Dynamic Nuclear Polarization of Oxygen-17

Michaelis, Vladimir K.; Markhasin, Evgeny; Daviso, Eugenio; Herzfeld, Judith; Griffin, Robert G.

doi:10.1021/jz300742w

Cited by 51 publications

(98 citation statements)

References 63 publications

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“…The 17 O quadrupolar coupling constants of all water sites within the various crystalline solids were determined experimentally to be between 6.9 and 7.1 MHz (Table 2). These results agree reasonably well with previous studies of various forms of ice 23,78 and other hydrates 79 , which have reported quadrupolar coupling constants between 6.6 and 7.0 MHz.…”

Section: Discussionsupporting

confidence: 93%

“…The 17 O quadrupolar coupling constant of the water is 7.0 MHz, larger than the C Q observed for ice. 23,78 The asymmetry parameter is 0.95, which is characteristic of a water molecule lying on a two-fold axis of rotation ( i.e. , C 2v local symmetry).…”

Section: Resultsmentioning

confidence: 99%

“…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. 23–26 While it is also possible to remove the second-order quadrupolar interaction to obtain simplified isotropic spectra, doing so requires advanced techniques and special instrumentation such as double rotation (DOR) or dynamic-angle spinning (DAS) probes. 27,28 More accessible approaches involve two-dimensional spectroscopic techniques such as multiple-quantum magic-angle spinning (MQMAS) 29 and satellite-transition magic-angle spinning (STMAS) 30 .…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Discussionsupporting

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2015

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“…These properties make the use of DNP particularly attractive. 29,40 Indeed, in spite of all of these shortcomings, DNP-enhanced NMR spectroscopy has enabled the measurement of 17 O NMR spectra at natural isotopic abundance. 41,42 For example, DNP-enhanced, natural abundance, 17 O{ 1 H} MAS spectra of inorganic hydroxides were recently obtained in our laboratory, enabling the swift measurements of O−H distances and heteronuclear correlation (HETCOR) spectra.…”

Section: Dnp Ssnmr Of Challenging Nucleimentioning

confidence: 99%

Dynamic Nuclear Polarization Solid-State NMR in Heterogeneous Catalysis Research

et al. 2015

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A revolution in solid-state nuclear magnetic resonance (SSNMR) spectroscopy is taking place, attributable to the rapid development of high-field dynamic nuclear polarization (DNP), a technique yielding sensitivity improvements of 2-3 orders of magnitude. This higher sensitivity in SSNMR has already impacted materials research, and the implications of new methods on catalytic sciences are expected to be profound. Disciplines Chemistry CommentsReprinted (adapted) with permission from ACS Catalysis 5 (2015): 7055,

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“…9 Another significant recent development is the application of dynamic nuclear polarization (DNP) to drastically boost the sensitivity of solid-state 17 O NMR experiments. [10][11][12] In the present work, we use solid-state 17 O NMR to study two platinum anticancer drugs: carboplatin and oxaliplatin (Scheme 1). Although several thousand platinum-based anticancer drug molecules have been developed in research laboratories over the past 30 years, only about two dozen have ever gone into clinical trials.…”

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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Dynamic Nuclear Polarization of Oxygen-17

Cited by 51 publications

References 63 publications

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

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

Dynamic Nuclear Polarization Solid-State NMR in Heterogeneous Catalysis Research

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

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Dynamic Nuclear Polarization of Oxygen-17

Cited by 51 publications

References 63 publications

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

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

Dynamic Nuclear Polarization Solid-State NMR in Heterogeneous Catalysis Research

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

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

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

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