pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au<sub>2</sub>L<sub>2</sub>]{Re<sub>6</sub>Q<sub>8</sub>} Colloids (L = PNNP Ligand; Q = S<sup>2−</sup> or Se<sup>2−</sup>)
The present work introduces a simple, electrostatically driven approach to engineered nanomaterial built from the highly cytotoxic [Au<sub>2</sub>L<sub>2</sub>]<sup>2+</sup> complex (Au<sub>2</sub>, L = 1,5-bis(p-tolyl)−3,7-bis(pyridine-2-yl)−1,5-diaza...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-09-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/12/18/3229 |
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| author | Bulat Faizullin Irina Dayanova Igor Strelnik Kirill Kholin Irek Nizameev Aidar Gubaidullin Alexandra Voloshina Tatiana Gerasimova Ilya Kashnik Konstantin Brylev Guzel Sibgatullina Dmitry Samigullin Konstantin Petrov Elvira Musina Andrey Karasik Asiya Mustafina |
| author_facet | Bulat Faizullin Irina Dayanova Igor Strelnik Kirill Kholin Irek Nizameev Aidar Gubaidullin Alexandra Voloshina Tatiana Gerasimova Ilya Kashnik Konstantin Brylev Guzel Sibgatullina Dmitry Samigullin Konstantin Petrov Elvira Musina Andrey Karasik Asiya Mustafina |
| author_sort | Bulat Faizullin |
| collection | DOAJ |
| description | The present work introduces a simple, electrostatically driven approach to engineered nanomaterial built from the highly cytotoxic [Au<sub>2</sub>L<sub>2</sub>]<sup>2+</sup> complex (Au<sub>2</sub>, L = 1,5-bis(p-tolyl)−3,7-bis(pyridine-2-yl)−1,5-diaza-3,7-diphosphacyclooctane (PNNP) ligand) and the pH-sensitive red-emitting [{Re<sub>6</sub>Q<sub>8</sub>}(OH)<sub>6</sub>]<sup>4−</sup> (Re<sub>6</sub>-Q, Q = S<sup>2−</sup> or Se<sup>2−</sup>) cluster units. The protonation/deprotonation of the Re<sub>6</sub>-Q unit is a prerequisite for the pH-triggered assembly of Au<sub>2</sub> and Re<sub>6</sub>-Q into Au<sub>2</sub>Re<sub>6</sub>-Q colloids, exhibiting disassembly in acidic (pH = 4.5) conditions modeling a lysosomal environment. The counter-ion effect of polyethylenimine causes the release of Re<sub>6</sub>-Q units from the colloids, while the binding with lysozyme restricts their protonation in acidified conditions. The enhanced luminescence response of Re<sub>6</sub>-S on the disassembly of Au<sub>2</sub>Re<sub>6</sub>-S colloids in the lysosomal environment allows us to determine their high lysosomal localization extent through the colocalization assay, while the low luminescence of Re<sub>6</sub>-Se units in the same conditions allows us to reveal the rapture of the lysosomal membrane through the use of the Acridine Orange assay. The lysosomal pathway of the colloids, followed by their endo/lysosomal escape, correlates with their cytotoxicity being on the same level as that of Au<sub>2</sub> complexes, but the contribution of the apoptotic pathway differentiates the cytotoxic effect of the colloids from that of the Au<sub>2</sub> complex arisen from the necrotic processes. |
| first_indexed | 2024-03-09T22:58:04Z |
| format | Article |
| id | doaj.art-5cfbeaf691f24bc98ee468745a362e68 |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-09T22:58:04Z |
| publishDate | 2022-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-5cfbeaf691f24bc98ee468745a362e682023-11-23T18:07:47ZengMDPI AGNanomaterials2079-49912022-09-011218322910.3390/nano12183229pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au<sub>2</sub>L<sub>2</sub>]{Re<sub>6</sub>Q<sub>8</sub>} Colloids (L = PNNP Ligand; Q = S<sup>2−</sup> or Se<sup>2−</sup>)Bulat Faizullin0Irina Dayanova1Igor Strelnik2Kirill Kholin3Irek Nizameev4Aidar Gubaidullin5Alexandra Voloshina6Tatiana Gerasimova7Ilya Kashnik8Konstantin Brylev9Guzel Sibgatullina10Dmitry Samigullin11Konstantin Petrov12Elvira Musina13Andrey Karasik14Asiya Mustafina15Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaDepartment of Nanotechnology in Electronics, Kazan National Research Technical University Named after A.N. Tupolev-KAI, 10 K. Marx Street, 420111 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaNikolaev Institute of Inorganic Chemistry, SB RAS, 3 Academician Lavrentiev Avenue, 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, SB RAS, 3 Academician Lavrentiev Avenue, 630090 Novosibirsk, RussiaKazan Institute of Biochemistry and Biophysics, FRC Kazan Scientific Center of RAS, 2/31 Lobachevski Street, 420111 Kazan, RussiaKazan Institute of Biochemistry and Biophysics, FRC Kazan Scientific Center of RAS, 2/31 Lobachevski Street, 420111 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaThe present work introduces a simple, electrostatically driven approach to engineered nanomaterial built from the highly cytotoxic [Au<sub>2</sub>L<sub>2</sub>]<sup>2+</sup> complex (Au<sub>2</sub>, L = 1,5-bis(p-tolyl)−3,7-bis(pyridine-2-yl)−1,5-diaza-3,7-diphosphacyclooctane (PNNP) ligand) and the pH-sensitive red-emitting [{Re<sub>6</sub>Q<sub>8</sub>}(OH)<sub>6</sub>]<sup>4−</sup> (Re<sub>6</sub>-Q, Q = S<sup>2−</sup> or Se<sup>2−</sup>) cluster units. The protonation/deprotonation of the Re<sub>6</sub>-Q unit is a prerequisite for the pH-triggered assembly of Au<sub>2</sub> and Re<sub>6</sub>-Q into Au<sub>2</sub>Re<sub>6</sub>-Q colloids, exhibiting disassembly in acidic (pH = 4.5) conditions modeling a lysosomal environment. The counter-ion effect of polyethylenimine causes the release of Re<sub>6</sub>-Q units from the colloids, while the binding with lysozyme restricts their protonation in acidified conditions. The enhanced luminescence response of Re<sub>6</sub>-S on the disassembly of Au<sub>2</sub>Re<sub>6</sub>-S colloids in the lysosomal environment allows us to determine their high lysosomal localization extent through the colocalization assay, while the low luminescence of Re<sub>6</sub>-Se units in the same conditions allows us to reveal the rapture of the lysosomal membrane through the use of the Acridine Orange assay. The lysosomal pathway of the colloids, followed by their endo/lysosomal escape, correlates with their cytotoxicity being on the same level as that of Au<sub>2</sub> complexes, but the contribution of the apoptotic pathway differentiates the cytotoxic effect of the colloids from that of the Au<sub>2</sub> complex arisen from the necrotic processes.https://www.mdpi.com/2079-4991/12/18/3229hexarhenium clustersAu(I) complexpH-triggered disassemblyrapture of lysosomal membraneapoptotic pathway |
| spellingShingle | Bulat Faizullin Irina Dayanova Igor Strelnik Kirill Kholin Irek Nizameev Aidar Gubaidullin Alexandra Voloshina Tatiana Gerasimova Ilya Kashnik Konstantin Brylev Guzel Sibgatullina Dmitry Samigullin Konstantin Petrov Elvira Musina Andrey Karasik Asiya Mustafina pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au<sub>2</sub>L<sub>2</sub>]{Re<sub>6</sub>Q<sub>8</sub>} Colloids (L = PNNP Ligand; Q = S<sup>2−</sup> or Se<sup>2−</sup>) Nanomaterials hexarhenium clusters Au(I) complex pH-triggered disassembly rapture of lysosomal membrane apoptotic pathway |
| title | pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au<sub>2</sub>L<sub>2</sub>]{Re<sub>6</sub>Q<sub>8</sub>} Colloids (L = PNNP Ligand; Q = S<sup>2−</sup> or Se<sup>2−</sup>) |
| title_full | pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au<sub>2</sub>L<sub>2</sub>]{Re<sub>6</sub>Q<sub>8</sub>} Colloids (L = PNNP Ligand; Q = S<sup>2−</sup> or Se<sup>2−</sup>) |
| title_fullStr | pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au<sub>2</sub>L<sub>2</sub>]{Re<sub>6</sub>Q<sub>8</sub>} Colloids (L = PNNP Ligand; Q = S<sup>2−</sup> or Se<sup>2−</sup>) |
| title_full_unstemmed | pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au<sub>2</sub>L<sub>2</sub>]{Re<sub>6</sub>Q<sub>8</sub>} Colloids (L = PNNP Ligand; Q = S<sup>2−</sup> or Se<sup>2−</sup>) |
| title_short | pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au<sub>2</sub>L<sub>2</sub>]{Re<sub>6</sub>Q<sub>8</sub>} Colloids (L = PNNP Ligand; Q = S<sup>2−</sup> or Se<sup>2−</sup>) |
| title_sort | ph driven intracellular nano to molecular disassembly of heterometallic au sub 2 sub l sub 2 sub re sub 6 sub q sub 8 sub colloids l pnnp ligand q s sup 2 sup or se sup 2 sup |
| topic | hexarhenium clusters Au(I) complex pH-triggered disassembly rapture of lysosomal membrane apoptotic pathway |
| url | https://www.mdpi.com/2079-4991/12/18/3229 |
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