Effects of Silver Island Films on the Luminescent Intensity and Decay Times of Lanthanide Chelates

We examined the emission intensity and decay times of chelates Tb³⁺ and Eu³⁺ in micron thick samples between films of sub-wavelength size silver particles. We observed modest increases in emission intensities for the complexes between the silver particles as compared to between unsilvered quartz plates. The intensity decay times were dramatically decreased by the silver particles, which was in part mediated by diffusion toward the silver particles. These results indicated that luminescent lanthanides in close proximity to silver particles display increased rates of radiative decay. The use of luminophore-metallic surface interactions provides new opportunities for creation of luminescent probes with novel spectral properties.     

Effects of light quenching on the emission spectra and intensity decays of fluorophore mixtures

We examined a series of fluorophore mixtures to determine the wavelength selectivity of light quenching and the effects of light quenching on the emission spectra and intensity decays. Light quenching can be accomplished using a single excitation pulse train and quenching wavelength (one-beam) or with longer-wavelength quenching pulses time-delayed relative to the excitation pulses (two-beam). Both one-beam and two-beam light quenching were found to alter the intensity decays of the mixtures. The frequency-domain intensity decay data were analyzed to reveal the fractional intensity of each fluorophore in the mixture and the effects of light quenching on the fractional contribution of each fluorophore to the total intensity. Fluorophores were selected to provide a range of decay times and emission wavelengths. The extent of quenching in the mixtures was dependent on which fluorophore had the higher radiative decay rate and emission intensity at the quenching wavelength. A general theory is presented which describes the intensity decays in terms of the extent of quenching of each fluorophore and the time delay between excitation and quenching pulses. The effects of light quenching on the fractional intensities of each fluorophore in the mixture, recovered from the intensity decay analysis, were found to be in quantitative agreement with that predicted from steady-state measurements of light quenching and from the spectral properties of the fluorophores. The data on light quenching of mixtures demonstrate that light quenching may be used for selective quenching of fluorophores and thus of potential value for studies of multichromophoric systems.     

NMR-Untersuchungen bei Prolin-enthaltenden Diketopiperazinen

The NMR-spectra of cis- and trans-isomers of proline-containing diketopiperazines were investigated. It was demonstrated that the differences in the spectra are connected to the different position (pseudoaxial or pseudoequatorial) of the substituent (α-hydrogen atom, α-methyl-group, α-isopropyl-group).     

Experimental and calculated complex formation curves for mixed, dynamic and semi-dynamic, metal–ligand systems.: A differential pulse polarographic study of Cu–sarcosine–OH and Cd–MIDA–OH systems at a fixed ligand to metal ratio and varied pH

The Cu–sarcosine–OH and Cd–MIDA–OH systems have been studied by differential pulse polarography (DPP) at a fixed total ligand to total metal concentration ratio and varied pH at 298 K and μ=0.5 mol dm⁻³ in the background of NaNO₃. Both the metal–ligand systems show initially dynamic (labile), followed by semi-dynamic behaviour on the DPP time scale. It has been shown that the experimental and calculated DPP complex formation curves used previously only for labile metal–ligand systems can be employed for the modelling of all species formed in a solution and optimisation of their stability constants. The stability constants of ML and ML₂ complexes as log β were estimated for Cu^II and Cd^II as 7.75±0.02, 14.49±0.01 and 6.67 ±0.02, 12.00±0.02, respectively (all known hydroxide species of copper and cadmium, including polynuclear species, were incorporated into the metal–ligand–OH systems). The formation of the complex CuL₂(OH) is suggested also and its stability constant as log β has been estimated to be 16.2±0.2. Results reported here seem to be reasonable when compared with the literature data reported at 298 K and different ionic strengths.     

Ratiometric FRET-based detection of DNA and micro-RNA on the surface using TIRF detection

A new FRET-based method for the ratiometric detection of DNA oligomers on a surface using TIRF detection mode is reported. The dual-labeled system consisting of two hybridized oligomers, Cy3oligoY:Cy5oligoX was immobilized on the surface, and the total internal reflection fluorescence (TIRF) was used to detect emission signals from the surface. Two signals, green and red, which originated from the green donor Cy3 and the red acceptor Cy5, have been simultaneously detected. When the target single-stranded complimentary oligomer was present in the solution, this oligomer replaced the Cy3oligoY in the donor:acceptor complex on the surface and the ratio of red-to-green signal was dramatically changed. This detection scheme is generally applicable to the detection of DNA or RNA on a surface.     

Self-quenching of uranin: Instrument response function for color sensitive photo-detectors

Concentration is a key determining factor in the fluorescence properties of organic fluorophores. We studied self-quenching of disodium fluorescein (uranin) fluorescence in polyvinyl alcohol (PVA) thin films. The concentration dependent changes in brightness and anisotropy were followed by a lifetime decrease. We found that at a concentration of 0.54 M, the lifetime decreases to 7 ps. At a concentration of 0.18 M the lifetime was 10 ps with the relatively high quantum yield of 0.002. In these conditions the fluorescence intensity decay was homogeneous (well approximated by a single lifetime). We realized that such a sample was an ideal fluorescence lifetime standard for spectroscopy and microscopy, and therefore characterized instrument response functions for a time-domain technique. We show that self-quenched uranin enables measurements free of the color effect, making it a superior choice for a lifetime reference over scattered light.     

The analysis of pH‐dependent protonated conformers of 1‐hydroxyethylidene‐1,1‐diphosphonic acid by means of FT‐Raman spectroscopy,multivariate curve resolution and DFT modelling

1‐Hydroxyethylidene‐1,1‐diphosphonic acid (HEDP) solutions in the pH range 0.98–13.00 were analysed using FT‐Raman spectroscopy and ³¹P and ²³Na NMR spectroscopy. Vibrational bands for different protonated species were observed in the Raman spectra, whereas only a single NMR signal that shifted with pH was observed for all samples over the entire pH range. No significant shift in the ²³Na NMR signal was observed, confirming that formation of Na⁺(aq) complexes did not take place; hence, no interference with the different protonated forms of HEDP occurred. Vibrational bands were assigned using density functional theory(DFT)‐calculated spectra of the most likely conformers in solution. Multivariate curve resolution was performed on the Raman spectra in the region containing the PO stretching vibrations to determine the number of protonated species formed over the entire pH range. Chemometric analysis compares very favourably with the experimental species distribution diagram which was generated using the reported log K_H values. Copyright © 2009 John Wiley & Sons, Ltd.     

Evaluation of the rate of abiotic degradation of biodegradable polyethylene in various environments

The rate of abiotic degradation of polyethylene (PE) films containing a manganese pro-degradant has been studied in various environments at 60 and 70 °C. The degradation was monitored from the change in molecular weight and the elongation at break after exposure to dry and humid air. It was observed that moisture had a strong accelerating effect on the rate of thermo-oxidation of PE films. However, despite the humidity level in the compost environment being similar to that in humid air, the rate of degradation in compost was much slower. It is proposed that ammonia and/or hydrogen peroxide generated by microorganisms in the compost can be responsible for the deactivating effect, as aqueous solutions of these compounds significantly retard the rate of degradation.     

Ratiometric FRET-based detection of DNA and micro-RNA in solution

A ratiometric method for detecting DNA oligomers in bulk solution based on Förster resonance energy transfer (FRET) is described. The two fluorescence signals (green and red), originating from Cy3 (donor, green) and Cy5 (acceptor, red) labels, are simultaneously detected from the pre-hybridized Cy3oligomerY:Cy5oligomerX system. The ratio of red to green intensities is sensitive to the presence of the single-stranded complimentary oligomer, which replaces single-stranded Cy3oligomerY in the donor:acceptor complex and perturbs the FRET. The detection scheme is generally applicable to the detection of DNA and RNA, and particularly micro-RNA. The proposed method is applicable to various double-stranded various lengths targets (manipulation of the sample preparation conditions, such as temperature, incubation time, denaturizing agent, may be needed).