Breath figure templated semifluorinated block copolymers with tunable surface properties and binding capabilities

Abstract

Patterning of functionalized polymeric surfaces enables the adjustment of their characteristics and use in novel applications. We prepared breath figure (BF) films from three semifluorinated diblock copolymers, which all are composed of a polystyrene block and a semifluorinated one to compare their surface properties. “Click” chemistry was employed to one of the polymers, containing a poly(pentafluorostyrene) block to incorporate hydrophilic sugar or carboxylic acid moieties. The structure of the polymer alters the obtained porous morphology of the films. Contact angle (CA) analyses of the BF films reveals that the surface porosity increases water CAs compared with solvent cast films, and, in the case of hydrophobic polymers, leads to significant increase in the CAs of dodecane. The hydrophobicity of the BF films is further amplified by the removal of the topmost layer which leads in some cases to superhydrophobic surfaces. BF films containing glucose units are hydrophilic exhibiting water CAs below 90°. These glycosylated porous surfaces are shown to bind lectin Con A‐FITC or can be labelled with isothiocyanate marker. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41225.

Breath Figure: A Nature-Inspired Preparation Method for Ordered Porous Films

“…Most of the peanut agglutinin protein was conjugated to the glycopolymer inside the pore, indicating the excellent selectivity of the template. 124 Furthermore, glycopolymer BFA films could be used to recognize Con A, 125,143,241 and their bioactivity can be tuned between "on" and "off" states based on temperature due to the thermoresponsive property of PNIPAm. 505 Another strategy to pattern proteins is to fill the pores of BFA films with microspheres decorated with biomolecules or bioactive molecules.…”

“…As a result, under these circumstances, the number of pores in the BFA film was obviously small. In other examples, fluoride BCPs of polystyrene- b -poly­(perfluorooctyl ethyl methacrylate) (PS- b -PFMA, 31 ), polystyrene- b -poly­(2,3,5,6-tetrafluoro-4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecaoxy)­styrene) (PS- b -PFSF, 33 ), polystyrene- b -polypentafluorostyrene (PS- b -PFS, 33 ), PM- b -P­(St- co -PFSt) ( 34 ), poly­( tert -butyl acrylate)- b -poly­(2-[(perfluorononenyl) oxy]­ethyl methacrylate) (PtBA- b -PFNEMAs, 35 ), PTFEMA- b -PMMA- b -PEG- b -PMMA- b -PTFEMA ( 36 ), , and poly­(vinylidenefluoride- co -hexafluoropropylene) (PVDF–HFP, 37 ) (Scheme ) were synthesized and used to prepare BFA films with dichloromethane, chloroform, or CS 2 as the solvent. The influences of the solvent, the molecular weight of copolymers, the relative humidity, and the temperature on the morphology of the BFA films were investigated.…”

Ordered Honeycomb‐Pattern Membrane†

“…Other examples of hydrophilic modification based on PS were shown in Scheme 4(C). [ 9,53,60‐64 ] When the polymers had hydrophilic groups, the membrane pores will be increased, because the hydrophilic chain segments will interact with the solvent to prevent the solvent from volatilization and reduce the temperature difference. It increases the time for the growth of water droplets.…”

In Search of a Green Process: Polymeric Films with Ordered Arrays via a Water Droplet Technique

“…The solvent properties of boiling point, density, miscibility with water, and the thermodynamic affinity with a polymer solution have to be taken into account when it comes to the choice of solvent for proper water–solution interfacial tension. Because of this, most of the reported honeycomb-like films via the BF process were obtained using volatile solvents such as CS 2 , chloroform, dichloromethane, benzene, and chlorobenzene [87,96,97,98,99]. However, according to various solvent selection guides, including the CHEM21 selection guide of classical and less classical solvents, GlaxoSmithKline (GSK), AstraZeneca, and the American Chemical Society Green Chemistry Institute (ACS GCI), these commonly-used solvents were considered as highly hazardous (marked in bold in Table 1) [100,101,102,103].…”