Bei-Bei Ke

Ordered microporous membranes templated by breath figures for size-selective separation.

Membranes with highly uniform pore size are important in various fields. Here we report the preparation and performance of ordered membranes, the pore diameter of which is on the micrometer scale. The ordered membranes fabricated at two-phase interfaces enable a high-resolution and energy-saving separation process. Moreover, a possible mechanism for the formation of through-pores has been proposed and experimentally verified.

Honeycomb-Patterned Film Segregated with Phenylboronic Acid for Glucose Sensing

Phenylboronic acid (PBA)-functionalized materials have attracted considerable attention because of their potential applications in many fields. In this paper, we report a PBA-segregated honeycomb-patterned porous film (HPPF) for glucose sensing. Polystyrene-block-poly(acrylic acid-co-acrylamidophenylboronic acid) with different contents of PBA pendants was synthesized via atom transfer radical polymerization (ATRP) followed by a coupling reaction. PBA-functionalized HPPFs were then fabricated by the breath figure method. Results indicate that the composition of the copolymers and the relative humidity play key roles in pore size and regularity of the films. Using Alizarin Red S (ARS) that does not emit fluorescence itself as a fluorescent probe, it is confirmed that PBA pendants are mainly distributed at the pore wall, instead of at the outer surface of HPPFs. This distribution is caused by the segregation of hydrophilic PBA-blocks toward the condensed water droplets, which act as templates for the pore formation. Quartz crystal microbalance results demonstrate that the PBA-functionalized HPPFs show high sensitivity in glucose sensing, which is owing to the segregation of PBA pendants at the pore wall as well as the large specific surface area of the porous films.

Controllable Construction of Carbohydrate Microarrays by Site-Directed Grafting on Self-Organized Porous Films

Carbohydrate-protein interactions are critical in many biological processes. However, the interactions between individual carbohydrates and proteins are often of low affinity and difficult to study. Recent development of carbohydrate microarrays provides an effective tool to explore the interaction. In this work, carbohydrate microarrays were controllably constructed by grafting of a carbohydrate-containing monomer on self-organized honeycomb-patterned films. The films were prepared from an amphiphilic block copolymer, poly(styrene-block-(2-hydroxyethyl methacrylate)), by a breath figure method. Three-dimensional fluorescence results demonstrate that the hydroxyl groups aggregate mainly inside the pores, which afford a chance of site-directed surface modification. 2-(2,3,4,6-Tetra-O-acetyl-beta-D-glucosyloxy)ethyl methacrylate was selectively grafted in the pores by a surface-initiated atom transfer radical polymerization. Characterization by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, and contact angle measurements confirms the site-directed growth of the glycopolymer chains. Further specific recognition of the carbohydrate microarrays to lectin (concanavalin A) leads to an organized microarray of protein, and hence this approach also opens a new route to fabricating other functional microarrays such as protein-patterned surfaces.

Tunable Assembly of Nanoparticles on Patterned Porous Film

This paper describes an approach to fully selective assembly of nanoparticles on patterned porous surface. Copolymers of polystyrene-block-poly(N,N-dimethylaminoethyl methacrylate) synthesized by atom transfer radical polymerization were used to prepare honeycomb-patterned porous films by the breath figure method. The regularity and pore size of the films can be modulated by changing the polymer composition and casting conditions such as concentration and airflow speed. Positively charged films were fabricated directly from the quaternized copolymers or by surface quaternization. X-ray photoelectron spectroscopy and adsorption of negatively charged fluorescein sodium salt confirmed the quaternization. Then assembly of negatively charged silica nanoparticles from its aqueous dispersion was performed. Results indicate that they assemble on the external surface of patterned porous films that without prewetting. For prewetted films, the nanoparticles assemble both on the external surface and in the pores. Poly(acrylic acid) deposited from its aqueous solution can serve as an effective blocking layer, which directs the selective assembly of nanoparticles into the pores, instead of the external surface of the film. It is concluded that the Cassie-Wenzel transition is the key to the selective assembly on the highly porous films. The well-defined selective assembly forms unique hierarchical structures of nanoparticles and greatly enlarges the diversity of structures of nanoparticle aggregates. This general approach also opens a straightforward route to the selective modification of patterned porous films.

Pore shape of honeycomb-patterned films: modulation and interfacial behavior.

The control of the pore size of honeycomb-patterned films has been more or less involved in most work on the topic of breath figures. Modulation of the pore shape was largely ignored, although it is important to applications in replica molding, filtration, particle assembly, and cell culture. This article reports a tunable pore shape for patterned films prepared from commercially available polystyrene (PS). We investigated the effects of solvents including tetrahydrofuran (THF) and chloroform (CF) and hydrophilic additives including poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), poly(ethylene glycol) (PEG), and poly(N-vinyl pyrrolidone) (PVP). Water droplets on/in the polymer solutions were observed and analyzed for simulating the formation and stabilization of breath figures. Interfacial tensions of the studied systems were measured and considered as a main factor to modulate the pore shape. Results indicate that the pores gradually change from near-spherical to ellipsoidal with the increase of additive content when using CF as the solvent; however, only ellipsoidal pores are formed from the THF solution. It is demonstrated that the aggregation of the additives at the water/polymer solution interface is more efficient in the THF solution than that in the CF solution. This aggregation decreases the interfacial tension, stabilizes the condensed water droplets, and shapes the pores of the films. The results may facilitate our understanding of the dynamic breath figure process and provide a new pathway to prepare patterned films with different pore structures.

Facilitated and Site-Specific Assembly of Functional Polystyrene Microspheres on Patterned Porous Films

Functional patterned materials have received considerable attention because of their potential applications in biochips, sensors, and optical or electronic materials. Here, we report a versatile approach to functional patterned films based on facilitated and site-specific assembly of microspheres. This method includes the hierarchical formation of honeycomb-patterned porous films from amphiphilic block copolymers and the assembly of functional polystyrene microspheres driven by the gravity and the electrostatic interaction. Polystyrene microspheres containing carboxyl groups with a narrow size distribution were synthesized by dispersion polymerization. Honeycomb-patterned porous films were prepared from polystyrene-block-poly(N,N-dimethylaminoethyl methacrylate) (PS-b-PDMAEMA) by the breath figure method and then quaternized. We found that direct deposition of the microspheres on the patterned films reaches high filling ratio only when using ethanol dispersions that can wet the film pores. Plasma treatment of the films improves the hydrophilicity and introduces charged species to the external surface as well as the pore surface, leading to nonspecific assembly of microspheres. Negatively charged microspheres dispersed in buffer solution show a facilitated and site-specific assembly on the quaternized film. The electrostatic interaction as well as the gravity facilitates the assembly and the suborder arrangement of the hydrophilic PDMAEMA block around the pores is responsible for the site-specific assembly. In addition, we demonstrate the applicability of this method in preparing photoluminescent patterns by the assembly of porphyrinated microspheres, which is useful in various fields such as intelligent sensing.

Selective layer-by-layer self-assembly on patterned porous films modulated by Cassie–Wenzel transition

We describe a robust and facile approach to the selective modification of patterned porous films via layer-by-layer (LBL) self-assembly. Positively charged honeycomb-patterned films were prepared from polystyrene-block-poly(N,N-dimethyl-aminoethyl methacrylate) (PS-b-PDMAEMA) and a PS/PDMAEMA blend by the breath figure method followed by surface quaternization. Alginate and chitosan were alternately deposited on the films via LBL self-assembly. The assembly on the PS-b-PDMAEMA film exhibits two stages with different growth rates, as elucidated by water contact angles, fluorescence microscopy, and quartz crystal microbalance results. The assembly can be controlled on the top surface or across all surfaces of the film by changing the number of deposition cycles. We confirm that there exists a Cassie-Wenzel transition with an increase in deposition cycles, which is responsible for the tunable assembly. For the PS/PDMAEMA film, the pores can be completely wetted and the polyelectrolytes selectively assemble inside the pores, instead of on the top surface. The controllable selective assembly forms unique hierarchical structures and opens a new route for surface modification of patterned porous films.

Macroporous, protein-containing films cast from water-in-oil emulsions featuring a block-copolymer

Patterned biohybrid films show great potential for application in biosensing, bioconversion, and biochips. Their preparation generally involves a multistep procedure including patterned film fabrication and biomolecule immobilization. Here, we report a one-step approach to well-ordered protein-containing films by the self-assembly of a reverse emulsion (water-in-oil), which was stabilized by an amphiphilic block copolymer polystyrene-block-poly(2-hydroxyethyl methacrylate) (PS-b-PHEMA). We investigated the effects of the solvent, polymer concentration, PHEMA chain length, and substrate on the surface morphologies. The merging of the as-formed emulsion droplets, the formation and refilling of the gaps between the pores, and the hierarchical fine structures surrounding the pores were observed. Dynamic evolution results revealed the formation process of the films. One-step preparation of protein-containing films was achieved by introducing proteins into the reverse emulsion droplets. The protein pattern was further enhanced by the reduced-pressure method, which largely confined the capillary flow. This method is versatile to various water-soluble functional substances and opens a straightforward route for functional honeycomb-patterned porous films.