Up to 100% Improvement in Dynamic Nuclear Polarization Solid‐State NMR Sensitivity Enhancement of Polymers by Removing Oxygen

Lê, Dao; Ziarelli, Fabio; Phan, Trang N. T.; Mollica, Giulia; Thureau, Pierre; Aussenac, Fabien; Ouari, Olivier; Gigmès, Didier; Tordo, Paul; Viel, Stéphane

doi:10.1002/marc.201500133

Cited by 21 publications

(21 citation statements)

References 36 publications

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“…DNP-NMR has been applied to the characterization of organic polymers. The sensitivity provided by DNP has notably allowed the observation of the 13 C NMR signals of chain-ends of living polystyrene (PS) and poly(ethylene oxide) (see Figure 21) [88,168] as well as of residues with low abundance in wild spider silks [244]. DNP high sensitivity has also been exploited to detect 77 Se signal of diluted selenate ions in water remediation polymer material, despite the low natural abundance of 77 Se (7.63%) and the modest amount of selenate ions (5.5 wt%) in the investigated material [245].…”

Section: Polymersmentioning

confidence: 99%

Recent developments in MAS DNP-NMR of materials

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et al. 2019

Solid State Nuclear Magnetic Resonance

145

137

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Solid-state NMR spectroscopy is a powerful technique for the characterization of the atomic-level structure and dynamics of materials. Nevertheless, the use of this technique is often limited by its lack of sensitivity, which can prevent the observation of surfaces, defects or insensitive isotopes. Dynamic Nuclear Polarization (DNP) has been shown to improve by one to three orders of magnitude the sensitivity of NMR experiments on materials under Magic-Angle Spinning (MAS), at static magnetic field B0 ≥ 5 T, conditions allowing for the acquisition of high-resolution spectra. The field of DNP-NMR spectroscopy of materials has undergone a rapid development in the last ten years, spurred notably by the availability of commercial DNP-NMR systems. We provide here an in-depth overview of MAS DNP-NMR studies of materials at high B0 field. After a historical perspective of DNP of materials, we describe the DNP transfers under MAS, the transport of polarization by spin diffusion and the various contributions to the overall sensitivity of DNP-NMR experiments. We discuss the design of tailored polarizing agents and the sample preparation in the case of materials. We present the DNP-NMR hardware and the influence of key experimental parameters, such as microwave power, magnetic field, temperature and MAS frequency. We give an overview of the isotopes, which have been detected by this technique, and the NMR methods, which have been combined with DNP. Finally, we show how MAS DNP-NMR has been applied to gain new insights into the structure of organic, hybrid and inorganic materials with applications in fields, such as health, energy, catalysis, optoelectronics etc.

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Section: Polymersmentioning

confidence: 99%

Recent developments in MAS DNP-NMR of materials

Rankin

Trébosc

Pourpoint

et al. 2019

Solid State Nuclear Magnetic Resonance

145

137

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“…DNP corresponds to the efficient transfer of polarization at low temperature (~ 100 K) from unpaired electrons (present in radicals or biradicals such as TOTAPOL 19 or AMUPol 20 ) to NMR active nuclei. The gain in notoriety of DNP is associated to very large gain in sensitivity (several orders in magnitude) and impressive applications for low abundant nuclei 21,22,23,24,25,26,27,28,29,30,31,32,33,34,35 .…”

Section: Introductionmentioning

confidence: 99%

Hydroxyapatites: Key Structural Questions and Answers from Dynamic Nuclear Polarization

et al. 2017

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We demonstrate that NMR/DNP (Dynamic Nuclear Polarization) allows an unprecedented description of carbonate substituted hydroxyapatite (CHAp). Key structural questions related to order/disorder and clustering of carbonates are tackled using distance sensitive DNP experiments using C-C recoupling. Such experiments are easily implemented due to unprecedented DNP gain (orders of magnitude). DNP is efficiently mediated by quasi one-dimensional spin diffusion through the hydroxyl columns present in the CHAp structure (thought of as "highways" for spin diffusion). For spherical nanoparticles and ϕ < 100 nm, it is numerically shown that spin diffusion allows their study as a whole. Most importantly, we demonstrate also that the DNP study at 100 K leads to data which are comparable to data obtained at room temperature (in terms of spin dynamics and line shape resolution). Finally, all 2D DNP experiments can be interpreted in terms of domains exhibiting well identified types of substitution: local order and carbonate clustering are clearly favored.

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“…In all cases, no attempt was made to remove molecular oxygen from the samples even though this has been shown to increase NMR sensitivity, [28] especially for PS-containing polymers. [29]…”

Section: Sample Preparationmentioning

confidence: 99%

“…All DNP solid-state NMR experiments were recorded on a Bruker 9.4T wide-bore magnet (400 and 100 MHz for the 1 H and 13 C Larmor frequency, respectively) operated by an AVANCE-III NMR spectrometer and equipped with a Bruker 3.2-mm low-temperature double-resonance DNP 1 H/ 29 Si- 13 C CP MAS probe head. The spectrometer was equipped with a gyrotron that allowed microwave (μW) irradiation of the sample.…”

Section: Nmr Experimentsmentioning

confidence: 99%

Solvent suppression in solid‐state DNP NMR using Electronic Mixing‐Mediated Annihilation (EMMA)

Ziarelli

Thureau

Viel

et al. 2020

Magnetic Reson in Chemistry

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We show here that the Electronic Mixing-Mediated Annihilation (EMMA) method, previously reported for the suppression of background signals in solid-state nuclear magnetic resonance spectra, can be successfully applied to remove the solvent signals observed in the case of nuclear magnetic resonance spectra obtained with dynamic nuclear polarization. The methodology presented here is applied to two standard sample preparation methods for dynamic nuclear polarization, namely, glass forming and incipient wetness impregnation. It is demonstrated that the Electronic Mixing-Mediated Annihilation method is complementary to the different methods for solvent suppression based on relaxation filters and that it can be used to preserve the quantitative information that might be present in the pristine spectra.

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Up to 100% Improvement in Dynamic Nuclear Polarization Solid‐State NMR Sensitivity Enhancement of Polymers by Removing Oxygen

Cited by 21 publications

References 36 publications

Recent developments in MAS DNP-NMR of materials

Recent developments in MAS DNP-NMR of materials

Hydroxyapatites: Key Structural Questions and Answers from Dynamic Nuclear Polarization

Solvent suppression in solid‐state DNP NMR using Electronic Mixing‐Mediated Annihilation (EMMA)

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