David B. Cordes

Evaluation of Pyranine Derivatives in Boronic Acid Based Saccharide Sensing: Significance of Charge Interaction Between Dye and Quencher in Solution and Hydrogel

In an ongoing program to synthesize a glucose sensing polymer that could be used for real time glucose monitoring in vivo, we have been exploring the use of boronic acid functional viologens as glucose responsive quenchers for fluorescent dyes. The present study focuses on the effect of ionic interactions between pyranine or its various sulfonamide derivatives and the viologen quenchers. Dyes bearing anionic groups were quenched more efficiently when compared to dyes with nonionic substituents. The anionic dyes in conjunction with the cationic quenchers exhibited a broader range of glucose response both in solution and when immobilized in a hydrogel. The interaction of glucose with the sensing components was similar whether they are soluble or immobilized.

Optical glucose detection across the visible spectrum using anionic fluorescent dyes and a viologen quencher in a two-component saccharide sensing system

A very general system is described in which anionic fluorescent dyes possessing a wide range of absorbance and emission wavelengths are used in combination with a boronic acid-modified viologen quencher to sense glucose at pH 7.4 in buffered aqueous solution. The present study demonstrates this capability with the use of eleven anionic fluorescent dyes of various structural types. Signal modulation occurs as the monosaccharide binds to the viologen quencher and alters its efficiency in quenching the fluorescence of the anionic dyes. The degree of quenching and the magnitude of the glucose signal were found to correlate roughly with the number of anionic groups on the dye. Optimal quencher : dye ratios were determined for each dye to provide a fairly linear signal in response to changes in glucose concentration across the physiological range.

A unique, two-component sensing system for fluorescence detection of glucose and other carbohydrates*

In our glucose-sensing system, a boronic acid-modified viologen molecule quenches the fluorescence of a separate dye molecule. When glucose or other monosaccharides are added and bind to the boronic acid, the quenching ability of the viologen is diminished and fluorescence increases. Thus, changes in the fluorescence of the dye can be correlated with changing glucose concentration. Quenching and sugar-sensing results are explained by an electrostatic interaction between dye and quencher. This modular system can be configured in a nearly unlimited number of ways through substitution and multiplexing of the two fundamental quencher and dye components. Significantly, fluorescent quantum dots (QDs) can also be used as the reporter component. The system can also be immobilized in a hydrogel polymer to provide real-time, reversible sugar sensing.

The Photophysical Properties of CdTe/ZnS Core/Shell Quantum Dots

The distinctive fluorescent properties of semiconductor nanocrystal quantum dots (QDs) make them advantageous for use in optoelectronic and biological applications. We report on experiments done to characterize the optical properties and the general photostability of CdTe QDs with varying ZnS shell thicknesses. Steady-state and time-resolved absorption and fluorescence spectroscopy measurements indicate that increasing the ZnS shell thickness results in longer absorption and emission wavelengths, increased quantum yield, and improved photostability.

Development and Evaluation of a Borohydride- palladium System for Selective Reduction of the C=C Bond of α,β-unsaturated Carbonyl Compounds

Selective reduction of the carbon-carbon double bond of α,β-unsaturated carbonyl compounds is most commonly and reliably effected using a palladium metal catalyst together with molecular hydrogen from a pressurized tank. Sodium borohydride, like other hydrides, is ordinarily associated with reduction of the more polarized carbonyl of such compounds. However, we have developed an alternative means of employing sodium borohydride in combination with palladium metal to selectively reduce the carbon-carbon double bonds of these compounds. In this survey study, we introduce sodium borohydride as an alternative hydrogen source for such selective, palladium-catalyzed reductions. We also compare the results of this new, heterogeneous borohydride-palladium method with that of traditional palladium-catalyzed hydrogenation. A third method using only sodium borohydride with no palladium is included for comparison.