Preparation and characterization of dual-responsive spiropyran-based random copolymer brushes via surface-initiated atom transfer radical polymerization

<p>Silica nanoparticles (SiO₂) were grafted with the precursor random copolymer of 1′-(2-acryloxyethyl)-3′,3′-dimethyl-6-nitrospiro-(2H-1-benzopyran-2,2′-indoline) (SPMA) and tert-butyl methacrylate (tBMA) by surface-initiated atom transfer radical polymerization (SI-ATRP), and SiO₂-g-P(SPMA-co-methacrylic acid (MAA)) was obtained via chemical hydrolysis of the resulting precursor random copolymer in acidic conditions. From transmission electron microscopy, we observed the spherical morphology of monodispersed silica nanoparticles and core-shell structure of SiO₂-g-P(SPMA-co-MAA). Energy dispersive spectroscopy, Fourier transform infrared spectra, X-ray photoelectron spectroscopy, and the thermogravimetric analysis indicated that the polymer had been successfully grafted onto the surface of silica nanoparticles. The dual-responsive properties were characterized by means of ultraviolet-visible spectrophotometer and dynamic light scattering. The average hydrodynamic diameter of SiO₂-g-P(SPMA-co-MAA) increased from 185.7 to 212.7 nm under ultraviolet light irradiation for 5 min. Also, the particle size of SiO₂-g-P(SPMA-co-MAA) increased with the rising pH value of surrounding condition.</p

Breath-Taking Patterns: Discontinuous Hydrophilic Regions for Photonic Crystal Beads Assembly and Patterns Revisualization

Surfaces patterned with hydrophilic and hydrophobic regions provide robust and versatile means for investigating the wetting behaviors of liquids, surface properties analysis, and producing patterned arrays. However, the fabrication of integral and uniform arrays onto these open systems remains a challenge, thus restricting them from being used in practical applications. Here, we present a simple yet powerful approach for the fabrication of water droplet arrays and the assembly of photonic crystal bead arrays based on hydrophilic–hydrophobic patterned substrates. Various integral arrays are simply prepared in a high-quality output with a low cost, large scale, and uniform size control. By simply taking a breath, which brings moisture to the substrate surface, complex hydrophilic–hydrophobic outlined images can be revisualized in the discontinuous hydrophilic regions. Integration of hydrogel photonic crystal bead arrays into the “breath-taking” process results in breath-responsive photonic crystal beads, which can change their colors upon a mild exhalation. This state-of-the-art technology not only provides an effective methodology for the preparation of patterned arrays but also demonstrates intriguing applications in information storage and biochemical sensors

Regulation Effects of Biomimetic Hybrid Scaffolds on Vascular Endothelium Remodeling

The formation of complete and well-functioning endothelium is critical for the success of tissue-engineered vascular grafts yet remaining a fundamental challenge. Endothelium remodeling onto the lumen of tissue-engineered vascular grafts is affected by their topographical, mechanical, and biochemical characteristics. For meeting multiple requirements, composite strategies have recently emerged for fabricating hybrid scaffolds, where the integrated properties are tuned by varying their compositions. However, the underlying principle how the integrated properties of hybrid scaffolds regulate vascular endothelium remodeling remains unclear. To uncover the regulation effects of hybrid scaffolds on vascular endothelium remodeling, we prepared different biomimetic hybrid scaffolds using gelatin methacrylamide (GelMA) and poly-ε-caprolactone (PCL) and then investigated vascular endothelial cell responses on them. GelMA and PCL, respectively, conferred the resulting scaffolds with biomimetic bioactivity and mechanical properties, which were tuned by varying GelMA/PCL mass ratios (3:1, 1:1, or 1:3). On different GelMA/PCL hybrid scaffolds, distinct vascular endothelial cell responses were observed. Firm cell–scaffold/cell–cell interactions were rapidly established on the hybrid scaffolds with the highest mass ratio of bioactive GelMA. However, they were mechanically insufficient as vascular grafts. On the contrary, the scaffolds with the highest mass ratio of PCL showed significantly reinforced mechanical properties but poor biological performance. Between the two extremes, the scaffolds with the same GelMA/PCL mass ratio balanced the pros and cons of two materials. Therefore, they could meet the mechanical requirements of vascular grafts and support the early-stage vascular endothelial cell remodeling by appropriate biological signaling and mechanotransduction. This investigation experimentally proves that scaffold bioactivity is the dominant factor affecting vascular endothelial cell adhesion and remodeling, whereas mechanical properties are crucial factors for the integrity of endothelium. This work offers a universal design strategy for desirable vascular grafts for improved endothelium remodeling