Noneffervescent Method for Catalysis-Based Palladium Detection with Color or Fluorescence.

Palladium is a highly valuable metal in automobile, chemical, and pharmaceutical industries. The metal is generally quantified by atomic absorption spectrometry or inductively coupled plasma mass spectrometry. These techniques are tedious and require expensive instruments that are operated mostly off site. As cost-effective and user-friendly alternatives to these techniques, we previously reported two practical fluorometric or colorimetric methods to quantify palladium. Both methods rely on the use of NaBH4, which cannot be stored in solution for more than 10 days. Commercially available solutions of NaBH4 are partially or fully degraded to di- or triborohydride species and cannot be used for palladium(0)-catalyzed allylic C-O bond cleavage for quantification purposes. Here, we report a new method that replaces NaBH4 with NH2NH2 for the palladium-catalyzed deallylation of fluorogenic and colorimetric chemodosimeter resorufin allyl ether. This method is slower but as sensitive as the most recent method from our laboratory. The method is selective for palladium and depends on the presence of tri(2-furyl)phosphine as a palladium ligand and NH2NH2 as a palladium-reducing reagent.

A competitive and reversible deactivation approach to catalysis-based quantitative assays.

Catalysis-based signal amplification makes optical assays highly sensitive and widely useful in chemical and biochemical research. However, assays must be fine-tuned to avoid signal saturation, substrate depletion and nonlinear performance. Furthermore, once stopped, such assays cannot be restarted, limiting the dynamic range to two orders of magnitude with respect to analyte concentrations. In addition, abundant analytes are difficult to quantify under catalytic conditions due to rapid signal saturation. Herein, we report an approach in which a catalytic reaction competes with a concomitant inactivation of the catalyst or consumption of a reagent required for signal generation. As such, signal generation proceeds for a limited time, then autonomously and reversibly stalls. In two catalysis-based assays, we demonstrate restarting autonomously stalled reactions, enabling accurate measurement over five orders of magnitude, including analyte levels above substrate concentration. This indicates that the dynamic range of catalysis-based assays can be significantly broadened through competitive and reversible deactivation.

Fluorometric imaging methods for palladium and platinum and the use of palladium for imaging biomolecules.

Neither palladium nor platinum is an endogenous biological metal. Imaging palladium in biological samples, however, is becoming increasingly important because bioorthogonal organometallic chemistry involves palladium catalysis. In addition to being an imaging target, palladium has been used to fluorometrically image biomolecules. In these cases, palladium species are used as imaging-enabling reagents. This review article discusses these fluorometric methods. Platinum-based drugs are widely used as anticancer drugs, yet their mechanism of action remains largely unknown. We discuss fluorometric methods for imaging or quantifying platinum in cells or biofluids. These methods include the use of chemosensors to directly detect platinum, fluorescently tagging platinum-based drugs, and utilizing post-labeling to elucidate distribution and mode of action.