Photoreactive composite thin layers with tunable wetting properties from superhydrophilic to superhydrophobic nature were prepared. To achieve extreme wetting properties, the adequate surface roughness is a crucial factor, which was achieved by the incorporation of plasmonic Ag-TiO 2 particles, as polymer filler, into the smooth polymer film with adjusted hydrophilicity. The initial copolymer films were synthesized from hydrophilic 2-hydroxyethyl-acrylate (HEA) and hydrophobic perfluorodecyl-acrylate (PFDAc) monomers. In the case of hydrophobic PFDAc, the photocatalyst-roughened thin films displayed superhydrophobic behavior (γ s tot~ 2.3±1.7 mJ/m 2 , Θ > 150°), while the roughened hydrophilic pHEA layers possessed superhydrophilicity (γ s tot~ 72.1±0.2 mJ/m 2 , Θ~ 0°). The photoactivity of the composites was presented both in solid/ gas (S/G) and solid/ liquid (S/L) interfaces. According to the light-emitting diode (LED) light photodegradation tests on ethanol (EtOH) as volatile organic compound (VOC) model-molecules at the S/L interface, the superhydrophobic hybrid layer was photooxidized 88.3% of the initial EtOH (0.36 mM). At S/L interface the photocatalytic efficiency was depended on the polarity of the model pollutant molecules: the photooxidation of hydrophobic SUDAN IV (c 0 = 0.25 mg/mL) dye reached 80%, while in the case of the hydrophilic Methylene Blue dye (c 0 = 0.002 mg/mL) it was only 17.3% after 90 min blue LED light (λ = 405 nm) illumination.
The pH-responsive intelligent drug release facility of hydrophobically modified chitosan nanoparticles (Chit NPs) (d = 5.2 ± 1.1 nm) was presented in the case of poorly water soluble Ca channel blocker nimodipine (NIMO) drug molecules. The adequate pH-sensitivity, i.e. the suitable drug carrier properties of the initial hydrophilic Chit were achieved by reductive amination of Chit with hexanal (C-) and dodecanal (C-) aldehydes. The successful modifications of the macromolecule were evidenced via FTIR measurements: the band appearing at 1412 cm (CN stretching in aliphatic amines) in the cases of the hydrophobically modified Chit samples shows that the CN bond successfully formed between the Chit and the aldehydes. Hydrophobization of the polymer unambiguously led to lower water contents with lower intermolecular interactions in the prepared hydrogel matrix: the initial hydrophilic Chit has the highest water content (78.6 wt%) and the increasing hydrophobicity of the polymer resulted in decreasing water content (C-chit.: 74.2 wt% and C-chit.: 47.1 wt%). Furthermore, it was established that the length of the side chain of the aldehyde influences the pH-dependent solubility properties of the Chit. Transparent homogenous polymer solution was obtained at lower pH, while at higher pH the formation of polymer (nano)particles was determined and the corresponding cut-off pH values showed decreasing tendency with increasing hydrophobic feature (pH = 7.47, 6.73 and 2.49 for initial Chit, C-chit and C-chit, respectively). Next the poorly water soluble NIMO drug was encapsulated with the C-chit with adequate pH-sensitive properties. The polymer-stabilized NIMO particles with 10 wt% NIMO content resulted in stable dispersion in aqueous phase, the formation of polymer shell increased in the water solubility/dispersibility of the initial hydrophobic drug. According to the drug release experiments, we clearly confirmed that the encapsulated low crystallinity NIMO drug remained closed in the polymer NPs at normal tissue pH (pH = 7.4, PBS buffer, physiological condition) but at pH < 6.5 which is typical for seriously ischemic brain tissue, 93.6% of the available 0.14 mg/ml NIMO was released into the buffer solution under 8 h release time. According to this in vitro study, the presented pH-sensitive drug carrier system could be useful to selectively target ischemic brain regions characterized by acidosis, to achieve neuroprotection at tissue zones at risk of injury, without any undesirable side effects caused by systemic drug administration.
With the increasing demand for liquid manipulation and microfluidic techniques, surfaces with real-time tunable wetting properties are becoming the focus of materials science researches. In this study, we present a simple preparation method for a 0.5–4 µm carbonyl iron (carbonyl Fe) loaded polydimethylsiloxane (PDMS)-based magnetic composite coating with magnetic field-tailored wetting properties. Moreover, the embedded 6.3–16.7 wt.% Ag-TiO2 plasmonic photocatalyst (d~50 nm) content provides additional visible light photoreactivity to the external stimuli-responsive composite grass surfaces, while the efficiency of this photocatalytic behavior also turned out to be dependent on the external magnetic field. The inclusion of the photocatalyst introduced hierarchical surface roughness to the micro-grass, resulting in the broadening of the achievable contact and sliding angle ranges. The photocatalyst-infused coatings are also capable of catching and releasing water droplets, which alongside their multifunctional (photocatalytic activity and tunable wetting characteristics) nature makes surfaces of this kind the novel sophisticated tools of liquid manipulation.
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