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Title: Atomic-Level Structure Characterization of Biomass Pre- and Post-Lignin Treatment by Dynamic Nuclear Polarization-Enhanced Solid-State NMR

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [4];  [2]
  1. Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50011, United States
  2. Department of Chemistry, School of Chemical Engineering, and the Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio), Purdue University, West Lafayette, Indiana 47907, United States
  3. Laboratory of Renewable Resources Engineering, Department of Agricultural and Biological Engineering, and the Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio), Purdue University, West Lafayette, Indiana 47907, United States
  4. Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50011, United States; Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388244
DOE Contract Number:
SC000997
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; Journal Volume: 121; Journal Issue: 3; Related Information: C3Bio partners with Purdue University (lead); Argonne National Laboratory; National Renewable Energy Laboratory; Northeastern University; University of Tennessee
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), biofuels (including algae and biomass), bio-inspired, materials and chemistry by design, synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Perras, Frédéric A., Luo, Hao, Zhang, Ximing, Mosier, Nathan S., Pruski, Marek, and Abu-Omar, Mahdi M. Atomic-Level Structure Characterization of Biomass Pre- and Post-Lignin Treatment by Dynamic Nuclear Polarization-Enhanced Solid-State NMR. United States: N. p., 2017. Web. doi:10.1021/acs.jpca.6b11121.
Perras, Frédéric A., Luo, Hao, Zhang, Ximing, Mosier, Nathan S., Pruski, Marek, & Abu-Omar, Mahdi M. Atomic-Level Structure Characterization of Biomass Pre- and Post-Lignin Treatment by Dynamic Nuclear Polarization-Enhanced Solid-State NMR. United States. doi:10.1021/acs.jpca.6b11121.
Perras, Frédéric A., Luo, Hao, Zhang, Ximing, Mosier, Nathan S., Pruski, Marek, and Abu-Omar, Mahdi M. Fri . "Atomic-Level Structure Characterization of Biomass Pre- and Post-Lignin Treatment by Dynamic Nuclear Polarization-Enhanced Solid-State NMR". United States. doi:10.1021/acs.jpca.6b11121.
@article{osti_1388244,
title = {Atomic-Level Structure Characterization of Biomass Pre- and Post-Lignin Treatment by Dynamic Nuclear Polarization-Enhanced Solid-State NMR},
author = {Perras, Frédéric A. and Luo, Hao and Zhang, Ximing and Mosier, Nathan S. and Pruski, Marek and Abu-Omar, Mahdi M.},
abstractNote = {},
doi = {10.1021/acs.jpca.6b11121},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 3,
volume = 121,
place = {United States},
year = {Fri Jan 13 00:00:00 EST 2017},
month = {Fri Jan 13 00:00:00 EST 2017}
}
  • Here, lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear 13C– 13C correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic-level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determinemore » structure–function relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.« less
  • Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less
  • Here, we report that spatial (<1 nm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13C– 13C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution.
  • The host–guest interaction between metal ions (Pt 2+ and Cu 2+) and a zirconium metal–organic framework (UiO-66-NH2) was explored using dynamic nuclear polarization-enhanced 15N{1H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt 2+ coordinates with two NH2 groups from the MOF and two Cl - from the metal precursor, whereas Cu 2+ do not form chemical bonds with the NH2 groups of the MOF framework. Density functional calculations reveal that Pt 2+ prefers a square-planar structure with the four ligands and resides in the octahedral cage of themore » MOF in either cis or trans configurations.« less
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