TY - JOUR
T1 - A Short-Chain Multibranched Perfluoroalkyl Thiol for More Sustainable Hydrophobic Coatings
AU - Dichiarante, Valentina
AU - Martinez Espinoza, Maria I.
AU - Gazzera, Lara
AU - Vuckovac, Maja
AU - Latikka, Mika
AU - Cavallo, Gabriella
AU - Raffaini, Giuseppina
AU - Oropesa-Nunez, Reinier
AU - Canale, Claudio
AU - Dante, Silvia
AU - Marras, Sergio
AU - Carzino, Riccardo
AU - Prato, Mirko
AU - Ras, Robin H.A.
AU - Metrangolo, Pierangelo
PY - 2018/8/6
Y1 - 2018/8/6
N2 - Perfluorocarbons (PFCs) have proven to be very efficient in building up omniphobic surfaces because of the peculiar properties of fluorine atoms. However, due to their environmental impact and bioaccumulative potential, perfluorinated surfactants with chains longer than six carbon atoms have been banned, and other alternatives had to be found. Herein, we demonstrate the possibility to build omniphobic self-assembled monolayers (SAMs) using a multibranched fluorinated thiol (BRFT) bearing ultrashort fluorinated alkyl groups, surrounding a hydrocarbon polar core. This unique design allows us to multiply the number of fluorine atoms in the molecule (27 F atoms per molecule), affording a high fluorine density on the surface and a low surface free energy. Moreover, the presence of four ether bonds in the core may hasten molecular degradation in the environment because of the cleavage of such bonds in physiological conditions, thus overcoming bioaccumulation issues. BRFT may effectively represent a valuable substitute of long-chain perfluoroalkyl thiols. In fact, BRFT SAMs show the same hydrophobic and oleophobic performances of standard linear perfluoroalkyl thiols (such as 1H,1H,2H,2H-perfluorodecanethiol, PFDT), giving rise to more stable surfaces with a better frictional behavior. Superhydrophobicity was also observed with SAMs grown on nanostructured Cu/Ag surfaces. Our results have proven the ability of short-chain multibranched fluorous molecules to behave as suitable replacements for long-chain perfluoroalkanes in the field of surface coatings. Our molecules may be applied to various surfaces because of the available multiple choice of linker chemistry.
AB - Perfluorocarbons (PFCs) have proven to be very efficient in building up omniphobic surfaces because of the peculiar properties of fluorine atoms. However, due to their environmental impact and bioaccumulative potential, perfluorinated surfactants with chains longer than six carbon atoms have been banned, and other alternatives had to be found. Herein, we demonstrate the possibility to build omniphobic self-assembled monolayers (SAMs) using a multibranched fluorinated thiol (BRFT) bearing ultrashort fluorinated alkyl groups, surrounding a hydrocarbon polar core. This unique design allows us to multiply the number of fluorine atoms in the molecule (27 F atoms per molecule), affording a high fluorine density on the surface and a low surface free energy. Moreover, the presence of four ether bonds in the core may hasten molecular degradation in the environment because of the cleavage of such bonds in physiological conditions, thus overcoming bioaccumulation issues. BRFT may effectively represent a valuable substitute of long-chain perfluoroalkyl thiols. In fact, BRFT SAMs show the same hydrophobic and oleophobic performances of standard linear perfluoroalkyl thiols (such as 1H,1H,2H,2H-perfluorodecanethiol, PFDT), giving rise to more stable surfaces with a better frictional behavior. Superhydrophobicity was also observed with SAMs grown on nanostructured Cu/Ag surfaces. Our results have proven the ability of short-chain multibranched fluorous molecules to behave as suitable replacements for long-chain perfluoroalkanes in the field of surface coatings. Our molecules may be applied to various surfaces because of the available multiple choice of linker chemistry.
KW - Gold
KW - Perfluorocarbons
KW - Self-assembled monolayer
KW - Superhydrophobic surfaces
KW - Thiol
UR - http://www.scopus.com/inward/record.url?scp=85050184579&partnerID=8YFLogxK
U2 - 10.1021/acssuschemeng.8b00777
DO - 10.1021/acssuschemeng.8b00777
M3 - Article
AN - SCOPUS:85050184579
SN - 2168-0485
VL - 6
SP - 9734
EP - 9743
JO - ACS Sustainable Chemistry and Engineering
JF - ACS Sustainable Chemistry and Engineering
IS - 8
ER -