Sulfonated Styrene-Grafted Polyvinylidene Fluoride Copolymers for Proton Exchange Membranes for AQDS/Bromine Redox Flow Batteries.

This study presents the preparation and electrochemical testing of sulfonated styrene-grafted poly(vinylidene fluoride) (pVDF) copolymers as proton exchange membranes (PEMs) for semi-organic redox flow batteries (RFBs) based on 9,10-anthraquinone-2,7-disulfonic acid (AQDS)/bromine. The copolymers are synthesized via a two-step procedure, involving i) atom transfer radical polymerization of styrene (Sty) for the grafting to the pVDF backbone and ii) the sulfonation of the polystyrene grafted side chains. Copolymers with different amounts of sulfonated styrene (SSty) in the side chains (i.

Interrupting marine fouling with active buffered coatings.

Biofouling on marine surfaces causes immense material and financial harm for maritime vessels and related marine industries. Previous reports have shown the effectiveness of amphiphilic coating systems based on poly(dimethylsiloxane) (PDMS) against such marine foulers. Recent studies on biofouling mechanisms have also demonstrated acidic microenvironments in biofilms and stronger adhesion at low-pH conditions.

Amphiphilic Fluorinated Unimer Micelles as Nanocarriers of Fluorescent Probes for Bioimaging.

The unique self-assembly properties of unimer micelles are exploited for the preparation of fluorescent nanocarriers embedding hydrophobic fluorophores. Unimer micelles are constituted by a (meth)acrylate copolymer with oligoethyleneglycol and perflurohexylethyl side chains (PEGMA90--FA10) in which the hydrophilic and hydrophobic comonomers are statistically distributed along the polymeric backbone. Thanks to hydrophobic interactions in water, the amphiphilic copolymer forms small nanoparticles (<10 nm), with tunable properties and functionality.

The Nanostructured Self-Assembly and Thermoresponsiveness in Water of Amphiphilic Copolymers Carrying Oligoethylene Glycol and Polysiloxane Side Chains.

Amphiphilic copolymer self-assembly is a straightforward approach to obtain responsive micelles, nanoparticles, and vesicles that are particularly attractive for biomedicine, i.e., for the delivery of functional molecules.

Nitroxide-Containing Amphiphilic Random Terpolymers for Marine Antifouling and Fouling-Release Coatings.

Two types of amphiphilic random terpolymers, poly(ethylene glycol methyl ether methacrylate)--poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate)--poly(polydimethyl siloxane methacrylate) (PEGMEMA--PTMA--PDMSMA), were synthesized and evaluated for antifouling (AF) and fouling-release (FR) properties using diverse marine fouling organisms. In the first stage of production, the two respective precursor amine terpolymers containing (2,2,6,6-tetramethyl-4-piperidyl methacrylate) units (PEGMEMA--PTMPM--PDMSMA) were synthesized by atom transfer radical polymerization using various comonomer ratios and two initiators: alkyl halide and fluoroalkyl halide. In the second stage, these were selectively oxidized to introduce nitroxide radical functionalities.

Self-Assembled Amphiphilic Fluorinated Random Copolymers for the Encapsulation and Release of the Hydrophobic Combretastatin A-4 Drug.

Water-soluble amphiphilic random copolymers composed of tri(ethylene glycol) methacrylate (TEGMA) or poly(ethylene glycol) methyl ether methacrylate (PEGMA) and perfluorohexylethyl acrylate (FA) were synthesized by ARGET-ATRP, and their self-assembling and thermoresponsive behavior in water was studied by dynamic light scattering (DLS) and UV-vis spectroscopy. The copolymer ability to self-fold in single-chain nano-sized structures (unimer micelles) in aqueous solutions was exploited to encapsulate Combretastatin A-4 (CA-4), which is a very hydrophobic anticancer drug. The cloud point temperature () was found to linearly decrease with increasing drug concentration in the drug/copolymer system.

New amphiphilic copolymers for PDMS-based nanocomposite films with long-term marine antifouling performance.

Amphiphilic methacrylate copolymers (Si-co-EF) containing polysiloxane (Si) and mixed poly(oxyethylene)-perfluorohexyl (EF) side chains were synthesized with different compositions and used together with polysiloxane-functionalized nanoparticles as additives of condensation cured nanocomposite poly(siloxane) films. The mechanical properties of the nanocomposite films were consistent with the elastomeric behavior of the poly(siloxane) matrix without significant detriment from either the copolymer or the nanoparticles. Films were found to be markedly hydrophobic and liphophobic, with both properties being maximized at an intermediate content of EF units.

The Effect of Poly(ethylene glycol) (PEG) Length on the Wettability and Surface Chemistry of PEG-Fluoroalkyl-Modified Polystyrene Diblock Copolymers and Their Two-Layer Films with Elastomer Matrix.

Diblock copolymers composed of a polystyrene first block and a PEG-fluoroalkyl chain-modified polystyrene second block were synthesized by controlled atom transfer radical polymerization (ATRP), starting from the same polystyrene macroinitiator. The wettability of the polymer film surfaces was investigated by measurements of static and dynamic contact angles. An increase in advancing water contact angle was evident for all the films after immersion in water for short times (10 and 1000 s), consistent with an unusual contraphilic switch of the PEG-fluoroalkyl side chains.

Amphiphilic hydrolyzable polydimethylsiloxane--poly(ethyleneglycol methacrylate--trialkylsilyl methacrylate) block copolymers for marine coatings. II. Antifouling laboratory tests and field trials.

Poly(dimethylsiloxane) (PDMS) elastomer coatings containing an amphiphilic hydrolyzable diblock copolymer additive were prepared and their potential as marine antifouling and antiadhesion materials was tested. The block copolymer additive consisted of a PDMS first block and a random poly(trialkylsilyl methacrylate (TRSiMA, R = butyl, isopropyl)--poly(ethyleneglycol) methacrylate (PEGMA) copolymer second block. PDMS--TRSiMA block copolymer additives without PEGMA units were also used as additives.

Fluorinated vs. Zwitterionic-Polymer Grafted Surfaces for Adhesion Prevention of the Fungal Pathogen .

Fluorinated (F6) and zwitterionic, as well as phosphorylcholine (MPC) and sulfobetaine (MSA), copolymers containing a low amount (1 and 5 mol%) of 3-(trimethoxysilyl)propyl methacrylate (PTMSi) were prepared and covalently grafted to glass slides by using the trimethoxysilyl groups as anchorage points. Glass-surface functionalization and polymer-film stability upon immersion in water were proven by contact angle and angle-resolved X-ray photoelectron spectroscopy (AR-XPS) measurements. Antifouling performance of the grafted films was assayed against the yeast , the most common species, which causes over 80% of candidiasis.

Model Amphiphilic Block Copolymers with Tailored Molecular Weight and Composition in PDMS-Based Films to Limit Soft Biofouling.

A set of controlled surface composition films was produced utilizing amphiphilic block copolymers dispersed in a cross-linked poly(dimethylsiloxane) network. These block copolymers contained oligo(ethylene glycol) (PEGMA) and fluoroalkyl (AF6) side chains in selected ratios and molecular weights to control surface chemistry including antifouling and fouling-release performance. Such properties were assessed by carrying out assays using two algae, the green macroalga Ulva linza (favors attachment to polar surfaces) and the unicellular diatom Navicula incerta (favors attachment to nonpolar surfaces).

Amphiphilic Polymer Platforms: Surface Engineering of Films for Marine Antibiofouling.

A range of amphiphilic polymers with diverse macromolecular architectures has been developed and incorporated into films and coatings with potential for marine antibiofouling applications, without resorting to addition of currently used biocidal, toxic agents. Novel "green" chemical technologies employ different building blocks to endow the polymer film with surface activity, functionality, structure, and reconstruction according to the outer environment as a result of a tailored amphiphilic character of the polymer platform. We emphasise how these features can interplay and add synergistically to affect antifouling and fouling-release against common, widespread marine micro- and macro-fouling organisms.

Effects of surface-active block copolymers with oxyethylene and fluoroalkyl side chains on the antifouling performance of silicone-based films.

Block copolymers made from a poly(dimethyl siloxane) (Si) and a poly(meth)acrylate carrying oxyethylene (EG) or fluoroalkyl (AF) side chains were synthesized and incorporated as surface-active components into a silicone matrix to produce cross-linked films with different surface hydrophilicity/phobicity. Near-edge X-ray absorption fine structure (NEXAFS) studies showed that film surfaces containing Si-EG were largely populated by the siloxane, with the oxyethylene chains present only to a minor extent. In contrast, the fluorinated block was selectively segregated to the polymer-air interface in films containing Si-AF as probed by NEXAFS and X-ray photoelectron spectroscopy (XPS) analyses.

Photopolymerized Network Polysiloxane Films with Dangling Hydrophilic/Hydrophobic Chains for the Biofouling Release of Invasive Marine Serpulid Ficopomatus enigmaticus.

Novel photopolymerized network films based on a polysiloxane matrix containing varied amounts of polyoxyethylene (P3) or perfluorohexylethyl (F) dangling side chains were investigated. For films containing less than 10 wt % P3 and F, the wettability and elastic modulus were similar to those of the photopolymerized network matrix. However, angle-resolved X-ray photoelectron spectroscopy measurements proved that the surface of films with F dangling chains was highly enriched in fluorine depending on both the amount of P3 and F and their relative ratio in the films.

Evidence of Cybotactic Order in the Nematic Phase of a Main-Chain Liquid Crystal Polymer with Bent-Core Repeat Unit.

We report the synthesis and structural characterization of a main-chain liquid crystal polymer constituted by a 1,2,4-oxadiazole-based bent-core repeat unit. For the first time, a liquid crystal polymer made of bent mesogenic units is demonstrated to exhibit cybotactic order in the nematic phase. Coupled with the chain-bond constraints, cybotaxis results in maximized molecular correlations that make this material of great potential in the search for the elusive biaxial and ferroelectric nematic phases.

An ecotoxicological study on tin- and bismuth-catalysed PDMS based coatings containing a surface-active polymer.

Novel films were prepared by condensation curing reaction of a poly(dimethyl siloxane) (PDMS) matrix with bismuth neodecanoate and dibutyltin diacetate catalysts. An ecotoxicological study was performed on the leachates of the coatings using the bacterium Vibrio fischeri, the unicellular alga Dunaliella tertiolecta, the crustacean Artemia salina and the fish Sparus aurata (larvae) as testing organisms. A copper-based self-polishing commercial paint was also tested as reference.

Poly(dimethyl siloxane) (PDMS) network blends of amphiphilic acrylic copolymers with poly(ethylene glycol)-fluoroalkyl side chains for fouling-release coatings. II. Laboratory assays and field immersion trials.

Amphiphilic copolymers containing different amounts of poly(ethylene glycol)-fluoroalkyl acrylate and polysiloxane methacrylate units were blended with a poly(dimethyl siloxane) (PDMS) matrix in different proportions to investigate the effect of both copolymer composition and loading on the biological performance of the coatings. Laboratory bioassays revealed optimal compositions for the release of sporelings of Ulva linza, and the settlement of cypris larvae of Balanus amphitrite. The best-performing coatings were subjected to field immersion tests.

Amphiphilic block copolymer/poly(dimethylsiloxane) (PDMS) blends and nanocomposites for improved fouling-release.

Amphiphilic diblock copolymers, Sz6 and Sz12, consisting of a poly(dimethylsiloxane) block (average degree of polymerisation = 132) and a PEGylated-fluoroalkyl modified polystyrene block (Sz, average degree of polymerisation = 6, 12) were prepared by atom transfer radical polymerization (ATRP). Coatings were obtained from blends of either block copolymer (1-10 wt%) with a poly(dimethylsiloxane) (PDMS) matrix. The coating surface presented a simultaneous hydrophobic and lipophobic character, owing to the strong surface segregation of the lowest surface energy fluoroalkyl chains of the block copolymer.

More fluorous surface modifier makes it less oleophobic: fluorinated siloxane copolymer/PDMS coatings.

A copolyacrylate with semifluorinated and polydimethylsiloxane side chains (D5-3) was used as a surface modifier for a condensation-cured PDMS coating. The decyl fluorous group is represented by "D"; "5" is a 5 kDa silicone, and "3" is the mole ratio of fluorous to silicone side chains. Wetting behavior was assessed by dynamic contact angle (DCA) analysis using isopropanol, which differentiates silicone and fluorous wetting behavior.

The surface-segregated nanostructure of fluorinated copolymer-poly(dimethylsiloxane) blend films.

Two fluorinated/siloxane copolymers, O5/19 and D5/3, carrying 6 and 8 CF(2) groups in the fluoroalkyl tail, respectively, were used as the surface-active components of cured poly(dimethylsiloxane) (PDMS) blends at different loadings (0.3-5.0 wt % with respect to PDMS).

Fluorinated/siloxane copolymer blends for fouling release: chemical characterisation and biological evaluation with algae and barnacles.

Fouling-release coatings were prepared from blends of a fluorinated/siloxane copolymer with a poly(dimethyl siloxane) (PDMS) matrix in order to couple the low modulus character of PDMS with the low surface tension typical for fluorinated polymers. The content of the surface-active copolymer was varied in the blend over a broad range (0.15-10 wt % with respect to PDMS).

Nanostructured films of amphiphilic fluorinated block copolymers for fouling release application.

New amphiphilic block copolymers S nSz m consisting of blocks with varied degrees of polymerization, n and m, of polystyrene, S, and polystyrene carrying an amphiphilic polyoxyethylene-polytetrafluoroethylene chain side-group, Sz, were prepared by controlled atom transfer radical polymerization (ATRP). The block copolymers, either alone or in a blend with commercial SEBS (10 wt% SEBS), were spin-coated in thinner films (200-400 nm) on glass and spray-coated in thicker films ( approximately 500 nm) on a SEBS underlayer (150-200 microm). Angle-resolved X-ray photoelectron spectroscopy (XPS) measurements proved that at any photoemission angle, varphi, the atomic ratio F/C was larger than that expected from the known stoichiometry.

Intercalated smectic a phases in banana-shaped liquid crystals with carbonate end groups.

Novel, symmetrical, bent-core mesogens, namely substituted 1,3-phenylenebis{4'-[(ethoxycarbonyl)oxy]-1,1'-biphenyl}-4-carboxylates, are prepared with carbonate groups at both ends of the molecules. The mesophase properties are investigated for different electron-donating and -withdrawing substituents connected to the central ring at different positions. These compounds exhibit nematic and/or smectic A intercalated (SmA(int)) mesophases.

Control of surface properties using fluorinated polymer brushes produced by surface-initiated controlled radical polymerization.

Surface-grafted styrene-based homopolymer and diblock copolymer brushes bearing semifluorinated alkyl side groups were synthesized by nitroxide-mediated controlled radical polymerization on planar silicon oxide surfaces. The polymer brushes were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and time-dependent water contact angle measurements. Angle-resolved XPS studies and water contact angle measurements showed that, in the case of the diblock copolymer brushes, the second block to be added was always exposed at the polymer-air interface regardless of its surface energy.

Tapping mode AFM evidence for an amorphous reticular phase in a condensation-cured hybrid elastomer: alpha,omega-dihydroxypoly(dimethylsiloxane)/poly(diethoxysiloxane)/fumed silica nanoparticles.

A new surface phenomenon is reported for hybrid nanocomposites comprising (1) a low Tg poly(dimethylsiloxane) (PDMS) phase cross-linked by (2) a siliceous phase (SP) generated by in situ hydrolysis/condensation of poly(diethoxysiloxane) (PDES), and (3) fumed silica nanoparticles (FSN). After ambient temperature cure, tapping mode atomic force microscopy (TM-AFM) easily reveals near-surface FSN. For nanocomposites with higher PDES content, FSN surprisingly "disappear" after a further cure at 100 degrees C.