Fakhri O Yousef, Raed Ghanem, Haitham H Al-Sa’doni, Omar K Almashaqbeh, Baraah M Mashagba, Ihsan A Shehadi, Raed A Al-Qawasmeh, Hussein M Elmehdi
{"title":"The effect of n-type and p-type semiconductors on the photoconversion of colchicine. Experimental and computational study","authors":"Fakhri O Yousef, Raed Ghanem, Haitham H Al-Sa’doni, Omar K Almashaqbeh, Baraah M Mashagba, Ihsan A Shehadi, Raed A Al-Qawasmeh, Hussein M Elmehdi","doi":"10.1007/s12039-025-02376-9","DOIUrl":null,"url":null,"abstract":"<div><p>The effect of n-type (CeO<sub>2</sub>, SnO<sub>2</sub> and TiO<sub>2</sub>) and p-type (SnO and TiO) semiconductors on the photoconversion of colchicine (COL) was investigated. All investigated semiconductors induced quenching of the fluorescence emission of COL with Stern–Volmer quenching constants <span>\\({k}_{sv}\\)</span>, ranging from (1.8 ± 0.1) × 10<sup>4</sup> mol<sup>−1</sup> · L for CeO<sub>2</sub> to (3.5 ± 0.1) × 10<sup>3</sup> mol<sup>−1</sup> · L for TiO<sub>2</sub>. n-type semiconductors (SnO<sub>2</sub> and TiO<sub>2</sub>) exhibited the most reduction in photo conversion rate constant and yields, achieving ≈50% inhibition in the presence of 8×10<sup>−5</sup> mol · L<sup>−1</sup> of TiO<sub>2</sub> and SnO<sub>2</sub>. While p-types showed minimal effects. Density functional theory (DFT) calculations were used to provide a clear insight into the effects of semiconductors on Frontier Molecular Orbitals (FMO) structure and HOMO-LUMO energy gaps of COL. DFT calculations showed the presence of n-type semiconductors reduces the HOMO-LUMO energy gap. Moreover, in the presence of n-type semiconductors, changes in the electronic topologies and dihedral angles of phenyl, 7-membered ring and tropolone ring in COL indicate a noticeable involvement of the tropolone and phenyl <i>π</i>-systems of COL with the conduction band of the semiconductors. These results support the observed fluorescence quenching and reduction of the photoconversion rate of COL in the presence of n-type semiconductors. The combined experimental and computational results elucidate the mechanism underlying fluorescence quenching and photoconversion inhibition, highlighting the crucial role of semiconductor type in modulating COL’s photochemical behavior.</p><h3>Graphical abstract</h3><p>We investigate the role of n and p-type semiconductors on the photoconversion of colchicine. Both the semiconductors were found to quench the colchicine fluorescence, and n-type semiconductors exhibited a more pronounced effect. Moreover, it reduced colchicine, and the HOMO-LUMO energy gap influenced its electronic structure, leading to decreased photoconversion rates.\n</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0000,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Sciences","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s12039-025-02376-9","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The effect of n-type (CeO2, SnO2 and TiO2) and p-type (SnO and TiO) semiconductors on the photoconversion of colchicine (COL) was investigated. All investigated semiconductors induced quenching of the fluorescence emission of COL with Stern–Volmer quenching constants \({k}_{sv}\), ranging from (1.8 ± 0.1) × 104 mol−1 · L for CeO2 to (3.5 ± 0.1) × 103 mol−1 · L for TiO2. n-type semiconductors (SnO2 and TiO2) exhibited the most reduction in photo conversion rate constant and yields, achieving ≈50% inhibition in the presence of 8×10−5 mol · L−1 of TiO2 and SnO2. While p-types showed minimal effects. Density functional theory (DFT) calculations were used to provide a clear insight into the effects of semiconductors on Frontier Molecular Orbitals (FMO) structure and HOMO-LUMO energy gaps of COL. DFT calculations showed the presence of n-type semiconductors reduces the HOMO-LUMO energy gap. Moreover, in the presence of n-type semiconductors, changes in the electronic topologies and dihedral angles of phenyl, 7-membered ring and tropolone ring in COL indicate a noticeable involvement of the tropolone and phenyl π-systems of COL with the conduction band of the semiconductors. These results support the observed fluorescence quenching and reduction of the photoconversion rate of COL in the presence of n-type semiconductors. The combined experimental and computational results elucidate the mechanism underlying fluorescence quenching and photoconversion inhibition, highlighting the crucial role of semiconductor type in modulating COL’s photochemical behavior.
Graphical abstract
We investigate the role of n and p-type semiconductors on the photoconversion of colchicine. Both the semiconductors were found to quench the colchicine fluorescence, and n-type semiconductors exhibited a more pronounced effect. Moreover, it reduced colchicine, and the HOMO-LUMO energy gap influenced its electronic structure, leading to decreased photoconversion rates.
研究了n型（CeO2、SnO2和TiO2）和p型（SnO和TiO）半导体对秋水仙碱（COL）光转化的影响。所有研究的半导体诱导COL荧光发射猝灭的Stern-Volmer猝灭常数\({k}_{sv}\)为CeO2的（1.8±0.1）× 104 mol−1·L到TiO2的（3.5±0.1）× 103 mol−1·L。n型半导体（SnO2和TiO2）的光转化率常数和产率降低幅度最大，达到≈50% inhibition in the presence of 8×10−5 mol · L−1 of TiO2 and SnO2. While p-types showed minimal effects. Density functional theory (DFT) calculations were used to provide a clear insight into the effects of semiconductors on Frontier Molecular Orbitals (FMO) structure and HOMO-LUMO energy gaps of COL. DFT calculations showed the presence of n-type semiconductors reduces the HOMO-LUMO energy gap. Moreover, in the presence of n-type semiconductors, changes in the electronic topologies and dihedral angles of phenyl, 7-membered ring and tropolone ring in COL indicate a noticeable involvement of the tropolone and phenyl π-systems of COL with the conduction band of the semiconductors. These results support the observed fluorescence quenching and reduction of the photoconversion rate of COL in the presence of n-type semiconductors. The combined experimental and computational results elucidate the mechanism underlying fluorescence quenching and photoconversion inhibition, highlighting the crucial role of semiconductor type in modulating COL’s photochemical behavior.Graphical abstractWe investigate the role of n and p-type semiconductors on the photoconversion of colchicine. Both the semiconductors were found to quench the colchicine fluorescence, and n-type semiconductors exhibited a more pronounced effect. Moreover, it reduced colchicine, and the HOMO-LUMO energy gap influenced its electronic structure, leading to decreased photoconversion rates.
期刊介绍：
Journal of Chemical Sciences is a monthly journal published by the Indian Academy of Sciences. It formed part of the original Proceedings of the Indian Academy of Sciences – Part A, started by the Nobel Laureate Prof C V Raman in 1934, that was split in 1978 into three separate journals. It was renamed as Journal of Chemical Sciences in 2004. The journal publishes original research articles and rapid communications, covering all areas of chemical sciences. A significant feature of the journal is its special issues, brought out from time to time, devoted to conference symposia/proceedings in frontier areas of the subject, held not only in India but also in other countries.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
