"Selective One-Dimensional <sup>13</sup>C-<sup>13</sup>C Spin-Diffusion" by Bennett Addison, Dillan Stengel et al.

Faculty Publications

Title

Selective One-Dimensional ¹³C-¹³C Spin-Diffusion Solid-State Nuclear Magnetic Resonance Methods to Probe Spatial Arrangements in Biopolymers including Plant Cell Walls, Peptides, and Spider Silk

Authors

Bennett Addison, Renewable Resources and Enabling Sciences Center
Dillan Stengel, San Diego State University
Vivek S. Bharadwaj, Renewable Resources and Enabling Sciences Center
Renee M. Happs, Renewable Resources and Enabling Sciences Center
Crissa Doeppke, Renewable Resources and Enabling Sciences Center
Tuo Wang, Louisiana State University
Yannick J. Bomble, Biosciences Center
Gregory P. Holland, San Diego State University
Anne E. Harman-Ware, Renewable Resources and Enabling Sciences Center

Document Type

Article

Publication Date

11-5-2020

Abstract

© 2020 American Chemical Society. All rights reserved. Two-dimensional (2D) and 3D through-space 13C-13C homonuclear spin-diffusion techniques are powerful solid-state nuclear magnetic resonance (NMR) tools for extracting structural information from 13C-enriched biomolecules, but necessarily long acquisition times restrict their applications. In this work, we explore the broad utility and underutilized power of a chemical shift-selective one-dimensional (1D) version of a 2D 13C-13C spin-diffusion solid-state NMR technique. The method, which is called 1D dipolar-assisted rotational resonance (DARR) difference, is applied to a variety of biomaterials including lignocellulosic plant cell walls, microcrystalline peptide fMLF, and black widow dragline spider silk. 1D 13C-13C spin-diffusion methods described here apply in select cases in which the 1D 13C solid-state NMR spectrum displays chemical shift-resolved moieties. This is analogous to the selective 1D nuclear Overhauser effect spectroscopy (NOESY) experiment utilized in liquid-state NMR as a faster (1D instead of 2D) and often less ambiguous (direct sampling of the time domain data, coupled with increased signal averaging) alternative to 2D NOESY. Selective 1D 13C-13C spin-diffusion methods are more time-efficient than their 2D counterparts such as proton-driven spin diffusion (PDSD) and dipolar-assisted rotational resonance. The additional time gained enables measurements of 13C-13C spin-diffusion buildup curves and extraction of spin-diffusion time constants TSD, yielding detailed structural information. Specifically, selective 1D DARR difference buildup curves applied to 13C-enriched hybrid poplar woody stems confirm strong spatial interaction between lignin and acetylated xylan polymers within poplar plant secondary cell walls, and an interpolymer distance of ∼0.45-0.5 nm was estimated. Additionally, Tyr/Gly long-range correlations were observed on isotopically enriched black widow spider dragline silks.

Publication Source (Journal or Book title)

Journal of Physical Chemistry B

First Page

9870

Last Page

9883

Recommended Citation

Addison, B., Stengel, D., Bharadwaj, V., Happs, R., Doeppke, C., Wang, T., Bomble, Y., Holland, G., & Harman-Ware, A. (2020). Selective One-Dimensional ¹³C-¹³C Spin-Diffusion Solid-State Nuclear Magnetic Resonance Methods to Probe Spatial Arrangements in Biopolymers including Plant Cell Walls, Peptides, and Spider Silk. Journal of Physical Chemistry B, 124 (44), 9870-9883. https://doi.org/10.1021/acs.jpcb.0c07759

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