An efficient NMR method for the characterisation of 14N sites through indirect 13C detection

Jarvis, James A.; Haies, Ibraheem M.; Williamson, Philip T. F.; Carravetta, Marina

doi:10.1039/c3cp50787d

Cited by 38 publications

(39 citation statements)

References 39 publications

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“…The power level was calibrated to give an overtone nutation frequency of o OT nut /2p = 21 kHz for the 14 Both rotors rotate in a clockwise direction.…”

Section: Solid State Nmrmentioning

confidence: 99%

“…This has led to the development of a number of promising techniques including ultra-wideband acquisition, 2,3,5 indirect detection 4,6-14 and excitation of 14 N overtone transitions. [21][22][23]25 More recently, 14 N overtone spectra acquired under magic-angle spinning (MAS) have been reported, demonstrating the existence of only five 14 N spinning sidebands. 25 The experimental feasibility of directly detecting the 14 N overtone transition by NMR was first demonstrated in the 1980's by Tycko and Opella on static samples.…”

Section: Introductionmentioning

confidence: 99%

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¹⁴N overtone transition in double rotation solid-state NMR

Haies

Jarvis

Brown

et al. 2015

Phys. Chem. Chem. Phys.

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Solid-state NMR transitions involving outer energy levels of the spin-1 (14)N nucleus are immune, to first order in perturbation theory, to the broadening caused by the nuclear quadrupole interaction. The corresponding overtone spectra, when acquired in conjunction with magic-angle sample spinning, result in lines, which are just a few kHz wide, permitting the direct detection of nitrogen compounds without the need for labeling. Despite the success of this technique, "overtone" resonances are still broadened due to indirect, second order effects arising from the large quadrupolar interaction. Here we demonstrate that another order of magnitude in spectral resolution may be gained by using double rotation. This brings the width of the (14)N solid-state NMR lines much closer to the region commonly associated with high-resolution solid-state NMR spectroscopy of (15)N and demonstrates the improvements in resolution that may be possible through the development of pulsed methodologies to suppress these second order effects.

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“…The power level was calibrated to give an overtone nutation frequency of o OT nut /2p = 21 kHz for the 14 Both rotors rotate in a clockwise direction.…”

Section: Solid State Nmrmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

¹⁴N overtone transition in double rotation solid-state NMR

Haies

Jarvis

Brown

et al. 2015

Phys. Chem. Chem. Phys.

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“…In contrast to nuclei with half‐integer spins I =3/2, 5/2, etc., that have a central transition m 1 =±1/2↔∓1/2 which is not affected by the quadrupolar interaction to first order, nuclei with integer spins I =1 only have two allowed single‐quantum transitions m 1 =±1↔ m 1 that are displaced by ± ω Q with respect to the center of the spectrum, which is itself affected by a second‐order quadrupolar term. Nonetheless, NMR methodologies for the acquisition of 14 N spectra in the solid state have been developed over the past 15 years for both static and spinning samples . Techniques involving overtone irradiation have been explored .…”

Section: Introductionmentioning

confidence: 99%

Self‐Assembly of DNA and RNA Building Blocks Explored by Nitrogen‐14 NMR Crystallography: Structure and Dynamics

2020

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The isotopic enrichment of nucleic acids with nitrogen-15 is often carried out by solid-phase synthesis of oligonucleotides using phosphoramidite precursors that are synthetically demanding and expensive. These synthetic challenges, combined with the overlap of chemical shifts, explain the lag of nitrogen-15 NMR studies of nucleic acids behind those of proteins. For the structural characterization of DNA and RNA-related systems, new NMR methods that exploit the naturally occurring 99.9 % abundant nitrogen-14 isotope are therefore highly desirable. In this study, we have investigated nitrogen-14 spectra of selfassembled quartets based on the nucleobase guanine in the solid state by means of magic-angle spinning NMR spectro-scopy. The network of dipolar proton-nitrogen couplings between neighboring stacked purine units is probed by 2D spectra based on 1 H! 14 N! 1 H double cross-polarization. Interplane dipolar contacts are identified between the stacked G quartets. The assignment is supported by density functional theory (DFT) calculations of the anisotropic chemical shifts and quadrupolar parameters. The experimental spectra are fully consistent with internuclear distances obtained in silico. Averaging of chemical shifts due to internal motions can be interpreted by semiempirical calculations. This method can easily be extended to synthetic G quartets based on nucleobase or nucleoside analogs and potentially to oligonucleotides.[a] Dr.

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“…It contains multiple periods that have identical Hamiltonians -the caching algorithm identifies those automatically and avoids their recalculation. [31] for a 14 N- 13 C spin pair in glycine with different matrix exponential caching settings in Spinach [19]. Light grey columns correspond to running with matrix caching switched off, medium grey columns are for runs with the caching switched on and a cache that is empty at the start of the simulation.…”

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confidence: 99%

“…Dark grey columns correspond to simulations where all required matrix exponentials are already present in the cache. Details of the NMR pulse sequence and the spin Hamiltonians involved are given in Reference [31].…”

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confidence: 99%

Modified Newton-Raphson GRAPE methods for optimal control of spin systems

Goodwin

2016

The Journal of Chemical Physics

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Quadratic convergence throughout the active space is achieved for the gradient ascent pulse engineering (GRAPE) family of quantum optimal control algorithms. We demonstrate in this communication that the Hessian of the GRAPE fidelity functional is unusually cheap, having the same asymptotic complexity scaling as the functional itself. This leads to the possibility of using very efficient numerical optimization techniques. In particular, the Newton-Raphson method with a rational function optimization (RFO) regularized Hessian is shown in this work to require fewer system trajectory evaluations than any other algorithm in the GRAPE family. This communication describes algebraic and numerical implementation aspects (matrix exponential recycling, Hessian regularization, etc.) for the RFO Newton-Raphson version of GRAPE and reports benchmarks for common spin state control problems in magnetic resonance spectroscopy.

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An efficient NMR method for the characterisation of 14N sites through indirect 13C detection

Abstract: An efficient NMR methods for the characterisation of 14N sites has been developed with efficiencies suitable for the quantitative analysis of biomolecular and natural abundance systems.

Cited by 38 publications

References 39 publications

¹⁴N overtone transition in double rotation solid-state NMR

¹⁴N overtone transition in double rotation solid-state NMR

Self‐Assembly of DNA and RNA Building Blocks Explored by Nitrogen‐14 NMR Crystallography: Structure and Dynamics

Modified Newton-Raphson GRAPE methods for optimal control of spin systems

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An efficient NMR method for the characterisation of 14N sites through indirect 13C detection

Abstract: An efficient NMR methods for the characterisation of 14N sites has been developed with efficiencies suitable for the quantitative analysis of biomolecular and natural abundance systems.

Cited by 38 publications

References 39 publications

14N overtone transition in double rotation solid-state NMR

14N overtone transition in double rotation solid-state NMR

Self‐Assembly of DNA and RNA Building Blocks Explored by Nitrogen‐14 NMR Crystallography: Structure and Dynamics

Modified Newton-Raphson GRAPE methods for optimal control of spin systems

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¹⁴N overtone transition in double rotation solid-state NMR

¹⁴N overtone transition in double rotation solid-state NMR