Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 124, Issue 44, Pages 9870-9883Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.0c07759
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Funding
- U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (BETO) [DE-AC3608GO28308]
- National Renewable Energy Laboratory
- BioEnergy Science Center, U.S. Department of Energy Research Center - Office of Biological and Environmental Research in the DOE Office of Science
- Center for Bioenergy Innovation, U.S. Department of Energy Research Center - Office of Biological and Environmental Research in the DOE Office of Science
- Center for Lignocellulose Structure and Formation, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0001090]
- U.S. Department of Defense, Air Force Office of Research (DOD-AFOSR) [FA9550-17-1-0282, FA9950-20-10103]
- Army Research Office (DOD-ARO) [W911NF2010143]
- U.S. Department of Defense (DOD) [W911NF2010143] Funding Source: U.S. Department of Defense (DOD)
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Two-dimensional (2D) and 3D through-space C-13-C-13 homonuclear spin-diffusion techniques are powerful solid-state nuclear magnetic resonance (NMR) tools for extracting structural information from C-13-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 C-13-C-13 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 C-13-C-13 spin-diffusion methods described here apply in select cases in which the 1D C-13 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 C-13-C-13 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 C-13-C-13 spin-diffusion buildup curves and extraction of spin-diffusion time constants T-SD, yielding detailed structural information. Specifically, selective 1D DARR difference buildup curves applied to C-13-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 similar to 0.45-0.5 nm was estimated. Additionally, Tyr/Gly long-range correlations were observed on isotopically enriched black widow spider dragline silks.
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