Live-Cell-Permeant Thiophene Fluorophores and Cell-Mediated Formation of Fluorescent Fibrils

Palamà, Ilaria Elena; Maria, Francesca Di; Viola, Ilenia; Fabiano, Eduardo; Gigli, Giuseppe; Bettini, Cristian; Barbarella, Giovanna

doi:10.1021/ja2065522

Cited by 63 publications

(77 citation statements)

References 38 publications

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“…[1][2][3][4][5][6] In addition, the recent development of simple methods for their preparation has enabled the synthesis of unexplored families of sulfur-oxygenated oligoand polythiophenes with potential applications spanning from organic electronics to chemical biology. [7][8][9][10][11][12][13][14][15][16][17][18][19] The incorporation of strong electron acceptor TDO moieties deeply affects the HOMO-LUMO energy levels of the material causing a substantial reduction of the energy gap. [20][21][22][23][24] Moreover, it may induce a change in the charge transport properties from p-to n-type, 7,10,25 as well as in the self-assembly properties due to additional intra-and intermolecular hydrogen nonbonding interactions.…”

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confidence: 99%

Poly(3-hexylthiophene) Nanoparticles Containing Thiophene-S,S-dioxide: Tuning of Dimensions, Optical and Redox Properties, and Charge Separation under Illumination

et al. 2017

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We describe the preparation of poly(3-hexylthiophene-S,S-dioxide) nanoparticles using Rozen's reagent, HOF•CH 3 CN, either on poly(3-hexylthiophene) (P3HT) or on preformed P3HT nanoparticles (P3HT-NPs). In the latter case, core−shell nanoparticles (P3HT@PTDO-NPs) are formed, as confirmed by X-ray photoelectron spectroscopy measurements, indicating the presence of oxygen on the outer shell. The different preparation modalities lead to a finetuning of the chemical−physical properties of the nanoparticles. We show that absorption and photoluminescence features, electrochemical properties, size, and stability of colloidal solutions can be finely modulated by controlling the amount of oxygen present. Atomic force microscopy measurements on the nanoparticles obtained by a nanoprecipitation method from preoxidized P3HT (PTDO-NPs) display spherical morphology and dimensions down to 5 nm. Finally, Kelvin probe measurements show that the coexistence of p-and n-type charge carriers in all types of oxygenated nanoparticles makes them capable of generating and separating charge under illumination. Furthermore, in core−shell nanoparticles, the nanosegregation of the two materials, in different regions of the nanoparticles, allows a more efficient charge separation.

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Poly(3-hexylthiophene) Nanoparticles Containing Thiophene-S,S-dioxide: Tuning of Dimensions, Optical and Redox Properties, and Charge Separation under Illumination

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“…Theoretical calculations carried out on a system consisting of three sequences of the tripeptide Gly-Pro-HyPro (as a model for procollagen chains) in the presence of 5 support this hypothesis. 25 The calculations predicted an energetically favorable configuration ( Figure 7C) involving a hydrogen bond between the HyPro and one of the oxygen atoms of 5.…”

Section: ■ Microfibers Spontaneously Coassembled With Proteins Insidementioning

confidence: 96%

“…25 When dissolved in physiological solution, they were spontaneously taken up by live mouse embryonic fibroblasts (NIH-3T3) and HeLa cells. 25 DTTO 5 was also successfully tested with bone-marrow-derived human fibroblasts (BMFbs) 36 and mouse neuroblastoma cells (B104). 37 Figure 6A shows laser scanning confocal microscopy (LSCM) images of the spontaneous uptake of 5 by BMFbs as a function of time.…”

Section: ■ Microfibers Spontaneously Coassembled With Proteins Insidementioning

confidence: 99%

“…Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) of the fluorescent microfibers isolated from the cell milieu, immune-blotting analysis of nitrocellulose-blotted gels with an anticollagen type-I antibody, and colocalization experiments of isolated microfibers obtained using NIH-3T3 fibroblasts with anticollagen type-I antibody allowed us to establish that the fluorescent microfibers formed by fibroblasts upon uptake of 5 were mainly made of type-I collagen. 25 39 To account for our experimental results, we assumed that DTTO 5 is specifically recognized by some component of protocollagen polypeptide chains at some stage of its formation and incorporated via hydrogen bonding. 25,36 The progressive aggregation of polypeptide chains into the triple helix then drives the simultaneous self-assembly of 5 inside the triple helix itself in a process of coassembly, leading to a unique supramolecular fibrillar architecture that is more stable than those that would be obtained by isolated self-assembly of either building block.…”

Section: ■ Microfibers Spontaneously Coassembled With Proteins Insidementioning

confidence: 99%

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Supramolecular Oligothiophene Microfibers Spontaneously Assembled on Surfaces or Coassembled with Proteins inside Live Cells

Barbarella

Maria

2015

Acc. Chem. Res.

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During the last few decades, multifunctional nano- and microfibers made of semiconducting π-conjugated oligomers and polymers have generated much interest because of a broad range of applications extending from sensing to bioelectronic devices and (opto)electronics. The simplest technique for the fabrication of these anisotropic supramolecular structures is to let the molecules do the work by spontaneous organization driven by the information encoded in their molecular structure. Oligothiophenes-semiconducting and fluorescent compounds that have been extensively investigated for applications in thin-film field-effect transistors and solar cells and to a lesser extent as dyes for fluorescent labeling of proteins, DNA, and live cells-are particularly suited as building blocks for supramolecular architectures because of the peculiar properties of the thiophene ring. Because of the great polarizability of sulfur outer-shell electrons and the consequent facile geometric deformability and adaptability of the ring to the environment, thiophene can generate multiple nonbonding interactions to promote non-covalent connections between blocks. Furthermore, sulfur can be hypervalent, i.e., it can accommodate more than the eight electrons normally associated with s and p shells. Hypervalent oligothiophene-S,S-dioxides whose oxygen atoms can be involved in hydrogen bonding have been synthesized. These compounds are amphiphilic, and some of them are able to spontaneously cross the membrane of live cells. Hypervalent nonbonding interactions of divalent sulfur, defined as weak coordination to a proximate nitrogen or oxygen, have also been invoked in the solid-state packing of many organic molecules and in the architecture of proteins. In this Account, we describe two different types of thiophene-based building blocks that can induce the spontaneous formation of nanostructured microfibers in very different environments. The first, based on the synthesis of "sulfur-overrich" hexamers and octamers, leads to surface-independent self-assembly of microfibers-helical or rodlike depending on the groups attached to the same identical inner core-that are crystalline, fluorescent, and conductive and display chirality despite the lack of chiral carbon atoms on the building blocks. Supramolecular polymorphic microfibers are also formed, and they are characterized by very different functional properties. The second, based on a rigid oligothiophene-S,S-dioxide, leads to coassembled protein-oligothiophene microfibers that are physiologically formed inside live cells. The oligothiophene-S,S-dioxide can indeed spontaneously cross the membrane of live cells and be directed toward the perinuclear region, where it is recognized and incorporated by specific peptides during the formation of fibrillar proteins without being harmful to the cells. Coassembled oligothiophene-protein microfibers are progressively formed through a cell-mediated physiological process. Thanks to the oligothiophene blocks, the microfibers possess fluorescence and charge-conduct...

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“…Giovanna Barbarella group (University of Bologna, Italy) has succeeded in developing oligothiophenes for stem cell imaging [77] and has also shown that selected oligothiophenes have the capability to distinguish protein types inside living cells [78]- [80]. It is most likely that Barbarellas thiophene probes, due to a succinimidyl ester group, covalently binds to amino groups of the intracellular protein target.…”

Section: Lcos As Fluorescent Reportersmentioning

confidence: 99%

Poly-and oligothiophenes : Optical probes for multimodal fluorescent assessment of biological processes

Magnusson¹

2015

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IICover: Fibroblasts and melanoma cells stained with a fluorescent thiophene probe called p-HTIm, DAPI and antibodies against ER, proteasomes, α-tubulin, fibronectin, or mitotracker against mitochondria.During the course of the research underlying this thesis, Karin Magnusson was enrolled in Forum Scientium, a multidisciplinary doctoral program at Linköping University, Sweden. ABSTRACTOne interesting class of molecules in the research field of imaging biological processes is luminescent conjugated polythiophenes, LCPs. These fluorescent probes have a flexible backbone consisting of repetitive thiophene units. Due to this backbone, the probes possess unique abilities to give rise to different spectral signatures depending on their target and environment. LCPs are a polydispersed material meaning there is an uneven distribution of lengths of the probe. Recently, monodispersed chemically well-defined material denoted luminescent conjugated oligothiophenes, LCOs, with an exact number of repetitive units and distinct sidechain functionalities along the backbone has been developed. LCOs have the advantages of being smaller which leads to higher ability to cross the blood brain barrier. The synthesis of minor chemical alterations is also more simplified due to the well-defined materials. During my doctoral studies I have used both LCPs and LCOs to study biological processes such as conformational variation of protein aggregates in prion diseases and cellular uptake in normal cells and cancer cells. The research has generally been based on the probes capability to emit light upon irradiation and the interaction with their targets has mainly been assessed through variations in fluorescence intensity, emission-and excitation profiles and fluorescence lifetime decay. These studies verified the utility of LCPs and LCOs for staining and discrimination of both prion strains and cell phenotypes. The results also demonstrated the pronounced influence minor chemical modifications have on the LCO´s staining capacity. IV POPULÄRVETENSKAPLIG SAMMANFATTNING LYSANDE MOLEKYLER FÖR STUDIER AV BIOLOGISKA PROCESSERLuminiscenta konjugerade polytiofener, LCPs, är en väldigt intressant typ av molekyl som kan användas för att studera processer i biologiska system. Strukturen hos dessa fluorescerande molekyler kan liknas vid olika element som är fästa vid en ryggrad. De olika elementen ger molekylen dess affinitet för sin målmolekyl, medan ryggraden är mest ansvarig för molekylens optiska egenskaper. Ryggraden ändrar sin struktur beroende på målmolekylen och resultatet kan avläsas med ett flertal fluorescens-metoder. Längden på ryggraden hos LCPs varierar och varje parti av en LCP består därmed av en blandning längder och storlekar. De senaste åren har Peter Nilssons forskargrupp utvecklat LCPs till molekyler med väldefinierad längd på ryggraden som då betecknas luminiscenta konjugerade oligotiofener, LCOs. Dessa mindre molekyler har större möjlighet att passera blodhjärnbarriären samt att syntesen för små kemiska modifieringar av elementen ...

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Live-Cell-Permeant Thiophene Fluorophores and Cell-Mediated Formation of Fluorescent Fibrils

Cited by 63 publications

References 38 publications

Poly(3-hexylthiophene) Nanoparticles Containing Thiophene-S,S-dioxide: Tuning of Dimensions, Optical and Redox Properties, and Charge Separation under Illumination

Poly(3-hexylthiophene) Nanoparticles Containing Thiophene-S,S-dioxide: Tuning of Dimensions, Optical and Redox Properties, and Charge Separation under Illumination

Supramolecular Oligothiophene Microfibers Spontaneously Assembled on Surfaces or Coassembled with Proteins inside Live Cells

Poly-and oligothiophenes : Optical probes for multimodal fluorescent assessment of biological processes

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