Publications

The accumulation of microplastics (& micro;Pls) in ecosystems has become a serious environmental concern. Despite increasing awareness, the development of efficient technologies for their removal and remediation remains a major challenge. Herein, we investigate the photocatalytic degradation of polypropylene (PP) & micro;Pls using nanocomposite catalysts composed of permanently polarized hydroxyapatite microparticles (pp-HAp) and rutile TiO2 nanoparticles (TiO2 NPs). pp-HAp, a macroporous bioceramic, is known for its ability to convert gases (CO2 or/and N2) into small value-added chemical products. While pp-HAp serves both as the substrate and thermocatalytic part of the composite, TiO2 NPs are incorporated as the photocatalytic component. A series of XTiO2/ pp-HAp photocatalyts, where X represents the weight percentage of TiO2 (X = 2.5, 5, 10 and 20), were prepared applying a thermal stimulated polarization treatment. The resulting materials show no formation of undesirable calcium titanate. After thorough chemical and physical characterization, the photocatalytic performance of the XTiO2/pp-HAp in the degradation of PP-& micro;Pls was evaluated. Under 1 sun irradiation, the process is selective toward ethanol, which indicates the cleavage of consecutive C-C bonds along the PP chains, with the highest yield obtained for 2.5TiO2/pp-HAp. When the irradiation intensity decreases (0.5 sun), ethanol and isopropanol are produced, suggesting a reduction in the efficiency of the C-C cleavage. In all cases, the nanocomposite catalysts exhibit significantly higher yields than TiO2 NPs or pp-HAp individually, which indicates cooperative electronic effects between both components. Regarding selectivity, in addition to the solar irradiation, the TiO2: pp-HAp ratio also determines which product is obtained. Within the framework of circular economy, our strategy yields added-value chemical products from PP waste using only sunlight and an environmentally friendly catalyst.

JTD Keywords: Anatase, Heterogeneous catalysis, Microplastics, Microplastics removal, Nanocomposites, Photocatalysts, Polypropylene photodegradation, Water treatment plants

A new methodology for the pH-triggered degradation of polymers or for the release of drugs under visible light irradiation based on the cyclization of ortho-hydroxy-cinnamates (oHC) to coumarins is described. The key oHC structural motif can be readily incorporated into the rational design of novel photocleavable polymers via click chemistry. This main-chain moiety undergoes a fast photocleavage when irradiated with 455 nm light provided that a suitable base is added. A series of polyethylene glycol-alt-ortho-hydroxy cinnamate (polyethylene glycol (PEG)(n)-alt-oHC)-based polymers are synthesized and the time-dependent visible-light initiated cleavage of the photoactive monomer and polymer is investigated in solution by a variety of spectroscopic and chromatographic techniques. The photo-degradation behavior of the water-soluble poly(PEG(2000)-alt-oHC) is investigated within a broad pH range (pH = 2.1-11.8), demonstrating fast degradation at pH 11.8, while the stability of the polymer is greatly enhanced at pH 2.1. Moreover, the neat polymer shows long-term stability under daylight conditions, thus allowing its storage without special precautions. In addition, two water-soluble PEG-based drug-carrier molecules (mPEG(2000)-oHC-benzhydrol/phenol) are synthesized and used for drug delivery studies, monitoring the process by UV-vis spectroscopy in an ON/OFF intermittent manner.

JTD Keywords: coumarins, drug delivery, e/z-double bond isomerization, o-hydroxy cinnamates, polymer degradation, Aliphatic compounds, Antioxidant activity, Antitumor, Chromatographic techniques, Chromatography, Cis/trans isomerization, Controlled drug delivery, Coumarin derivatives, Coumarins, Drug delivery, Drug delivery system, E/z-double bond isomerization, Films, Hydrogels, Image enhancement, Light, Long term stability, O-hydroxy cinnamates, Particles, Photoactive monomers, Photodegradation, Polyethylene glycols, Polyethylenes, Polymer degradation, Responsive polymers, Salts, Structural motifs, Synthesis (chemical), Targeted drug delivery, Visible light photocatalysis, Visible-light irradiation