Designing Nanoporous Membranes through Templateless Electropolymerization of Thieno[3,4-b]thiophene Derivatives with High Water Content.

In this work, we present the synthesis of original thieno[3,4-b]thiophene monomers with rigid substituents (e.g., perfluorinated chains, and aromatic groups) and demonstrate the ability to prepare nanotubular and nanoporous structures via templateless, surfactant-free electropolymerization in organic solvents (dichloromethane). For the majority of synthesized monomers, including a significant amount of water in the electropolymerization solvent leads to the formation of nanoporous membranes with tunable size and surface hydrophobicity. If water is not included in the electropolymerization solvent, most of the surfaces prepared are relatively smooth. Tests with different water contents show that the formation of nanoporous membranes pass through the formation of vertically aligned nanotubes and that the increase in water content induces an increase in the number of nanotubes while their diameter and height remain unchanged. An increase in surface hydrophobicity is observed with the formation of nanopores up to ≈300 nm in diameter, but as the nanopores further increase in diameter, the surfaces become more hydrophilic with an observed decrease in the water contact angle. These materials and the ease with which they can be fabricated are extremely interesting for applications in separation membranes, opto-electronic devices, as well as for sensors.

Designing bioinspired coral-like structures using a templateless electropolymerization approach with a high water content.

Here, with the aim of obtaining densely packed porous nanostructures of various shape using templateless electropolymerization in organic solvent (dichloromethane), original thieno[3,4- b]thiophene-based monomers with different substituents are studied. First of all, the adding of water in solution has a huge influence on the formation of porous structures because a much higher amount of gas (O2 and/or H2) is released. Rigid substituents such as aromatic groups have a beneficial effect on the formation of nanotubular structures contrary to flexible ones such as alkyl chains. Special results are obtained with the pyrene substituent (Thieno-Pyr). With this monomer, coral-like structures are obtained. These structures are obtained by the formation first on long nanotubular structures and their sagging due to their weight. Then, the released gas is trapped inside these structures leading to huge craters. These exceptional surfaces could be used in the future in various potential applications such as in drug delivery, cell growth, sensors, optical devices or surface adhesion. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology (part 2)'.

Parahydrophobic and Nanostructured Poly(3,4-ethylenedioxypyrrole) and Poly(3,4-propylenedioxypyrrole) Films with Hyperbranched Alkyl Chains.

Here, we control the surface hydrophobicity and the adhesion of water droplets by electrodeposition of poly(3,4-ethylenedioxypyrrole) (PEDOP) and poly(3,4-propylenedioxypyrrole) (PProDOP) with branched alkyl chains placed preferentially on the bridge to favor the formation of nanofibers. Branched alkyl chains of various sizes from very short (C3) to hyperbranched (C18) are studied because they have lower surface hydrophobicity than long alkyl or fluoroalkyl chains (preferable for parahydrophobic properties). The electrodeposition is much more favored with the PEDOP derivatives because the ProDOP films are more soluble. However, the formation of nanoparticles is favored with the PEDOP polymers in contrast to the formation of fibers, resembling the wax nanoclusters observed on lotus leaves, with the ProDOP polymers. With both these PEDOP and PProDOP derivatives, it is possible to reach parahydrophobic properties characterized by a sticking behavior toward water droplets. This kind of surfaces could be used in the future in water harvesting systems, for example.

Surface Nanostructuration and Wettability of Electrodeposited Poly(3,4-ethylenedioxypyrrole) and Poly(3,4-propylenedioxypyrrole) Films Substituted by Aromatic Groups.

In the aim to obtain parahydrophobic materials (both high contact angles and high hysteresis) for possible applications in water harvesting systems, we report the synthesis of novel 3,4-ethylenedioxypyrrole (EDOP) and 3,4-propylenedioxypyrrole (ProDOP) monomers with aromatic rings on the 3,4-alkylenedioxy bridge and the resulting conducting polymer films were prepared by electropolymerization. We show that the surface properties can be tuned by the nature of the aromatic ring (phenyl, biphenyl, diphenyl, naphthalene, fluorene, and pyrene) and the polymerizable core (EDOP or ProDOP). The best results are obtained with both EDOP and diphenyl, with which extremely high hydrophobic properties (up to 116°) are obtained, even if the polymers are intrinsically hydrophilic. These surfaces could be applied in the future, for example, in water harvesting systems or in water/oil separation membranes. The synthesis strategy is extremely interesting, and many other molecules will be envisaged in the future.

Formation of Nanofibers with High Water Adhesion by Electrodeposition of Films of Poly(3,4-ethylenedioxypyrrole) and Poly(3,4-propylenedioxypyrrole) Substituted by Alkyl Chains.

Invited for this month's cover are the collaborating groups of Dr. Thierry Darmanin at Université Côte d'Azur, France, and Dr. Alioune Diouf at Université Cheikh Anta Diop de Dakar, Senegal. The front cover shows nanofibrous surfaces prepared by the electropolymerization of 3,4-ethylenedioxypyrrole (EDOP) and 3,4-propylenedioxypyrrole (ProDOP) derivatives in which an alkyl chain is grafted to the 3,4-alkylenedioxy bridge. Depending on whether an EDOP or a ProDOP monomer is used, and the length of the alkyl chain, the surface properties of the resulting polymer are very different. Read the full text of the article at 10.1002/cplu.201800279.

Formation of Nanofibers with High Water Adhesion by Electrodeposition of Films of Poly(3,4-ethylenedioxypyrrole) and Poly(3,4-propylenedioxypyrrole) Substituted by Alkyl Chains.

With the aim of controlling the surface hydrophobicity and water adhesion, nanofibrous surfaces were prepared by electropolymerization of 3,4-ethylenedioxypyrrole (EDOP) and 3,4-propylenedioxypyrrole (ProDOP) derivatives having various alkyl chains (C3 to C17 ) grafted to a 3,4-alkylenedioxy bridge. Depending on whether an EDOP or a ProDOP was used, and the length of the alkyl chain, the surface properties of the resulting polymer were very different. The formation of nanofibrous surfaces was much more favored for ProDOP derivatives. The alkyl chain length has also a huge influence on the formation of nanofibers, and alkyl chains of intermediate length (C9 and C11 ) gave the best results. Apparent contact angles (θw ) of up to 150° were obtained, and the water adhesion properties were highly variable. This work is important for many applications in which the control of interaction forces with a medium is required, such as in oil-water separation membranes or water-harvesting systems.

Superhydrophobic (low adhesion) and parahydrophobic (high adhesion) surfaces with micro/nanostructures or nanofilaments.

Controlling the water adhesion is extremely important for various applications such as for water harvesting. Here, superhydrophobic (low adhesion) and parahydrophobic (high adhesion) substrates are both obtained from hydrophilic polymers. We show in the work that a judicious choice in the monomer structure used for electropolymerization can lead to these two properties. Using a phenyl group, parahydrophobic properties are reached due to the formation of nanofilaments. By contrast, using a naphthalene or a biphenyl group, superhydrophobic properties are obtained due the formation of both micro- and nanostructures.

One F-octyl versus two F-butyl chains in surfactant aggregation behavior.

An easy synthetic procedure in two or three steps from perfluoroalkylethyl iodide derivatives led to six novel fluorinated carboxylates monomeric and gemini surfactants with one or two hydrophobic tails, respectively: RF(C2H4)CH(CO2(-))2,2Na(+) and [RF(C2H4)]2C(CO2(-)),Na(+), where RF = C4F9, C6F13, and C8F17. These anionic surfactants exhibited very low surface tension from 15 to 33 mN/m as well as low critical micelle concentration until 1.3 × 10(-4) mol/L. Furthermore, the surface properties of the gemini compound with two short fluoroalkyl chains (RF = C4F9) were found to be almost equal to those of the monomeric surfactant with one long fluoroalkyl chain (RF = C8F17), which could provide an interesting alternative to the bioaccumulative long-chain perfluorinated surfactant.

Giant brainlike aggregates from new fluorocarbon/hydrocarbon hybrid cationic surfactants.

A rapid synthetic procedure in two steps from perfluoroalkylethyl iodide derivatives led to 18 novel ammonium type hybrid surfactants of the general formula: R(F)(CH(2))(2)S(CH(2))(2)N(+)(CH(3))(2)R(H)Br(-) (R(F) = C(4)F(9), C(6)F(13), C(8)F(17); R(H) = C(4)H(9), C(6)H(13), C(8)H(17), C(10)H(21), C(12)H(25), C(14)H(29)). These hybrid surfactants exhibited very low surface tension (from 16 to 25 mN/m) as well as low critical micellar concentration until 1.5 × 10(-5) mol/L. A special focus was made on aggregation phenomenon as giant multilamellar "brainlike" vesicles were observed via cryogenic scanning electron microscopy (cryoSEM) and transmission electron microscopy (TEM; with a contrast agent) suggesting a high encapsulation ability and a very important specific surface of these particular organizations.