Search results for "MR"
showing 10 items of 3001 documents
1H,13C and17O NMR study of chlorovanillins and some related compounds
1992
1H, 13C and 17O NMR chemical shifts and nJ(H,H), 1J(C,H) and 3J(C-6, H-formyl) spin—spin coupling constants of chlorinated vanillins (3-methoxy-4-hydroxybenzaldehydes) were determined. The variation in the long-range 4J(H,H) value between the formyl proton and an ortho-proton suggests that the ortho-substituent strongly forces the formyl group out of the aromatic plane. This can also be observed by considering the 3J(C-6,H-formyl) values and the 13C and 17O NMR chemical shifts. The 17O NMR chemical shifts show a linear correlation with the torsion angle of the formyl group calculated by molecular mechanics. The 13C and 17O NMR chemical shifts of the methoxyl group also possess strong predic…
Dynamics of cross polarization in solid state nuclear magnetic resonance experiments of amorphous and heterogeneous natural organic substances
2008
Nuclear magnetic resonance (NMR) experiments on carbon-13 in the solid state were done with cross polarization (CP) and magic angle spinning (MAS) in order to overcome the low NMR sensitivity of (13)C and the chemical shift anisotropy, respectively. In the present research, CPMAS (13)C-NMR spectra were collected by modulating the contact time needed for cross polarization (variable contact times experiments, VCT) on two different humic acids (a soil-HA and a coal-HA). VCT data were fitted by a model containing either a monotonic or a non-monotonic cross polarization term. The non-monotonic model, which fitted the experimental results better than the monotonic one, provided two cross-polariz…
Synthesis of a New pH-Dependent Ligand: Conformational and Complexation Studies
2003
A new macrocyclic ligand, 3, which exhibits pH-induced conformational changes, has been prepared. This ligand consists of a crown ether derived from a trans-anti-trans 1,2,4,5-tetrasubstituted cyclohexane. Due to the stereochemistry of the substituents on the carbocyclic ring, two different low-energy conformations of the crown ether are possible. Ligand 3 has been studied in solution by 1H NMR spectroscopy at different values of pH and temperature, showing that the conformation of the crown ether, and thus its complexing ability, is strongly pH-dependent. The solid-state structure of the ligand has been determined by X-ray diffraction.
Insights into the determinants of ��-sheet stability: 1H and 13C���NMR conformational investigation of three-stranded antiparallel ��-sheet-forming p…
2008
In a previous study we designed a 20-residue peptide able to adopt a significant population of a three-stranded antiparallel beta-sheet in aqueous solution (de Alba et al. [1999]Protein Sci.8, 854-865). In order to better understand the factors contributing to beta-sheet folding and stability we designed and prepared nine variants of the parent peptide by substituting residues at selected positions in its strands. The ability of these peptides to form the target motif was assessed on the basis of NMR parameters, in particular NOE data and 13Calpha conformational shifts. The populations of the target beta-sheet motif were lower in the variants than in the parent peptide. Comparative analysis…
Two-Component Hydrogels Formed by Cyclodextrins and Dicationic Imidazolium Salts
2013
In the framework of our recent interest in studying the gelling behaviour of imidazolium salts, we took into account the possibility of obtaining two-component hydrogels by combining cyclodextrins and dicationic imidazolium salts. In particular, we used diimidazolium salts differing in the alkyl chain length and in the size, shape, and coordination ability of the anion, namely the 3,3′-di-n-decyl- and 3,3′-di-n-dodecyl-1,1′-(1,4-phenylenedimethylene)diimidazolium dibromide, and 3,3′-di-n-dodecyl-1,1′-(1,4-phenylenedimethylene)diimidazolium ditetrafluoroborate and dihexafluorophosphate. As far as cyclodextrins are concerned, to gain information on the effects of different sized cyclic oligos…
Preparation and Structures of Isoindolone- or Pyrimidone-Condensed Heterocycles Containing a Hydroxy Group on a Cyclohexane or Norbornane Moiety
2009
With DL-valinol, 3-amino-1-propanol and o-aminothiophenol, aroyl(bi/tri)cyclic lactones 1 and 2 were cy- clized to isoindole- 4-6, 8, 9, pyrimidinone- 10 or thiazepine- 7 condensed heterocycles. The ketal lactone 3 furnished the benzthiazoloisoindole 9 and mixtures of epimeric hydroxyphthalazinoquinazolinones 11 and 12. The structures were es- tablished by means of 1 H and 13 C NMR spectroscopy and in some cases by X-ray crystallography.
Protein Unfolding:1H-NMR Studies of Paramagnetic Ferricytochrome c-550 from Horse Heart
2005
Electronic transfer protein cytochrome c-550 from horse heart is studied in the unfolded state by means of paramagnetic 1H NMR. The protein contains 104 aminoacid residues and a heme group with low spin FeIII ion in the oxidized form of protein. The global secondary structure is of the α-helix type as occurs in the case of very other cytochromes c investigated such as cyt c-550 from Thiobacillus versutus or cyt c-551 from Pseudomonas aeruginosa. We have studied the coordination characteristic and electronic properties of heme iron horse heart ferricytochrome c-550 at increasing denaturing conditions (up to 3.1 M GuHCl and 288-323 K). The 1H T1 values of the signals were measured and some re…
1H NMR studies of paramagnetic ferricytochrome c-551 from Pseudomonas aeruginosa at high pH: The role of histidine 16 in the spin transition
2005
Abstract Cytochrome c-551 from the mesophile Pseudomonas aeruginosa is an electronic transfer protein that contains 82 amino-acid residues and a c-type heme as the prosthetic group with low spin Fe(II) in the reduced form and low spin Fe(III) in the oxidized form of cytochrome c-551. We have studied the electronic properties of ferricytochrome c-551 from P. aeruginosa at high pH (9–11.4) by means of paramagnetic 1H NMR spectra and the T1 and T2 values of isotropically shifted proton resonances. We have also analyzed the temperature dependence of the hyperfine-shifts. Resonance assignment of some signals was based on 2D saturation transfer experiments, EXSY. These results indicate the existe…
Historical and current progress in understanding the origin and structure of humic substances
2010
Research into humic substances (HS) has focused selectively on the search for aromatic structures. All aromatic compounds are regarded as eligible HS constituents, whereas aliphatic, polysaccharide structural constituents are considered non-HS. Wet chemical methods for analysing HS produce 2–5% aromatic compounds from the original starting material. Only those compounds in the hydrophobic extraction phases are studied carefully. Compounds in the hydrophilic extraction phases, containing mainly aliphatics, are discarded. Solid-state NMR spectra from HS show 30–40% of carbon–carbon unsaturation, which is selectively interpreted as ‘aromatic’. No recognition is given to the fact that NMR spect…
Chemical characterization of peat fulvic acid fractions
1993
Abstract Milled peat fulvic acid (FA) preparation was fractionated by XAD-8 and conventional extraction methods. The fractions were further analyzed by IR and NMR and subjected to cupric oxide (CuO) oxidation. Carbohydrates of polydisperse FA were mostly not retained in the XAD-8 fractionation. The intensity of the signals due to double bonded carbons was much greater in the 13 C and proton NMR spectrum of the XAD-8 retained fraction than in the spectra of the XAD-8 non-retained or XAD-8 non-treated fractions. In CuO oxidation the main products of all FA fractions were 4-hydroxybenzaldehyde and 4-hydroxyacetophenone, both indicators of 4-hydroxyphenylpropane building blocks. Their concentra…