13C NMR measurements of acid-base equilibrium constants in alkaline aqueous solutions of D-glucose anomers

The concentration dissociation constants pK _c of the α and β D-glucose anomers were measured at pH 12–14 by the ¹³C NMR method. The pK _c values for L ? H_?1L + H equilibria at 25°C and an ionic strength of 1.0 mol/l (NaCl) were pK _c ^α = 12.31 ± 0.03 and pK _c ^β = 12.03 ± 0.01. Dissociation was found to shift all the spectrum lines downfield. The most probable hydroxyl group responsible for the dissociation of β-D-glucose was determined.     

A 13C NMR study of mesomorphic solutions of poly(p-phenylene terephthalamide)

Solutions of poly(p-phenylene terephthalamide) in fuming sulfuric acid were characterized by ¹³C NMR spectroscopy and solution viscosity measurements over the 2–28% w/w concentration range. The spectra showed the presence of two distinct amide carbonyl resonances at low concentration, tentatively assigned to cis and trans conformations. As the concentration increased, additional carbonyl lines were observed along with significant broadening. Peak area measurements showed that only the polymer molecules in the isotropic environments contributed to the ¹³C NMR spectra and a considerable amount of the polymer remained in the isotropic phase at concentrations previously considered to consist of polymer in highly anisotropic regions. Spin-lattice relaxation times were measured at six concentrations using the inversion recovery method. The aromatic carbons relaxed at a much faster rate (ca. 0.10 s) than the carbonyls (ca. 0.45 s), but the relaxation rates for both carbons were essentially constant over the concentration range, indicating that the observed isotropic phase is not affected by changes in the macroscopic solution behavior so as to alter spin-lattice relaxation mechanisms.     

A13C spin-lattice relaxation study of micelle formation in aqueous solutions of sodium n-hexanoate

Summary The concentration dependence of the¹³C-relaxation times of the alkyl carbons in aqueous solutions of sodium hexanoate have been measured. Below CMC the relaxation is dominated by the overall motion of the hexanoate ion. In the micelles the overall motion is slower and the internal rotations around the C-C bonds contribute to the relaxation.

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Zusammenfassung Die Konzentrationsabhängigkeit der¹³C-Relaxationszeiten von Natriumhexanoat in wässriger Lösung wurde bestimmt. Unter CMC ist die Relaxation von der Bewegung des ganzen Moleküls bestimmt. In den Mizellen ist die Bewegung des ganzen Moleküls langsamer, und die inneren Rotationen in der Alkylkette tragen zu der Relaxation bei.

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With 2 figures and 1 table     

A study of the binding of manganese (II) with the sodium salts of nucleosides in aqueous solutions by the13C NMR method

The binding of manganese(II) with nucleosides — adenosine (A), guanosine (G), cytidine (C), and uridine (U) — in an alkaline D₂O solution has been investigated by the¹³C NMR method. It has been established that the structure of the paramagnetic Mn(II)—nucleoside complexes differs substantially in neutral and in alkaline media. The broadening of the resonance lines (C-2′, C-3′ > C-1′, C-4′ > C-5′) shows the localization of the Mn(II) in the C-2′ and C-3′ hydroxyls of the ribose in an alkaline medium. It has been shown for the case of U that the degree of complex-formation depends on the pH of the solution. It is assumed that the nucleoside forms intramolecular complexes (I) with Mn(OH)₂.     

The mechanism of the hantzsch pyridine synthesis: A study by 15N and 13C NMR spectroscopy

The mechanism of the reactions of ammonia and benzaldehyde with three different beta-dicarbonyl compounds to form the corresponding dihyropyridines has been followed by NMR. In each case the pathway is shown to involve the reaction of benzaldehyde with one molecule of beta-dicarbonyl to give chalcone, and of the ammonia with a second molecule of beta-dicarbonyl to give an enamine. The rate determining stage is shown to be the Michael addition of the chalcone to the enamine.     

Conformational study of phosphothreonine in aqueous solution. H and 13C NMR results

The 270 MHz ¹H and 22.6 MHz ¹³C NMR spectra of DL -phosphothreonine in D₂O have been measured and analysed as a function of pD. The trans-trans conformation of the fragment H-α? C-α? C-β? O? P predominates at all pD values. The C-β—O gauche contribution is notably larger for pD values in the range 7≤pD<10 than for acidic or more basic solutions which is in accordance with earlier results for phosphoserine (PSer).     

A 13C CP-MAS NMR study of irradiated polyethylene

Solid-state ¹³C-NMR was used to analyze several polyethylene samples, irradiated at room temperature with gamma rays in vacuum or with electrons in air up to a maximum dose of 200 Mrad. The main observed events were the formation of methyl ends and interior double bonds (vinylenes), as well as the disappearance of the initial vinyl ends. No signals associated with “H” or “Y” crosslinks were found in any of the samples. The partitioning of methyl ends and interior vinylenes between the crystalline and noncrystalline regions was determined only for the irradiated ultrahigh-molecular-weight polyethylene (UHMWPE) samples. Although concentration of methyl ends in the crystalline regions was approximately half that in the noncrystalline regions, the vinylenes had very similar concentrations in the two phases. Although some evidence for both cis and trans vinylenes appears in the spectrum of the noncrystalline regions, only one configuration (trans) seems to exist in the crystalline regions. No appreciable effect on the partitioning was detected after annealing the electron-irradiated UHMWPE samples for 16 h at 130°C.     

13C NMR study of D-pantothenic acid complexes with heavy lanthanide ions in aqueous solution

The ¹³C NMR study of the interaction between the trivalent lanthanide ions (from Dy to Lu) and D-pantothenic acid in aqueous solution was presented. The unambiguous resonance assignments were made on the basis of pH dependence and the analysis of molecular geometry. ¹³C paramagnetic shifts were separated into the contact and dipolar components by Reilley's method. The complex stability constant is 12.0 L / mol for the 1:1 ytterbium complex. An analysis of the shift data shows that heavy lanthanide ions form isostructural complexes with the substrate and the hyperfine coupling constant is independent of the ions used in the study. D-pantothenic acid is coordinated to the metal via the two oxygens of the carboxyl group with 2.25Å of Ln—O distances. The electron spin density distribution and the structural details of the complex were elucidated from the shift data. It is stated that contact contributions, while small for nuclei of several bonds away from the metal, should not be dismissed a priori.     

A 13C NMR study of tautomerism in phenoxymethylisoxazol-5-ones

A ¹³C NMR study of new isoxazol-5-ones has been carried out in different solvents. Mathematical analysis of the tautomeric ring proton exchange in pyridine solvent indicates that the relative contributions of the NH, CH and OH tautomers are respectively 10 ± 5, 15 ± 3, 10 ± 8%, while the anionic form represents the remaining 65 ± 8%.     

A 13C NMR study of some metal acetylacetone complexes

¹³C NMR spectra of nine metal acetylacetonates in (H₃C)₂SO-d₆ and ten metal acetylacetonates in CDCl₃ are reported. The complexes are of the type M(acac)_n where n is 1,2,3 or 4. The downfield shift of the methyl, methine and carbonyl carbon resonances from tetramethylsilane (TMS) are interpreted in terms of the complexed metal and a solvent effect. ¹³C¹⁹⁵Pt spin coupling is also observed for the Pt(acac)₂ complex.     

Metallic nature and surface diffusion of CO adsorbed on Ru nanoparticles in aqueous media: A 13C NMR study

We report the first observation of the 13C nuclear magnetic resonance spectroscopy (NMR) of 13CO, adsorbed from 13CO saturated 0.5 M sulfuric acid solutions, onto the surfaces of commercial Ru-black nanoparticles. The 13C NMR spectra consist of a symmetrically broadened peak having a large isotropic shift as compared to CO adsorbed onto supported Ru catalysts. The variation of the spin-lattice relaxation rate follows Korringa behavior, indicating the metallic nature of adsorbed CO, in addition to varying across the spectrum in a Korringa-like manner. Motional narrowing of the NMR spectrum at higher temperatures, together with an additional contribution to the spin-lattice relaxation rate, indicate that adsorbed CO undergoes rapid diffusion on the particle surfaces. A two-band model analysis of the NMR results indicates that the CO adsorption bond is weaker on Ru as compared to either Pt or Pd. This is also supported by a reduction in the activation energy for CO diffusion on Ru vs either Pt or Pd nanoparticles.     

N-Oxides of polychloropyridines.13C NMR study

The effect ofN-oxidation of a series of polychloropyridines on¹³C NMR parameters has been studied. It has been established that inN-oxides of polychloropyridines an electric field through-space effect of theN-oxide group predominates in the shielding of the -carbon atom compared to the other carbon atoms. A linear correlation between¹³C NMR chemical shifts and total charge densities calculated by the MNDO method for the carbon atoms ofN-oxides of polychloropyridines has been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2425–2428, December, 1995.The authors are grateful to V. V. Kolchanov for help in the synthesis of compounds under study.     

A 1H and 13C NMR study of carminic acid

The ¹H and ¹³C NMR spectra of carminic acid were completely assigned, thus confirming its structure and the conformation of the glucose residue.