Deuterium Isotope Effects on Carbonyl Carbon Chemical Shifts of BPTI. Hydrogen Bonding and Structure Determination in Proteins.

Hansen, Poul Erik; Tüchsen, Erik; Brænden, Jon Erik; Eliason, Robert; Kondow, A. J.; Boettner, W. A.; Mulichak, A. M.; Alminger, Tomas; Erickson, Magnus; Grundevik, Inger; Hagin, Inger; Hoffman, Kurt-Jürgen; Johansson, Svante; Larsson, Sam; Löfberg, Ingalil; Ohlson, Kristina; Persson, Björn; Skånberg, Inger; Tekenbergs-Hjelte, Lija

doi:10.3891/acta.chem.scand.43-0710

Cited by 12 publications

(6 citation statements)

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“…The plot of Figure 10 shows that in general a shorter the O•••O distance is related to a higher hydrogen bond energy, but also that it is necessary to divide the compounds into two groups, sterically hindered and non-sterically hindered. The two lower outliers among the sterically hindered ones are 6-t-butyl-(20) and 6-isopropylsalicylaldehyde (19), whereas the one above is the phenanthrene derivative (10). The plot of Figure 10 shows that in general a shorter the O•••O distance is related to a higher hydrogen bond energy, but also that it is necessary to divide the compounds into two groups, sterically hindered and non-sterically hindered.…”

Section: Correlationsmentioning

confidence: 99%

Section: Correlationsmentioning

confidence: 99%

“…This led to the equation ln( 2 ∆) = 2.783 + 0.34 • E, in which E is the hydrogen bond energy in kcal/mol and the two-bond isotope effect is in ppb. This equation was later used in proteins [19,20].…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular Hydrogen Bonds in Normal and Sterically Compressed o-Hydroxy Aromatic Aldehydes. Isotope Effects on Chemical Shifts and Hydrogen Bond Strength

et al. 2019

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A number of o-hydroxy aromatic aldehydes have been synthesized to illustrate the effect of steric compression and O···O distances on the intramolecular hydrogen bond and the hydrogen bond energies. Hydrogen bond energies have been calculated using the ‘hb and out’ method using either the MP2 method or the B3LYP functional with the basis set 6-311++G(d,p). However, several compounds cannot be treated this way. Hydrogen bond energies are also determined using electron densities at bond critical points and these results are in good agreement with the results of the ‘hb and out’ model. Two-bond deuterium isotope effects on 13C chemical shifts are suggested as an experimental way to obtain information on hydrogen bond energies as they easily can be measured. Isotope effects on aldehyde proton chemical shifts have also been measured. The former show very good correlation with the hydrogen bond energies and the latter are related to short O···O distances. Short O···O distances can be obtained as the result of short C=C bond lengths, conjugative effects, and steric compression of the aldehyde group. Short O···O distances are in general related to high hydrogen bond energies in these intramolecularly hydrogen-bonded systems of resonance assisted hydrogen bond (RAHB) type.

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Section: Correlationsmentioning

confidence: 99%

Section: Correlationsmentioning

confidence: 99%

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Intramolecular Hydrogen Bonds in Normal and Sterically Compressed o-Hydroxy Aromatic Aldehydes. Isotope Effects on Chemical Shifts and Hydrogen Bond Strength

et al. 2019

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“…The latter may have the advantage in that isotope effects like OH chemical shifts may depend on ring current effects (see below), and energies for compounds for which the hb–out method cannot be used can be estimated. The use of isotope effects on 13 C chemical shifts was originally suggested by Reuben and later tested for amides …”

Section: Discussionmentioning

confidence: 77%

Strong intramolecular hydrogen bonds and steric effects involving C═S groups: An NMR and computational study

Elias

Saeed

Kamounah

et al. 2019

Magnetic Reson in Chemistry

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A number of 5-acyl rhodanines and thiorhodanines with bulky acyl groups (pivaloyl and adamantoyl), not previously available, have been synthesized.The compounds are shown to exist in the enol form. Structures have been calculated using both the MP2 approach and the B3LYP-GD3BJ functional and the 6-311++G(d,p) basis set. Hydrogen bond energies are estimated by subtracting energies of a structure with the OH group turned 180°from those of the intramolecularly hydrogen-bonded one. Properties such as OH chemical shifts, two-bond isotope effects on 13 C chemical shifts, electron densities at the bond critical point from atoms in molecules analysis, and the hydrogen bond energies show that the sterically hindered compounds have stronger hydrogen bonds than methyl or isopropyl derivatives. The combination of oxygen and sulfur derivatives enables a detailed analysis of hydrogen bond energies.

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“…[10] Traditionally, the large backbone 2 D 13 C'(ND) isotope effects are used for resonance assignments of peptides [25][26] and small proteins. [27][28] These two-bond isotope effects are also considered to be correlated with intraresidual H bonds in antiparallel b sheets, as demonstrated in the small protein BPTI, [29] although the reported magnitude falls into a rather narrow range, 60-90 ppb, in this case. The backbone amide proton of a residue is in the trans configuration with respect to the carbonyl oxygen of the preceding residue, which is characterized by the positive two-bond scalar coupling constant, 2 J HC' , between the amide proton and carbonyl carbon.…”

Section: Differential Two-bond H/d Isotope Effect On Side-chain a C Hmentioning

confidence: 99%

Hydrogen‐Bond Detection, Configuration Assignment and Rotamer Correction of Side‐Chain Amides in Large Proteins by NMR Spectroscopy through Protium/Deuterium Isotope Effects

Liu

Wang

et al. 2008

ChemBioChem

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In this study, the configuration and hydrogen-bonding network of side-chain amides in a 35 kDa protein are determined via measuring differential and across-hydrogen-bond H/D isotope effects by the IS-TROSY technique, which leads to a reliable recognition and correction of erroneous rotamers frequently found in protein structures. First, the differential two-bond isotope effects on carbonyl 13C′ shifts, defined as Δ2Δ13C′ (ND) = 2Δ13C′ (NDE) − 2Δ13C′ (NDZ), provide a reliable means for the configuration assignment for side-chain amides, as environmental effects (hydrogen bonds and charges etc.) are greatly attenuated over the two bonds separating the carbon and hydrogen atoms and the isotope effects fall into a narrow range of positive values. Second and more importantly, the significant variations in the differential one-bond isotope effects on 15N chemical shifts, defined as Δ1Δ15N(D) = 1Δ15N(DE) − 1Δ15N(DZ), can be correlated with hydrogen-bonding interactions, particularly those involving charged acceptors. The differential one-bond isotope effects are additive with major contributions from intrinsic differential conjugative interactions between the E and Z configurations, H-bonding interactions, and charge effects. Furthermore, the pattern of across-H-bond H/D isotope effects can be mapped onto more complicated hydrogen-bonding networks involving bifurcated hydrogen-bonds. Third, the correlations between Δ1Δ15N(D) and hydrogen-bonding interactions afford an effective means for the correction of erroneous rotamer assignments of side-chain amides. The rotamer correction via differential isotope effects is not only robust but simple and can be applied to large proteins.

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Deuterium Isotope Effects on Carbonyl Carbon Chemical Shifts of BPTI. Hydrogen Bonding and Structure Determination in Proteins.

Cited by 12 publications

References 0 publications

Intramolecular Hydrogen Bonds in Normal and Sterically Compressed o-Hydroxy Aromatic Aldehydes. Isotope Effects on Chemical Shifts and Hydrogen Bond Strength

Intramolecular Hydrogen Bonds in Normal and Sterically Compressed o-Hydroxy Aromatic Aldehydes. Isotope Effects on Chemical Shifts and Hydrogen Bond Strength

Strong intramolecular hydrogen bonds and steric effects involving C═S groups: An NMR and computational study

Hydrogen‐Bond Detection, Configuration Assignment and Rotamer Correction of Side‐Chain Amides in Large Proteins by NMR Spectroscopy through Protium/Deuterium Isotope Effects

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