An introduction to hydrogen bond scalar couplings

Dingley, Andrew J.; Cordier, Florence; Grzesiek, Stephan

doi:10.1002/1099-0534(2001)13:2<103::aid-cmr1001>3.0.co;2-m

Cited by 101 publications

(93 citation statements)

References 131 publications

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“…The impact of the mutations on the Fe(II) oxidation state was investigated by using 1 H- 15 N HSQC to measure the His16 Hδ1-Nδ1 cross peak for the ferrous species. Formation of hydrogen bonds has been observed in some systems to cause proton chemical shift differences of 15–20 ppm,57–58 and as a function of hydrogen bond strength in diamagnetic proteins, amide proton chemical shift changes of up to 4 ppm are expected 58–59. His ring nitrogen chemical shift differences of ~10 ppm have been observed when the His ring NH proton forms a hydrogen bonding interaction in model complexes 60.…”

Section: Results and Analysismentioning

confidence: 99%

Variation and Analysis of Second-Sphere Interactions and Axial Histidinate Character inc-type Cytochromes

Bowman

Bren

2010

Inorg. Chem.

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The electron-donating properties of the axial His ligand to heme iron in cytochromes c (cyts c) are found to be correlated with midpoint reduction potential (E m ) in variants of Hydrogenobacter thermophilus cytochrome c 552 (Ht cyt c 552 ) in which mutations have been made in and near the Cys-X-X-Cys-His (CXXCH) heme-binding motif. To probe the strength of the His-Fe(III) interaction, we have measured 13 C nuclear magnetic resonance (NMR) chemical shifts for 13 CN − bound to heme iron trans to the axial His in Ht Fe(III) cyt c 552 variants. We observe a linear relationship between these 13 C chemical shifts and E m , indicating that the His-Fe(III) bond strength correlates with E m . To probe a conserved hydrogen bonding interaction between the axial His Hδ1 and the backbone carbonyl of a Pro residue, we measured the pK a of the axial His Hδ1 proton (pK a(2) ), which we propose to relate to the His-Fe(III) interaction, reduction potential and local electrostatic effects. The observed linear relationship between the axial His 13 Cβ chemical shift and E m is proposed to reflect histidinate (anionic) character of the ligand. A linear relationship also is seen between the average heme methyl 1 H chemical shift and E m which may reflect variation in axial His electron-donating properties or in the ruffling distortion of the heme plane. In summary, chemical shifts of the axial His and exogenous CN − bound trans to His are shown to be sensitive probes of the His-Fe(III) interaction in variants of Ht cyt c 552 and display trends that correlate with E m .

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Section: Results and Analysismentioning

confidence: 99%

Variation and Analysis of Second-Sphere Interactions and Axial Histidinate Character inc-type Cytochromes

Bowman

Bren

2010

Inorg. Chem.

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“…23, and for the nuclear magnetism of liquid system in the Earth's field range, interested readers may refer to Ref. J is the scalar coupling constant and m P is the z-component of 31 P nuclear spin.…”

Section: ͑2͒mentioning

confidence: 99%

A study of J-coupling spectroscopy using the Earth’s field nuclear magnetic resonance inside a laboratory

Liao

Chen

Hong

et al. 2010

Review of Scientific Instruments

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In this paper, an instrumentation of the Earth's field nuclear magnetic resonance (EFNMR) inside a laboratory is presented. A lock-in analysis (LIA) technique was proposed to enhance the signal-to-noise ratio (SNR). A SNR of 137.8 was achieved in a single measurement for 9 ml tap water, and the LIA technique significantly enhanced the SNR to 188 after a 10-average in a noisy laboratory environment. The proton-phosphorus coupling in trimethyl phosphate ((CH(3)O)(3)PO) with J-coupling J[H,F]=(10.99±0.013) Hz has been demonstrated. The LIA technique improves the SNR, and a 2.6-fold improvement in SNR over that of the frequency-adjusted averaging is achieved. To reduce the noise in EFNMR, it was suggested that the LIA technique and the first order gradient shim be used to achieve a subhertz linewidth.

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“…1−9 Therefore, the understanding of factors that determine H-bond properties and, as a consequence, those of molecular systems in which they intervene, has been and is a field of intense research. 10 In particular, NMR spectroscopy is one of the main techniques for experimentally characterizing H-bond interactions, 11,12 and computational studies have been devoted to explain the observations. 13−20 …”

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confidence: 99%

“…The shift of the 1 H signal to higher frequencies has been associated with a shortening of the H bond; that is, the shorter the H bond, the larger the proton deshielding. 4,12,25 Several studies have attempted to find a correlation between H-bond lengths and 1 H shieldings. Although the shape of this relationship is unclear and cannot be generalized (for some hydrogen-bond distance intervals, a linear relationship was found, but when the interval is extended, that kind of dependence is not kept), all studies suggest that when the donor–acceptor distance decreases, 1 H shielding becomes smaller.…”

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confidence: 99%

NMR ¹H-Shielding Constants of Hydrogen-Bond Donor Reflect Manifestation of the Pauli Principle

Zarycz

Guerra

2018

J. Phys. Chem. Lett.

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NMR spectroscopy is one of the most useful methods for detection and characterization of hydrogen bond (H-bond) interactions in biological systems. For H bonds X–H···Y, where X and Y are O or N, it is generally believed that a decrease in 1H-shielding constants relates to a shortening of H-bond donor–acceptor distance. Here we investigated computationally the trend of 1H-shielding constants for hydrogen-bonded protons in a series of guanine C8-substituted GC pair model compounds as a function of the molecular structure. Furthermore, the electron density distribution around the hydrogen atom was analyzed with the Voronoi deformation density (VDD) method. Our findings demonstrate that 1H-shielding values of the hydrogen bond are determined by the depletion of charge around the hydrogen atom, which stems from the fact that electrons obey the Pauli exclusion principle.

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An introduction to hydrogen bond scalar couplings

Cited by 101 publications

References 131 publications

Variation and Analysis of Second-Sphere Interactions and Axial Histidinate Character inc-type Cytochromes

Variation and Analysis of Second-Sphere Interactions and Axial Histidinate Character inc-type Cytochromes

A study of J-coupling spectroscopy using the Earth’s field nuclear magnetic resonance inside a laboratory

NMR ¹H-Shielding Constants of Hydrogen-Bond Donor Reflect Manifestation of the Pauli Principle

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An introduction to hydrogen bond scalar couplings

Cited by 101 publications

References 131 publications

Variation and Analysis of Second-Sphere Interactions and Axial Histidinate Character inc-type Cytochromes

Variation and Analysis of Second-Sphere Interactions and Axial Histidinate Character inc-type Cytochromes

A study of J-coupling spectroscopy using the Earth’s field nuclear magnetic resonance inside a laboratory

NMR 1H-Shielding Constants of Hydrogen-Bond Donor Reflect Manifestation of the Pauli Principle

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NMR ¹H-Shielding Constants of Hydrogen-Bond Donor Reflect Manifestation of the Pauli Principle