Nanoconfinement and Chemical Structure Effects on Permeation Selectivity of Self-Assembling Graft Copolymers

Permeation of small molecule solutes through thin films is typically described by the solution-diffusion model, but this model cannot predict the effects of nanostructure due to self-assembly or additives. Other models focusing on diffusion through isolated nanopores indicate that confining permeation to channels slightly larger than the size of the solute can lead to an increased influence of solute–pore wall interactions on permeation rate. In this study, we analyze how differences in polymer nanostructure affect the relative contributions of solute size and polymer–solute interactions on transport rate. We compared the diffusion rates of several small molecules through two polymer thin films: A cross-linked, homogeneous film of poly­(ethylene glycol phenyl ether acrylate) (PEGPEA) and a graft copolymer with a poly­(vinylidene fluoride-<i>co</i>-chlorotrifluoroethylene) (P­(VDF-<i>co</i>-CTFE)) backbone and PEGPEA side chains that self-assemble into continuous ∼1–3 nm PEGPEA domains through which transport occurs. We correlated these rates with the size of each solute and its chemical affinity to PEGPEA, as measured by the difference between their solubility parameters. Diffusion rate through the homogeneous polymer film was controlled by solute size, whereas diffusion rate through the copolymer was strongly controlled by the difference between the solubility parameters. Furthermore, permeation selectivity between two selected molecules was 2.5× higher for the nanostructured copolymer, likely enhanced by the nanoconfinement effects. These initial results indicate that polymer self-assembly is a promising tool for designing polymeric membranes that can differentiate between solutes of similar size but differing chemical structures

Selective Transport through Membranes with Charged Nanochannels Formed by Scalable Self-Assembly of Random Copolymer Micelles

Membranes that can separate compounds based on molecular properties can revolutionize the chemical and pharmaceutical industries. This study reports membranes capable of separating organic molecules of similar size based on their electrostatic charge. These membranes feature a network of carboxylate-functionalized 1–3 nm nanochannels, manufactured by a simple, scalable coating process: a porous support is coated with a packed array of polymer micelles in alcohol, formed by the self-assembly of a water-insoluble random copolymer with fluorinated and carboxyl functional repeat units. The interstices between these micelles serve as charged nanochannels through which water and solutes can pass. The negatively charged carboxylate groups lead to high separation selectivities between organic solutes of similar size but different charge. In single-solute diffusion experiments, neutral solutes permeate up to 263 times faster than negatively charged compounds of similar size. This selectivity is further enhanced in experiments with mixtures of these solutes. No permeation of the anionic compound was observed for over 24 h. In filtration experiments, these membranes separate anionic and neutral organic compounds while exhibiting water fluxes comparable to that of commercial membranes. Furthermore, carboxylate groups can be functionalized, creating membranes with nanopores with customizable functionality to enable a broad range of selective separations

Self-Assembling Zwitterionic Copolymers as Membrane Selective Layers with Excellent Fouling Resistance: Effect of Zwitterion Chemistry

Membranes with high flux, ∼1 nm pore size, and unprecedented protein fouling resistance were prepared by forming selective layers of self-assembling zwitterionic amphiphilic random copolymers on porous supports by a simple coating method. Random copolymers were prepared from the hydrophobic monomer 2,2,2-trifluoroethyl methacrylate (TFEMA) and four zwitterionic monomers (sulfobetaine methacrylate, sulfobetaine 2-vinylpyridine, sulfobutylbetaine 2-vinylpyridine, and 2-methacryloyloxyethyl phosphorylcholine) by free radical polymerization. All copolymers microphase separated to form bicontinuous ∼1.2 nm nanodomains with the zwitterionic domains acting as nanochannels for the permeation of water and solutes. The resultant membranes all had a ∼1 nm size cutoff independent of zwitterion chemistry. There were, however, significant differences in the hydrophilicity, water uptake, water flux, and fouling resistance among membranes prepared with different zwitterionic monomers. Membranes prepared from the copolymer with 2-methacryloyloxyethyl phosphorylcholine were the most hydrophilic and had the highest water permeance, higher than that of commercial membranes of similar pore size. Furthermore, these membranes showed unprecedented fouling resistance, exhibiting no measurable flux decline throughout a 24 h protein fouling experiment. The structure–property relationships gleaned from this survey of different zwitterion structures serves as a guideline to develop new zwitterionic materials for various applications such as membranes, drug delivery, and sensors

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

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-<i>random</i>-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

Zwitterion-Containing Ionogel Electrolytes

Zwitterion-Containing Ionogel Electrolyte