Study of Hydrogen Bonding in Systems of Hydroxylic Compounds in Carbon Tetrachloride through the Use of NMR

Saunders, Martin; Hyne, J. B.

doi:10.1063/1.1744715

Cited by 183 publications

(59 citation statements)

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“…5 k c a l m o l~' ) a n d A S~ z -95Jmol-' K -' ( -2 3 cal mol-' K-') (bimolecular model). Translated into the thermodynamics of the isodesmic model one finds ASA z -89 J mol-' K-' (-21.5cal mol-' K-I), substituting Ki,, = 2 Kbi [34]. We conclude that the thermodynamics of association of the dimer cannot be predicted safely from the known association of the monomer.…”

Section: Associationmentioning

confidence: 87%

“…a chemical shift. In the latter case the mathematical expressions for the bimolecular and the isodesmic models differ by a factor of two in the association constant [34].…”

Section: Differential Concentration1 Temperature Profile ( Dctp) Methodsmentioning

confidence: 99%

“…An accurate thermodynamic approach of stacking in dimers, applied to CD data, was first given by Powell et al [32]. A quantitative formalism which describes the isodesmic association model was published by Kempter and Mecke [33]; later, Saunders and Hyne [34] stated that bimolecular association and the isodesmic model in general can be distinguished from each other only when a given experimental method allows independent assignment of properties of the separate participating states. This condition is not fulfilled when a single time-averaged value is monitored, e.g.…”

Section: Differential Concentration1 Temperature Profile ( Dctp) Methodsmentioning

confidence: 99%

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Thermodynamics of Stacking and of Self‐Association of the Dinucleoside Monophosphate m⁶₂A‐U from Proton NMR Chemical Shifts:

Hartel

Lankhorst

Altona

1982

European Journal of Biochemistry

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Chemical shifts of base and sugar protons of the modified ribodinucleoside monophosphate Nh-dimethyladenylyl(3'-5')uridine (m4A-U) were measured at 100, 360 and 400 MHz in aqueous solution. Seven different samples were used with concentrations ranging from 0.28 mM to 32.7 mM. The temperature was varied from -5 "C to 105 "C. An internal temperature calibration was used. The effects of intermolecular self-association and of intramolecular stacking on the chemical shifts were quantitatively separated by means of a new approach: differential concentration/temperature profiles (DCTP). Several computational models were tested and the analysis allowed deeper insight into the behaviour of mgA-U at the molecular level. The simple two-state approach for both self-association and stacking already afforded a significant improvement over models in which the association is entirely neglected. A computer least-squares analysis of the chemical shift behaviour of each individual proton yielded thermodynamic parameters for self-association and stacking. However, the two-state model did not suffice to reproduce accurately all of the observations. A satisfactory fit required two additional assumptions : (a) the aromatic protons experience different association shifts in stacked and in unstacked molecules ; (b) a temperature-dependent conformational equilibrium exists between sets of unstacked microstates. The stacked state is taken to represent a single conformational species. The implementation of this extended model in the leastsquares optimization allowed the reproduction of over one thousand chemical shift observations within experimental error. Thermodynamic equilibrium parameters deduced for intramolecular stacking are : AH; = -28.8 kJ rnol-', A S ; = -93 J mol-' K-'. These numbers agree well with those obtained earlier by us from circular dichroism spectra. The equilibrium enthalpy and entropy values deduced for the association process are : AH; = -35 kJ mol-' and AS2 = -95 J mol-' K-'.The question of whether short oligonucleotides are really suitable as models for longer regions in nucleic acids has been raised [l], but cannot be answered until many careful systematic studies are carried out with experimental probes at atomic resolution. The most potent approach is offered by nuclear magnetic resonance (NMR) measurements, supplemented with thermodynamic information from independent techniques such as circular dichroism (CD) and ultraviolet hypochromism, and guided by information on geometrical details by X-ray methods.The shortest nuclei acid fragments available for studies of these properties, the dinucleoside monophosphates or dimers (L-M) represent at the same time 3'-terminal and 5'-terminal fragments of RNA (or DNA); therefore; these fragments constitute a limiting case. Therefore, attempts at This paper is part 24 in the series Nucleic Acid Cotzstituents from this laboratory; part 23 appeared elsewhere [4].Ahhrcviurions. CD, circular dichroism; NMR, nuclear magnetic resonance; Me4NC1, tetramethylammonium chloride; m$A...

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Section: Associationmentioning

confidence: 87%

“…a chemical shift. In the latter case the mathematical expressions for the bimolecular and the isodesmic models differ by a factor of two in the association constant [34].…”

Section: Differential Concentration1 Temperature Profile ( Dctp) Methodsmentioning

confidence: 99%

Section: Differential Concentration1 Temperature Profile ( Dctp) Methodsmentioning

confidence: 99%

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Thermodynamics of Stacking and of Self‐Association of the Dinucleoside Monophosphate m⁶₂A‐U from Proton NMR Chemical Shifts:

Hartel

Lankhorst

Altona

1982

European Journal of Biochemistry

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“…Complicating the treatment of these systems as involving simple 1 :I complex formation, is the well-known self-association of alcohols (6,7), even at very low concentrations. Figure 1 shows the concentration dependence of the OH-proton shielding ofphenylmethanol from 0.002 to 0.2 M; the three points of the most dilute solutions were obtained from spectra accumulated on the C-1024 computer, using as many as 300 scans per spectrum.…”

Section: Analysis Of Nmr Slzielding Us Concentrationmentioning

confidence: 99%

Anion–molecule complexes in solution. III. Nuclear magnetic resonance studies of halide ion–alcohol association

Green¹,

Martin²,

Cassie³

et al. 1969

Can. J. Chem.

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Certain alkyl-, aryl-, and arene-substituted alcohols form linear, hydrogen bonded complexes with bromide and other halide ions in tetrachloromethane. The hydroxyl proton shifts ca. 4 p.p.m. downfield in the complex, regardless of the degree or type of substitution. The interaction is enhanced by inductive electron withdrawal by substituents on the C-0-H moiety. A comparison of the present results with infrared spectroscopy shows that the absorption at ca. 3300 cm-I is entirely due to 1 :I alcohol-anion complexes. The a coefficient in Buckingham's equation for electrostatic interaction of a molecule with an ion, 8csE = aE, -bE2, is found to be 5.5 for alcohol 0-H bonds.Canadian Journal of Chemistry, 47, 1639 (1969) Nuclear magnetic resonance (n.m.r.) and infrared (i.r.) spectroscopy have been used extensively in the detection and characterization of the hydrogen bonding of alcohols and other hydroxyl bearing compounds to a variety of bases (1-3). Characteristically, hydrogen bond formation results in a decrease in shielding of the hydrogen nucleus. The extent of this deshielding has been regarded as a measure of hydrogen bond strength, in much the same way as have hydrogen bond shifts and intensities in the i.r. (1,3,4). Both the i.r. frequency shift and the n.m.r. shielding change have been correlated with the enthalpy of hydrogen bond formation (5).Pursuant to our studies of specific complexes to anions in weakly interacting solvents, we have observed deshielding of hydroxyl protons in methanol, pjimary, secondary, and tertiary alcohols, and a phenol, of magnitude up to 4.5 p.p.m., on addition of a tetrabutylammonium salt to a dilute solution of the alcohol in tetrachloromethane. We interpret the monotonic salt concentration dependence of the hydroxyl proton shifts as arising from specific hydrogen bonded interaction of the alcohols with the anions. alcohol to alcohol hydrogen bonding, and the proton shielding observed as a function of the halide ion concentration. Experimental MaterialsMetllartol This was Shawinigan reagent grade, and contained less than 0.2% water when received. This material was dried by storing over 4A molecular sieves (m.s.) for several days; tlie initial vigorous effervescence ceased after about 24 h. The tightly stoppered vial was kept in tlie dry-box. Samples containing nietlianol and tetrabutylammonium bromide decomposed slowly, the n.ni.r. spectrum showing a change after 1 day, but no observable change within 1 11 of sample preparation. All speclra were obtained within 1 11 of preparation of the sample. E t l~a~~o lThis was 98 %, as received, and showed no benzene in the n.m.r. and, at most, traces of water. This niaterial was distilled, and a center fraction totalling ca. 75% collected on n1.s. The fraction collected was refluxed over tlie m.s. for 1 11. The material was then redistilled with a center fraction totalling ca. 50% being collected on m.s. (boiling range 0.4 "C). The tightly-stoppered flask was immediately transferred to the dry-box, where the ethanol was placed in a ...

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“…The association that occurs in phenols has been well established. In nonpolar solvents, phenol (27) and many phenol derivatives (28) generally exist as a monomer-trimer equilibrium. In dimethyl sulfoxide (DMSO) solution, Ouellette has shown from 'H nmr studies that these aggregates are eliminated as the phenolic hydrogen preferentially interacts with solvent molecules (29).…”

Section: Introductionmentioning

confidence: 99%

Determination of substituent effects by factor analysis and multiple linear regression for the carbon-13 nuclear magnetic resonance chemical shifts in 4-substituted phenols and 2-nitrophenols

Hutton¹,

Kunz²,

Bozek³

et al. 1987

Can. J. Chem.

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. Can. J. Chem. 65, 1316Chem. 65, (1987. Carbon-13 nuclear magnetic resonance chemical shifts are reported for a series of 4-substituted phenols and 2-nitrophenols in dimethyl sulfoxide solution. For chemical shift correlations, it was found by factor analysis and iterative multiple linear regression that the para chemical shifts require two substituent factors whereas the ipso, ortho, and meta chemical shifts require three factors. Regression analyses were performed using the field and resonance parameters (uF, uRO) and the appropriate ipso, ortho, and meta parameters (I, 0, M) determined by Reynolds. Good correlations were obtained except for the three meta carbon analyses, where the correlation coefficients range from 0.877 to 0.963. On a dttermint les dCplacements chimiques, en rmn I3c, d'une strie de phtnols substituts en position 4 ainsi que de nitro-2 phtnols en solution dans le dimCthylsulfoxyde. Pour les corrtlations des dtplacements chimiques, on a trouvt par des analyses factorielles et par des rtgressions IinCaires multiples itCratives que les diplacements chimiques des positions para requikrent deux facteurs de substituants alors que les diplacements chimiques des positions ipso, ortho et me'trr requikrent trois facteurs. On a effectuk des analyses de regression en utilisant les paramktres de champ et de risonance (uF, uR0) ainsi que les paramktres ipso, ortho et me'ta appropriis (I, 0 et M) diterminCs par Reynolds. On a obtenu de bonnes corrilations, excepti pour trois analyses de carbones tnita pour lesquelles on a obtenu des coefficients de corrClation allant de 0,877 i 0,963.[Traduit par la revue]

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Study of Hydrogen Bonding in Systems of Hydroxylic Compounds in Carbon Tetrachloride through the Use of NMR

Cited by 183 publications

References 9 publications

Thermodynamics of Stacking and of Self‐Association of the Dinucleoside Monophosphate m⁶₂A‐U from Proton NMR Chemical Shifts:

Thermodynamics of Stacking and of Self‐Association of the Dinucleoside Monophosphate m⁶₂A‐U from Proton NMR Chemical Shifts:

Anion–molecule complexes in solution. III. Nuclear magnetic resonance studies of halide ion–alcohol association

Determination of substituent effects by factor analysis and multiple linear regression for the carbon-13 nuclear magnetic resonance chemical shifts in 4-substituted phenols and 2-nitrophenols

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Study of Hydrogen Bonding in Systems of Hydroxylic Compounds in Carbon Tetrachloride through the Use of NMR

Cited by 183 publications

References 9 publications

Thermodynamics of Stacking and of Self‐Association of the Dinucleoside Monophosphate m62A‐U from Proton NMR Chemical Shifts:

Thermodynamics of Stacking and of Self‐Association of the Dinucleoside Monophosphate m62A‐U from Proton NMR Chemical Shifts:

Anion–molecule complexes in solution. III. Nuclear magnetic resonance studies of halide ion–alcohol association

Determination of substituent effects by factor analysis and multiple linear regression for the carbon-13 nuclear magnetic resonance chemical shifts in 4-substituted phenols and 2-nitrophenols

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Thermodynamics of Stacking and of Self‐Association of the Dinucleoside Monophosphate m⁶₂A‐U from Proton NMR Chemical Shifts:

Thermodynamics of Stacking and of Self‐Association of the Dinucleoside Monophosphate m⁶₂A‐U from Proton NMR Chemical Shifts: