Timothée Lathion, Julie Bourseguin, Svetlana V. Eliseeva, Matthias Zeller, Stéphane Petoud, Vincent L. Pecoraro
{"title":"新型镧系(III)/镓(III)金属冠,附加可见吸收有机增敏剂,用于活细胞的分子近红外成像","authors":"Timothée Lathion, Julie Bourseguin, Svetlana V. Eliseeva, Matthias Zeller, Stéphane Petoud, Vincent L. Pecoraro","doi":"10.1039/d5sc01320h","DOIUrl":null,"url":null,"abstract":"Optical imaging of biological samples in the near-infrared (NIR) domain is of major interest for non-invasive experiments due to reduced light scattering, absorption and autofluorescence. Taking advantage of the maleimide moieties in the [Ln<small><sub>2</sub></small>Ga<small><sub>8</sub></small>(shi)<small><sub>8</sub></small>(mip)<small><sub>4</sub></small>]<small><sup>2−</sup></small> metallacrowns (MCs; <strong>shi<small><sup>3−</sup></small></strong> = salicylhydroximate; mip<small><sup>2−</sup></small> = 5-maleimido-isophthalate; Ln = Nd<small><sup>III</sup></small>, Gd<small><sup>III</sup></small>, Er<small><sup>III</sup></small>, Yb<small><sup>III</sup></small> and Y<small><sup>III</sup></small>), we appended visible-absorbing thiol-coumarin (<strong>C</strong>) sensitizers through a thiol-Michael addition click reaction, affording the functionalized [Ln<small><sub>2</sub></small>Ga<small><sub>8</sub></small>(shi)<small><sub>8</sub></small>(C-mip)<small><sub>4</sub></small>]<small><sup>2−</sup></small> MCs. By using this approach, the sensitization of NIR-emitting Nd<small><sup>III</sup></small>, Er<small><sup>III</sup></small> and Yb<small><sup>III</sup></small> was achieved upon excitation in the visible range (<em>λ</em><small><sub>exc</sub></small> = 420 nm) through the appended coumarins. NIR epifluorescence microscopy of living HeLa cells incubated with the Nd<small><sup>III</sup></small> derivative confirmed unambiguous detection of the signal arising from the <small><sup>4</sup></small>F<small><sub>3/2</sub></small> → <small><sup>4</sup></small>I<small><sub>11/2</sub></small> electronic transition in the range of 1050–1080 nm in the cells. These results demonstrate that the [Ln<small><sub>2</sub></small>Ga<small><sub>8</sub></small>(shi)<small><sub>8</sub></small>(mip)<small><sub>4</sub></small>]<small><sup>2−</sup></small> MC can be used as a versatile molecule for tuning the chemical and photophysical properties of the [Ln<small><sub>2</sub></small>Ga<small><sub>8</sub></small>] MC family.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"70 1","pages":""},"PeriodicalIF":7.6000,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Novel lanthanide(III)/gallium(III) metallacrowns with appended visible-absorbing organic sensitizers for molecular near-infrared imaging of living cells\",\"authors\":\"Timothée Lathion, Julie Bourseguin, Svetlana V. Eliseeva, Matthias Zeller, Stéphane Petoud, Vincent L. Pecoraro\",\"doi\":\"10.1039/d5sc01320h\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Optical imaging of biological samples in the near-infrared (NIR) domain is of major interest for non-invasive experiments due to reduced light scattering, absorption and autofluorescence. Taking advantage of the maleimide moieties in the [Ln<small><sub>2</sub></small>Ga<small><sub>8</sub></small>(shi)<small><sub>8</sub></small>(mip)<small><sub>4</sub></small>]<small><sup>2−</sup></small> metallacrowns (MCs; <strong>shi<small><sup>3−</sup></small></strong> = salicylhydroximate; mip<small><sup>2−</sup></small> = 5-maleimido-isophthalate; Ln = Nd<small><sup>III</sup></small>, Gd<small><sup>III</sup></small>, Er<small><sup>III</sup></small>, Yb<small><sup>III</sup></small> and Y<small><sup>III</sup></small>), we appended visible-absorbing thiol-coumarin (<strong>C</strong>) sensitizers through a thiol-Michael addition click reaction, affording the functionalized [Ln<small><sub>2</sub></small>Ga<small><sub>8</sub></small>(shi)<small><sub>8</sub></small>(C-mip)<small><sub>4</sub></small>]<small><sup>2−</sup></small> MCs. By using this approach, the sensitization of NIR-emitting Nd<small><sup>III</sup></small>, Er<small><sup>III</sup></small> and Yb<small><sup>III</sup></small> was achieved upon excitation in the visible range (<em>λ</em><small><sub>exc</sub></small> = 420 nm) through the appended coumarins. NIR epifluorescence microscopy of living HeLa cells incubated with the Nd<small><sup>III</sup></small> derivative confirmed unambiguous detection of the signal arising from the <small><sup>4</sup></small>F<small><sub>3/2</sub></small> → <small><sup>4</sup></small>I<small><sub>11/2</sub></small> electronic transition in the range of 1050–1080 nm in the cells. These results demonstrate that the [Ln<small><sub>2</sub></small>Ga<small><sub>8</sub></small>(shi)<small><sub>8</sub></small>(mip)<small><sub>4</sub></small>]<small><sup>2−</sup></small> MC can be used as a versatile molecule for tuning the chemical and photophysical properties of the [Ln<small><sub>2</sub></small>Ga<small><sub>8</sub></small>] MC family.\",\"PeriodicalId\":9909,\"journal\":{\"name\":\"Chemical Science\",\"volume\":\"70 1\",\"pages\":\"\"},\"PeriodicalIF\":7.6000,\"publicationDate\":\"2025-06-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d5sc01320h\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5sc01320h","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Novel lanthanide(III)/gallium(III) metallacrowns with appended visible-absorbing organic sensitizers for molecular near-infrared imaging of living cells
Optical imaging of biological samples in the near-infrared (NIR) domain is of major interest for non-invasive experiments due to reduced light scattering, absorption and autofluorescence. Taking advantage of the maleimide moieties in the [Ln2Ga8(shi)8(mip)4]2− metallacrowns (MCs; shi3− = salicylhydroximate; mip2− = 5-maleimido-isophthalate; Ln = NdIII, GdIII, ErIII, YbIII and YIII), we appended visible-absorbing thiol-coumarin (C) sensitizers through a thiol-Michael addition click reaction, affording the functionalized [Ln2Ga8(shi)8(C-mip)4]2− MCs. By using this approach, the sensitization of NIR-emitting NdIII, ErIII and YbIII was achieved upon excitation in the visible range (λexc = 420 nm) through the appended coumarins. NIR epifluorescence microscopy of living HeLa cells incubated with the NdIII derivative confirmed unambiguous detection of the signal arising from the 4F3/2 → 4I11/2 electronic transition in the range of 1050–1080 nm in the cells. These results demonstrate that the [Ln2Ga8(shi)8(mip)4]2− MC can be used as a versatile molecule for tuning the chemical and photophysical properties of the [Ln2Ga8] MC family.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.