Solid‐State <sup>17</sup>O NMR Spectroscopy of Large Protein–Ligand Complexes

Zhu, Jianfeng; Ye, Eric; Terskikh, Victor V.; Wu, Gang

doi:10.1002/anie.201002041

Cited by 48 publications

(51 citation statements)

References 30 publications

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“…Over the past decade, 17 O QC and CS tensors have been experimentally determined for many oxygen-containing organic functional groups. At the present time the solid-state 17 O NMR method finds its use not only for studying protein-ligand complexes, 5 but also for obtaining dynamic information about molecular motions in organic solids. 6 The most recent advances in solid-state 17 O NMR include studies of pharmaceuticals 7,8 and paramagnetic coordination compounds.…”

Section: Introductionmentioning

confidence: 99%

A solid-state¹⁷O NMR study of platinum-carboxylate complexes: carboplatin and oxaliplatin

et al. 2015

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We report synthesis and solid-state NMR characterization of two 17 O-labeled platinum anticancer drugs: cis-diammine(1,1-cyclobutane-[ 17 O 4 ]dicarboxylato)platinum(II) (carboplatin) and ([ 17 O 4 ]oxalato)[(1R, 2R)-(−)-1,2-cyclohexanediamine)]platinum(II) (oxaliplatin). Both 17 O chemical shift (CS) and quadrupolar coupling (QC) tensors were measured for the carboxylate groups in these two compounds. With the aid of plane wave DFT computations, the 17 O CS and QC tensor orientations were determined in the molecular frame of reference. Significant changes in the 17 O CS and QC tensors were observed for the carboxylate oxygen atom upon its coordination to Pt(II). In particular, the 17 O isotropic chemical shifts for the oxygen atoms directly bonded to Pt(II) are found to be smaller (more shielded) by 200 ppm than those for the non-Pt-coordinated oxygen atoms within the same carboxylate group. Examination of the 17 O CS tensor components reveals that such a large 17 O coordination shift is primarily due to the shielding increase along the direction that is within the O=C-O-Pt plane and perpendicular to the O-Pt bond. This result is interpreted as due to the donation from the oxygen nonbonding orbital (electron lone pair) to the Pt(II) empty d yz orbital, which results in large energy gaps between (Pt-O) and unoccupied molecular orbitals, thus reducing the paramagnetic shielding contribution along the direction perpendicular to the O-Pt bond. We found that the 17 O QC tensor of the carboxylate oxygen is also sensitive to Pt(II) coordination, and that 17 O CS and QC tensors provide complementary information about the O-Pt bonding.

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Section: Introductionmentioning

confidence: 99%

A solid-state¹⁷O NMR study of platinum-carboxylate complexes: carboplatin and oxaliplatin

et al. 2015

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“…Specifically, 17 O MAS NMR spectra typically display residual second-order broadening not averaged to zero by MAS. 10,11 Modest sensitivity gains for studying 17 O NMR have been achieved in the past by using isotopic enrichment 12–15 , performing the experiments in magnetic fields greater than 16.4 T 16–20 , and applying population transfer techniques. 21,22 Recently dynamic nuclear polarization (DNP) of 17 O has provided effective gains in sensitivity in a series of biological and inorganic chemical systems.…”

Section: Introductionmentioning

confidence: 99%

Structural Insights into Bound Water in Crystalline Amino Acids: Experimental and Theoretical ¹⁷O NMR

et al. 2015

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Direct 17O NMR structural studies of bound water in crystalline hydrates and biological macromolecules are challenging due to the low natural abundance and quadrupolar nature of 17O nuclei. However, the advent of high field NMR positions 17O NMR to become an important tool to address structural problems in biological solids. We show herein that the NMR properties of 17O in a series of amino acids and dipeptides can be determined by a combination of non-spinning and magic-angle spinning experiments using a range of magnetic field strengths from 9.4 to 21.1 T. Furthermore, we propose a 17O chemical shift fingerprint region for bound water molecules in biological solids that is well outside the previously determined ranges for carbonyl, carboxylic, and hydroxyl oxygens, thereby offering the ability to resolve multiple 17O environments using rapid one-dimensional NMR techniques. Finally, we compare our experimental data against quantum chemical calculations using GIPAW and hybrid-DFT, finding intriguing discrepancies between the electric field gradients calculated from structures determined by x-ray and neutron diffraction.

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“…Furthermore it has the advantage that the chemical shift anisotropy can be readily obtained. 17 With the advances in quadrupole NMR methodologies, a significant increase in 17 O NMR studies of bio/organic materials have been reported recently, 6,7 including a high-field 17 O solidstate NMR study of two large (64 and 80 kDa) protein-ligand complexes, 14 illustrating the potential of 17 O NMR spectroscopy toward large biological systems. In particular, recent demonstrations on 17 O DOR spectroscopy have reported ultra-high spectral resolution with linewidths of <1 ppm).…”

Section: Introductionmentioning

confidence: 99%

Ultra-high resolution 17O solid-state NMR spectroscopy of biomolecules: A comprehensive spectral analysis of monosodium L-glutamate·monohydrate

Wong

Howes

Yates

et al. 2011

Phys. Chem. Chem. Phys.

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Solid‐State ¹⁷O NMR Spectroscopy of Large Protein–Ligand Complexes

Cited by 48 publications

References 30 publications

A solid-state¹⁷O NMR study of platinum-carboxylate complexes: carboplatin and oxaliplatin

A solid-state¹⁷O NMR study of platinum-carboxylate complexes: carboplatin and oxaliplatin

Structural Insights into Bound Water in Crystalline Amino Acids: Experimental and Theoretical ¹⁷O NMR

Ultra-high resolution 17O solid-state NMR spectroscopy of biomolecules: A comprehensive spectral analysis of monosodium L-glutamate·monohydrate

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Solid‐State 17O NMR Spectroscopy of Large Protein–Ligand Complexes

Cited by 48 publications

References 30 publications

A solid-state17O NMR study of platinum-carboxylate complexes: carboplatin and oxaliplatin

A solid-state17O NMR study of platinum-carboxylate complexes: carboplatin and oxaliplatin

Structural Insights into Bound Water in Crystalline Amino Acids: Experimental and Theoretical 17O NMR

Ultra-high resolution 17O solid-state NMR spectroscopy of biomolecules: A comprehensive spectral analysis of monosodium L-glutamate·monohydrate

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Product

Resources

About

Solid‐State ¹⁷O NMR Spectroscopy of Large Protein–Ligand Complexes

A solid-state¹⁷O NMR study of platinum-carboxylate complexes: carboplatin and oxaliplatin

A solid-state¹⁷O NMR study of platinum-carboxylate complexes: carboplatin and oxaliplatin

Structural Insights into Bound Water in Crystalline Amino Acids: Experimental and Theoretical ¹⁷O NMR