Synthesis and characterization of hyperbranched polyesters incorporating the AB2 monomer 3,5-bis(3-hydroxylprop-1-ynyl)benzoic acid

The AB₂ monomer, 3,5-bis(3-hydroxylprop-1-ynyl)benzoic acid 1, has been synthesized using a Sonogashira cross-coupling with a palladium catalyst system developed for use with deactivated aryl halides. Numerous condensation methods have then been assessed in the homopolymerization of the acid-diol monomer 1 to afford hyperbranched polyesters. However, as a result of the thermal instability of the monomer, direct thermal polymerizations could not be employed. Alternative approaches using carbodiimide-coupling reagents enabled the production of soluble polyesters possessing molecular weights and degrees of branching ranging from 2500 to 11,000 and 0.22 to 0.33, respectively.     

Optimization of the sensitivity and stability of the PRESAGE™ dosimeter using trihalomethane radical initiators

The aim of this study is to investigate the effect of trihalomethane radical initiators on the radiological properties, radiation dose sensitivity and post response photo-stability of the PRESAGE dosimeter. Different PRESAGE dosimeters containing 50 and 100 mM of iodoform (CHI₃), bromoform (CHBr₃) or chloroform (CHCl₃) radical initiators where fabricated and irradiated with 6 MV photons for a range of radiation doses from 0 to 30 Gy. A comparison between sensitivity and radiological properties of the PRESAGE dosimeters with the different radical initiators was carried out. Optical density changes of the dosimeters before and after irradiation were measured using a spectrophotometer. The incorporation of different radical initiators in the composition of the PRESAGE dosimeter resulted in variation of the radiation dose sensitivity and radiological properties of the dosimeters depending on the type and concentration of the radical initiator used, with iodoform showing the highest dose-response slope followed by bromoform and chloroform. However, at 100 mM iodoform, the effective atomic number was significantly higher than water (Z_eff=16). This enhancement in dose-response was found to be directly related to the carbon–halogen bond dissociation energy and to the radiological properties of each individual radical initiator used in this study. Furthermore, the post-response stability of the PRESAGE dosimeters over two weeks remained stable regardless of the trihalomethane radical initiator employed, with negligible change in the post-response stability and linearity of the PRESAGE dosimeters.