Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model Dioxetanone
Chemi-/bioluminescence are phenomena in which chemical energy is converted into electronically excited singlet states, which decay with light emission. Given this feature, along with high quantum yields and other beneficial characteristics, these systems have gained numerous applications in bioanaly...
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| Format: | Article |
| Language: | English |
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Wiley
2017-01-01
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| Series: | Journal of Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2017/1903981 |
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| author | Luís Pinto da Silva Rui F. J. Pereira Joaquim C. G. Esteves da Silva |
| author_facet | Luís Pinto da Silva Rui F. J. Pereira Joaquim C. G. Esteves da Silva |
| author_sort | Luís Pinto da Silva |
| collection | DOAJ |
| description | Chemi-/bioluminescence are phenomena in which chemical energy is converted into electronically excited singlet states, which decay with light emission. Given this feature, along with high quantum yields and other beneficial characteristics, these systems have gained numerous applications in bioanalysis, in biomedicine, and in the pharmaceutical field. Singlet chemiexcitation is made possible by the formation of cyclic peroxides (as dioxetanones) as thermolysis provides a route for a ground state reaction to produce singlet excited states. However, such thermolysis can also lead to the formation of triplet states. While triplet states are not desired in the typical applications of chemi-/bioluminescence, the efficient production of such states can open the door for the use of these systems as sensitizers in photocatalysis and triplet-triplet annihilation, among other fields. Thus, the goal of this study is to assess the effect of heavy atom addition on the thermolysis and triplet chemiexcitation of a model dioxetanone. Monobromination does not affect the thermolysis reaction but can improve the efficiency of intersystem crossing, depending on the position of monobromination. Addition of bromine atoms to the triplet state reaction product has little effect on its properties, except on its electron affinity, in which monobromination can increase between 3.1 and 8.8 kcal mol−1. |
| format | Article |
| id | doaj-art-98cf3e8ccadd4ae99a9b9530f9c68270 |
| institution | Kabale University |
| issn | 2090-9063 2090-9071 |
| language | English |
| publishDate | 2017-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Journal of Chemistry |
| spelling | doaj-art-98cf3e8ccadd4ae99a9b9530f9c682702025-08-20T03:37:23ZengWileyJournal of Chemistry2090-90632090-90712017-01-01201710.1155/2017/19039811903981Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model DioxetanoneLuís Pinto da Silva0Rui F. J. Pereira1Joaquim C. G. Esteves da Silva2Chemistry Research Unit (CIQUP), Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto, PortugalChemistry Research Unit (CIQUP), Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto, PortugalChemistry Research Unit (CIQUP), Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto, PortugalChemi-/bioluminescence are phenomena in which chemical energy is converted into electronically excited singlet states, which decay with light emission. Given this feature, along with high quantum yields and other beneficial characteristics, these systems have gained numerous applications in bioanalysis, in biomedicine, and in the pharmaceutical field. Singlet chemiexcitation is made possible by the formation of cyclic peroxides (as dioxetanones) as thermolysis provides a route for a ground state reaction to produce singlet excited states. However, such thermolysis can also lead to the formation of triplet states. While triplet states are not desired in the typical applications of chemi-/bioluminescence, the efficient production of such states can open the door for the use of these systems as sensitizers in photocatalysis and triplet-triplet annihilation, among other fields. Thus, the goal of this study is to assess the effect of heavy atom addition on the thermolysis and triplet chemiexcitation of a model dioxetanone. Monobromination does not affect the thermolysis reaction but can improve the efficiency of intersystem crossing, depending on the position of monobromination. Addition of bromine atoms to the triplet state reaction product has little effect on its properties, except on its electron affinity, in which monobromination can increase between 3.1 and 8.8 kcal mol−1.http://dx.doi.org/10.1155/2017/1903981 |
| spellingShingle | Luís Pinto da Silva Rui F. J. Pereira Joaquim C. G. Esteves da Silva Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model Dioxetanone Journal of Chemistry |
| title | Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model Dioxetanone |
| title_full | Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model Dioxetanone |
| title_fullStr | Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model Dioxetanone |
| title_full_unstemmed | Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model Dioxetanone |
| title_short | Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model Dioxetanone |
| title_sort | theoretical analysis of the effect provoked by bromine addition on the thermolysis and chemiexcitation of a model dioxetanone |
| url | http://dx.doi.org/10.1155/2017/1903981 |
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