Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range

Abstract The work introduces hydrophilic PSS-[Tb2(TCAn)2] nanoparticles to be applied as highly sensitive intracellular temperature nanosensors. The nanoparticles are synthesized by solvent-induced nanoprecipitation of [Tb2(TCAn)2] complexes (TCAn - thiacalix[4]arenes bearing different upper-rim sub...

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Autores principales:	Rustem R. Zairov, Alexey P. Dovzhenko, Anastasiia S. Sapunova, Alexandra D. Voloshina, Kirill A. Sarkanich, Amina G. Daminova, Irek R. Nizameev, Dmitry V. Lapaev, Svetlana N. Sudakova, Sergey N. Podyachev, Konstantin A. Petrov, Alberto Vomiero, Asiya R. Mustafina
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2020
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/1ae0059bbe1f4b10b3d99b68176735a3
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spelling	oai:doaj.org-article:1ae0059bbe1f4b10b3d99b68176735a32021-12-02T16:08:37ZTerbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range10.1038/s41598-020-77512-12045-2322https://doaj.org/article/1ae0059bbe1f4b10b3d99b68176735a32020-11-01T00:00:00Zhttps://doi.org/10.1038/s41598-020-77512-1https://doaj.org/toc/2045-2322Abstract The work introduces hydrophilic PSS-[Tb2(TCAn)2] nanoparticles to be applied as highly sensitive intracellular temperature nanosensors. The nanoparticles are synthesized by solvent-induced nanoprecipitation of [Tb2(TCAn)2] complexes (TCAn - thiacalix[4]arenes bearing different upper-rim substituents: unsubstituted TCA1, tert-buthyl-substituted TCA2, di- and tetra-brominated TCA3 and TCA4) with the use of polystyrenesulfonate (PSS) as stabilizer. The temperature responsive luminescence behavior of PSS-[Tb2(TCAn)2] within 293–333 K range in water is modulated by reversible changes derived from the back energy transfer from metal to ligand (M* → T1) correlating with the energy gap between the triplet levels of ligands and resonant 5D4 level of Tb3+ ion. The lowering of the triplet level (T1) energies going from TCA1 and TCA2 to their brominated counterparts TCA3 and TCA4 facilitates the back energy transfer. The highest ever reported temperature sensitivity for intracellular temperature nanosensors is obtained for PSS-[Tb2(TCA4)2] (SI = 5.25% K−1), while PSS-[Tb2(TCA3)2] is characterized by a moderate one (SI = 2.96% K−1). The insignificant release of toxic Tb3+ ions from PSS-[Tb2(TCAn)2] within heating/cooling cycle and the low cytotoxicity of the colloids point to their applicability in intracellular temperature monitoring. The cell internalization of PSS-[Tb2(TCAn)2] (n = 3, 4) marks the cell cytoplasm by green Tb3+-luminescence, which exhibits detectable quenching when the cell samples are heated from 303 to 313 K. The colloids hold unprecedented potential for in vivo intracellular monitoring of temperature changes induced by hyperthermia or pathological processes in narrow range of physiological temperatures.Rustem R. ZairovAlexey P. DovzhenkoAnastasiia S. SapunovaAlexandra D. VoloshinaKirill A. SarkanichAmina G. DaminovaIrek R. NizameevDmitry V. LapaevSvetlana N. SudakovaSergey N. PodyachevKonstantin A. PetrovAlberto VomieroAsiya R. MustafinaNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 10, Iss 1, Pp 1-13 (2020)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Rustem R. Zairov Alexey P. Dovzhenko Anastasiia S. Sapunova Alexandra D. Voloshina Kirill A. Sarkanich Amina G. Daminova Irek R. Nizameev Dmitry V. Lapaev Svetlana N. Sudakova Sergey N. Podyachev Konstantin A. Petrov Alberto Vomiero Asiya R. Mustafina Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range
description	Abstract The work introduces hydrophilic PSS-[Tb2(TCAn)2] nanoparticles to be applied as highly sensitive intracellular temperature nanosensors. The nanoparticles are synthesized by solvent-induced nanoprecipitation of [Tb2(TCAn)2] complexes (TCAn - thiacalix[4]arenes bearing different upper-rim substituents: unsubstituted TCA1, tert-buthyl-substituted TCA2, di- and tetra-brominated TCA3 and TCA4) with the use of polystyrenesulfonate (PSS) as stabilizer. The temperature responsive luminescence behavior of PSS-[Tb2(TCAn)2] within 293–333 K range in water is modulated by reversible changes derived from the back energy transfer from metal to ligand (M* → T1) correlating with the energy gap between the triplet levels of ligands and resonant 5D4 level of Tb3+ ion. The lowering of the triplet level (T1) energies going from TCA1 and TCA2 to their brominated counterparts TCA3 and TCA4 facilitates the back energy transfer. The highest ever reported temperature sensitivity for intracellular temperature nanosensors is obtained for PSS-[Tb2(TCA4)2] (SI = 5.25% K−1), while PSS-[Tb2(TCA3)2] is characterized by a moderate one (SI = 2.96% K−1). The insignificant release of toxic Tb3+ ions from PSS-[Tb2(TCAn)2] within heating/cooling cycle and the low cytotoxicity of the colloids point to their applicability in intracellular temperature monitoring. The cell internalization of PSS-[Tb2(TCAn)2] (n = 3, 4) marks the cell cytoplasm by green Tb3+-luminescence, which exhibits detectable quenching when the cell samples are heated from 303 to 313 K. The colloids hold unprecedented potential for in vivo intracellular monitoring of temperature changes induced by hyperthermia or pathological processes in narrow range of physiological temperatures.
format	article
author	Rustem R. Zairov Alexey P. Dovzhenko Anastasiia S. Sapunova Alexandra D. Voloshina Kirill A. Sarkanich Amina G. Daminova Irek R. Nizameev Dmitry V. Lapaev Svetlana N. Sudakova Sergey N. Podyachev Konstantin A. Petrov Alberto Vomiero Asiya R. Mustafina
author_facet	Rustem R. Zairov Alexey P. Dovzhenko Anastasiia S. Sapunova Alexandra D. Voloshina Kirill A. Sarkanich Amina G. Daminova Irek R. Nizameev Dmitry V. Lapaev Svetlana N. Sudakova Sergey N. Podyachev Konstantin A. Petrov Alberto Vomiero Asiya R. Mustafina
author_sort	Rustem R. Zairov
title	Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range
title_short	Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range
title_full	Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range
title_fullStr	Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range
title_full_unstemmed	Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range
title_sort	terbium(iii)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 k range
publisher	Nature Portfolio
publishDate	2020
url	https://doaj.org/article/1ae0059bbe1f4b10b3d99b68176735a3
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Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303–313 K range

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