Amine-Containing Block Copolymers for the Bottom-Up Preparation of Functional Porous Membranes

Abstract

The remarkable ability of biological systems to specifically recognize, sort, and process molecules encourages the development of novel bio-inspired membranes and interfaces. Herein, we focus on the functionalization of amphiphilic polystyrene-block-poly­(2-hydroxyethyl methacrylate) (PS-b-PHEMA) with the amino acid glycine yielding polar block segments with primary amine functionalities. Excellent control over the tailored block copolymer (BCP) synthesis and functionalization is proven by size exclusion chromatography (SEC), 1H solution NMR, and 15N solid state NMR spectroscopy. For the first time, BCPs containing primary amines were used for the self-assembly and non-solvent induced phase separation (SNIPS) process for the preparation of isoporous and integral asymmetric membranes. Hexagonally arranged open pores with diameters of 19 nm were obtained as shown by scanning electron microscopy (SEM), atomic force microscopy (AFM), and pH-dependent water flux measurements. Additionally, the primary amine was subjected to convenient postmodification protocols. For instance, (fluorescent) dye molecules could be easily incorporated into the membrane structure, and peptide synthesis on the inner pore wall of the membrane could be accomplished. These novel and tailored porous materials will pave the way to a new generation of BCP membranes containing bio-inspired moieties and functionalities at the interfaces.

Emerging Functional Porous Polymeric and Carbonaceous Materials for Environmental Treatment and Energy Storage

“…[236][237][238][239] Ingenious functionalization of isoporous membranes by decorating functional groups inside the pores and on the surface of the membrane will endow stimuliresponsiveness, controlled selectivity and enhanced antifouling ability. [240][241][242][243][244][245][246] For example, Abetz and co-workers attached poly(N-isopropylacrylamide) to the asymmetric polystyreneb-poly(4-vinylpyridine) diblock copolymer membranes through surface linking reaction. [240] The as-obtained pH and thermodouble sensitive membrane was able to determine the water flux under different temperature and pH conditions.…”

“…Moreover, the primary amine was also exploited for stepwise synthesis of tripeptide, and thus provided the functional membranes with more possibilities in biological systems. [242]…”

Small Molecules, Non-Covalent Interactions, and Confinement

“…As mentioned above these mesoporous silica materials permit the comparatively simple synthesis of surface functionalized host systems with well-defined tunable narrow pore diameters [ 175 , 176 , 177 , 178 ], employing a synthesis protocol, which is based on Grünberg et al [ 106 ] and Grün et al [ 179 ]. Details of the synthesis and characterization are given in [ 176 , 180 ] and will not be repeated here.…”

The Key Role of Modifications in Biointerfaces toward Rendering Antibacterial and Antifouling Properties in Polymeric Membranes for Water Remediation: A Critical Assessment

“…[256] The second associated demerit is Adv. [223] Copyright 2019, American Chemical Society. 2019, 3, 1900017 Figure 11.…”

“…b) SEM micrograph of SNIPS membrane prepared with 18 (w/w)% of PS 74 ‐b‐P(HEMA‐co‐(HEMA‐GlyNH2)) 26 where GlyNH 2 is glycinamide and drying time is 5 s. Herein 74 and 26 corresponds to the molar concentrations of the blocks. Reproduced with permission . Copyright 2019, American Chemical Society.…”