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Proton Signals (proton + signal)
Selected AbstractsPreparation, characterization, and thermal properties of hydrophilic copolymers: p -chlorophenylmaleimides with hydroxylethyl methacrylate and ,-methyl itaconatePOLYMER INTERNATIONAL, Issue 9 2007Guadalupe del C Pizarro Abstract This work describes the synthesis, characterization, and thermal behavior of copolymers of p -chlorophenylmaleimide (Cl-PhMI) with ,-methyl itaconate (,-MHI) and 2-hydroxyethyl methacrylate (HEMA). Copolymerization was carried out with a radical initiator by varying the feed mole fraction of Cl-PhMI from 0.25 to 0.75. The copolymer composition was determined from the N/C ratio based on elemental analysis data and with 1H NMR spectroscopy for poly(Cl-PhMI- co -HEMA) using a proton signal attributed to the CH3 of HEMA (, = 0.7,1.4 ppm) and the area of aromatic ring protons (, = 7.2,7.8 ppm), where the proton/area relationship confirmed the copolymer compositions calculated by elemental analysis. The monomer reactivity ratios r1 and r2 were determined using the Kelen,Tüdös method. These values demonstrated that copolymerization produced random copolymers with an alternation tendency. The molecular weight and polydispersity were also determined. The thermal behavior can be correlated with the copolymer composition. An increase of the thermal decomposition temperature occurred when the content of Cl-PhMI increased. The glass transition temperature and thermal stability of poly(,-MHI) or poly(HEMA) increased with an increasing amount of Cl-PhMI in the polymer backbone. Copyright © 2007 Society of Chemical Industry [source] Dynamic Stereochemical Behaviour of Congested Ruthenium(II) Complexes Containing Asymmetric Thioether Ligands Based on Pyridine and PyrimidineEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 30 2008Giuseppe Tresoldi Abstract The asymmetric thioethers L [L = 2-pyridylmethyl 2,-pyrimidyl sulfide (pps) and 2-(4-methylpyrimidyl) 2,-pyridylmethyl sulfide (mps)] reacted with cis -[RuCl2(N,N -L,)2] [L, = di-2-pyridyl sulfide (dps); 2,2,-bis(4-methylpyridyl) sulfide (4mdps); 2,2,-bis(5-methylpyridyl) sulfide (5mdps)] to give the five-membered-ring chelate complexes [Ru(N,N -L,)2(Npyridine,S -L)]++ as the major products (92,95,%). Because the sulfur and ruthenium atoms are stereogenic centres, with (R) and (S) and , and , configurations, respectively, four isomers, including the enantiomers were obtained. At low temperature and in the methylene region of the 1H NMR spectra, two AB systems due to the enantiomer couples ,S ,R (a) and ,R ,S (b) were observed with abundances of 77,89 and 6,18,%, respectively. Furthermore, NMR spectroscopic investigations showed that the hybrid polydentate ligands L change their coordination mode. Thus, although a and b largely predominate, a mixture of species containing L and the Ru(N,N -L,)2 unit in the ratio 1:1 are present. The four-membered-ring chelate complexes [Ru(N,N -L,)2(Npyrimidine,S -L)]++ (c), as minor species (abundance 1,8,%), are always observed, whereas the dinuclear species [{Ru(N,N -L,)2}2(,-L)2]+4 (d, e) are observed when L, = dps or 5mdps. In these cases, four AB systems are assigned to dinuclear species d and e containing two bridging L that act as Npyridine,S- or Npyridine,Npyrimidine -donor ligands. The 1H NMR spectra are temperature dependent in that at low temperature the complexes undergo inversion of the chiral centre of the coordinated sulfur atom (a [rlhar2] b) and the dimer (d, e) and monomer (c) are in equilibrium; at higher temperatures the complexes undergo a structural dynamic rearrangement, which involves exchange between the coordinated and uncoordinated N atoms (b [rlhar2] c). One-dimensional band-shape analysis of the exchanging methylene and methyl proton signals showed that the energy barriers for inversion of the sulfur centre are in the 50,53 kJ,mol,1 range, whereas those for the higher-temperatures process are in the 62,68 kJ,mol,1 range. The possible mechanisms of the processes are discussed. NMR spectroscopic findings suggest that inversion at the sulfur centre occurs without any bond rupture, whereas the exchange, at higher temperatures (b [rlhar2] c), is a dissociative process involving the breaking of a Ru,Npyridine bond.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Fast 1H,13C correlation data for use in automatic structure confirmation of small organic compoundsMAGNETIC RESONANCE IN CHEMISTRY, Issue 2 2005Adrian J. Dunn Abstract A method of speeding up the acquisition of 1H,13C correlation data has been developed. It is applicable in situations where the experiment time is determined by the need to sample the second dimension adequately rather than by signal-to-noise ratio requirements. Two spectra with different, reduced, 13C sweep widths are measured, time being saved by reducing the number of increments in line with the reduction in the sweep width. Rules are presented for the selection of the two reduced sweep widths so that the correct 13C chemical shifts can be easily and unambiguously calculated. The benefits and limitations of this approach, in the context of the structure confirmation of small (MW , 450) organic compounds, is discussed. The use of a third spectrum to resolve problems that may be encountered when proton signals overlap is demonstrated. Copyright © 2004 John Wiley & Sons, Ltd. [source] Isolation and spectral study of 4-methyl-6,8-dihydroxy-7H -benz[de]anthracen-7-oneMAGNETIC RESONANCE IN CHEMISTRY, Issue 4 2003H. M. Wang Abstract 4-Methyl-6,8-dihydroxy-7H -benz[de]anthracen-7-one was isolated from the sap of Aloe by column chromatography. Its 1H and 13C NMR spectra were completely assigned by utilizing two-dimensional 1H-detected heteronuclear one-bond (HMQC) and multiple-bond (HMBC) chemical shift correlation experiments together with 1H,1H COSY and DEPT techniques. These techniques were also valuable in assigning the protons and carbons of those benzanthrone compounds which were previously incompletely reported because of the overlap of proton signals. The molecular structure was elucidated by 2D NMR analysis. The spectral properties (MS, IR and UV) are also presented. Copyright © 2003 John Wiley & Sons, Ltd. [source] Aromatic,Carbohydrate Interactions: An NMR and Computational Study of Model SystemsCHEMISTRY - A EUROPEAN JOURNAL, Issue 25 2008Sophie Vandenbussche Ir. Abstract The interactions of simple carbohydrates with aromatic moieties have been investigated experimentally by NMR spectroscopy. The analysis of the changes in the chemical shifts of the sugar proton signals induced upon addition of aromatic entities has been interpreted in terms of interaction geometries. Phenol and aromatic amino acids (phenylalanine, tyrosine, tryptophan) have been used. The observed sugar,aromatic interactions depend on the chemical nature of the sugar, and thus on the stereochemistries of the different carbon atoms, and also on the solvent. A preliminary study of the solvation state of a model monosaccharide (methyl ,-galactopyranoside) in aqueous solution, both alone and in the presence of benzene and phenol, has also been carried out by monitoring of intermolecular homonuclear solvent,sugar and aromatic,sugar NOEs. These experimental results have been compared with those obtained by density functional theory methods and molecular mechanics calculations. [source] Radical Ions from 3,3,,,,3,,,,-Tris(butylsulfanyl)-2,2,:5,,2,:5,,2,,,,5,,,,2,,,,:5,,,,,2,,,,-sexithiophene: An Experimental and Theoretical Study of the p - and n -Doped OligomerCHEMPHYSCHEM, Issue 11 2003Angelo Alberti Dr. Abstract The 3,3,,,,3,,,,-tris(butylsulfanyl)-2,2,:5,,2,:5,,2,,,,5,,,,2,,,,:5,,,,,2,,,,-sexithiophene 1 was investigated through spectroscopic (NMR, EPR, UV/Vis-NIR), electrochemical, spectroelectrochemical and theoretical (DFT) studies. The charged species obtained upon its oxidation and reduction were characterised, showing that 1 can exist in at least five different oxidation states, that is, a neutral species, a radical cation, a dication, a radical anion, and a dianion. The long term stability of the radical cation 1+. was evidenced by the 1H NMR study in the presence of small quantities of trifluoroacetic acid (TFA). This approach allowed a comparison of the relative broadening of proton signals of 1, induced by the electron exchange process with traces of radical cation 1+., and the hfc (hyperfine coupling) constants obtained from the EPR study and DFT calculations. In the radical cation, all of the heterocyclic sulphur atoms are not significantly involved in the delocalisation of the unpaired electron, whereas the opposite holds for the radical anion. Time-dependent DFT calculations reproduced well the wavelengths of the optical transitions observed in the spectroelectrochemical experiments for all the five oxidation states and support the formation of the dianion 12,. [source] | ||||||||||