Hierarchical structures are commonly observed in nature and possess unique properties. The fabrication of hierarchical structures with well-controlled sizes in different length scales, however, is still a great challenge. To further understand the morphologies and properties of the hierarchical structures, here we present a novel strategy to prepare hierarchical polymer structures by combining the modified breath figure method and the template method. Poly(methyl methacrylate) (PMMA) honeycomb films with regular micropores are first prepared using the modified breath figure method by dipping PMMA films into mixtures of chloroform and methanol. The polymer chains on the honeycomb films are then annealed and wetted into the nanopores of anodic aluminum oxide templates via capillary forces, resulting in the formation of hierarchical polymer structures. The morphologies of the polymer structures, which can be controlled by the molecular weights of the polymers and the concentrations of the polymer solutions, are characterized by scanning electron microscopy. The surface wettabilities of the polymer structures are also examined by water contact angle measurements, and the hierarchical structures are observed to be more hydrophobic than the flat films and honeycomb films. This work not only provides a feasible approach to fabricate hierarchical polymer structures with controlled sizes but also gives a better understanding of the relationship between surface morphologies and properties.

Monitoring undesired pH deviations in the surroundings is one of the most pervasive issues of environment and industry, and developing efficient, economical, portable, and reusable membranes for pH monitoring is urgently needed. Herein, we report novel smart nanomembranes (SNMs) that are made up of anodic aluminum oxide (AAO) templates grafted with spiropyran molecules. The ultraviolet and visible light responses of the SNMs under acid vapors are investigated. Under UV irradiation, the ring-closed spiropyran on the AAO templates transform to ring-opened merocyanine, which contains phenolate oxygen and can be further protonated by acids. Such a protonation process not only shows evident color changes but also endows SNMs with pH-responsive properties, which are further investigated by UV–vis diffuse reflectance spectroscopy. Furthermore, to demonstrate the pH-responsive properties of the SNM, common volatile acids such as hydrochloric acid, nitric acid, formic acid, and acetic acid are tested. The SNM shows conspicuous sensibility, reusability, and reversibility during the processes of irradiation, protonation, and deprotonation. Therefore, the newly developed SNM can be an excellent alternative to the existing pH sensors for the detection of pH variations in environment and industry.

Recently, anodic aluminum oxide (AAO) membranes with ordered and monodispersed nanopores have attracted significant attention because the pore sizes and lengths of the AAO membranes can be systematically controlled by changing the anodization parameters. Asymmetries of geometry, wettability, charge, and polarity in nanoporous AAO membranes are now highly desired for applications such as drug delivery, membrane filtration, and catalysis. Although the asymmetries in AAO membranes have been widely studied, AAO membranes whose nanopores simultaneously possess more than two asymmetric properties still need to be developed. In this work, we present a simple method to fabricate asymmetric AAO membranes by combining the post-treatments with the three-step anodization method. The asymmetries of the AAO membranes simultaneously possessing larger nanopores with higher hydrophobicity and smaller nanopores with lower hydrophobicity are characterized by scanning electron microscopy, water contact angle measurements, and energy-dispersive X-ray spectroscopy. Using the asymmetric AAO membranes, nanowires of polystyrene and poly(styreneblock-dimethylsiloxane) with double-sized diameters are also fabricated via the melt and solvent wetting methods, exhibiting that the AAO membranes with double-sized diameters can be used as the templates for generating double-sized polymer nanowires.