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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: closed (30 January 2024) | Viewed by 9728

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Dr. Irina Rusakova

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A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, 664033 Irkutsk, Russia
Interests: NMR spectroscopy; quantum chemistry; relativistic quantum theory
Special Issues, Collections and Topics in MDPI journals

Dr. Lyudmila I. Larina

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A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, 664033 Irkutsk, Russia
Interests: quantum chemical methods; NMR spin-spin coupling constants; NMR chemical shifts

Special Issue Information

Dear Colleagues,

The determination of the structure of compounds using the nuclear magneticresonance spectral analysis has now become an integral part of physical-chemical research in organic and inorganic chemistry. Chemical shifts and spin-spin coupling constants observed by NMR spectroscopy are very sensitive to the valence and core electronic structures of molecules and represent an indispensable strategic tool of their structural elucidation. Nowadays, it is rare that modern synthetic work can do without the combination of the state-of-the-art homo- and heteronuclear NMR techniques with high-quality quantum chemical calculations. This especially concerns synthesis of novel compounds containing heavy elements, for which there may occur mis-assignments of NMR signals. In this sense, the development of new computational approaches, relativistic or not, to the NMR parameters that are intended to increase the accuracy of NMR spectra simulation is of paramount importance for today. This Special Issue entitled "NMR Spectroscopy in Materials Chemistry" will provide researchers with the opportunity to publish their most recent discoveries in the field of high-quality experimental NMR studies of organic and inorganic compounds as well as the theoretical studies of the NMR spectral parameters.

Dr. Irina L. Rusakova
Dr. Lyudmila I. Larina
Guest Editors

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Keywords

NMR
gas-phase NMR
solid-state NMR
quantum chemistry
chemical shift
shielding constant
spin-spin coupling constant

Published Papers (6 papers)

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Research

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17 pages, 1951 KiB

Open AccessArticle

On the Efficiency of the Density Functional Theory (DFT)-Based Computational Protocol for ¹H and ¹³C Nuclear Magnetic Resonance (NMR) Chemical Shifts of Natural Products: Studying the Accuracy of the pecS-n (n = 1, 2) Basis Sets

by Yuriy Yu. Rusakov, Valentin A. Semenov and Irina L. Rusakova

Int. J. Mol. Sci. 2023, 24(19), 14623; https://doi.org/10.3390/ijms241914623 - 27 Sep 2023

Cited by 1 | Viewed by 873

Abstract

The basis set issue has always been one of the most important factors of accuracy in the quantum chemical calculations of NMR chemical shifts. In a previous paper, we developed new pecS-n (n = 1, 2) basis sets purposed for the calculations of the NMR chemical shifts of the nuclei of the most popular NMR-active isotopes of 1–2 row elements and successfully approbated these on the DFT calculations of chemical shifts in a limited series of small molecules. In this paper, we demonstrate the performance of the pecS-n (n = 1, 2) basis sets on the calculations of as much as 713 ¹H and 767 ¹³C chemical shifts of 23 biologically active natural products with complicated stereochemical structures, carried out using the GIAO-DFT(PBE0) approach. We also proposed new alternative contraction schemes for our basis sets characterized by less contraction depth of the p-shell. New contraction coefficients have been optimized with the property-energy consistent (PEC) method. The accuracies of the pecS-n (n = 1, 2) basis sets of both the original and newly contracted forms were assessed on massive benchmark calculations of proton and carbon chemical shifts of a vast variety of natural products. It was found that less contracted pecS-n (n = 1, 2) basis sets provide no noticeable improvement in accuracy. These calculations represent the most austere test of our basis sets as applied to routine calculations of the NMR chemical shifts of real-life compounds. Full article

(This article belongs to the Special Issue NMR Spectroscopy in Materials Chemistry)

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18 pages, 969 KiB

Open AccessArticle

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

by Yuriy Yu. Rusakov and Irina L. Rusakova

Int. J. Mol. Sci. 2023, 24(9), 7841; https://doi.org/10.3390/ijms24097841 - 25 Apr 2023

Cited by 3 | Viewed by 1078

Abstract

We present new compact pecJ-n (n = 1, 2) basis sets for the selenium atom developed for the quantum–chemical calculations of NMR spin–spin coupling constants (SSCCs) involving selenium nuclei. These basis sets were obtained at the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes (SOPPA(CCSD)) level with the property-energy consistent (PEC) method, which was introduced in our previous papers. The existing SSCC-oriented selenium basis sets are rather large in size, while the PEC method gives more compact basis sets that are capable of providing accuracy comparable to that reached using the property-oriented basis sets of larger sizes generated with a standard even-tempered technique. This is due to the fact that the PEC method is very different in its essence from the even-tempered approaches. It generates new exponents through the total optimization of angular spaces of trial basis sets with respect to the property under consideration and the total molecular energy. New basis sets were tested on the coupled cluster singles and doubles (CCSD) calculations of SSCCs involving selenium in the representative series of molecules, taking into account relativistic, solvent, and vibrational corrections. The comparison with the experiment showed that the accuracy of the results obtained with the pecJ-2 basis set is almost the same as that provided by a significantly larger basis set, aug-cc-pVTZ-J, while that achieved with a very compact pecJ-1 basis set is only slightly inferior to the accuracy provided by the former. Full article

(This article belongs to the Special Issue NMR Spectroscopy in Materials Chemistry)

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14 pages, 3081 KiB

Open AccessArticle

Investigation of Dynamic Behavior of Confined Ionic Liquid [BMIM]⁺[TCM]⁻ in Silica Material SBA-15 Using NMR

by Lydia Gkoura, Nikolaos Panopoulos, Marina Karagianni, George Romanos, Aris Chatzichristos, George Papavassiliou, Jamal Hassan and Michael Fardis

Int. J. Mol. Sci. 2023, 24(7), 6739; https://doi.org/10.3390/ijms24076739 - 4 Apr 2023

Viewed by 1284

Abstract

The molecular dynamics of 1-butyl-3-methyl imidazolium tricyanomethanide ionic liquid [BMIM]⁺[TCM]⁻ confined in SBA-15 mesoporous silica were examined using ¹H NMR spin-lattice (T₁) relaxation and diffusion measurements. An extensive temperature range (100 K–400 K) was considered in order to study both the liquid and glassy states. The hydrogen dynamics in the two states and the self-diffusion coefficients of the cation [BMIM]⁺ above the glass transition temperature were extracted from the experimental data. The results were then compared to the corresponding bulk substance. The effects of confinement on the dynamic properties of the ionic liquid clearly manifest themselves in both temperature regimes. In the high-temperature liquid state, the mobility of the confined cations reduces significantly compared to the bulk; interestingly, confinement drives the ionic liquid to the glassy state at a higher temperature T_g than the bulk ionic liquid, whereas an unusual T₁ temperature dependence is observed in the high-temperature regime, assigned to the interaction of the ionic liquid with the silica-OH species. Full article

(This article belongs to the Special Issue NMR Spectroscopy in Materials Chemistry)

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24 pages, 5684 KiB

Open AccessArticle

On the Utmost Importance of the Basis Set Choice for the Calculations of the Relativistic Corrections to NMR Shielding Constants

by Irina L. Rusakova and Yuriy Yu. Rusakov

Int. J. Mol. Sci. 2023, 24(7), 6231; https://doi.org/10.3390/ijms24076231 - 25 Mar 2023

Cited by 3 | Viewed by 1833

Abstract

The investigation of the sensitivity of the relativistic corrections to the NMR shielding constants (σ) to the configuration of angular spaces of the basis sets used on the atoms of interest was carried out within the four-component density functional theory (DFT). Both types of relativistic effects were considered, namely the so-called heavy atom on light atom and heavy atom on heavy atom effects, though the main attention was paid to the former. As a main result, it was found that the dependence of the relativistic corrections to σ of light nuclei (exemplified here by ¹H and ¹³C) located in close vicinity to a heavy atom (exemplified here by In, Sn, Sb, Te, and I) on the basis set used on the light spectator atom was very much in common with that of the Fermi-contact contribution to the corresponding nonrelativistic spin-spin coupling constant (J). In general, it has been shown that the nonrelativistic J-oriented and σ-oriented basis sets, artificially saturated in the tight s-region, provided much better accuracy than the standard nonrelativistic σ-oriented basis sets when calculating the relativistic corrections to the NMR shielding constants of light nuclei at the relativistic four-component level of the DFT theory. Full article

(This article belongs to the Special Issue NMR Spectroscopy in Materials Chemistry)

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15 pages, 3480 KiB

Open AccessArticle

Utilizing the ¹H-¹⁵N NMR Methods for the Characterization of Isomeric Human Milk Oligosaccharides

by Zsófia Garádi, András Tóth, Tamás Gáti, András Dancsó and Szabolcs Béni

Int. J. Mol. Sci. 2023, 24(3), 2180; https://doi.org/10.3390/ijms24032180 - 22 Jan 2023

Cited by 1 | Viewed by 1881

Abstract

Human milk oligosaccharides (HMOs) are structurally complex unconjugated glycans that are the third largest solid fraction in human milk after lactose and lipids. HMOs are in the forefront of research since they have been proven to possess beneficial health effects, especially on breast-fed neonates. Although HMO research is a trending topic nowadays, readily available analytical methods suitable for the routine investigation of HMOs are still incomplete. NMR spectroscopy provides detailed structural information that can be used to indicate subtle structural differences, particularly for isomeric carbohydrates. Herein, we propose an NMR-based method to identify the major isomeric HMOs containing GlcNAc and/or Neu5Ac building blocks utilizing their amide functionality. Experimental conditions were optimized (H₂O:D₂O 9:1 v/v solvent at pH 3.0) to obtain ¹H-¹⁵N HSQC and ¹H-¹⁵N HSQC-TOCSY NMR spectra of the aforementioned building blocks in HMOs. Four isomeric HMO pairs, LNT/LNnT, 3’SL/6’SL, LNFP II/LNFP III, and LSTa/LSTb, were investigated, and complete NMR resonance assignments were provided. In addition, ¹H and ¹⁵N NMR resonances were found to be indicative of various linkages, thereby facilitating the distinction of isomeric tri-, tetra-, and pentasaccharide HMOs. The rapid growth of HMO products (from infant formulas and dietary supplements to cosmetics) undoubtedly requires expanding the range of applicable analytical methods. Thus, our work provides a ¹⁵N NMR-based method to advance this challenging field of carbohydrate analysis. Full article

(This article belongs to the Special Issue NMR Spectroscopy in Materials Chemistry)

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Review

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40 pages, 14340 KiB

Open AccessReview

C- and N-Phosphorylated Enamines—An Avenue to Heterocycles: NMR Spectroscopy

by Lyudmila Larina

Int. J. Mol. Sci. 2023, 24(11), 9646; https://doi.org/10.3390/ijms24119646 - 1 Jun 2023

Viewed by 1494

Abstract

The review presents extensive data (from the works of the author and literature) on the structure of C- and N-chlorophosphorylated enamines and the related heterocycles obtained by multipulse multinuclear ¹H, ¹³C, and ³¹P NMR spectroscopy. The use of phosphorus pentachloride as a phosphorylating agent for functional enamines enables the synthesis of various C- and N-phosphorylated products that are heterocyclized to form various promising nitrogen- and phosphorus-containing heterocyclic systems. ³¹P NMR spectroscopy is the most convenient, reliable and unambiguous method for the study and identification of organophosphorus compounds with different coordination numbers of the phosphorus atom, as well as for the determination of their Z- and E-isomeric forms. An alteration of the coordination number of the phosphorus atom in the phosphorylated compounds from 3 to 6 leads to a drastic screening of the ³¹P nucleus from about +200 to −300 ppm. The unique structural features of nitrogen–phosphorus-containing heterocyclic compounds are discussed. Full article

(This article belongs to the Special Issue NMR Spectroscopy in Materials Chemistry)

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