Rare earth metal containing polymers. 3. Characterization of ion-containing polymer structures using rare earth metal fluorescence probes

Abstract

Eu3+, Tb3+, and Co2+ salts of polymers containing carboxylic acid and sulfonic acid ligands were prepared and characterized. The polymers investigated were poly(acrylic acid) (PAA), copolymers of styrene-acrylic acid (PSAA), styrene-maleic acid (PSM), and methyl methacrylate-methacrylic acid (PMM/MA), and partially carboxylated and sulfonated polystyrenes (CPS and SPS). The lanthanide salts of these polymers showed characteristic lanthanide ion fluorescence in the solid state on excitation with UV light. The fluorescence excitation and emission spectra of these salts excepting carboxylated polystyrene showed characteristic spectra of the free ions, indicating that no energy is transferred from the polymer matrix to the ions. The carboxylated polystyrene-Eu3+ and -Tb3+ showed broad excitation spectra similar to the spectrum of the polymer and emission from the lanthanide ions, suggesting energy transfer from the polymer to the ion. The fluorescence intensities of the lanthanide salts of PAA, PSM, CPS, and SPS were found to increase linearly with the metal ion content. However, the salts of PSAA and PMM/MA displayed typical fluorescence concentration quenching behavior, reaching a maximum at 4-6 wt % of metal and decreasing with further increases in metal content. These results suggest that PSAA and PMM/MA contain ionic aggregates in which Eu and Tb ions are located close together. The energy transfer from Tb3+ to Co2+ and Eu3+ was evaluated from the Tb3+ fluorescence quenching. This was much more efficient in PSAA than in CPS and SPS systems.These results confirm that ion aggregates exist in PMM/MA and PSAA but not in the CPS and SPS systems at low metal concentration (<6 mol %). The probability Pd~a of dipole-dipole transfer between Tb3+ and Co2+ statistically distributed in a polymer matrix and the quenching characteristics were calculated by using Forster's equation. Experimental fluorescence quenching behaviors for PASS, CPS, and SPS are discussed as compared with the calculated quenching curve.

Study on the Self-polymerization and Co-polymerization Properties of Gadolinium Methacrylate

“…The chemical attachment method consists of two parts: (Ⅰ) the interaction of rare earth ion with linear functionalized(such as carboxyl-containing) polymers; (Ⅱ) the polymerization and copolymerization of rare earth monomers. Okamoto had produced a lot of rare earth containing polymers through method (Ⅰ) as the first time in 1980 [8]. They found that the fluorescence intensities of the rare earth containing polymers were increase linearly with the rare earth ion content.…”

Synthesis, characterization, and fluorescence properties of lanthanide complexes with the copolymers of 2‐butenedioic acid (z)‐mono‐ethyl ester and styrene

“…6,7 Recently, macromolecular lanthanide complexes (MLnC) are of increasing interest in supermolecular chemistry, biology, and functional materials. 8,9 They are excellent photoluminescent materials being extensively studied as potential molecular and supermolecular devices, 10 fluorescent probes and luminescent labels in chemical, biological systems, and medical diagnostics. 11,12 As a part of our continuing studies on the macromolecular metal complexes, [13][14][15][16][17] we synthesized the luminescent Ln-PSt/BAME (Ln ¼ Y, Sm, Dy, Eu and Tb; St ¼ styrene; BAME ¼ 2-butenedioic acid (z)-mono-ethyl ester) complexes, and a detailed research on the structure and characterization for both the copolymers and the Ln-PSt/BAME complexes had been performed.…”

Effects of gamma and electron beam irradiation on polymer electrolytes

“…These results indicated that the radiolysis caused chain degradation of PEO and produced carbonyl group (aldehyde moiety) at the end of the cleaved polymer chain. The chromophore moiety produced transfer the energy to the Tb3+ ion sited within the non-radiative energy transfer distance (14). The Tb-fluorescence sensitizing technique is effective in detecting such dilute species in PEO.…”