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Hypothesis: In this original work, we aim to control both the surface wetting and fluorescence properties of extremely ordered and porous conducting polymer nanotubes prepared by soft template electropolymerization and post-grafting. For reaching this aim, various substituents of different hydrophobicity and fluorescence were post-grafted and the post-grafting yields were evaluated by surface analyses. We show that the used polymer is already fluorescent before post-grafting while the post-grafting yield and as a consequence the surface hydrophobicity highly depend on the substituent., Experiments: Here, we have chosen to chemically grafting various fluorinated and aromatic substituents using a post-grafting in order to keep the same surface topography. Flat conducting polymer surfaces with similar properties have been also prepared for determining the surface energy with the Owens-Wendt equation and estimating the post-grafting yield by X-ray Photoemission Spectroscopy (XPS) and Time of Flight Secondary Emission Spectrometry (ToF-SIMS). For example, using fluorinated chains of various length (C 4 F 9 , C 6 F 13 and C 8 F 17 ), it is demonstrated that the surface hydrophobicity and oleophobicity do not increase with the fluorinated chain length due to the different post-grafting yields and because of the presence of nanoroughness after post-grafting., Findings: These surfaces have high apparent water contact angle up to 130.5° but also strong water adhesion, comparable to rose petal effect even if there are no nanotubes on petal surface. XPS and ToF-SIMS analyses provided a detailed characterisation of the surface chemistry with a qualitative classification of the grafted surfaces (F6 > F4 > F8). SEM analysis shows that grafting does not alter the surface morphology. Finally, fluorescence analyses show that the polymer surfaces before post-treatment are already nicely fluorescent. Although the main goal of this paper was and is to understand the role of surface chemistry in tailoring the wetting properties of these surfaces rather than provide specific application examples, we believe that the obtained results can help the development of specific nanostructured materials for potential applications in liquid transport, or in stimuli responsive antimicrobial surfaces., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Hypothesis: The formation of porous nanostructures on surfaces and the control of their size and shape is fundamental for various applications. The creation of nanotubes is particularly difficult to implement without the aid of hard and rigid templates. Recently, methods that form nanotubular structures in a straightforward manner and without direct templating, e.g. soft templating, have been highly sought after. Here we propose the use of "soft templating" via self-assembly of conducting monomers during electropolymerization in organic solvents as a mean to form porous, nanotubular features., Experiments: Naphtho[2,3-b]thieno[3,4-e][1,4]dioxine (NaphDOT) is employed as monomer for electropolymerizations conducted in dichloromethane and chloroform containing varying amounts of water. SEM analyses of the resulting surfaces confirms the strong capacity of NaphDOT to form vertically aligned nanotubes. Polymerization solutions analyzed by DLS and TEM reveal the presence of micelles prior to electropolymerization, and the size of the micelles correlates with the inner diameter of the nanotubes formed., Findings: We show that micelles in polymerization solutions are stabilized by both monomers and electrolytes. We propose a mechanism where reverse micelles are forming a soft-template responsible for the formation of porous nanostructures during electropolymerization in organic, non-polar solvents. In this mechanism, the monomer and electrolyte assume the role of surfactant in the reverse micelle system., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Taking inspiration from the hydrophilic and superhydrophilic properties observed from the nanostructures present on the leaves of plants such as Alocasia odora , Calathea zebrina , and Ruelia devosiana , we were able to synthesize cupric oxide (CuO) nanostructures from the plasma surface modification of copper (Cu) that exhibits hydrophilic and superhydrophilic properties. The Cu sheets were exposed to oxygen plasma produced from the P300 plasma device (Alliance Concept, Cran-Gevrier, France) at varying power, irradiation times, gas flow rates, and pulsing duty cycles. The untreated and plasma-treated Cu sheets were characterized by contact angle measurements, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) to determine the changes in the surface of Cu before and after plasma treatment. Results showed that plasma-treated Cu sheets exhibited enhanced wetting properties compared to untreated Cu. We attributed the decrease in the measured water contact angles after plasma treatment to increased surface roughness, formation of CuO nanostructures, and transformation of Cu to either CuO 2 or Cu 2 O 3 . The presence of the CuO nanostructures on the surface of Cu is very useful in terms of its possible applications, such as: (1) in antimicrobial and anti-fouling tubing; (2) in the improvement of heat dissipation devices, such as microfluidic cooling systems and heat pipes; and (3) as an additional protection to Cu from further corrosion. This study also shows the possible mechanisms on how CuO, CuO 2 , and Cu 2 O 3 were formed from Cu based on the varying the plasma parameters.

We study the wetting and the adhesive behavior of substrates made by electropolymerization of copolymers of pyrene substituted with fluoroalkyl and adamantyl groups. The hydrophobicity and water adhesion properties can be tuned by the molar percentage (mol %) of each pyrene monomer so that the substrate properties can vary from superhydrophobic to parahydrophobic, with respectively low and high water adhesion. The ejection test method (ETM) is proposed as an original tool to discriminate and characterize such substrates. Using a catapult-like apparatus, a droplet initially at rest on the surface is subject to a large acceleration and is subsequently ejected. Depending on the surface properties and initial catapult acceleration, the ejection is more or less efficient and occurs with or without fragmentation of the droplet. The ETM is shown to be a complementary test to the lateral adhesion and hysteresis classical measurements. This work is of importance for the understanding of adhesion phenomena on various surfaces and for a better quantitative characterization of their adhesive properties.

Due to their small size, nanoparticles possess unique properties. Cerium oxide nanoparticles have been already studied for their capacity to adsorb and neutralize toxic compounds including organophosphates. By covalently grafting these nanoparticles to a thickening polymer, their potential aggregation resulting in a loss of surface area and their potential toxicity are avoided. Indeed, copolymers easily form gels in water at neutral pH thanks to low interactions occurring between polymeric chains; thus, gels can be spread on membrane supports to afford protective barriers. However, as we demonstrated previously, a formulation step of these hydride nanoparticle-polymeric compounds is necessary to overcome the cracking of the coating during drying. This work reports the impact of many factors on the efficiency of a new active Topical Skin Protectant (aTSP) including: (1) the presence of CeO 2 nanoparticles in the protective coating and their amount, (2) their grafting to a perfluorocarbon thickening polymer and (3) the formulation of the CeO 2 nanoparticle-grafted polymer. The combination of all the benefit parameters led to a very effective new aTSP against paraoxon penetration. The major in vitro diffusion studies were performed in Franz-type diffusion cells on two artificial membranes (silicone and Strat-M) and final validation on ex vivo human skin. The comparison of 24 h-exposure between membrane results indicated a difference in the behavior between the two artificial supports and the biological model; Strat-M membranes seeming closer to human skin results. Therefore, positive results regarding occlusive conditions should be confirmed with human skin., (Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.)

To reinforce skin protection against organophosphates (OPs), the development of new topical skin protectants (TSP) has received a great interest. Nanoparticles like cerium dioxide (CeO 2 ) known to adsorb and neutralize OPs are interesting candidates for TSP. However, NPs are difficult to disperse into formulations and they are suspected of toxicological issues. Thus, we want to study: (1) the effect of the addition of CeO 2 NPs in formulations for the skin protection (2) the impact of the doping of CeO 2 NPs by calcium; (3) the effect of two methods of dispersion of CeO 2 NPs: an O/W emulsion or a suspension of a fluorinated thickening polymer (HASE-F) grafted with these NPs. As a screening approach we used silicone membranes as a skin equivalent and Franz diffusion cells for permeation tests. The addition of pure CeO 2 NPs in both formulations permits the penetration to decrease by a 3-4-fold factor. The O/W emulsion allows is the best approach to obtain a film-forming coating with a good reproducibility of the penetration results; whereas the grafting of NPs to a thickener is the best way to obtain an efficient homogenous suspension of CeO 2 NPs with a decreased of toxicological impact but the coating is less film-forming which slightly impacts the reproducibility of the penetration results.

Novel hybrid hydrocarbon/fluorocarbon ammonium type surfactant monomers (surfmers) of the general formula RF (CH2)l N(CH3)2(CH2)mOCOCH=CH2 with (RF=C4F9, C6F13, C8F17, l=4, 6, 11, and m=2-11) were synthesized and characterized. They exhibit very low surface tension as well as low critical micellar concentrations down to 1.39×10(-5)mol/L. Special attention was focused on theeffect of the polymerizable moiety, the length of the hydrocarbon spacers, and the fluorinated chains on surface activities of the reactive surfactants as compared to hydrocarbon surfmer analogs. Results indicate that the acrylic function has a pronounced effect on increasing the hydrophobic micelle character. This was confirmed by surface tensions and average surfaces occupied by these molecules at the water-gas interface. The micellar sizes were investigated by dynamic light scattering., (Copyright © 2013 Elsevier Inc. All rights reserved.)

The interest in superhydrophobic surfaces has grown exponentially over recent decades. Since the lotus leaf dual hierarchical structure was discovered, researchers have investigated the foundations of self-cleaning behavior. Generally, surface micro/nanostructuring combined with low surface energy of materials leads to extreme anti-wetting properties. The great number of papers on this subject attests the efforts of scientists in mimicking nature to generate superhydrophobicity. Besides the thirst for knowledge, scientists have been driven by the many possible industrial applications of superhydrophobic materials in several fields. Many methods and techniques have been developed to fabricate superhydrophobic surfaces, and the aim of this paper is to review the recent progresses in preparing manmade superhydrophobic surfaces., (Copyright © 2013 Elsevier Inc. All rights reserved.)