The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin
Abstract In this paper, thermal properties, atomic-scale structure, and molecular dynamics (at ambient and high pressure) of native melatonin (MLT) and its partially-deuterated derivative (MLT-d2) have been investigated. Based on infrared spectroscopy, it was shown that treating MLT with D2O causes...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2022-08-01
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| Series: | Scientific Reports |
| Online Access: | https://doi.org/10.1038/s41598-022-18478-0 |
| _version_ | 1811188827777138688 |
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| author | Paulina Jesionek Barbara Hachuła Dawid Heczko Karolina Jurkiewicz Magdalena Tarnacka Maciej Zubko Marian Paluch Kamil Kamiński Ewa Kamińska |
| author_facet | Paulina Jesionek Barbara Hachuła Dawid Heczko Karolina Jurkiewicz Magdalena Tarnacka Maciej Zubko Marian Paluch Kamil Kamiński Ewa Kamińska |
| author_sort | Paulina Jesionek |
| collection | DOAJ |
| description | Abstract In this paper, thermal properties, atomic-scale structure, and molecular dynamics (at ambient and high pressure) of native melatonin (MLT) and its partially-deuterated derivative (MLT-d2) have been investigated. Based on infrared spectroscopy, it was shown that treating MLT with D2O causes the replacement of hydrogen atoms attached to the nitrogen by deuterium. The degree of such substitution was very high (> 99%) and the deuterated sample remained stable after exposure to the air as well as during the melting and vitrification processes. Further calorimetric studies revealed the appearance of a peculiar thermal event before the melting of crystalline MLT-d2, which was assigned by the X-ray diffraction to a local negative thermal expansion of the unit cell. Finally, the high-pressure dielectric experiments indicated a few interesting findings, including the variation in the shape of the structural relaxation peak during compression, the difference in the pressure evolution of the glass transition temperature, and the temperature dependence of activation volume for both MLT species. The variations in these parameters manifest a different impact of the compression/densification on the dynamics of hydrogen and deuterium bonds in the native and partially-deuterated MLT, respectively. |
| first_indexed | 2024-04-11T14:25:48Z |
| format | Article |
| id | doaj.art-a9988b0d917b4b5f8493a081e62da7e7 |
| institution | Directory Open Access Journal |
| issn | 2045-2322 |
| language | English |
| last_indexed | 2024-04-11T14:25:48Z |
| publishDate | 2022-08-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj.art-a9988b0d917b4b5f8493a081e62da7e72022-12-22T04:18:53ZengNature PortfolioScientific Reports2045-23222022-08-0112111210.1038/s41598-022-18478-0The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatoninPaulina Jesionek0Barbara Hachuła1Dawid Heczko2Karolina Jurkiewicz3Magdalena Tarnacka4Maciej Zubko5Marian Paluch6Kamil Kamiński7Ewa Kamińska8Institute of Chemistry, Faculty of Science and Technology, University of Silesia in KatowiceInstitute of Chemistry, Faculty of Science and Technology, University of Silesia in KatowiceDepartment of Pharmacognosy and Phytochemistry, Faculty of Pharmaceutical Sciences in Sosnowiec, Medical University of Silesia in KatowiceInstitute of Physics, Faculty of Science and Technology, University of Silesia in KatowiceInstitute of Physics, Faculty of Science and Technology, University of Silesia in KatowiceInstitute of Materials Engineering, Faculty of Science and Technology, University of Silesia in KatowiceInstitute of Physics, Faculty of Science and Technology, University of Silesia in KatowiceInstitute of Physics, Faculty of Science and Technology, University of Silesia in KatowiceDepartment of Pharmacognosy and Phytochemistry, Faculty of Pharmaceutical Sciences in Sosnowiec, Medical University of Silesia in KatowiceAbstract In this paper, thermal properties, atomic-scale structure, and molecular dynamics (at ambient and high pressure) of native melatonin (MLT) and its partially-deuterated derivative (MLT-d2) have been investigated. Based on infrared spectroscopy, it was shown that treating MLT with D2O causes the replacement of hydrogen atoms attached to the nitrogen by deuterium. The degree of such substitution was very high (> 99%) and the deuterated sample remained stable after exposure to the air as well as during the melting and vitrification processes. Further calorimetric studies revealed the appearance of a peculiar thermal event before the melting of crystalline MLT-d2, which was assigned by the X-ray diffraction to a local negative thermal expansion of the unit cell. Finally, the high-pressure dielectric experiments indicated a few interesting findings, including the variation in the shape of the structural relaxation peak during compression, the difference in the pressure evolution of the glass transition temperature, and the temperature dependence of activation volume for both MLT species. The variations in these parameters manifest a different impact of the compression/densification on the dynamics of hydrogen and deuterium bonds in the native and partially-deuterated MLT, respectively.https://doi.org/10.1038/s41598-022-18478-0 |
| spellingShingle | Paulina Jesionek Barbara Hachuła Dawid Heczko Karolina Jurkiewicz Magdalena Tarnacka Maciej Zubko Marian Paluch Kamil Kamiński Ewa Kamińska The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin Scientific Reports |
| title | The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin |
| title_full | The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin |
| title_fullStr | The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin |
| title_full_unstemmed | The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin |
| title_short | The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin |
| title_sort | impact of h d exchange on the thermal and structural properties as well as high pressure relaxation dynamics of melatonin |
| url | https://doi.org/10.1038/s41598-022-18478-0 |
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