Visible Light Photocleavable Ruthenium-Based Molecular Gates to Reversibly Control Release from Mesoporous Silica Nanoparticles
Herein we present hybrid mesoporous silica nanomaterials (MSN) with visible light-sensitive ruthenium complexes acting as gates. Two different [Ru(bpy)<sub>2</sub>L1L2]<sup>2+</sup> complexes were investigated by grafting [Ru(bpy)<sub>2</sub>(4AMP)<sub>2<...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-05-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/10/6/1030 |
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| author | Yolanda Salinas Oliver Brüggemann Uwe Monkowius Ian Teasdale |
| author_facet | Yolanda Salinas Oliver Brüggemann Uwe Monkowius Ian Teasdale |
| author_sort | Yolanda Salinas |
| collection | DOAJ |
| description | Herein we present hybrid mesoporous silica nanomaterials (MSN) with visible light-sensitive ruthenium complexes acting as gates. Two different [Ru(bpy)<sub>2</sub>L1L2]<sup>2+</sup> complexes were investigated by grafting [Ru(bpy)<sub>2</sub>(4AMP)<sub>2</sub>](PF<sub>6</sub>)<sub>2</sub> (RC1) and [Ru(bpy)<sub>2</sub>(PPh<sub>3</sub>)Cl]Cl (RC2) via two or one ligands onto the surface of mesoporous silica nanoparticles (MSNs), to give MSN1-RC1 and MSN2-RC2, respectively. The pores were previously loaded with a common dye, safranin O, and release studies were conducted. The number and position of the ligands were shown to influence the photocages behavior and thus the release of the cargo. Release studies from MSN1-RC1 in acetonitrile showed that in the dark the amount of dye released was minimal after 300 min, whereas a significant increase was measured upon visible light irradiation (ca. 90%). While successful as a photochemically-controlled gated system, RC1 was restricted to organic solvents since it required cleavage of two ligands in order to be cleaved from the surface, and in water only one is cleaved. Release studies from the second nanomaterial MSN2-RC2, where the complex RC2 was bound to the MSN via only one ligand, showed stability under darkness and in aqueous solution up to 180 min and, rapid release of the dye when irradiated with visible light. Furthermore, this system was demonstrated to be reversible, since, upon heating to 80 °C, the system could effectively re-close the pores and re-open it again upon visible light irradiation. This work, thus, demonstrates the potential reversible gate mechanism of the ruthenium-gated nanomaterials upon visible light irradiation, and could be envisioned as a future design of photochemically-driven drug delivery nanosystems or on/off switches for nanorelease systems. |
| first_indexed | 2024-03-10T19:32:48Z |
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| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-10T19:32:48Z |
| publishDate | 2020-05-01 |
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| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-8ad460847cc0439380117db852e5d2fa2023-11-20T02:01:09ZengMDPI AGNanomaterials2079-49912020-05-01106103010.3390/nano10061030Visible Light Photocleavable Ruthenium-Based Molecular Gates to Reversibly Control Release from Mesoporous Silica NanoparticlesYolanda Salinas0Oliver Brüggemann1Uwe Monkowius2Ian Teasdale3Institute of Polymer Chemistry, Johannes Kepler University Linz, Altenberger Straße 69, 4040 Linz, AustriaInstitute of Polymer Chemistry, Johannes Kepler University Linz, Altenberger Straße 69, 4040 Linz, AustriaLinz School of Education, Johannes Kepler University Linz, Altenberger Straße 69, 4040 Linz, AustriaInstitute of Polymer Chemistry, Johannes Kepler University Linz, Altenberger Straße 69, 4040 Linz, AustriaHerein we present hybrid mesoporous silica nanomaterials (MSN) with visible light-sensitive ruthenium complexes acting as gates. Two different [Ru(bpy)<sub>2</sub>L1L2]<sup>2+</sup> complexes were investigated by grafting [Ru(bpy)<sub>2</sub>(4AMP)<sub>2</sub>](PF<sub>6</sub>)<sub>2</sub> (RC1) and [Ru(bpy)<sub>2</sub>(PPh<sub>3</sub>)Cl]Cl (RC2) via two or one ligands onto the surface of mesoporous silica nanoparticles (MSNs), to give MSN1-RC1 and MSN2-RC2, respectively. The pores were previously loaded with a common dye, safranin O, and release studies were conducted. The number and position of the ligands were shown to influence the photocages behavior and thus the release of the cargo. Release studies from MSN1-RC1 in acetonitrile showed that in the dark the amount of dye released was minimal after 300 min, whereas a significant increase was measured upon visible light irradiation (ca. 90%). While successful as a photochemically-controlled gated system, RC1 was restricted to organic solvents since it required cleavage of two ligands in order to be cleaved from the surface, and in water only one is cleaved. Release studies from the second nanomaterial MSN2-RC2, where the complex RC2 was bound to the MSN via only one ligand, showed stability under darkness and in aqueous solution up to 180 min and, rapid release of the dye when irradiated with visible light. Furthermore, this system was demonstrated to be reversible, since, upon heating to 80 °C, the system could effectively re-close the pores and re-open it again upon visible light irradiation. This work, thus, demonstrates the potential reversible gate mechanism of the ruthenium-gated nanomaterials upon visible light irradiation, and could be envisioned as a future design of photochemically-driven drug delivery nanosystems or on/off switches for nanorelease systems.https://www.mdpi.com/2079-4991/10/6/1030mesoporous silica nanoparticles (MSNs)visible light photocleavagemolecular gatesreversibilitycargo release on demandruthenium complex |
| spellingShingle | Yolanda Salinas Oliver Brüggemann Uwe Monkowius Ian Teasdale Visible Light Photocleavable Ruthenium-Based Molecular Gates to Reversibly Control Release from Mesoporous Silica Nanoparticles Nanomaterials mesoporous silica nanoparticles (MSNs) visible light photocleavage molecular gates reversibility cargo release on demand ruthenium complex |
| title | Visible Light Photocleavable Ruthenium-Based Molecular Gates to Reversibly Control Release from Mesoporous Silica Nanoparticles |
| title_full | Visible Light Photocleavable Ruthenium-Based Molecular Gates to Reversibly Control Release from Mesoporous Silica Nanoparticles |
| title_fullStr | Visible Light Photocleavable Ruthenium-Based Molecular Gates to Reversibly Control Release from Mesoporous Silica Nanoparticles |
| title_full_unstemmed | Visible Light Photocleavable Ruthenium-Based Molecular Gates to Reversibly Control Release from Mesoporous Silica Nanoparticles |
| title_short | Visible Light Photocleavable Ruthenium-Based Molecular Gates to Reversibly Control Release from Mesoporous Silica Nanoparticles |
| title_sort | visible light photocleavable ruthenium based molecular gates to reversibly control release from mesoporous silica nanoparticles |
| topic | mesoporous silica nanoparticles (MSNs) visible light photocleavage molecular gates reversibility cargo release on demand ruthenium complex |
| url | https://www.mdpi.com/2079-4991/10/6/1030 |
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