Oligothiophene Amphiphiles as Planarizable and Polarizable Fluorescent Membrane Probes

Fin, Andréa; Jentzsch, Andreas Vargas; Sakai, Naomi; Matile, Stefan

doi:10.1002/ange.201206446

Cited by 42 publications

(26 citation statements)

References 42 publications

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“…The concept of planarizable push‐pull probes has been introduced in 2012 with mechanophore 1 ( Figs. and ) . This original probe 1 and its optimized congener 2 consist of an oligothiophene with methoxy donors and cyanovinyl acceptors ( Fig.…”

Section: Introductionmentioning

confidence: 99%

Twisted Push‐Pull Probes with Turn‐On Sulfide Donors

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Molin

Colom

et al. 2017

Helvetica Chimica Acta

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Planarizable and polarizable dithieno[3,2‐b;2′,3′‐d]thiophene (DTT) dimers have been introduced recently as fluorescent probes that report on membrane fluidity with red shifts in excitation, i.e. planarization in the ground state. In this study, we elaborate on the hypothesis that twisted push‐pull probes could perform best in the presence of one unorthodox substituent that acts as a weak acceptor with electron‐rich and as a strong donor with electron‐poor aromatics. According to Hammett constants, we thought that sulfides could provide access to such a conceptually innovative donor‐acceptor switch. To elaborate on this hypothesis, we here describe the design, synthesis and evaluation of a comprehensive series of twisted push‐pull probes with turn‐on sulfide donors. Their planarization is explored in lipid bilayer membranes of different thickness and fluidity from liquid‐disordered to liquid‐ordered and solid‐ordered phases. Results from membranes are compared to the planarization of turn‐on mechanophores in crystals, proteins, and cyclodextrin macrocycles of varied diameter.

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Section: Introductionmentioning

confidence: 99%

Twisted Push‐Pull Probes with Turn‐On Sulfide Donors

Vérolet

Molin

Colom

et al. 2017

Helvetica Chimica Acta

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“…The fluorescence imaging of physical forces is one of the current challenges in biology that cannot be addressed without input from chemistry . To tackle this problem, planarizable push‐pull (PP) chromophores were introduced as a mechanosensitive fluorescent membrane probe . The first operational “flipper” probe consists of twisted dithienothiophene (DTT) dimers (Figure ) .…”

Section: Figurementioning

confidence: 99%

Methyl Scanning for Mechanochemical Chalcogen‐Bonding Cascade Switches

2019

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Chalcogen‐bonding cascade switching was introduced recently to produce the chemistry tools needed to image physical forces in biological systems. In the original flipper probe, one methyl group appeared to possibly interfere with the cascade switch. In this report, this questionable methyl group is replaced by a hydrogen. The deletion of this methyl group in planarizable push‐pull probes was not trivial because it required the synthesis of dithienothiophenes with four different substituents on the four available carbons. The mechanosensitivity of the resulting demethylated flipper probe was nearly identical to that of the original. Thus methyl groups in the switching region are irrelevant for function, whereas those in the twisting region are essential. This result supports the chalcogen‐bonding cascade switching concept and, most importantly, removes significant synthetic demands from future probe development.

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“…20 The EYPC LUV in buffer solution alone did not show any uorescence. Firstly, large unilamellar vesicles from egg yolk phosphatidylcholine (EYPC LUV) were constructed.…”

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confidence: 94%

“…14 Thus, in an aqueous environment, a clustering of biologically active ligands such as carbohydrates might be favored and increase binding affinities to transmembrane receptor proteins similar as natural archetype lipopolysaccharides (LPS) endowed with a hydrophobic aglycon. The unique sensitivity of the photophysical properties of the quaterthiophene (4T)-scaffold towards slight conformational alterations 19,20 should enable to use carbohydrate-functionalized "rods" as specic uorescent membrane probes to track cellular uptake or cell trafficking. As various non-charged alkylglycosides such as octylglucoside are wellknown to form at sublytic concentrations stable co-assemblies with phospholipidic membrane constituents 18 we decided to combine uorescent linear OTs with a pyranose moiety such as mannose.…”

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confidence: 99%