Cyanoacrylate photopolymerization has already been described, but it generally requires the use of organometallic photoinitiators and highly reactive monomers, which often leads to photoinitiator−monomer mixtures with limited stability. In this work we report a method to tackle these limitations, which relies on the use of amines bearing photoremovable protecting groups as light-responsive nucleophilic cyanoacrylate initiators. By exploiting the versatility of amine photorelease strategies, we have developed a series of all-organic initiators that (a) enable fast, on demand photocuring of commercial formulations of various cyanoacrylates, including less reactive, biologically relevant long alkyl chain monomers; (b) show wavelength tunability along the UV−vis spectrum and good thermal stability in the dark; and (c) lead to polymeric materials with excellent adhesive behavior. Because of this combination of properties, photogenerated amines appear as ideal candidates to bring cyanoacrylate photopolymerization into real application, especially in the biomedical field.
Glutathione-S-transferase (GST) activity and glutathione (GSH) content have been studied in human urinary bladder (UB) specimens obtained from healthy controls (HC) (n = 8 ) and from patients with superficial transitional cell carcinoma (TCC) (n = 91, either in TCC and in adjacent normal (ANE) tissues of the same patient. The GST activity was significantly higher in TCC in comparison with ANE (ten fold) and with HC (five fold). This activity was also significantly higher in HC than in ANE (two fold). The K, values obtained in the whole population (1.26 I~I 0.3 X i O P mol/l) suggest that a unique form of isoenzyme is present in the UB epithelium and that it is the same acidic form "p'' described in erythrocytes. The GSH content was significantly higher in TCC than in ANE (2.5 fold) and also that in HC (three fold). A good correlation between GST activity and GSH content was observed in HC hut not in TCC or ANE. These results demonstrate the relation between the activity of the GST system and the development of the TCC as well as its role in the cellular resistance to chemotherapy. A possible decrease of the GST activity before the development of the tumor is also discussed.
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