A Comprehensive Computational NMR Analysis of Organic Polyarsenicals including the Marine Sponge-Derived Arsenicins A–D and Their Synthetic Analogs
The adamantane structure of arsenicin A and nor-adamantane structures of arsenicins B–D have gained attention as unique natural polyarsenicals, as well as hits showing promising anticancer activity. The purpose of this study is to apply the predictive power of NMR DFT calculations in order to identi...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-09-01
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| Series: | Marine Drugs |
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| Online Access: | https://www.mdpi.com/1660-3397/21/10/511 |
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| author | Andrea Defant Ines Mancini |
| author_facet | Andrea Defant Ines Mancini |
| author_sort | Andrea Defant |
| collection | DOAJ |
| description | The adamantane structure of arsenicin A and nor-adamantane structures of arsenicins B–D have gained attention as unique natural polyarsenicals, as well as hits showing promising anticancer activity. The purpose of this study is to apply the predictive power of NMR DFT calculations in order to identify a valid tool to be used in the structural elucidation of similar molecules. <sup>1</sup>H- and <sup>13</sup>C-NMR chemical shifts of twelve natural and synthetic polyarsenical analogs were calculated and validated by comparison with experimental data acquired in CDCl<sub>3</sub> solutions, in regard to mean absolute error (MAE) values under various combinations of two methods (GIAO and CSGT), four functionals and five basis sets, also considering relativistic effects. The best computational approaches are highlighted for predicting the chemical shifts of <sup>1</sup>H and <sup>13</sup>C nuclei and <i>J</i>(<sup>1</sup>H,<sup>1</sup>H) coupling constants in the series of O- and S-polyarsenicals. This comprehensive analysis contributes to making NMR spectroscopy appealing for the structural elucidation of such molecules, contrary to the first structural elucidation of natural arsenicin A, in which the experimental NMR analysis was limited by the poor presence of proton and carbon atoms in its structure and by the shortage of reference data. |
| first_indexed | 2024-03-10T21:05:36Z |
| format | Article |
| id | doaj.art-3909c24d1fb34b6290b5c23bc0957b9d |
| institution | Directory Open Access Journal |
| issn | 1660-3397 |
| language | English |
| last_indexed | 2024-03-10T21:05:36Z |
| publishDate | 2023-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Marine Drugs |
| spelling | doaj.art-3909c24d1fb34b6290b5c23bc0957b9d2023-11-19T17:09:16ZengMDPI AGMarine Drugs1660-33972023-09-01211051110.3390/md21100511A Comprehensive Computational NMR Analysis of Organic Polyarsenicals including the Marine Sponge-Derived Arsenicins A–D and Their Synthetic AnalogsAndrea Defant0Ines Mancini1Laboratory of Bioorganic Chemistry, Department of Physics, University of Trento, Via Sommarive 14, I-38123 Trento, ItalyLaboratory of Bioorganic Chemistry, Department of Physics, University of Trento, Via Sommarive 14, I-38123 Trento, ItalyThe adamantane structure of arsenicin A and nor-adamantane structures of arsenicins B–D have gained attention as unique natural polyarsenicals, as well as hits showing promising anticancer activity. The purpose of this study is to apply the predictive power of NMR DFT calculations in order to identify a valid tool to be used in the structural elucidation of similar molecules. <sup>1</sup>H- and <sup>13</sup>C-NMR chemical shifts of twelve natural and synthetic polyarsenical analogs were calculated and validated by comparison with experimental data acquired in CDCl<sub>3</sub> solutions, in regard to mean absolute error (MAE) values under various combinations of two methods (GIAO and CSGT), four functionals and five basis sets, also considering relativistic effects. The best computational approaches are highlighted for predicting the chemical shifts of <sup>1</sup>H and <sup>13</sup>C nuclei and <i>J</i>(<sup>1</sup>H,<sup>1</sup>H) coupling constants in the series of O- and S-polyarsenicals. This comprehensive analysis contributes to making NMR spectroscopy appealing for the structural elucidation of such molecules, contrary to the first structural elucidation of natural arsenicin A, in which the experimental NMR analysis was limited by the poor presence of proton and carbon atoms in its structure and by the shortage of reference data.https://www.mdpi.com/1660-3397/21/10/511marine metabolitepolyarsenicalstructural characterizationcalculated NMR spectrumchemical shiftdensity functional theory |
| spellingShingle | Andrea Defant Ines Mancini A Comprehensive Computational NMR Analysis of Organic Polyarsenicals including the Marine Sponge-Derived Arsenicins A–D and Their Synthetic Analogs Marine Drugs marine metabolite polyarsenical structural characterization calculated NMR spectrum chemical shift density functional theory |
| title | A Comprehensive Computational NMR Analysis of Organic Polyarsenicals including the Marine Sponge-Derived Arsenicins A–D and Their Synthetic Analogs |
| title_full | A Comprehensive Computational NMR Analysis of Organic Polyarsenicals including the Marine Sponge-Derived Arsenicins A–D and Their Synthetic Analogs |
| title_fullStr | A Comprehensive Computational NMR Analysis of Organic Polyarsenicals including the Marine Sponge-Derived Arsenicins A–D and Their Synthetic Analogs |
| title_full_unstemmed | A Comprehensive Computational NMR Analysis of Organic Polyarsenicals including the Marine Sponge-Derived Arsenicins A–D and Their Synthetic Analogs |
| title_short | A Comprehensive Computational NMR Analysis of Organic Polyarsenicals including the Marine Sponge-Derived Arsenicins A–D and Their Synthetic Analogs |
| title_sort | comprehensive computational nmr analysis of organic polyarsenicals including the marine sponge derived arsenicins a d and their synthetic analogs |
| topic | marine metabolite polyarsenical structural characterization calculated NMR spectrum chemical shift density functional theory |
| url | https://www.mdpi.com/1660-3397/21/10/511 |
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