RESUMEN
This study reports new luminescent oxygen sensors in which the luminophore is covalently bound to the polymer matrix and compares their behavior to related sensors in which the luminophore is dispersed within the matrix. The cyclometalated iridium complex [Ir(ppy)(2)(vpy)Cl], 1, has been synthesized and characterized spectroscopically (absorption and emission) and by 1-D and 2-D (1)H NMR, elemental analysis, and X-ray crystallography. Complex 1 was attached via hydrosilation to hydride-terminated poly(dimethylsiloxane) (PDMS), yielding material 2. Successful luminophore attachment was determined spectroscopically from the emission properties, and through the altered physical behavior of 2 compared to a dispersion of 1 in PDMS. Hydrosilation of 1 with dimethylphenylsilane yielded [Ir(ppy)(2)(DMPSEpy)Cl], 3, which was fully characterized and used to probe the effect of hydrosilation on the spectroscopic properties of the luminophore. Evaluation of 2 as a luminescent oxygen sensor revealed significantly improved sensitivity over dispersions of 1 in PDMS. Material 2 was also blended with polystyrene (PS) to improve the physical properties of the sensor films. The blend sensors exhibited increased sensitivity relative to films of 2 alone and maintained short response times to rapid changes in air pressure. In contrast, 1 partitioned into the PS phase when dispersed in a PDMS/PS blend, resulting in longer sensor response times.
RESUMEN
Several cyanoalkyl radicals are reported to be unreactive toward oxygen; spin delocalization on nitrogen is proposed to be the most important factor to explain this unusual behaviour.
RESUMEN
The absorption and fluorescence spectra, fluorescence quantum yields, lifetimes and time-resolved fluorescence spectra are reported for nine different fluorescent DNA-dyes. The work was initiated in search of a quantitative method to detect the ratio of single-to-double stranded DNA (ssDNA/dsDNA) in solution based on the photophysics of dye-DNA complexes; the result is a comprehensive study providing a vast amount of information for users of DNA strains. The dyes examined were the bisbenzimide or indole-derived stains (Hoechst 33342, Hoechst 33258 and 4',6-diamidino-2-phenylindole), phenanthridinium stains (ethidium bromide and propidium iodide) and cyanine dyes (PicoGreen, YOYO-1 iodide, SYBR Green I and SYBR Gold). All were evaluated under the same experimental conditions in terms of ionic strength, pH and dye-DNA ratio. Among the photophysical properties evaluated only fluorescence lifetimes for the cyanine stilbene dyes allowed a convenient differentiation between ssDNA and dsDNA. The bisbenzimide dyes showed multiexponential decays when bound to either form of DNA, making lifetime-based analysis cumbersome with inherent errors. These dyes also presented biexponential decay when free in aqueous buffered solutions at different pH. A mechanism for their deactivation is proposed based on two different conformers decaying with different kinetics. The phenanthridinium dyes showed monoexponential decays with ssDNA and dsDNA, but there was no discrimination between them. High dye-DNA ratios (e.g. 1:1) resulted in multiexponential decays for cyanine dyes, resulting from energy transfer or self-quenching deactivation. Shifts in both absorption and fluorescence maxima for both ssDNA and dsDNA DNA-cyanine dye complexes were small. Broadening of dye-ssDNA absorption and fluorescence bands for the cyanine dyes relative to dye-dsDNA bands was detected and attributed to higher degrees of rotational freedom in the former.