Recent progress in nuclear magnetic resonance strategies for time-resolved atomic-level investigation of crystallization from solution

Juramy, Marie; Mollica, Giulia

doi:10.1016/j.cocis.2022.101663

“…Microscopic and X-Ray techniques have been shown to offer some insight into the structure and dynamics of PNCs 4 ; however, due to PNCs time transient nature in solution, these techniques are not sufficient or applicable for the study of most PNCs. Low temperature solid-state nuclear magnetic resonance (ssNMR) is uniquely suited to offer atomic-scale structural information of PNC samples prepared at various time points in nonclassical growth pathways by vitrification at 100 K [5][6][7][8] . Vitrification by rapid cryogenic temperature transfer solidifies the sample into a glass rather than a crystalline structure by limiting the time atoms can rearrange into a crystalline orientation or an alternate temperature-dependent energetically favorable orientation, thus enabling the use of ssNMR on a sample that closely resembles the native state conditions.…”

mentioning

confidence: 99%

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

Nowotarski,

Potnuru,

Straub

et al. 2024

Preprint

0

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Crystallization pathways are essential to various industrial, geological, and biolog- ical 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 small size (0.5 - 3 nm) and time stability constraints. We present a new approach for analyzing PNC formation based on 31P NMR spin counting of vitrified molecular assemblies. The use of glassing agents en- sures that vitrification generates amorphous aqueous samples, and offers conditions to perform dynamic nuclear polarization (DNP) amplified NMR spectroscopy. We demon- strate that molecular adenosine triphosphate, along with crystalline, amorphous, and clustered calcium phosphate materials formed via a non-classical growth pathway can be differentiated from one another by the number of dipolar coupled 31P spins. We also present an innovative approach to examine 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 ex- isting frequencies. This is the first report of multi-quantum 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.

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“…Low temperature solid-state nuclear magnetic resonance (ssNMR) is uniquely suited to offer atomic-scale structural information of PNC samples prepared at various time points in nonclassical growth pathways by vitrification at 100 K [5][6][7][8] . Vitrification by rapid cryogenic temperature transfer solidifies the sample into a glass rather than a crystalline structure by limiting the time atoms can rearrange into a crystalline orientation or an alternate temperature-dependent energetically favorable orientation, thus enabling the use of ssNMR on a sample that closely resembles the native state conditions.…”

mentioning

confidence: 99%

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

Potnuru,

Nowotarski,

Straub

et al. 2024

Preprint

0

View full text Add to dashboard Cite

Crystallization pathways are essential to various industrial, geological, and biolog- ical 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 small size (0.5 - 3 nm) and time stability constraints. We present a new approach for analyzing PNC formation based on 31P NMR spin counting of vitrified molecular assemblies. The use of glassing agents en- sures that vitrification generates amorphous aqueous samples, and offers conditions to perform dynamic nuclear polarization (DNP) amplified NMR spectroscopy. We demon- strate that molecular adenosine triphosphate, along with crystalline, amorphous, and clustered calcium phosphate materials formed via a non-classical growth pathway can be differentiated from one another by the number of dipolar coupled 31P spins. We also present an innovative approach to examine 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 ex- isting frequencies. This is the first report of multi-quantum 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.

show abstract

“…Low-temperature solid-state nuclear magnetic resonance (ssNMR) is uniquely suited to offer atomic-scale structural information about PNC samples prepared at various time points in nonclassical growth pathways by vitrification at 100 K. − Vitrification by rapid cryogenic temperature transfer solidifies the sample into a glass rather than a crystalline structure by limiting the time atoms can rearrange into a crystalline orientation or an alternate temperature-dependent energetically favorable orientation, thus enabling the use of ssNMR on a sample that closely resembles the native-state conditions. Sample vitrification without rapid freezing technology requires the use of a glassing agent.…”

mentioning

confidence: 99%

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

Nowotarski,

Potnuru,

Straub

et al. 2024

J. Phys. Chem. Lett.

1

0

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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 31 P 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 31 P 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.

show abstract

Recent progress in nuclear magnetic resonance strategies for time-resolved atomic-level investigation of crystallization from solution

Cited by 5 publications

References 52 publications

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

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

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

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

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