TinyPols: a family of water-soluble binitroxides tailored for dynamic nuclear polarization enhanced NMR spectroscopy at 18.8 and 21.1 T

Lund, Alicia; Casano, Gilles; Menzildjian, Georges; Kaushik, Monu; Stevanato, Gabriele; Yulikov, Maxim; Jabbour, Ribal; Wisser, Dorothea; Renom‐Carrasco, Marc; Thieuleux, Chloé; Bernada, Florian; Karoui, Hakim; Siri, Didier; Rosay, Mélanie; Sergeyev, Ivan V.; Gajan, David; Lelli, Moreno; Emsley, Lyndon; Ouari, Olivier; Lesage, Anne

doi:10.1039/c9sc05384k

Cited by 86 publications

(109 citation statements)

References 47 publications

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“…It should be noted that MAS-DNP is still undergoing revolution; tremendous efforts have been devoted to further improving its efficiency. Multiple biradicals have been developed recently, such as the AsymPolPOK family that shortens the DNP build-up time [ 33 ] and the Tinypol and TEMTRIPol-I radicals that have shown improved performance over AMUPol on high-field (18.8 and 21.1 T) DNP instruments [ 31 , 59 , 60 ]. The resolution improvement at high-field MAS-DNP (e.g., 800 MHz/527 GHz) will allow us to better analyze biomolecular structures, at least for the molecules bearing structural order [ 61 , 62 ].…”

Section: Discussionmentioning

confidence: 99%

“…Regarding the plant biomass, three exploratory studies have been conducted to reveal the restructuring effect of ball milling on cotton cellulose [23], the alternation of xylan conformations induced by genetic mutations of rice [24], and the compositional changes of lignin in high-S and low-S poplar [25]. With the rapid development of DNP instrumentation [26][27][28][29] and radical design [30][31][32][33], this is certainly a direction of great potential but not yet explicitly explored for plant materials.…”

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confidence: 99%

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Solid-state NMR of unlabeled plant cell walls: high-resolution structural analysis without isotopic enrichment

Zhao

Kirui

Deligey

et al. 2021

Biotechnol Biofuels

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Background Multidimensional solid-state nuclear magnetic resonance (ssNMR) spectroscopy has emerged as an indispensable technique for resolving polymer structure and intermolecular packing in primary and secondary plant cell walls. Isotope (13C) enrichment provides feasible sensitivity for measuring 2D/3D correlation spectra, but this time-consuming procedure and its associated expenses have restricted the application of ssNMR in lignocellulose analysis. Results Here, we present a method that relies on the sensitivity-enhancing technique Dynamic Nuclear Polarization (DNP) to eliminate the need for 13C-labeling. With a 26-fold sensitivity enhancement, a series of 2D 13C–13C correlation spectra were successfully collected using the unlabeled stems of wild-type Oryza sativa (rice). The atomic resolution allows us to observe a large number of intramolecular cross peaks for fully revealing the polymorphic structure of cellulose and xylan. NMR relaxation and dipolar order parameters further suggest a sophisticated change of molecular motions in a ctl1 ctl2 double mutant: both cellulose and xylan have become more dynamic on the nanosecond and microsecond timescale, but the motional amplitudes are uniformly small for both polysaccharides. Conclusions By skipping isotopic labeling, the DNP strategy demonstrated here is universally extendable to all lignocellulose materials. This time-efficient method has landed the technical foundation for understanding polysaccharide structure and cell wall assembly in a large variety of plant tissues and species.

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Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

Solid-state NMR of unlabeled plant cell walls: high-resolution structural analysis without isotopic enrichment

Zhao

Kirui

Deligey

et al. 2021

Biotechnol Biofuels

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“…A solid state source, with output of up to 250 mW, enables nearly comparable DNP efficiencies at 400 MHz and a broader range of microwave frequencies [ 22 , 23 ]. MAS-DNP NMR instruments operating at 1 H frequencies up to 900 MHz [ 16 , 50 , 51 ] are now in operation with MAS probes using rotors of 3.2–1.3 mm outer diameter and reaching spinning speeds of 12–40 kHz. Shown in Figure 1 B is a 600 MHz MAS-DNP NMR instrument installed at the National High Magnetic Field Laboratory which uses a quasi-optic setup to control microwave irradiation [ 20 ].…”

Section: Dnp-enhanced Solid-state Nmr Spectroscopymentioning

confidence: 99%

“…Magic angle spinning DNP (MAS-DNP) NMR has made large strides in improving the sensitivity of biomolecular ssNMR experiments and illuminating answers to important biological mechanisms not amenable to traditional ssNMR methods [ 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. Current efforts in MAS-DNP NMR are being invested in the design and synthesis of efficient polarizing agents (PAs) for high field NMR applications [ 14 , 15 , 16 , 17 , 18 , 19 ] and in engineering stable microwave sources and NMR probes that can uniformly deliver microwaves into NMR samples [ 20 , 21 , 22 , 23 , 24 ]. Recent mechanistic studies characterizing polarization transfer pathways within large spin systems under MAS-DNP conditions have provided insights into how further gains might be realized [ 25 , 26 ].…”

Section: Introductionmentioning

confidence: 99%

Dynamic Nuclear Polarization of Biomembrane Assemblies

2020

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While atomic scale structural and dynamic information are hallmarks of nuclear magnetic resonance (NMR) methodologies, sensitivity is a fundamental limitation in NMR studies. Fully exploiting NMR capabilities to study membrane proteins is further hampered by their dilution within biological membranes. Recent developments in dynamic nuclear polarization (DNP), which can transfer the relatively high polarization of unpaired electrons to nuclear spins, show promise for overcoming the sensitivity bottleneck and enabling NMR characterization of membrane proteins under native-like conditions. Here we discuss fundamental aspects of DNP-enhanced solid-state NMR spectroscopy, experimental details relevant to the study of lipid assemblies and incorporated proteins, and sensitivity gains which can be realized in biomembrane-based samples. We also present unique insights which can be gained from DNP measurements and prospects for further development of the technique for elucidating structures and orientations of membrane proteins in native lipid environments.

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“…(b) paramagnetic agents for dynamic nuclear polarization (DNP) both in solutions and as solids [ 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 ];…”

Section: Introductionmentioning

confidence: 99%

Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals

Zaytseva

Mazhukin

2021

Molecules

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Spirocyclic nitroxyl radicals (SNRs) are stable paramagnetics bearing spiro-junction at α-, β-, or γ-carbon atom of the nitroxide fragment, which is part of the heterocyclic system. Despite the fact that the first representatives of SNRs were obtained about 50 years ago, the methodology of their synthesis and their usage in chemistry and biochemical applications have begun to develop rapidly only in the last two decades. Due to the presence of spiro-function in the SNRs molecules, the latter have increased stability to various reducing agents (including biogenic ones), while the structures of the biradicals (SNBRs) comprises a rigid spiro-fused core that fixes mutual position and orientation of nitroxide moieties that favors their use in dynamic nuclear polarization (DNP) experiments. This first review on SNRs will give a glance at various strategies for the synthesis of spiro-substituted, mono-, and bis-nitroxides on the base of six-membered (piperidine, 1,2,3,4-tetrahydroquinoline, 9,9′(10H,10H′)-spirobiacridine, piperazine, and morpholine) or five-membered (2,5-dihydro-1H-pyrrole, pyrrolidine, 2,5-dihydro-1H-imidazole, 4,5-dihydro-1H-imidazole, imidazolidine, and oxazolidine) heterocyclic cores.

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TinyPols: a family of water-soluble binitroxides tailored for dynamic nuclear polarization enhanced NMR spectroscopy at 18.8 and 21.1 T

Abstract: TinyPol binitroxides provide significantly higher DNP enhancement factors for solid-state NMR spectroscopy at high magnetic fields than today's reference radical AMPUPol.

Cited by 86 publications

References 47 publications

Solid-state NMR of unlabeled plant cell walls: high-resolution structural analysis without isotopic enrichment

Solid-state NMR of unlabeled plant cell walls: high-resolution structural analysis without isotopic enrichment

Dynamic Nuclear Polarization of Biomembrane Assemblies

Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals

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