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/ange.201002041

Cited by 9 publications

(17 citation statements)

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“…Results show that the overall calculated 17 O NMR chemical shift tensor principal elements (δ 11 , δ 22 , and δ 33 ) in an experimental range of 1455 ppm have an excellent theory-versus-experiment correlation coefficient of R 2 = 0.9926, and the mean absolute deviation (MAD) of the predicted δ iso is 13 ppm, with 5.7% MPD. These results shall help future computational studies of 17 O NMR chemical shifts, which may also help structure refinement of some substrate-bound proteins 16 as done previously by using quantum chemical studies of other NMR chemical shifts. 26,27…”

Section: ■ Introductionmentioning

confidence: 70%

“…However, recent experimental techniques have dramatically advanced this field and a number of types of oxygen-containing systems have been experimentally investigated, 1-4 including various kinds of biologically relevant systems, such as those with CO, 5, 6 NO, 7, 8 and PO 9 groups, amino acids, 10-13 nucleic acid bases, 14 pharmaceutical compounds, 15 and large protein-ligand complexes. 16 More recently, the solid-state 17 O NMR studies have even been extended to some paramagnetic metal complexes with organic ligands. 17 …”

Section: Introductionmentioning

confidence: 99%

“…However, recent experimental techniques have dramatically advanced this field, and a number of types of oxygen-containing systems have been experimentally investigated, 1−4 including various kinds of biologically relevant systems, such as those with CO, 5,6 NO, 7,8 and PO 9 groups, amino acids, 10−13 nucleic acid bases, 14 pharmaceutical compounds, 15 and large protein−ligand complexes. 16 More recently, the solid-state 17 O NMR studies have even been extended to some paramagnetic metal complexes with organic ligands. 17 To help understand experimental solid-state 17 O NMR results, a number of theoretical investigations, such as those on the calculated 17 O NMR shifts of amides, 5 nucleic acid bases, 14,18−20 amino acids, 11−13 carboxylic compounds, 21−23 and peptides, 24 as well as a few metal-containing compounds, have been reported.…”

Section: ■ Introductionmentioning

confidence: 99%

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Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State ¹⁷O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

et al. 2015

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Oxygen is an important element in most biologically significant molecules and experimental solid-state 17O NMR studies have provided numerous useful structural probes to study these systems. However, computational predictions of solid-state 17O NMR chemical shift tensor properties are still challenging in many cases and in particular each of the prior computational work is basically limited to one type of oxygen-containing systems. This work provides the first systematic study of the effects of geometry refinement, method and basis sets for metal and non-metal elements in both geometry optimization and NMR property calculations of some biologically relevant oxygen-containing compounds with a good variety of XO bonding groups, X= H, C, N, P, and metal. The experimental range studied is of 1455 ppm, a major part of the reported 17O NMR chemical shifts in organic and organometallic compounds. A number of computational factors towards relatively general and accurate predictions of 17O NMR chemical shifts were studied to provide helpful and detailed suggestions for future work. For the studied various kinds of oxygen-containing compounds, the best computational approach results in a theory-versus-experiment correlation coefficient R2 of 0.9880 and mean absolute deviation of 13 ppm (1.9% of the experimental range) for isotropic NMR shifts and R2 of 0.9926 for all shift tensor properties. These results shall facilitate future computational studies of 17O NMR chemical shifts in many biologically relevant systems, and the high accuracy may also help refinement and determination of active-site structures of some oxygen-containing substrate bound proteins.

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Section: ■ Introductionmentioning

confidence: 70%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State ¹⁷O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

et al. 2015

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“…However, when the quadrupole coupling is large (> 5 MHz) the excitation efficiency of these approaches drops dramatically; in the case of MQMAS spectra, to about ~5% 11,12 . Thus, although there are a number of exciting MQMAS studies of 17 O labeled biological samples, the experimental results are clearly limited by signal-to-noise 3,13-20 . In order to enable 17 O NMR as an important spectroscopic technique, a dramatic increase in sensitivity is required.…”

mentioning

confidence: 99%

“…In more detail, 17 O MAS spectra display residual second-order broadening characteristic of a fourth-rank tensor that is not averaged to zero by MAS. , To observe isotropic chemical shifts in the presence of and convolved with the second-order interaction requires either special instrumentation, as in case of double rotation (DOR) and dynamic angle spinning (DAS), , or special spectroscopic techniques, as in the case of multiple-quantum magic angle spinning (MQMAS) and/or satellite transition magic angle spinning (STMAS) . However, when the quadrupole coupling is large (>5 MHz), the excitation efficiency of these approaches drops dramatically, in the case of MQMAS spectra, to about ∼5%. , Thus, although there are a number of exciting MQMAS studies of 17 O-labeled biological samples, the experimental results are clearly limited by signal-to-noise. ,− In order to enable 17 O NMR as an important spectroscopic technique, a dramatic increase in sensitivity is required.…”

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confidence: 99%

Dynamic Nuclear Polarization of Oxygen-17

Michaelis

Markhasin

Daviso

et al. 2012

J. Phys. Chem. Lett.

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Solid‐State ¹⁷O NMR Spectroscopy of Paramagnetic Coordination Compounds

et al. 2015

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High-quality solid-state 17 O( I=5/2) NMR spectra can be successfully obtained for paramagnetic coordination compounds in which oxygen atoms are directly bonded to the paramagnetic metal centers.For complexes containing V III (S = 1), Cu II (S = 1/2), and Mn III (S = 2) metal centers,t he 17 O isotropic paramagnetic shifts were found to span ar ange of more than 10 000 ppm. In several cases,h igh-resolution 17 O NMR spectra were recorded under very fast magic-angle spinning (MAS) conditions at 21.1 T. Quantum-chemical computations using density functional theory (DFT) qualitatively reproduced the experimental 17 Ohyperfine shift tensors.NMR signals from paramagnetic substances are generally more difficult to detect than those from diamagnetic compounds.T his is because the hyperfine interactions between magnetic dipoles of unpaired electrons and atomic nuclei are substantially stronger than the typical nuclear spin interactions such as magnetic shielding, nuclear quadrupolar,a nd dipolar couplings.A saresult, the NMR signals from paramagnetic compounds are significantly shifted and broadened compared with diamagnetic compounds.Despite experimental difficulties,s olid-state NMR studies of paramagnetic compounds can be traced back to the early NMR studies on single crystals of CuSO 4 ·5 H 2 O, [1] CuCl 2 ·H 2 O, [2] and MnF 2 . [3] In more recent years,t here have been considerable interest in solution [4] and solid-state [5][6][7][8][9][10][11][12][13][14][15][16] NMR studies of organic and biological systems containing paramagnetic metal ions.T o date,m ost NMR studies of paramagnetic compounds have relied on detection of 1 Ha nd 13 Cn uclei, because hydrogen and carbon atoms are generally remote from the paramagnetic metal centers,t hus experiencing relatively weak hyperfine interactions.Incontrast, as oxygen atoms are often directly bonded to the paramagnetic metal centers, 17 ONMR for paramagnetic coordination compounds is expected to be more challenging than the corresponding 1 Ha nd 13 CNMR studies.F urthermore,t he only NMR-active oxygen isotope, 17 O, has very low natural abundance (0.037 %) and its nuclear spin is quadrupolar (I = 5/2). In light of the recent advances in solid-state 17 ON MR studies of diamagnetic molecules including biological macromolecules, [17] we decided to explore the possibility of using solid-state 17 ON MR to study paramagnetic coordination compounds.Weshould note that solidstate 17 ONMR has been used previously to study ionic high T c superconductors [18] and simple paramagnetic inorganic complexes. [19] Thefocus of our study is on solid-state 17 ONMR of paramagnetic coordination complexes containing organic ligands (that is,containing H, C, N, and Oatoms).We first examined two vanadium(III) (S = 1) complexes: [V([ 17 O 2 ]acac) 3 ]a nd K 3 [V([ 17 O 4 ]oxalate) 3 ]·3 H 2 O. Synthetic details for the preparation of 17 O-labeled paramagnetic coordination compounds are given in the Supporting Information. As seen in Figure 1, the static solid-state 17 ON MR spectrum for [V([ 17...

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

Cited by 9 publications

References 32 publications

Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State ¹⁷O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State ¹⁷O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

Dynamic Nuclear Polarization of Oxygen-17

Solid‐State ¹⁷O NMR Spectroscopy of Paramagnetic Coordination Compounds

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

Cited by 9 publications

References 32 publications

Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State 17O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State 17O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

Dynamic Nuclear Polarization of Oxygen-17

Solid‐State 17O NMR Spectroscopy of Paramagnetic Coordination Compounds

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Product

Resources

About

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

Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State ¹⁷O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State ¹⁷O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

Solid‐State ¹⁷O NMR Spectroscopy of Paramagnetic Coordination Compounds