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Design and Synthesis of Mixed Oligomers with Thiophenes, Dithienothiophene S,S-Dioxides, Thieno[3,4]pyrazines and 2,1,3-Benzothiadiazoles: Flipper Screening for Mechanosensitive Systems.

Verolet Q, Soleimanpour S, Fujisawa K, Dal Molin M, Sakai N, Matile S - ChemistryOpen (2015)

Bottom Line: Monomers with large surface area and high quantum yield, that is fluorescent flippers, have been engineered into twisted push-pull oligomers to create membrane probes with high mechanosensitivity and long fluorescence lifetime.Here, the synthesis and characterization of thieno[3,4]pyrazines and 2,1,3-benzothiadiazoles are described in comparison with the original dithienothiophene S,S-dioxides.Dithienothiophene S,S-dioxide flippers are confirmed as the best reported so far, and poor results with single flipper probes support that two flippers are needed for the probe to really "swim", that is, for high mechanosensitivity.

View Article: PubMed Central - PubMed

Affiliation: Department of Organic Chemistry, University of Geneva Quai Ernest Ansermet 30, 1211, Geneva, Switzerland.

ABSTRACT
Monomers with large surface area and high quantum yield, that is fluorescent flippers, have been engineered into twisted push-pull oligomers to create membrane probes with high mechanosensitivity and long fluorescence lifetime. Here, the synthesis and characterization of thieno[3,4]pyrazines and 2,1,3-benzothiadiazoles are described in comparison with the original dithienothiophene S,S-dioxides. Dithienothiophene S,S-dioxide flippers are confirmed as the best reported so far, and poor results with single flipper probes support that two flippers are needed for the probe to really "swim", that is, for high mechanosensitivity.

No MeSH data available.


Planarizable push–pull probes (A) and controls with fluorescent dithienothiophene S,S-dioxide flippers compared to thieno[3,4]pyrazines or 2,1,3-benzothiadiazoles.
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fig01: Planarizable push–pull probes (A) and controls with fluorescent dithienothiophene S,S-dioxide flippers compared to thieno[3,4]pyrazines or 2,1,3-benzothiadiazoles.

Mentions: The concept of planarizable push–pull probes has been introduced recently as a conceptually innovative approach to image lipid bilayer membranes (A in Figure 1).1 This combination of polarization and planarization in the ground state is attractive because it applies lessons from nature,1 is complementary to excited-state planarization in molecular rotors2 and thus reports changes in excitation rather than emission as most conventional membrane probes.2,3 However, the original approach with push–pull oligothiophenes suffered from increasing loss in fluorescence upon ground-state twisting, and red shifts in excitation were limited to about +40 nm. To increase mechanosensitivity4 and fluorescence lifetime (τ), monomers with large surface areas and high quantum yields (ϕ) were engineered into the twisted oligomers.5 Twisted push–pull probe 1 with two fluorescent flippers, an electron-rich dithienothiophene and a poorer dithienothiophene S,S-dioxide,6 gave quantum yields above 80 % also in fully deplanarized form, and shifts up to +80 nm and lifetimes up to 4.8 ns upon planarization.5 Here, we report synthetic efforts towards oligomers 2–7, designed to vary the number of dithienothiophene flippers per probe and secure access to complementary flippers such as thieno[3,4]pyrazines7 or 2,1,3-benzothiadiazoles.8


Design and Synthesis of Mixed Oligomers with Thiophenes, Dithienothiophene S,S-Dioxides, Thieno[3,4]pyrazines and 2,1,3-Benzothiadiazoles: Flipper Screening for Mechanosensitive Systems.

Verolet Q, Soleimanpour S, Fujisawa K, Dal Molin M, Sakai N, Matile S - ChemistryOpen (2015)

Planarizable push–pull probes (A) and controls with fluorescent dithienothiophene S,S-dioxide flippers compared to thieno[3,4]pyrazines or 2,1,3-benzothiadiazoles.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4522174&req=5

fig01: Planarizable push–pull probes (A) and controls with fluorescent dithienothiophene S,S-dioxide flippers compared to thieno[3,4]pyrazines or 2,1,3-benzothiadiazoles.
Mentions: The concept of planarizable push–pull probes has been introduced recently as a conceptually innovative approach to image lipid bilayer membranes (A in Figure 1).1 This combination of polarization and planarization in the ground state is attractive because it applies lessons from nature,1 is complementary to excited-state planarization in molecular rotors2 and thus reports changes in excitation rather than emission as most conventional membrane probes.2,3 However, the original approach with push–pull oligothiophenes suffered from increasing loss in fluorescence upon ground-state twisting, and red shifts in excitation were limited to about +40 nm. To increase mechanosensitivity4 and fluorescence lifetime (τ), monomers with large surface areas and high quantum yields (ϕ) were engineered into the twisted oligomers.5 Twisted push–pull probe 1 with two fluorescent flippers, an electron-rich dithienothiophene and a poorer dithienothiophene S,S-dioxide,6 gave quantum yields above 80 % also in fully deplanarized form, and shifts up to +80 nm and lifetimes up to 4.8 ns upon planarization.5 Here, we report synthetic efforts towards oligomers 2–7, designed to vary the number of dithienothiophene flippers per probe and secure access to complementary flippers such as thieno[3,4]pyrazines7 or 2,1,3-benzothiadiazoles.8

Bottom Line: Monomers with large surface area and high quantum yield, that is fluorescent flippers, have been engineered into twisted push-pull oligomers to create membrane probes with high mechanosensitivity and long fluorescence lifetime.Here, the synthesis and characterization of thieno[3,4]pyrazines and 2,1,3-benzothiadiazoles are described in comparison with the original dithienothiophene S,S-dioxides.Dithienothiophene S,S-dioxide flippers are confirmed as the best reported so far, and poor results with single flipper probes support that two flippers are needed for the probe to really "swim", that is, for high mechanosensitivity.

View Article: PubMed Central - PubMed

Affiliation: Department of Organic Chemistry, University of Geneva Quai Ernest Ansermet 30, 1211, Geneva, Switzerland.

ABSTRACT
Monomers with large surface area and high quantum yield, that is fluorescent flippers, have been engineered into twisted push-pull oligomers to create membrane probes with high mechanosensitivity and long fluorescence lifetime. Here, the synthesis and characterization of thieno[3,4]pyrazines and 2,1,3-benzothiadiazoles are described in comparison with the original dithienothiophene S,S-dioxides. Dithienothiophene S,S-dioxide flippers are confirmed as the best reported so far, and poor results with single flipper probes support that two flippers are needed for the probe to really "swim", that is, for high mechanosensitivity.

No MeSH data available.