The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphy
There is still a need for synthetic approaches that are much faster, easier to scale up, more robust and efficient for generating gold(I)–thiolates that can be easily converted into gold–thiolate nanoclusters. Mechanochemical methods can offer significantly reduced reaction times, increased yields a...
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| Format: | Article |
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Frontiers Media S.A.
2023-06-01
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| Series: | Frontiers in Chemistry |
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| Online Access: | https://www.frontiersin.org/articles/10.3389/fchem.2023.1178225/full |
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| author | Andrea Deák Pál T. Szabó Vendula Bednaříková Jaroslav Cihlář Attila Demeter Michaela Remešová Evelina Colacino Ladislav Čelko |
| author_facet | Andrea Deák Pál T. Szabó Vendula Bednaříková Jaroslav Cihlář Attila Demeter Michaela Remešová Evelina Colacino Ladislav Čelko |
| author_sort | Andrea Deák |
| collection | DOAJ |
| description | There is still a need for synthetic approaches that are much faster, easier to scale up, more robust and efficient for generating gold(I)–thiolates that can be easily converted into gold–thiolate nanoclusters. Mechanochemical methods can offer significantly reduced reaction times, increased yields and straightforward recovery of the product, compared to the solution-based reactions. For the first time, a new simple, rapid and efficient mechanochemical redox method in a ball-mill was developed to produce the highly luminescent, pH-responsive Au(I)–glutathionate, [Au(SG)]n. The efficient productivity of the mechanochemical redox reaction afforded orange luminescent [Au(SG)]n in isolable amounts (mg scale), usually not achieved by more conventional methods in solution. Then, ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters were prepared by pH-triggered dissociation of [Au(SG)]n. The pH-stimulated dissociation of the Au(I)–glutathionate complex provides a time-efficient synthesis of oligomeric Au10–12(SG)10–12 nanoclusters, it avoids high-temperature heating or the addition of harmful reducing agent (e.g., carbon monoxide). Therefore, we present herein a new and eco-friendly methodology to access oligomeric glutathione-based gold nanoclusters, already finding applications in biomedical field as efficient radiosensitizers in cancer radiotherapy. |
| first_indexed | 2024-03-13T07:15:44Z |
| format | Article |
| id | doaj.art-20de57ca15ed4a08bb439fd2bc781dae |
| institution | Directory Open Access Journal |
| issn | 2296-2646 |
| language | English |
| last_indexed | 2024-03-13T07:15:44Z |
| publishDate | 2023-06-01 |
| publisher | Frontiers Media S.A. |
| record_format | Article |
| series | Frontiers in Chemistry |
| spelling | doaj.art-20de57ca15ed4a08bb439fd2bc781dae2023-06-05T05:23:16ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462023-06-011110.3389/fchem.2023.11782251178225The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphyAndrea Deák0Pál T. Szabó1Vendula Bednaříková2Jaroslav Cihlář3Attila Demeter4Michaela Remešová5Evelina Colacino6Ladislav Čelko7Supramolecular Chemistry Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Budapest, HungaryCentre for Structure Study, Research Centre for Natural Sciences, Budapest, HungaryHigh-Performance Materials and Coatings for Industry Research Group, Central European Institute of Technology, Brno University of Technology, Brno, CzechiaHigh-Performance Materials and Coatings for Industry Research Group, Central European Institute of Technology, Brno University of Technology, Brno, CzechiaRenewable Energy Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Budapest, HungaryHigh-Performance Materials and Coatings for Industry Research Group, Central European Institute of Technology, Brno University of Technology, Brno, CzechiaICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, FranceHigh-Performance Materials and Coatings for Industry Research Group, Central European Institute of Technology, Brno University of Technology, Brno, CzechiaThere is still a need for synthetic approaches that are much faster, easier to scale up, more robust and efficient for generating gold(I)–thiolates that can be easily converted into gold–thiolate nanoclusters. Mechanochemical methods can offer significantly reduced reaction times, increased yields and straightforward recovery of the product, compared to the solution-based reactions. For the first time, a new simple, rapid and efficient mechanochemical redox method in a ball-mill was developed to produce the highly luminescent, pH-responsive Au(I)–glutathionate, [Au(SG)]n. The efficient productivity of the mechanochemical redox reaction afforded orange luminescent [Au(SG)]n in isolable amounts (mg scale), usually not achieved by more conventional methods in solution. Then, ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters were prepared by pH-triggered dissociation of [Au(SG)]n. The pH-stimulated dissociation of the Au(I)–glutathionate complex provides a time-efficient synthesis of oligomeric Au10–12(SG)10–12 nanoclusters, it avoids high-temperature heating or the addition of harmful reducing agent (e.g., carbon monoxide). Therefore, we present herein a new and eco-friendly methodology to access oligomeric glutathione-based gold nanoclusters, already finding applications in biomedical field as efficient radiosensitizers in cancer radiotherapy.https://www.frontiersin.org/articles/10.3389/fchem.2023.1178225/fullbioactive moleculesgold nanoclustergold thiolateglutathionemechanochemistry |
| spellingShingle | Andrea Deák Pál T. Szabó Vendula Bednaříková Jaroslav Cihlář Attila Demeter Michaela Remešová Evelina Colacino Ladislav Čelko The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphy Frontiers in Chemistry bioactive molecules gold nanocluster gold thiolate glutathione mechanochemistry |
| title | The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphy |
| title_full | The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphy |
| title_fullStr | The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphy |
| title_full_unstemmed | The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphy |
| title_short | The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphy |
| title_sort | first solid state route to luminescent au i glutathionate and its ph controlled transformation into ultrasmall oligomeric au10 12 sg 10 12 nanoclusters for application in cancer radiotheraphy |
| topic | bioactive molecules gold nanocluster gold thiolate glutathione mechanochemistry |
| url | https://www.frontiersin.org/articles/10.3389/fchem.2023.1178225/full |
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