University of Pittsburgh

Craig Wilcox

Contact Info:

Department of Chemistry
Chevron Science Center
219 Parkman Avenue
Pittsburgh, PA 15260

Office: 1407 CHVRN
Phone: 412-624-8270

Professor and Department Interim Chair

New Methods for Chemical Discovery; New Reactions; Models for Protein Folding; Precipitons; Molecular Torsion Balance; Physical Organic Chemistry of Solid Phase Synthesis

Chemical Separation

Imagine - after a homogeneous reaction is complete, the chemist adds a catalyst or exposes the reaction mixture to soft UV light and pure product precipitates from the reaction mixture. This can be achieved with "precipitons" - protecting groups that have controllable solubility states. The Wilcox group has reported the first advances toward that goal.

The precipiton method has now been applied to several chemical reactions. Because products can be isolated in high purity without extraction, distillation, or chromatography, the amount of solvent needed for a process may be reduced by more than 90%.

The precipiton method also provides a new method for catalyst recovery in soluble polymer synthesis. Homogeneous catalysis by metal complexes can lead to discolored polymer products. The precipiton method allows catalysts to be removed by filtration. The picture at right shows a solution of cuprous bromide and precipiton scavenger before (left) and after (right) exposure to 350 nm light.

Meso-scale Synthesis. Polystyrene microspheres (1-50 micron diameters) are commercially available. The Wilcox group has developed methods for creating small covalently bonded chemical patches on the surface of microspheres. For example (right), 10 micron spheres have been labeled with 2 micron patches of fluorescent dye. These unique anisotropic materials can be used as building blocks for larger functional devices.

Meso-Scale Synthesis

 Polystyrene microspheres (1-50 micron diameters) are commercially available. The Wilcox group has developed methods for creating small covalently bonded chemical patches on the surface of microspheres. For example (right), 10 micron spheres have been labeled with 2 micron patches of fluorescent dye. These unique anisotropic materials can be used as building blocks for larger functional devices.

Drug Discovery and Molecular Recognition

 

  Phosphatase enzymes play an important role in cell cycle regulation. We continue to test new electrophiles as active site directed inhibitors of dual-specificity phosphatase and tyrosine phosphatase enzymes. We have molecules that show sub-micromolar activity against cdc25b and that also inhibit tumor cell growth.

Field Effects and Reaction Control

 Electrostatic fields from ion pairs in nonpolar solvents or in hydrophobic environments can have a very useful effect on chemical reaction rates and specificity. We have demonstrated rate accelerations of up to 450-fold. The use of tethered ion pairs for increasing the stereoselectivity of reactions has been demonstrated. We are now investigating the use of ion pairs in forming chiral environments for asymmetric synthesis.

Publications

Total synthesis of a 28-member stereoisomer library of murisolins ,” Curran DP, Zhang QS, Richard C, Lu H, Gudipati V, Wilcox C, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 128, 2006, Pages 9561-9573 , http://pubs.acs.org/doi/pdf/10.1021/ja061801q
Precipitons for copper removal in atom transfer radical polymerization: Reversible isomerization ,” Ayres N, Honigfort ME, Brittain WJ, Wilcox CS, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 230, 2005, Pages U4197-U4197,
Intramolecularly sensitized precipitons: A model system for application to metal sequestration ,” Ams MR, Wilcox CS, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 128, 2006, Pages 250-256, http://pubs.acs.org/doi/pdf/10.1021/ja0561340
Hydrogel prepositioned, self assembled supramolecular complex for glucose recognition and signaling.,” Asher SA, Sharma AC, Alexeev VL, Lednev IK, Wilcox CS, Finegold DN, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 24, 2004, Pages U42-U42,