Fabrication of UV responsive micelles-containing multilayers and their influence on cell adhesion

Multilayers incorporated with stimuli-responsive substances by means of layer-by-layer (LbL) self-assembly are much attractive due to their advantages of stimuli-responsiveness and potential applications in different fields. In this study, pyrenemethyl acrylate (PA) was synthesized, and was copolymerized with acrylic acid (AA) to obtain the amphiphilic and photodegradable P(PA-co-AA) polymers with a PA:AA molar ratio of 1.3:3, and an average molecular weight of 6.9 kDa and polydispersity index of 1.04. They formed micelles spontaneously when dispersed in aqueous solution with a size of 27.5 nm in a dry state and 136.6 nm in a wet state. The micelles were readily decomposed to form aggregates as a result of the cleavage of the pyrenemethyl ester bonds under UV-irradiation. UV-responsive micelles-containing multilayers were prepared by LbL self-assembly of the UV-responsive micelles and polyallylamine hydrochloride (PAH). UV-irradiation of the multilayers resulted in the decomposition of micelles, leading to larger surface roughness, and enhanced swelling ratio and wettability of the multilayers. In vitro culture of A549, HepG2 and endothelial cells showed significantly better adhesion at 4 h on the UV-illuminated multilayers, whereas the cell proliferation was not affected significantly until 5 d.     

Cysteamine-modified ZIF-8 colloidal building blocks: Direct assembly of nanoparticulate MOF films on gold surfaces via thiol chemistry

Chemical modification of metal organic framework (MOF) nanocrystal colloids was used to endow them with chemical affinity for gold substrates. Modified nanocrystals were then used as building blocks for rapid and selective self-assembly of porous films. Cysteamine (Cys, 2-aminoetanethiol) was chosen as both chemical modulator and functionalizing agent of Zeolite Imidazolate Framework-8 (ZIF-8) MOF nanocrystals. Important parameters such as the impact of the modulator on the range of nanocrystals stability, size, polydispersity, morphology, and crystalline structure were assessed via both, small and wide angle x-ray scattering (SAXS and WAXS). Cysteamine modified ZIF-8 nanocrystals were assembled into films over conductive Au substrates and film growth was followed in-situ with Quartz Crystal Microbalance (QCM). Thiol moieties exposed out of the ZIF-8 surface after cysteamine modification, results in the formation of thiol bonds with Au conductive substrates as shown via Cyclic Voltammetry experiments. The strategy here presented allows for the synthesis of pre-designed building blocks for MOF films on metal surfaces.