Measurement of internuclear distances in polycrystalline solids. Rotationally enhanced transfer of nuclear spin magnetization

Raleigh, Daniel P.; Creuzet, F.; Gupta, S. K. Das; Levitt, Malcolm H.; Griffin, Robert G.

doi:10.1021/ja00194a057

Cited by 104 publications

(79 citation statements)

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“…In spite of the advances in pulse sequence design, the successful application of recoupling methods to the accurate measurement of 13 C- 13 C distance in macromolecules has typically been possible only when employing either specifically labeled spin-pair samples [26][27][28][29][30][31][32][33][34][35][36][37] or frequency-selective recoupling methods, [38][39][40][41][42][43][44][45][46][47] experiments in which a single internuclear distance is measured at a time. Although highly accurate ͑Ϯ5% is not difficult to achieve͒, both of these approaches are of limited practical utility in protein structure determinations that benefit from the availability of hundreds of constraints even for small proteins.…”

Section: Introductionmentioning

confidence: 99%

Dipolar truncation in magic-angle spinning NMR recoupling experiments

Bayro¹,

Huber²,

Ramachandran³

et al. 2009

The Journal of Chemical Physics

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169

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Quantitative solid-state NMR distance measurements in strongly coupled spin systems are often complicated due to the simultaneous presence of multiple noncommuting spin interactions. In the case of zeroth-order homonuclear dipolar recoupling experiments, the recoupled dipolar interaction between distant spins is attenuated by the presence of stronger couplings to nearby spins, an effect known as dipolar truncation. In this article, we quantitatively investigate the effect of dipolar truncation on the polarization-transfer efficiency of various homonuclear recoupling experiments with analytical theory, numerical simulations, and experiments. In particular, using selectively 13 C-labeled tripeptides, we compare the extent of dipolar truncation in model three-spin systems encountered in protein samples produced with uniform and alternating labeling. Our observations indicate that while the extent of dipolar truncation decreases in the absence of directly bonded nuclei, two-bond dipolar couplings can generate significant dipolar truncation of small, long-range couplings. Therefore, while alternating labeling alleviates the effects of dipolar truncation, and thus facilitates the application of recoupling experiments to large spin systems, it does not represent a complete solution to this outstanding problem.

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Section: Introductionmentioning

confidence: 99%

Dipolar truncation in magic-angle spinning NMR recoupling experiments

Bayro¹,

Huber²,

Ramachandran³

et al. 2009

The Journal of Chemical Physics

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169

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“…In previous studies with R2 experiments, magnetization transfer between spatially remote carbons up to 6 Å was generally detected. 5,20,21) In the parallel -sheet model (Fig. 4B), the intermolecular distance between C and C=O in the main chains would be proximal (4-6 Å ).…”

Section: Resultsmentioning

confidence: 99%

Verification of the Intermolecular Parallel β-Sheet in E22K-Aβ42 Aggregates by Solid-State NMR Using Rotational Resonance: Implications for the Supramolecular Arrangement of the Toxic Conformer of Aβ42

Masuda

Nakanishi

Ohashi

et al. 2008

Bioscience, Biotechnology, and Biochemistry

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“…However, under typical experimental conditions, this picture is often a poor approximation, as the interactions with protons are rarely negligible even at very high 1 H decoupling fields. It has been assumed 46,86 that the effects of these interactions can be described by the zero-quantum relaxation coefficients phenomenologically introduced into the equation of motion of the density matrix for the isolated two-spin system. This assumption postulates a Lorentzian lineshape for the zero-quantum coherence decay (as it operates with the zero-quantum relaxation times T ZQ 2 ).…”

Section: Diffusion In the Non-markovian Regimementioning

confidence: 99%

Proton-driven spin diffusion in rotating solids via reversible and irreversible quantum dynamics

Veshtort

Griffin

2011

The Journal of Chemical Physics

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Proton-driven spin diffusion (PDSD) experiments in rotating solids have received a great deal of attention as a potential source of distance constraints in large biomolecules. However, the quantitative relationship between the molecular structure and observed spin diffusion has remained obscure due to the lack of an accurate theoretical description of the spin dynamics in these experiments. We start with presenting a detailed relaxation theory of PDSD in rotating solids that provides such a description. The theory applies to both conventional and radio-frequency-assisted PDSD experiments and extends to the non-Markovian regime to include such phenomena as rotational resonance (R 2 ). The basic kinetic equation of the theory in the non-Markovian regime has the form of a memory function equation, with the role of the memory function played by the correlation function. The key assumption used in the derivation of this equation expresses the intuitive notion of the irreversible dissipation of coherences in macroscopic systems. Accurate expressions for the correlation functions and for the spin diffusion constants are given. The theory predicts that the spin diffusion constants governing the multi-site PDSD can be approximated by the constants observed in the two-site diffusion. Direct numerical simulations of PDSD dynamics via reversible Liouville-von Neumann equation are presented to support and compliment the theory. Remarkably, an exponential decay of the difference magnetization can be observed in such simulations in systems consisting of only 12 spins. This is a unique example of a real physical system whose typically macroscopic and apparently irreversible behavior can be traced via reversible microscopic dynamics. An accurate value for the spin diffusion constant can be usually obtained through direct simulations of PDSD in systems consisting of two 13 C nuclei and about ten 1 H nuclei from their nearest environment. Spin diffusion constants computed by this method are in excellent agreement with the spin diffusion constants obtained through equations given by the relaxation theory of PDSD. The constants resulting from these two approaches were also in excellent agreement with the results of 2D rotary resonance recoupling proton-driven spin diffusion (R 3 -PDSD) experiments performed in three model compounds, where magnetization exchange occurred over distances up to 4.9 Å. With the methodology presented, highly accurate internuclear distances can be extracted from such data. Relayed transfer of magnetization between distant nuclei appears to be the main (and apparently resolvable) source of uncertainty in such measurements. The non-Markovian kinetic equation was applied to the analysis of the R 2 spin dynamics. The conventional semi-phenomenological treatment of relxation in R 2 has been shown to be equivalent to the assumption of the Lorentzian spectral density function in the relaxatoin theory of PDSD. As this assumption is a poor approximation in real physical systems, the conventional R 2 treatment is li...

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Measurement of internuclear distances in polycrystalline solids. Rotationally enhanced transfer of nuclear spin magnetization

Cited by 104 publications

References 0 publications

Dipolar truncation in magic-angle spinning NMR recoupling experiments

Dipolar truncation in magic-angle spinning NMR recoupling experiments

Verification of the Intermolecular Parallel β-Sheet in E22K-Aβ42 Aggregates by Solid-State NMR Using Rotational Resonance: Implications for the Supramolecular Arrangement of the Toxic Conformer of Aβ42

Proton-driven spin diffusion in rotating solids via reversible and irreversible quantum dynamics

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