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Modern NMR Characterization of Materials

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Materials Science".

Deadline for manuscript submissions: closed (31 August 2023) | Viewed by 10065

Special Issue Editor

Special Issue Information

Dear Colleagues,

Nuclear magnetic resonance (NMR) spectroscopy remains an important tool in the atomic and molecular level characterization of materials. Developing and applying both solution and solid-state NMR techniques in material science is a rich field of study with extremely varied examples. By employing combinations of heteronuclear, multi-dimensional, multi-quantum, and dynamic nuclear polarization (DNP); relaxation filters; shaped pulses; magic angle spinning; and pulse field gradient (PFG) NMR diffusometry techniques, investigators can gain novel and valuable insights into materials. An almost endless range of material properties can be probed, including production and degradation chemistries, local- and medium-range structure, structural dynamics, binding events, surface interactions, phase transitions, morphology, kinetics, and hydrogen bond strengths, along with ion/molecular diffusion.

This Special Issue will focus on the use of NMR for the characterization of real-life materials, including biomaterials, biopolymers, biofuels, biomembranes, self-assembled materials, super-molecular and stimuli-responsive polymers, polymer membranes, composites, MOFS, inorganic materials, liquid crystalline polymers, ceramics, glasses, catalyst, surface-modified nanoparticles, and electrolytes. This Special Issue invites original research and reviews which explore the use of NMR spectroscopy in material characterization.

Prof. Dr. Todd M. Alam
Guest Editor

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Keywords

  • NMR
  • materials
  • dynamics
  • structure
  • diffusion
  • kinetics
  • morphology

Published Papers (7 papers)

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Research

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16 pages, 11338 KiB  
Article
Application of 2D NMR Spectroscopy in Combination with Chemometric Tools for Classification of Natural Lignins
by Anna V. Faleva, Ilya A. Grishanovich, Nikolay V. Ul’yanovskii and Dmitry S. Kosyakov
Int. J. Mol. Sci. 2023, 24(15), 12403; https://doi.org/10.3390/ijms241512403 - 03 Aug 2023
Cited by 1 | Viewed by 1110
Abstract
Lignin is considered a promising renewable source of valuable chemical compounds and a feedstock for the production of various materials. Its suitability for certain directions of processing is determined by the chemical structure of its macromolecules. Its formation depends on botanical origin, isolation [...] Read more.
Lignin is considered a promising renewable source of valuable chemical compounds and a feedstock for the production of various materials. Its suitability for certain directions of processing is determined by the chemical structure of its macromolecules. Its formation depends on botanical origin, isolation procedure and other factors. Due to the complexity of the chemical composition, revealing the structural differences between lignins of various origins is a challenging task and requires the use of the most informative methods for obtaining and processing data. In the present study, a combination of two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy and multivariate analysis of heteronuclear single quantum coherence (HSQC) spectra is proposed. Principal component analysis and hierarchical cluster analysis techniques demonstrated the possibility to effectively classify lignins at the level of belonging to classes and families of plants, and in some cases individual species, with an error rate for data classification of 2.3%. The reverse transformation of loading plots into the corresponding HSQC loading spectra allowed for structural information to be obtained about the latent components of lignins and their structural fragments (biomarkers) responsible for certain differences. As a result of the analysis of 34 coniferous, deciduous, and herbaceous lignins, 10 groups of key substructures were established. In addition to syringyl, guaiacyl, and p-hydroxyphenyl monomeric units, they include various terminal substructures: dihydroconiferyl alcohol, balanopholin, cinnamic acids, and tricin. It was shown that, in some cases, the substructures formed during the partial destruction of biopolymer macromolecules also have a significant effect on the classification of lignins of various origins. Full article
(This article belongs to the Special Issue Modern NMR Characterization of Materials)
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21 pages, 5133 KiB  
Article
Water Dynamics in Highly Concentrated Protein Systems—Insight from Nuclear Magnetic Resonance Relaxometry
by Danuta Kruk, Adam Kasparek, Elzbieta Masiewicz, Karol Kolodziejski, Radoslaw Cybulski and Bartosz Nowak
Int. J. Mol. Sci. 2023, 24(4), 4093; https://doi.org/10.3390/ijms24044093 - 17 Feb 2023
Cited by 1 | Viewed by 1258
Abstract
1H spin-lattice relaxation experiments have been performed for water–Bovine Serum Albumin (BSA) mixtures, including 20%wt and 40%wt of BSA. The experiments have been carried out in a frequency range encompassing three orders of magnitude, from 10 kHz to 10 MHz, versus temperature. [...] Read more.
1H spin-lattice relaxation experiments have been performed for water–Bovine Serum Albumin (BSA) mixtures, including 20%wt and 40%wt of BSA. The experiments have been carried out in a frequency range encompassing three orders of magnitude, from 10 kHz to 10 MHz, versus temperature. The relaxation data have been thoroughly analyzed in terms of several relaxation models with the purpose of revealing the mechanisms of water motion. For this purpose, four relaxation models have been used: the data have been decomposed into relaxation contributions expressed in terms of Lorentzian spectral densities, then three-dimensional translation diffusion has been assumed, next two-dimensional surface diffusion has been considered, and eventually, a model of surface diffusion mediated by acts of adsorption to the surface has been employed. In this way, it has been demonstrated that the last concept is the most plausible. Parameters describing the dynamics in a quantitative manner have been determined and discussed. Full article
(This article belongs to the Special Issue Modern NMR Characterization of Materials)
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10 pages, 1644 KiB  
Communication
SABRE Hyperpolarization with up to 200 bar Parahydrogen in Standard and Quickly Removable Solvents
by Anton Duchowny, Johannes Denninger, Lars Lohmann, Thomas Theis, Sören Lehmkuhl and Alina Adams
Int. J. Mol. Sci. 2023, 24(3), 2465; https://doi.org/10.3390/ijms24032465 - 27 Jan 2023
Cited by 3 | Viewed by 1657
Abstract
Parahydrogen (p-H2)-based techniques are known to drastically enhance NMR signals but are usually limited by p-H2 supply. This work reports p-H2-based SABRE hyperpolarization at p-H2 pressures of hundreds of bar, far [...] Read more.
Parahydrogen (p-H2)-based techniques are known to drastically enhance NMR signals but are usually limited by p-H2 supply. This work reports p-H2-based SABRE hyperpolarization at p-H2 pressures of hundreds of bar, far beyond the typical ten bar currently reported in the literature. A recently designed high-pressure setup was utilized to compress p-H2 gas up to 200 bar. The measurements were conducted using a sapphire high-pressure NMR tube and a 43 MHz benchtop NMR spectrometer. In standard methanol solutions, it could be shown that the signal intensities increased with pressure until they eventually reached a plateau. A polarization of about 2%, equal to a molar polarization of 1.2 mmol L−1, could be achieved for the sample with the highest substrate concentration. While the signal plateaued, the H2 solubility increased linearly with pressure from 1 to 200 bar, indicating that p-H2 availability is not the limiting factor in signal enhancement beyond a certain pressure, depending on sample composition. Furthermore, the possibility of using liquefied ethane and compressed CO2 as removable solvents for hyperpolarization was demonstrated. The use of high pressures together with quickly removable organic/non-organic solvents represents an important breakthrough in the field of hyperpolarization, advancing SABRE as a promising tool for materials science, biophysics, and molecular imaging. Full article
(This article belongs to the Special Issue Modern NMR Characterization of Materials)
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20 pages, 4225 KiB  
Article
Self-Diffusion in Confined Water: A Comparison between the Dynamics of Supercooled Water in Hydrophobic Carbon Nanotubes and Hydrophilic Porous Silica
by Michael Fardis, Marina Karagianni, Lydia Gkoura and George Papavassiliou
Int. J. Mol. Sci. 2022, 23(22), 14432; https://doi.org/10.3390/ijms232214432 - 20 Nov 2022
Cited by 1 | Viewed by 1285
Abstract
Confined liquids are model systems for the study of the metastable supercooled state, especially for bulk water, in which the onset of crystallization below 230 K hinders the application of experimental techniques. Nevertheless, in addition to suppressing crystallization, confinement at the nanoscale drastically [...] Read more.
Confined liquids are model systems for the study of the metastable supercooled state, especially for bulk water, in which the onset of crystallization below 230 K hinders the application of experimental techniques. Nevertheless, in addition to suppressing crystallization, confinement at the nanoscale drastically alters the properties of water. Evidently, the behavior of confined water depends critically on the nature of the confining environment and the interactions of confined water molecules with the confining matrix. A comparative study of the dynamics of water under hydrophobic and hydrophilic confinement could therefore help to clarify the underlying interactions. As we demonstrate in this work using a few representative results from the relevant literature, the accurate assessment of the translational mobility of water molecules, especially in the supercooled state, can unmistakably distinguish between the hydrophilic and hydrophobic nature of the confining environments. Among the numerous experimental methods currently available, we selected nuclear magnetic resonance (NMR) in a field gradient, which directly measures the macroscopic translational self-diffusion coefficient, and quasi-elastic neutron scattering (QENS), which can determine the microscopic translational dynamics of the water molecules. Dielectric relaxation, which probes the re-orientational degrees of freedom, are also discussed. Full article
(This article belongs to the Special Issue Modern NMR Characterization of Materials)
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20 pages, 4264 KiB  
Article
Four-Component Relativistic Calculations of NMR Shielding Constants of the Transition Metal Complexes—Part 2: Nitrogen-Coordinated Complexes of Cobalt
by Dmitry O. Samultsev, Valentin A. Semenov, Irina L. Rusakova and Leonid B. Krivdin
Int. J. Mol. Sci. 2022, 23(21), 13178; https://doi.org/10.3390/ijms232113178 - 29 Oct 2022
Cited by 4 | Viewed by 1103
Abstract
Both four-component relativistic and nonrelativistic computations within the GIAO-DFT(PBE0) formalism have been carried out for 15N and 59Co NMR shielding constants and chemical shifts of a number of the nitrogen-coordinated complexes of cobalt. It was found that the total values of [...] Read more.
Both four-component relativistic and nonrelativistic computations within the GIAO-DFT(PBE0) formalism have been carried out for 15N and 59Co NMR shielding constants and chemical shifts of a number of the nitrogen-coordinated complexes of cobalt. It was found that the total values of the calculated nitrogen chemical shifts of considered cobalt complexes span over a range of more than 580 ppm, varying from −452 to +136 ppm. At that, the relativistic corrections to nitrogen shielding constants and chemical shifts were demonstrated to be substantial, changing accordingly from ca. −19 to +74 ppm and from −68 to +25 ppm. Solvent effects on 15N shielding constants and chemical shifts were shown to have contributions no less important than the relativistic effects, namely from −35 to +63 ppm and from −74 to +23 ppm, respectively. Cobalt shielding constants and chemical shifts were found to vary in the ranges of, accordingly, −20,157 to −11,373 ppm and from +3781 to +13,811. The relativistic effects are of major importance in the cobalt shielding constants, resulting in about 4% for the shielding-type contributions, while solvent corrections to cobalt shielding constants appeared to be of less significance, providing corrections of about 1.4% to the gas phase values. Full article
(This article belongs to the Special Issue Modern NMR Characterization of Materials)
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Review

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36 pages, 4419 KiB  
Review
Nuclear Magnetic Resonance Relaxation Pathways in Electrolytes for Energy Storage
by Carla C. Fraenza, Steve G. Greenbaum and Sophia N. Suarez
Int. J. Mol. Sci. 2023, 24(12), 10373; https://doi.org/10.3390/ijms241210373 - 20 Jun 2023
Cited by 2 | Viewed by 1324
Abstract
Nuclear Magnetic Resonance (NMR) spin relaxation times have been an instrumental tool in deciphering the local environment of ionic species, the various interactions they engender and the effect of these interactions on their dynamics in conducting media. Of particular importance has been their [...] Read more.
Nuclear Magnetic Resonance (NMR) spin relaxation times have been an instrumental tool in deciphering the local environment of ionic species, the various interactions they engender and the effect of these interactions on their dynamics in conducting media. Of particular importance has been their application in studying the wide range of electrolytes for energy storage, on which this review is based. Here we highlight some of the research carried out on electrolytes in recent years using NMR relaxometry techniques. Specifically, we highlight studies on liquid electrolytes, such as ionic liquids and organic solvents; on semi-solid-state electrolytes, such as ionogels and polymer gels; and on solid electrolytes such as glasses, glass ceramics and polymers. Although this review focuses on a small selection of materials, we believe they demonstrate the breadth of application and the invaluable nature of NMR relaxometry. Full article
(This article belongs to the Special Issue Modern NMR Characterization of Materials)
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21 pages, 985 KiB  
Review
A Review of Applications of Solid-State Nuclear Magnetic Resonance (ssNMR) for the Analysis of Cyclodextrin-Including Systems
by Anna Helena Mazurek and Łukasz Szeleszczuk
Int. J. Mol. Sci. 2023, 24(4), 3648; https://doi.org/10.3390/ijms24043648 - 11 Feb 2023
Cited by 8 | Viewed by 1522
Abstract
Cyclodextrins, cyclic oligosaccharides composed of five or more α-D-glucopyranoside units linked by α-1,4 glycosidic bonds, are widely used both in their native forms as well as the components of more sophisticated materials. Over the last 30 years, solid-state nuclear magnetic resonance (ssNMR) has [...] Read more.
Cyclodextrins, cyclic oligosaccharides composed of five or more α-D-glucopyranoside units linked by α-1,4 glycosidic bonds, are widely used both in their native forms as well as the components of more sophisticated materials. Over the last 30 years, solid-state nuclear magnetic resonance (ssNMR) has been used to characterize cyclodextrins (CDs) and CD-including systems, such as host–guest complexes or even more sophisticated macromolecules. In this review, the examples of such studies have been gathered and discussed. Due to the variety of possible ssNMR experiments, the most common approaches have been presented to provide the overview of the strategies employed to characterize those useful materials. Full article
(This article belongs to the Special Issue Modern NMR Characterization of Materials)
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