TY - JOUR
T1 - Oxygen-sensing properties of 5, 10, 15, 20-tetraphenylporphinato platinum(II) and palladium(II) covalently bound on poly(isobutyl-co-2,2,2-trifluoroethyl methacrylate)
AU - Obata, Makoto
AU - Matsuura, Noriko
AU - Mitsuo, Kazunori
AU - Nagai, Hiroki
AU - Asai, Keisuke
AU - Harada, Masafumi
AU - Hirohara, Shiho
AU - Tanihara, Masao
AU - Yano, Shigenobu
PY - 2010/2/1
Y1 - 2010/2/1
N2 - A novel methacrylate monomer bearing 5, 10, 15, 20tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2-trifluoroethyl methacrylate (TFEM) to give poly (IBM-co-TFEM) bearing PdTPP (copolymer 2a) as a dye-conjugated oxygen-permeable polymer for pressure-sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV-vis spectroscopy and extended X-ray absorption fine structure analysis. The Stern-Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM-co-TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b) previously reported. The plots were successfully fitted with a two-site model to give two distinct Stern-Volmer constants (Ksv1 andKsv2 and the partition ratio f1. Interestingly, the f1 values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM-co-TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature-dependent and the other temperature-independent, in the mixture of PdTPP and poly(IBM-co-TFEM). The dye-conjugation approach effectively eliminates the temperature-dependent, but not the temperature-independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature-dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature-independent one appears to be inherent nature in PdTPP.
AB - A novel methacrylate monomer bearing 5, 10, 15, 20tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2-trifluoroethyl methacrylate (TFEM) to give poly (IBM-co-TFEM) bearing PdTPP (copolymer 2a) as a dye-conjugated oxygen-permeable polymer for pressure-sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV-vis spectroscopy and extended X-ray absorption fine structure analysis. The Stern-Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM-co-TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b) previously reported. The plots were successfully fitted with a two-site model to give two distinct Stern-Volmer constants (Ksv1 andKsv2 and the partition ratio f1. Interestingly, the f1 values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM-co-TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature-dependent and the other temperature-independent, in the mixture of PdTPP and poly(IBM-co-TFEM). The dye-conjugation approach effectively eliminates the temperature-dependent, but not the temperature-independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature-dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature-independent one appears to be inherent nature in PdTPP.
KW - Luminescence
KW - Metalloporphyrin
KW - Oxygen-sensing
KW - Photochemistry
KW - Pressure-sensitive paint
KW - Radical polymerization
KW - Sensors
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U2 - 10.1002/pola.23818
DO - 10.1002/pola.23818
M3 - Article
AN - SCOPUS:75749150185
VL - 48
SP - 663
EP - 670
JO - Journal of Polymer Science, Part A: Polymer Chemistry
JF - Journal of Polymer Science, Part A: Polymer Chemistry
SN - 0887-624X
IS - 3
ER -