Mechanothermally induced conformational switch of a porphyrin dimer in a polymer film

Doan, Hung Q.; Raut, Sangram; Yale, D. E. C.; Baláž, Milan; Dzyuba, Sergei V.; Gryczyński, Zygmunt

doi:10.1039/c6cc04306b

Cited by 22 publications

(18 citation statements)

References 42 publications

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“…Fortunately,r elativelyf ast and convenient measurements of viscosity can be achieved with an emergingc lass of fluorescent compounds-molecular rotors. [1,2] Previously,t hey have been used for viscosity sensing in polymers, [3,4] polymersomes, [5] aerosols, [6][7][8] model lipid bilayers, [9,10] protein aggregates, [11] and live cells. [12][13][14][15] Within cells, viscosity measurements have been performed in mitochondria, [16,17] lysosomes, [18] an endoplasmic reticulum, [19] anda plasma membrane.…”

Section: Introductionmentioning

confidence: 99%

Enhancing the Viscosity‐Sensitive Range of a BODIPY Molecular Rotor by Two Orders of Magnitude

Toliautas

Dodonova

Žvirblis

et al. 2019

Chemistry A European J

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Molecular rotors are ac lass of fluorophores that enable convenient imaging of viscosity inside microscopic sampless uch as lipid vesicleso rlive cells. Currently, rotor compounds containingaboron-dipyrromethene( BODIPY) group are among the most promisingv iscosity probes. In this work, it is reportedt hat by addingh eavy-electron-withdrawing ÀNO 2 groups, the viscosity-sensitiver ange of a BODIPYp robe is drasticallye xpandedf rom 5-1500cPt o 0.5-50 000 cP.T he improved range makes it, to our knowledge, the first hydrophobic molecular rotor applicable not only at moderate viscosities but also for viscosity measurements in highlyv iscous samples. Furthermore, the photo-physicalm echanism of the BODIPY molecular rotors under study has been determined by performing quantum chemical calculations and transienta bsorption experiments. This mechanism demonstrates how BODIPY molecular rotors work in general,w hy the ÀNO 2 group causes such an improvement, and why BODIPYm olecular rotors suffer from undesirable sensitivity to temperature. Overall,b esides reporting av iscosity probe with remarkable properties, the results obtainede xpandt he general understanding of molecular rotors and show away to use the knowledge of their molecular actionm echanism for augmenting their viscositysensing properties.[**] BODIPY = boron-dipyrromethene.Supporting Information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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Section: Introductionmentioning

confidence: 99%

Enhancing the Viscosity‐Sensitive Range of a BODIPY Molecular Rotor by Two Orders of Magnitude

Toliautas

Dodonova

Žvirblis

et al. 2019

Chemistry A European J

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“…The current best is the so‐called ‘flipper’ probe 1 ( Figure ) . Probe design considers, from top to bottom, a carboxylate (for delivery to and positioning in lipid bilayer membrane); a triazole (to prevent headgroup elimination); a thenyl ether donor and a sulfide‐bridged dithienothiophene (DTT) ‘flipper’ (as push component); two chalcogen anti‐bonds between methyl groups and endocyclic sulfur atoms next to the twistable bond connecting the two DTT planes (to twist them out of co‐planarity); a sulfone‐bridged DTT flipper and a cyano acceptor (as pull component).…”

Section: Introductionmentioning

confidence: 99%

Ganglioside‐Selective Mechanosensitive Fluorescent Membrane Probes

Straková

Soleimanpour

Diez-Castellnou

et al. 2018

Helvetica Chimica Acta

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The development of fluorescent probes to image forces in cells is an important challenge in chemistry and biology. Planarizable push‐pull probes have been introduced recently for this purpose. To provide most valuable information on forces in complex systems, these mechanosensitive ‘flipper’ probes will have to be localized by molecular recognition of targets of interest. Here we report fluorescent flippers that selectively recognize gangliosides on the surface of lipid bilayer membranes by formation of dynamic covalent boronate esters. The original flipper probes were equipped with 2‐fluorophenyl boronic acids and benzoboroxoles using consecutive triazole and oxime ligation. Evaluation was done in large unilamellar vesicles composed of EYPC/SM/CL/GM 40:40‐x:20:x to obtain mixed membranes with separate liquid‐disordered (Ld) and ganglioside (GM) containing liquid‐ordered (Lo) domains. With increasing GM concentration, fluorescence intensities increased and excitation maximum shifted to the red. Deconvolution of the spectra confirmed that these changes originate from a migration of the flipper probes from Ld to Lo domains upon binding to the gangliosides and thus the planarization in the more ordered environment. Control mechanophores without boronic acids failed to show the same response, and fructose partially inhibited the ganglioside sensitivity. These results demonstrate that it is possible to selectively accumulate mechanosensitive flipper probes in Lo domains and, more generally, that probe localization in complex membranes is possible and matters.

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“…Thecontrol of conformation changes using amacroscopic mechanical force as external stimulus was already reported in crystals but showing very low variation due to their highly rigid nature. [17,18] Using more flexible systems and also wellordered Langmuir-Blodgett 2D films,c onformational changes of biaryl-derived surfactants through compression forces allowed a1 0 8 8 variation of the dihedral angle. [19,20] In this work, we demonstrated the possibility to tune the molecular conformation of BINOL crosslinked within a3 D polymer architecture through am acroscopic stretching force applied unidirectionally to the material.…”

Section: Resultsmentioning

confidence: 99%

Reversible Soft Mechanochemical Control of Biaryl Conformations through Crosslinking in a 3D Macromolecular Network

et al. 2020

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Tuning the dihedral angle (DA) of axially chiral compounds can impact biological activity,c atalyst efficiency, molecular motor performance,orchiroptical properties.Herein, we report gradual, controlled, and reversible changes in molecular conformation of ac ovalentlyl inked binaphthyl moiety within a3 Dp olymeric network by application of amacroscopic stretching force.Wemanaged direct observation of DA changes by measuring the circular dichroism signal of an optically pure BINOL-crosslinked elastomer network. Stretching the elastomer resulted in aw idening of the DA between naphthyl rings when the BINOL was doubly grafted to the elastomer network;noeffect was observed when asingle naphthyl ring of the BINOL was grafted to the elastomer network. We have determined that ca. 170 %e xtension of the elastomers led to the transfer of am echanical force to the BINOL moiety of 2.5 kcal mol À1 À1 (ca. 175 pN) in magnitude and results in the opening of the DA of BINOL up to 1308 8.

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Mechanothermally induced conformational switch of a porphyrin dimer in a polymer film

Abstract: Stretching a polymer film induces a conformational change (from the twisted to planar state) in the embedded porphyrin dimer, as evidenced by steady-state and time-resolved emission spectra.

Cited by 22 publications

References 42 publications

Enhancing the Viscosity‐Sensitive Range of a BODIPY Molecular Rotor by Two Orders of Magnitude

Enhancing the Viscosity‐Sensitive Range of a BODIPY Molecular Rotor by Two Orders of Magnitude

Ganglioside‐Selective Mechanosensitive Fluorescent Membrane Probes

Reversible Soft Mechanochemical Control of Biaryl Conformations through Crosslinking in a 3D Macromolecular Network

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