Applications of spin-spin couplings

Kamieńska‐Trela, Krystyna; Wójcik, Jacek

doi:10.1039/9781849734851-00148

Cited by 5 publications

(10 citation statements)

References 334 publications

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“…The calculation and utilization of NMR spin system matrices may have applications beyond those focused on small molecule libraries, such as synthetic chemistry and educational projects. 31,32 …”

Section: Spin System Matrices As Fingerprints Of Metabolitesmentioning

confidence: 99%

Spin System Modeling of Nuclear Magnetic Resonance Spectra for Applications in Metabolomics and Small Molecule Screening

et al. 2017

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The exceptionally rich information content of nuclear magnetic resonance (NMR) spectra is routinely used to identify and characterize molecules and molecular interactions in a wide range of applications, including clinical biomarker discovery, drug discovery, environmental chemistry, and metabolomics. The set of peak positions and intensities from a reference NMR spectrum generally serves as the identifying signature for a compound. Reference spectra normally are collected under specific conditions of pH, temperature, and magnetic field strength, because changes in conditions can distort the identifying signatures of compounds. A spin system matrix that parametrizes chemical shifts and coupling constants among spins provides a much richer feature set for a compound than a spectral signature based on peak positions and intensities. Spin system matrices expand the applicability of NMR spectral libraries beyond the specific conditions under which data were collected. In addition to being able to simulate spectra at any field strength, spin parameters can be adjusted to systematically explore alterations in chemical shift patterns due to variations in other experimental conditions, such as compound concentration, pH, or temperature. We present methodology and software for efficient interactive optimization of spin parameters against experimental 1D-1H NMR spectra of small molecules. We have used the software to generate spin system matrices for a set of key mammalian metabolites and are also using the software to parametrize spectra of small molecules used in NMR-based ligand screening. The software, along with optimized spin system matrix data for a growing number of compounds, is available from http://gissmo.nmrfam.wisc.edu/.

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Section: Spin System Matrices As Fingerprints Of Metabolitesmentioning

confidence: 99%

Spin System Modeling of Nuclear Magnetic Resonance Spectra for Applications in Metabolomics and Small Molecule Screening

et al. 2017

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“…[1] Other J-couplings, including 1 J CH , 2 J CC , 2 J CH , 3 J CH , also share this sensitivity to structure. [2,3] The less frequently measured 1 J CC coupling also provides a valuable metric for evaluating structure. [2][3][4][5][6][7][8][9][10][11][12][13][14] In this study, 1 J CC coupling is exclusively emphasized because it directly provides 13 C─ 13 C connectivity in organic structures.…”

Section: Introductionmentioning

confidence: 99%

“…Studies of molecular structure that involve NMR have long relied upon the measurement of scalar couplings. Such couplings, also referred to as indirect couplings or J-couplings, are perhaps most widely utilized in structural studies that measure the three-bond proton-proton coupling (i.e., 3 J HH ). In this case, the magnitude of 3 J HH allows H─C─C─H dihedral angles to be predicted from the Karplus relationship.…”

Section: Introductionmentioning

confidence: 99%

“…[2,3] The less frequently measured 1 J CC coupling also provides a valuable metric for evaluating structure. [2][3][4][5][6][7][8][9][10][11][12][13][14] In this study, 1 J CC coupling is exclusively emphasized because it directly provides 13 C─ 13 C connectivity in organic structures. This is particularly relevant in hydrogenpoor compounds where structural characterization by more conventional NMR methods is challenging.…”

Section: Introductionmentioning

confidence: 99%

“…[2,11,18,24,28,[52][53][54][55][56][57][58] Recent theoretical work often relies upon the secondorder polarization propagator approximation technique [8,11,12,20,22,24,30,31,39,56,59] or density functional theory (DFT) computations [13,14,17,19,23,[26][27][28]33,[36][37][38]41,43,45,54,55,57,60] that employ the EPR-III [61,62] basis set. [3,26,28,30,39,53,54] The EPR-III basis, although originally developed to predict hyperfine coupling constants in electron ...…”

Section: Introductionmentioning

confidence: 99%

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Evaluating the accuracy of theoretical one‐bond ¹³C─¹³C scalar couplings and their ability to predict structure in a natural product

Powell

Valenti

Bobnar

et al. 2017

Magnetic Reson in Chemistry

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This study explores the feasibility of using a combination of experimental and theoretical 1-bond C─ C scalar couplings ( J ) to establish structure in organic compounds, including unknowns. Historically, J and J studies have emphasized 2 and 3-bond couplings, yet J couplings exhibit significantly larger variations. Moreover, recent improvements in experimental measurement and data processing methods have made J data more available. Herein, an approach is evaluated in which a collection of theoretical structures is created from a partial nuclear magnetic resonance structural characterization. Computed J values are compared to experimental data to identify candidates giving the best agreement. This process requires knowledge of the error in theoretical methods, thus the B3LYP, B3PW91, and PBE0 functionals are evaluated by comparing to 27 experimental values from INADEQUATE. Respective errors of ±1.2, ±3.8, and ±2.3 Hz are observed. An initial test of this methodology involves the natural product 5-methylmellein. In this case, only a single candidate matches experimental data with high statistical confidence. This analysis establishes the intramolecular hydrogen-bonding arrangement, ring heteroatom identity, and conformation at one position. This approach is then extended to hydroheptelidic acid, a natural product not fully characterized in prior studies. The experimental/theoretical approach proposed herein identifies a single best-fit structure from among 26 candidates and establishes, for the first time, 1 configuration and 3 conformations to complete the characterization. These results suggest that accurate and complete structural characterizations of many moderately sized organic structures (<800 Da) may be possible using only J data.

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ChemInform Abstract: Applications of Spin‐Spin Couplings

Kamieńska‐Trela

Wójcik

2013

ChemInform

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Applications of spin-spin couplings

Cited by 5 publications

References 334 publications

Spin System Modeling of Nuclear Magnetic Resonance Spectra for Applications in Metabolomics and Small Molecule Screening

Spin System Modeling of Nuclear Magnetic Resonance Spectra for Applications in Metabolomics and Small Molecule Screening

Evaluating the accuracy of theoretical one‐bond ¹³C─¹³C scalar couplings and their ability to predict structure in a natural product

ChemInform Abstract: Applications of Spin‐Spin Couplings

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Applications of spin-spin couplings

Cited by 5 publications

References 334 publications

Spin System Modeling of Nuclear Magnetic Resonance Spectra for Applications in Metabolomics and Small Molecule Screening

Spin System Modeling of Nuclear Magnetic Resonance Spectra for Applications in Metabolomics and Small Molecule Screening

Evaluating the accuracy of theoretical one‐bond 13C─13C scalar couplings and their ability to predict structure in a natural product

ChemInform Abstract: Applications of Spin‐Spin Couplings

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Evaluating the accuracy of theoretical one‐bond ¹³C─¹³C scalar couplings and their ability to predict structure in a natural product