Surface pressure-induced crystallization of poly(epsilon-caprolactone) (PCL) from a metastable region of the surface pressure-area per monomer (Pi-A) isotherm in Langmuir monolayers at the air/water (A/W) interface has been captured in real time by Brewster angle microscopy (BAM). Morphological features of PCL crystals grown in Langmuir films during the compression process exhibit four fully developed faces and two distorted faces. During expansion of the crystallized film, polymer chains slowly detach from the crystalline domains and diffuse back into the monolayer as the crystals "melt". Typical diffusion-controlled morphologies are revealed by BAM during the melting process as the secondary dendrites melt away faster, that is, at a higher surface pressure than the principal axes. Electron diffraction on Langmuir-Schaefer films suggests that the lamellar crystals are oriented with the polymer chain axes perpendicular to the substrate surface, while atomic force microscopy reveals a crystal thickness of approximately 7.6 nm.

This study reports the facile preparation and the dye removal efficiency of nanohybrids composed of graphene oxide (GO) and Fe3O4 nanoparticles with various geometrical structures. In comparison to previously reported GO/Fe3O4 composites prepared through the one-pot, in situ deposition of Fe3O4 nanoparticles, the GO/Fe3O4 nanohybrids reported here were obtained by taking advantage of the physical affinities between sulfonated GO and Fe3O4 nanoparticles, which allows tuning the dimensions and geometries of Fe3O4 nanoparticles in order to decrease their contact area with GO, while still maintaining the magnetic properties of the nanohybrids for easy separation and adsorbent recycling. Both the as-prepared and regenerated nanohybrids demonstrate a nearly 100% removal rate for methylene blue and an impressively high removal rate for Rhodamine B. This study provides new insights into the facile and controllable industrial scale fabrication of safe and highly efficient GO-based adsorbents for dye or other organic pollutants in a wide range of environmental-related applications.

This study reports the structural transition of electrospun poly(ε-caprolactone) (PCL)/poly[(propylmethacryl-heptaisobutyl-polyhedral oligomeric silsesquioxane)-co-(methyl meth-acrylate)] (POSS-MMA) blends, from PCL-rich fibers, to bicontinuous PCL core/POSS-MMA shell fibers, to POSS-MMA-rich fibers with a discontinuous PCL inner phase. A ternary phase diagram depicting the electrospinnability of PCL/POSS-MMA solutions is constructed by evaluating the morphological features of fibers electrospun from solutions with various concentrations and PCL/POSS-MMA blend ratios. X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry are further used to characterize the electrospun PCL/POSS-MMA hybrid fibers. These physicochemical characterization results are thoroughly discussed to understand the internal structures of the hybrid fibers, which are directly correlated to the phase separation behavior of the electrospun solutions. The current study provides further insight into the complex phase behavior of POSS-copolymer-based systems, which hold great potential for a broad spectrum of biomedical applications.

The performance of poly(ϵ-caprolactone) (PCL)-based biomaterials is defined by spatial distributions of PCL's amorphous and crystalline domains. Unfortunately, directly visualizing their inner architectures has been challenging. This study demonstrates, the superior degradation selectivity of Candida antarctica lipase B (CALB) enzyme; when used at low concentrations, it preferentially breaks down the amorphous chains prior to the crystalline chains. Top-down dissection using this enzyme is performed on several PCL-based systems. Self-assembled nanolamellae (e.g., thin films) or hierarchically nanostructured crystalline skeletons (e.g., fibers) are clearly captured. Thus, the spatial distribution of the amorphous compartments can be precisely mapped out, which otherwise cannot be achieved.