Co-Deposition of Stimuli-Responsive Microgels with Foulants During Ultrafiltration as a Fouling Removal Strategy.

In this study, we show that codeposition of temperature responsive microgels in the foulant cake layer and cleaning of the cake upon stimuli-induced size change of the microgels is an effective method of fouling removal. Humic acid in CaCl2 solution was used as a model foulant and poly( n-isopropylacrylamide) (p(NIPAm)) and poly( n-isopropylacrylamide- co-sulfobetainemethacrylate) (p(NIPAm- co-SBMA)) were used as temperature responsive microgels. Filtrations were done below the lower critical solution temperature (LCST) and temperature was increased to above the LCST for cleaning. As an extra cleaning a temperature swing of above, below and then again above the LCST was applied. P(NIPAm) was found to be ineffective in cleaning the foulant deposit despite the 20-fold change in its volume with temperature change at LCST. P(NIPAm- co-SBMA) microgels, on the other hand, provided high fouling reversibility on hydrophilic poly(ether sulfone)(PES)/poly(vinylpyrrolidone) (PVP) and hydrophobic PES membranes. Better fouling reversibility with these microgels was observed at low and high solution ionic strength. While the use of microgels alone increased fouling reversibility to some extent, even in the absence of temperature stimulus, 100% reversibility could only be obtained when a temperature switch was applied in the presence of microgels, showing the effect of microgels' volume change in cleaning.

New Family of Water-Soluble Sulfo-Fluoro Polyphosphazenes and Their Assembly within Hemocompatible Nanocoatings.

In this work, novel sulfo-fluoro polyphosphazenes (PPzs) were synthesized via macromolecular substitution of polydichlorophosphazene utilizing "non-covalent protection" methodology by converting acid functionalities into hydrophobic alkylammonium salts. Resulting PPzs showed excellent solubility in aqueous solutions over a broad pH range and contained ∼25% sulfo- groups and 20% either trifluoroethoxy- (FESP) or trifluoromethylphenoxy- (FPSP) side groups, as determined by NMR spectroscopy. Their polyelectrolyte behavior was evaluated by binding with an oppositely charged polyion, branched polyethylenimine (PEI), which resulted in the formation of interpolymer complexes as shown by dynamic light scattering (DLS). Contrary to a sulfonated, nonfluorinated PPz homopolymer (SP), fluorinated macromolecules effectively bound human serum albumin (HSA) as revealed by dynamic light scattering and asymmetric flow field flow fractionation (AF4) studies. Moreover, FESP and FPSP both displayed low hemolytic activity as evaluated in solution using porcine red blood cells. Using the layer-by-layer (LbL) technique, FESP and FPSP were assembled into nanocoatings with PEI. Both fluorinated and nonfluorinated sulfo PPzs showed linear growth with PEI because of strong ionic pairing between sulfo and amino groups. However, films of fluorinated PPzs displayed higher hydrophobicity, lower swelling, and improved stability in high ionic strength environment when compared to coatings formed by a sulfonated, nonfluorinated SP, or a carbon-chain polymer poly(styrene sulfonic acid). Hemocompatibility of FESP and FPSP nanofilms was demonstrated in vitro using whole rabbit blood hemolysis tests, which showed less than 1% hemolysis. Altogether, the present study introduces a new class of hemocompatible, sulfo-fluoropolymers that shows promise for life science applications.

Hydrophobic Antifouling Electrospun Mats from Zwitterionic Amphiphilic Copolymers.

A porous material that is both hydrophobic and fouling-resistant is needed in many applications, such as water purification by membrane distillation. In this work, we take a novel approach to fabricating such membranes. Using the zwitterionic amphiphilic copolymer poly(trifluoroethyl methacrylate- random-sulfobetaine methacrylate), we electrospin nonwoven, porous membranes that combine high hydrophobicity with resistance to protein adsorption. By changing the electrospinning parameters and the solution composition, membranes can be prepared with a wide range of fiber morphologies including beaded, bead-free, wrinkly, and ribbonlike fibers, with diameters ranging between ∼150 nm and 1.5 µm. The addition of LiCl to the spinning solution not only helps control the fiber morphology but also increases the segregation of zwitterionic groups on the membrane surface. The resultant electrospun membranes are highly porous and very hydrophobic, yet resist the adsorption of proteins and retain a high contact angle (∼140°) even after exposure to a protein solution. This makes these materials promising candidates for the membrane distillation of contaminated wastewater streams and as self-cleaning materials.

Self-Cleaning Membranes from Comb-Shaped Copolymers with Photoresponsive Side Groups.

In this study, we present a novel self-cleaning, photoresponsive membrane that is capable of removing predeposited foulant layers upon changes in surface morphology in response to UV or visible light irradiation while maintaining stable pore size and water permeance. These membranes were prepared by creating thin film composite (TFC) membranes by coating a porous support membrane with a thin layer of novel comb-shaped graft copolymers at two side-chain lengths featuring polyacrylonitrile (PAN) backbones and photoreactive side chains, synthesized by atom transfer radical polymerization (ATRP). Photoregulated control over membrane properties is attained through a light-induced transition, where the side chains switch between a hydrophobic spiropyran (SP) state and a zwitterionic, hydrophilic merocyanine (MC) state. The light-induced switch between the SP and MC forms changes surface hydrophilicity and causes morphological changes on the membrane surface as evidenced by atomic force microscopy (AFM). Before any phototreatment, the as-coated membrane surface comprises mostly hydrophobic SP groups that allow the adsorption of organic solutes such as proteins the membrane surface, reducing flow rate. Once exposed to UV light, conversion of the SP groups to hydrophilic MC groups leads to the release of adsorbed molecules and the full recovery of the initial water flux. A fouled membrane in the more hydrophilic MC form is also capable of self-cleaning upon conversion to the less hydrophilic SP form by visible light irradiation. The self-cleaning behavior observed for this system, where the surface became less hydrophilic but also experienced a morphological change, demonstrates a novel mechanism that has a mechanical component in addition to the changes in hydrophilicity. It is also the first report, to our knowledge, of self-cleaning performance accompanied by a decrease in hydrophilicity.

Physical characterization of functionalized spider silk: electronic and sensing properties.

This work explores functional, fundamental and applied aspects of naturally harvested spider silk fibers. Natural silk is a protein polymer where different amino acids control the physical properties of fibroin bundles, producing, for example, combinations of ß-sheet (crystalline) and amorphous (helical) structural regions. This complexity presents opportunities for functional modification to obtain new types of material properties. Electrical conductivity is the starting point of this investigation, where the insulating nature of neat silk under ambient conditions is described first. Modification of the conductivity by humidity, exposure to polar solvents, iodine doping, pyrolization and deposition of a thin metallic film are explored next. The conductivity increases exponentially with relative humidity and/or solvent, whereas only an incremental increase occurs after iodine doping. In contrast, iodine doping, optimal at 70 °C, has a strong effect on the morphology of silk bundles (increasing their size), on the process of pyrolization (suppressing mass loss rates) and on the resulting carbonized fiber structure (that becomes more robust against bending and strain). The effects of iodine doping and other functional parameters (vacuum and thin film coating) motivated an investigation with magic angle spinning nuclear magnetic resonance (MAS-NMR) to monitor doping-induced changes in the amino acid-protein backbone signature. MAS-NMR revealed a moderate effect of iodine on the helical and ß-sheet structures, and a lesser effect of gold sputtering. The effects of iodine doping were further probed by Fourier transform infrared (FTIR) spectroscopy, revealing a partial transformation of ß-sheet-to-amorphous constituency. A model is proposed, based on the findings from the MAS-NMR and FTIR, which involves iodine-induced changes in the silk fibroin bundle environment that can account for the altered physical properties. Finally, proof-of-concept applications of functionalized spider silk are presented for thermoelectric (Seebeck) effects and incandescence in iodine-doped pyrolized silk fibers, and metallic conductivity and flexibility of micron-sized gold-sputtered silk fibers. In the latter case, we demonstrate the application of gold-sputtered neat spider silk to make four-terminal, flexible, ohmic contacts to organic superconductor samples.