Dynamic Nuclear Polarization Enhanced Multiple-Quantum Spin Counting of Molecular Assemblies in Vitrified Solutions

Nowotarski, MS and Potnuru, LR and Straub, JS and Chaklashiya, R and Shimasaki, T and Pahari, B and Coffaro, H and Jain, S and Han, S (2024) Dynamic Nuclear Polarization Enhanced Multiple-Quantum Spin Counting of Molecular Assemblies in Vitrified Solutions. In: Journal of Physical Chemistry Letters, 15 (27). pp. 7084-7094.

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Abstract

Crystallization pathways are essential to various industrial, geological, and biological processes. In nonclassical nucleation theory, prenucleation clusters (PNCs) form, aggregate, and crystallize to produce higher order assemblies. Microscopy and X-ray techniques have limited utility for PNC analysis due to the small size (0.5-3 nm) and time stability constraints. We present a new approach for analyzing PNC formation based on 31P nuclear magnetic resonance (NMR) spin counting of vitrified molecular assemblies. The use of glassing agents ensures that vitrification generates amorphous aqueous samples and offers conditions for performing dynamic nuclear polarization (DNP)-amplified NMR spectroscopy. We demonstrate that molecular adenosine triphosphate along with crystalline, amorphous, and clustered calcium phosphate materials formed via a nonclassical growth pathway can be differentiated from one another by the number of dipolar coupled 31P spins. We also present an innovative approach for examining spin counting data, demonstrating that a knowledge-based fitting of integer multiples of cosine wave functions, instead of the traditional Fourier transform, provides a more physically meaningful retrieval of the existing frequencies. This is the first report of multiquantum spin counting of assemblies formed in solution as captured under vitrified DNP conditions, which can be useful for future analysis of PNCs and other aqueous molecular clusters. © 2024 American Chemical Society.

Item Type:	Journal Article
Publication:	Journal of Physical Chemistry Letters
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Keywords:	Adenosinetriphosphate; Calcium phosphate; Knowledge based systems; Spin polarization; Wave functions, Biological process; Crystallization pathway; Dynamic nuclear polarization; Geological process; Industrial processs; Molecular assembly; Polarization-enhanced; Pre-nucleation; Quantum spin; Spin counting, Nuclear magnetic resonance spectroscopy
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	18 Dec 2024 04:31
Last Modified:	18 Dec 2024 04:31
URI:	http://eprints.iisc.ac.in/id/eprint/85826

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