J. N. Demas

Applications of luminescent transition platinum group metal complexes to sensor technology and molecular probes

Abstract Luminescent transition metal complexes are currently revolutionizing many areas of photochemistry and photophysics. In particular, they are proving useful as molecular probes and sensors. We discuss the design consideration in producing useful sensors and probes. As we show, complexes are amenable to rational design. Applications of inorganic complexes to a variety of sensor technologies are discussed. In addition, problem areas such as sensor–support interactions are covered.

Error analysis of the rapid lifetime determination method for double-exponential decays and new windowing schemes.

The rapid lifetime determination method (RLD) is a mathematical technique for extremely rapid evaluations of lifetimes in exponential decays. It has been applied in luminescence microscopy and single-molecule lifetime evaluation. To date, the primary application has been in single-exponential evaluations. We present extensions of the method to double exponentials. Using Monte Carlo simulations, we assess the performance of both the double-exponential decay with known lifetimes and the double-exponential decay with unknown preexponential factors and lifetimes. Precision is evaluated as a function of the noise level (Poisson statistics), the ratios of the lifetimes, the ratios of their preexponential factors, and the fitting window. Optimum measurement conditions are determined. RLD is shown to work well over a wide range of practical experimental conditions. If the lifetimes are known, the preexponential factors can be determined with good precision even at low total counts (10(4)). With unknown preexponential factors and lifetimes, precisions decrease but are still acceptable. A new gating scheme (overlapped gating) is shown to offer improved precision for the case of a single-exponential decay. Theoretical predictions are tested against actual experimental data from a laser-based lifetime instrument.

Oxygen sensors based on luminescence quenching of metal complexes: osmium complexes suitable for laser diode excitation.

Oxygen quenching of a series of Os(II) complexes with α-diimine ligands has been studied in a predominantly poly(dimethylsiloxane) (PDMS) polymer and in Gp-163 (an acrylate modified PDMS). Unlike previous Ru(II) complexes used as oxygen sensors, the Os complexes can be excited by readily available, high-intensity, low-cost, red diode lasers at 635, 650, and 670 nm. Variations in the polymer properties have been made in order to delineate the structural features important for satisfactory use of supports for oxygen sensors. A key factor is matching the hydrophobicity of the sensor and support for optimal compatibility and minimizing the size of low oxygen diffusion domains.

Portable, Low-Cost, Solid-State Luminescence-Based O2 Sensor

A novel sensor for quantifying molecular O2 based entirely on solid-state electronics is presented. The sensor is based on the luminescence quenching of tris(4,7-diphenyl-1, 10-phenanthroline)ruthenium(II) ([Ru(dpp)3]2+) by molecular O2. The sensor involves immobilizing the ruthenium complex within a porous sol-gel-processed glass film and casting this film directly onto the surface of a blue quantum-well light-emitting diode (LED). The ruthenium complex is excited by the LED, the [Ru(dpp)3]2+ emission is filtered from the excitation with a low-cost acrylic color filter, and the emission is detected with an inexpensive silicon photodiode. The sensor response to gaseous O2 and dissolved O2 in water is presented. The sensor exhibits fast response times and good reversibility, and detection limits are 0.5%, 0.02%, and 110 ppb, respectively, for O2 in the gaseous (linear Stern–Vobner and multi-site Stern–Volmer analysis) and aqueous phase. This sensor provides a cost-effective alternative to traditional electrochemical-based O2 sensing and also provides a platform for other optically based sensors.

Versatile Room-Temperature-Phosphorescent Materials Prepared from N-Substituted Naphthalimides: Emission Enhancement and Chemical Conjugation

Purely organic materials with room-temperature phosphorescence (RTP) are currently under intense investigation because of their potential applications in sensing, imaging, and displaying. Inspired by certain organometallic systems, where ligand-localized phosphorescence ((3) π-π*) is mediated by ligand-to-metal or metal-to-ligand charge transfer (CT) states, we now show that donor-to-acceptor CT states from the same organic molecule can also mediate π-localized RTP. In the model system of N-substituted naphthalimides (NNIs), the relatively large energy gap between the NNI-localized (1) π-π* and (3) π-π* states of the aromatic ring can be bridged by intramolecular CT states when the NNI is chemically modified with an electron donor. These NNI-based RTP materials can be easily conjugated to both synthetic and natural macromolecules, which can be used for RTP microscopy.

Energy degradation pathways and binding site environment of micelle bound ruthenium(II) photosensitizers.

A series of ..cap alpha..-diimine Ru(II) sensitizers were studied in aqueous, alcohol, and sodium lauryl sulfate (NaLS) micellar solutions. The emission efficiency, lifetime, and spectra change dramatically on micellization. From the temperature dependence of the excited-state lifetime and luminescence quantum efficiencies, coupled with spectral fitting, they interpret these changes and elucidate the environment of the micellized sensitizer. The increased efficiencies and lifetimes on micellization arise from decreased rates of deactivation via the photoactive d-d state and by a decrease in other intramolecular nonradiative paths. Radiationless decay theory permits semiquantitative calculation of nonradiative rate constants. A model describing the binding site and local solvent environment for the sensitizers is proposed. Implications of the results for solar energy conversion schemes are described.

Comparison of Methods for Rapid Evaluation of Lifetimes of Exponential Decays

For evaluating exponential luminescence decays, there are a variety of computational rapid integral methods based on the areas of the decay under different binned intervals. Using both Monte Carlo methods and experimental photon counting data, we compare the standard rapid lifetime determination method (SRLD), optimized rapid lifetime determination methods (ORLD), maximum likelihood estimator method (MLE), and the phase plane method (PPM). The different techniques are compared with respect to precision, accuracy, sensitivity to binning range, and the effect of baseline interference. The MLE provides the best overall precision, but requires 10 bins and is sensitive to very small uncorrected baselines. The ORLD provides nearly as good precision using only two bins and is much more immune to uncompensated baselines. The PPM requires more bins than the MLE and has systematic errors, but is largely resistant to baseline issues. Therefore, depending on the data acquisition method and the number of bins that can be readily employed, the ORLD and MLE are the preferred methods for reasonable signal-to-noise ratios.

Reduction of Luminescent Background in Ultrasensitive Fluorescence Detection by Photobleaching

In luminescence-based ultrasensitive analysis, such as single-molecule detection by flow cytometry, the luminescence background from impurities present in the solvent or reagents can ultimately determine the detection limits. A simple, versatile method for reducing luminescence background is described. The method is based on photobleaching the reagent stream immediately before it enters the detection flow cell. Dramatic reduction (an order of magnitude or more) of both low-level continuous background and single-molecule fluorescence bursts is demonstrated. Application and enhancements of the technique are discussed.

Oxygen Sensors Based on Luminescence Quenching: Interactions of Tris(4,7-diphenyl-1,10- phenanthroline)ruthenium(II) Chloride and Pyrene with Polymer Supports

Oxygen quenching of [Ru(Ph2phen)3]Cl2 (Ph2phen = 4,7-diphenyl-1,10-phenanthroline) and pyrene has been studied in a series of polymer networks of Gp-163 (a methacryloxy functional polydimethylsiloxane) co-polymerized with one of several co-monomers: styrene, trimethylsilyl-methylmethacrylate (T3642), vinyl-tris(2-methoxy-ethoxy)silane, or vinyl-tris(trimethylsiloxy)silane. Sensor performance was studied as a function of the polymer composition in order to delineate the important features for satisfactory O2 sensor supports. Quenching behavior was examined as a function of polymer structure, including amount and type of co-monomer. This work shows that the earlier two-domain model is too simplistic. The relative affinities of the different domains for the [Ru(Ph2phen)3]Cl2 and pyrene and the efficacy of the domains for O2 quenching are important; however, subtle changes in microstructure within domains can also strongly affect behavior. In particular, T3642 exhibits excellent structural and good quenching properties with [Ru(Ph2phen)3]Cl2.

Luminescence-Based Oxygen Sensors

The area of oxygen sensors encompasses a broad range of sensing techniques, devices, and applications. The latter range from monitoring combustion mixtures to use in fish farming.1 The majority of the techniques and devices involve transduction of the changes in oxygen concentration or pressure to changes in an electrical parameter such as voltage, current, or resistance. This sensing approach is older and has more working devices on the market. A more recent approach involves transduction via changes in luminescence characteristics of both organic and inorganic dyes. This approach has attracted considerable interest for applications such as pressure sensitive paints (PSP) and for situations amenable to use of fiber optic technology