydrogel and studied in vitro to test its potential anti adhesive property against Staphylococcus aureus colonization. The copolymer obtained through atom transfer radical polymerization bears chargeable (carboxyl and amino groups) portions and it could be formulated as a hydrogel at a concentration of 10% w/v. The HA-EDA-BMP-MANa hydrogels, produced at three different pH values (5, 6 and 7, respectively), were formulated with or without the addition of vancomycin (2% w/v). The vancomycin releas…
Regioselectivity of the OH Radical Addition to Uracil in Nucleic Acids. A Theoretical Approach Based on QM/MM Simulations.
2017
Oxidation of nucleic acids is ubiquitous in living beings under metabolic impairments and/or exposed to external agents such as radiation, pollutants, or drugs, playing a central role in the development of many diseases mediated by DNA/RNA degeneration. Great efforts have been devoted to unveil the molecular mechanisms behind the OH radical additions to the double bonds of nucleobases; however, the specific role of the biological environment remains relatively unexplored. The present contribution tackles the study of the OH radical addition to uracil from the gas phase to a full RNA macromolecule by means of quantum-chemistry methods combined with molecular dynamics simulations. It is shown…
Radical cation salts of BEDT-TTF, enantiopure tetramethyl-BEDT-TTF, and TTF-Oxazoline (TTF-Ox) donors with the homoleptic TRISPHAT anion
2011
International audience; The synthesis and crystal structures of five radical cation salts based on the organic donors bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF), racemic ethylenedithio-methyl-oxazoline-tetrathiafulvalene (EDT-TTF-MeOx) and the enantiopure (S,S,S,S) and (R,R,R,R) tetramethyl-bis(ethylenedithio)tetrathiafulvalene (TMBEDT-TTF) and the D3-symmetric anion tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) are reported. The salts are formulated as [BEDT-TTF][(rac)-TRISPHAT]·CH2Cl2 (1), [BEDT-TTF][(rac)-TRISPHAT]·2CH3CN (2), [(rac)-EDT-TTF-Ox][(rac)-TRISPHAT]·CH3CN (3), [(S,S,S,S)-TMBEDT-TTF][(rac)-TRISPHAT]·2CH3CN (4), and [(R,R,R,R)-TMBEDT-TTF][(rac)-TRISPHAT]·2CH3CN (…
Copper complexes of polyaza[n]cyclophanes and their interaction with DNA and RNA
2001
Abstract The complexation properties of Cu 2+ ions with the cyclophane receptors 2,6,9,13-tetraaza[14]metacyclophane ( L1 ), 2,6,10,13,17,21-hexaaza[22]metacyclophane ( L2 ) and 2,6,10,13,17,21-hexaaza[22]paracyclophane ( L3 ) are presented. Formation of mononuclear complexes in the case of L1 and of mono- and binuclear complexes in the case of the hexaaazcyclophane ligands L2 and L3 is observed. The coordination numbers around each Cu 2+ in the binuclear complexes involve at most three nitrogen donors for each metal ion. Cyclophanes L1 – L3 and several acyclic polyamine ligands are tested for their affinity towards double-stranded nucleic acid models of RNA and DNA. The binding affinity of…
Synthesis, structure, and nuclease properties of several binary and ternary complexes of copper(II) with norfloxacin and 1,10 phenantroline
2007
Three new binary Cu(II) complexes of norfloxacin have been synthesized and characterized. We also report the synthesis, characterization and X-ray crystallographic structures of a new binary compound, [Cu(HNor)(2)]Cl(2).2H(2)O (2) and two new ternary complexes norfloxacin-copper(II)-phen, [Cu(Nor)(phen)(H(2)O)](NO(3)).3H(2)O (4), and [Cu(HNor)(phen)(NO(3))](NO(3)).3H(2)O (5). The structure of 2 consists of two crystallographically independent cationic monomeric units of [Cu(HNor)(2)](2+), chloride anions, and uncoordinated water molecules. The Cu(II) ion is placed at a center of symmetry and is coordinated to two norfloxacin ligands which are related through the inversion center. The struct…
Formation of New η5-Rhodium(III) Complexes from η5-Rh(I) Rhodacarborane-Containing Charge-Compensated Ligands
2004
A series of new Rh(I) half-sandwich complexes of formula [3,3-(PPh 3 ) 2 -8-L-closo-3,1,2-RhC 2 B 9 H 1 0 )] (L = SMe 2 (2a), SEt 2 (2b), S(CH 2 ) 4 (2c), SEtPh (2d)) and [1-Me-3,3-(PPh 3 ) 2 -8-L-closo-3,1,2-RhC 2 B 9 H 9 )] (L = SMe 2 (2e), SEt 2 (2f)) have been prepared by reaction of the respective monoanionic charge-compensated ligands [10-L-nido-7,8-C 2 B 9 H 1 0 ] - and [7-Me-10-L-7,8-C 2 B 9 H 9 ] - with [RhCl(PPh 3 ) 3 ]. Complex [3,3-(cod)-8-SMe2-closo-3,1,2-RhC 2 B 9 H 1 0 ] (3) has also been prepared by reaction of K[10-SMe 2 -nido-7,8-C 2 B 9 H 1 0 ] with [RhCl(cod)] 2 . Rh(I) complexes 2a-d may be easily oxidized to the corresponding Rh(III) complexes 4a-d under N 2 atmosphere…
Mass spectra of halogenated esters. Part IX—methyl esters of 2-butenoic acids containing chlorine and/or bromine atom(s)
1990
The electron impact mass spectra of methyl esters of chloro-, bromo-, dichloro-, bromochloro- and dibromo-2-butenoic acids (13 esters at all) have been investigated. Generally, the peaks due to the following fragments are abundant: M+·, [M OCH3]+, [M CH3OH]+·, [M X]+, [M OCH3 CO]+ or [M COOCH3]+, [M X CH3OH]+ or [M OCH3 HX]+, [M OCH3 CO HX]+, [M OCH3 X X]+ and [M OCH3 CO X X]+. Characteristic for the 2- and 4-halo isomers are the primary losses of a methyl radical and methanol, and for the 3-halo isomers the loss of X· from M+·. Disparities between the spectra of the E and Z isomers are shown, the effect of position of halogen substitution being much more pronounced, as reported previously …
The Importance of Electronic Dimensionality in Multiorbital Radical Conductors.
2019
The exceptional performance of oxobenzene-bridged bis-1,2,3-dithiazolyls 6 as single-component neutral radical conductors arises from the presence of a low-lying π-lowest unoccupied molecular orbital, which reduces the potential barrier to charge transport and increases the kinetic stabilization energy of the metallic state. As part of ongoing efforts to modify the solid-state structures and transport properties of these so-called multiorbital materials, we report the preparation and characterization of the acetoxy, methoxy, and thiomethyl derivatives 6 (R = OAc, OMe, SMe). The crystal structures are based on ribbonlike arrays of radicals laced together by S···N' and S···O' secondary bondin…