ABSTRACT
The functionalization of cotton fabric with photoactive TiO2-Ag-AgBr nanostructured layer has been successfully developed using a low temperature non-aqueous sol-gel route and aqueous suspension of AgBr. Evidence for the growth of TiO2 layer and the immobilization of AgBr nanoparticles have been confirmed by Raman, XRD and XPS. GSDR analysis revealed a strong absorption in the visible region brought by surface Plasmon resonance (SPR) of Ag nanocrystals generated at the surface of AgBr. The XPS evidenced the presence of Ag+, Ag0 and bromine, suggesting that Ag0 formed a shell around the deposited AgBr. The immobilized TiO2-Ag-AgBr heterostructured layer imparts a strong photocatalytic activity under visible light for the degradation of dyes in aqueous solution as well as of dimethyl methylphosphonate (DMMP), a chemical warfare agent simulant. These new catalytically active functionalized fabrics, with self-detoxification properties, have great potential for application in chemical protective clothes and might offer new opportunities for the design of functional materials for toxic chemical protection.
Subject(s)
Bromides/chemistry , Coloring Agents/chemistry , Cotton Fiber , Organophosphates/chemistry , Photochemical Processes , Silver Compounds/chemistry , Silver/chemistry , Titanium/chemistry , Catalysis , Coloring Agents/isolation & purification , Nanostructures/chemistry , Organophosphates/isolation & purification , Organophosphates/toxicity , Temperature , Water/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Water PurificationABSTRACT
Squaraine dyes have recently attracted interest as potential second generation photosensitizers for photodynamic therapy. Several cationic aminosquaraine dyes bearing benzoselenazole terminal nuclei were synthezised and their cytotoxic activity was tested against four different human tumor cell lines - breast (MCF-7), non-small cell lung (NCI-H460), cervical (HeLa) and hepatocellular (HepG2) carcinomas - and against a non-tumor porcine liver primary cell line (PLP2), both in the absence of light and under irradiation. All dyes, which displayed strong absorption within the phototherapeutic window, were found to exhibit photodynamic activity and were shown to be, in most cases, more cytotoxic, both in the dark and upon irradiation, than their benzothiazole analogues.
Subject(s)
Antineoplastic Agents/chemical synthesis , Antineoplastic Agents/pharmacology , Cyclobutanes/chemical synthesis , Cyclobutanes/pharmacology , Phenols/chemical synthesis , Phenols/pharmacology , Photochemical Processes , Selenium/chemistry , Antineoplastic Agents/chemistry , Cell Line, Tumor , Chemistry Techniques, Synthetic , Cyclobutanes/chemistry , Humans , Phenols/chemistryABSTRACT
Aiming the degradation of harmful molecules under visible light, new photocatalytic systems were created. For this purpose, the surface of chitosan thin films was modified in heterogeneous phase via a simple and straightforward mild chemical process: chemisorption of silver ions followed by the synthesis in situ of TiO2 at low temperature (100⯰C). A high photocatalytic activity under visible light was observed, leading to the degradation and/or mineralization of different organic products such as o-toluidine, salicylic acid and 4-aminomethyl benzoic acid. This efficiency is partly attributed to the formation of Ag NPs and also to the unexpected appearance of AgCl NPs, likely formed from the residual chlorine contained in the chitosan. The resulting TiO2/Ag/AgCl/Chitosan system is easy to prepare under mild conditions, avoiding calcination treatments and opens new perspectives for the production of visible light-driven photocatalysts. Samples were analysed by different techniques: XRD, Raman, FE-SEM, XPS, TGA, GSDR, LIF and LIP.
ABSTRACT
This work reports the surface photochemistry study of alloxazine adsorbed within nanochannels of MFI zeolites, namely in a series of Na+ and H+ ZSM-5 zeolites where the hydrophobic and hydrophilic character of the host varies systematically. Laser-induced room temperature and 77 K luminescence of air-equilibrated solid powdered samples of alloxazine adsorbed onto the two sets of zeolites, which we will name NaZSM-5 and HZSM-5, revealed the existence of a single emission of alloxazine as a broad band centred at about 450 nm in some cases, while in others an emission with a maximum at about 510 nm was detected. The decay times of the alloxazine emission vary greatly going from solution to entrapment within the nanochannels of the ZSM-5 zeolites. In the latter case a lifetime distribution analysis has shown that the longest lifetime for the alloxazine fluorescence emission exists in the case where an isoalloxazine-type emission was detected, i.e. whenever the hydrophobic character of the host increases. Alloxazine entrapped in the more acidic zeolites exists in the form of emissive monomers. However, alloxazine emits both from monomeric and aggregated emissive forms in the case of the hydrophobic zeolites. These data indicate the formation of planar dimers of alloxazine whenever the number of active sites in the zeolite decreases. These dimers have to be formed at the intersections of the zig-zag and linear nanochannels of the zeolite since there is no space available for their formation inside the zeolite channels. The isoalloxazine tautomers are formed due to the existence of alloxazine dimers which may undergo double proton transfer in the excited state, following laser excitation. Delayed fluorescence of alloxazine was also detected for the HZSM-5 and NaZSM-5 entrapment both at room temperature and at 77 K. The present study is paradigmatic as regards the host influence on the photochemistry of the guest.
