Dominic V Mcgrath

Dominic V Mcgrath

Professor, Chemistry and Biochemistry-Sci
Professor, BIO5 Institute
Primary Department
Department Affiliations
Contact
(520) 626-4690

Research Interest

Dominic Mcgrath, PhD, set forth a program which involves the use of organic synthesis for the design, development, and application of new concepts in macromolecular, supramolecular, and materials chemistry. Research efforts span a number of areas in the chemical sciences and include studies of: 1) chiral dendritic macromolecules and the effect of chiral subunits on dendrimer conformation, 2) photochromic dendrimers and linear polymers which undergo structural changes in response to visible light, 3) liquid crystalline materials based on dendritic and photochromic mesogens, and 4) synthesis of new ligands based on saturated nitrogen heterocycles.A continuing interest remains in the effect of structural perturbations on the properties and functional of dendritic macromolecules. Part of this research addresses the design, synthesis, and study of dendrimeric materials containing chiral moieties in the interior for influencing the conformational order of these 3-dimensional macromolecules. An ultimate goal is to develop materials active for the selective clathration of small guest molecules. Potential applications include chemical separations, sensor technology, environmental remediation, and asymmetric catalysis.Dr. Mcgrath and his lab team recently developed several new classes of dendritic materials containing photochromic subunits. As nature uses light energy to alter function in photoresponsive systems such as photosynthesis, vision, phototropism, and phototaxis, they use light energy to drive gross topological or constitutional changes in fundamentally new dendritic architectures with precisely placed photoresponsive subunits. In short, they can drive dendrimer properties with light stimuli. Two entirely new classes of photoresponsive dendritic macromolecules have been developed and include: 1) photochromic dendrimers and 2) photolabile dendrimers. Dr. Mcgrath anticipates that switchable and degradable dendrimers of this type will have application in small molecule transport systems based on their ability to reversibly encapsulate guest molecules. He continues to develop these materials as potential transport hosts and photoresponsive supramolecular assemblies.

Publications

Kevwitch, R. M., Shanahan, C. S., & McGrath, D. V. (2012). Vanillin and o-vanillin oligomers as models for dendrimer disassembly. New Journal of Chemistry, 36(2), 492-505. doi:http://doi.org/10.1039/c1nj20841a

Abstract:

Linear analogs have been synthesized to model disassembling dendrimers. These linear analogs provide a facile synthesis to molecules that can be used to test new trigger groups and cleavage vectors. Vanillin and o-vanillin were used as the monomer units of these analogs and two trigger groups, allyl and o-nitrobenzyl, were chosen to test the disassembly process. Allyl triggered analogs 1a-d and 3a-d and o-nitrobenzyl triggered analogs 2a-c and 4a-c showed good to excellent disassembly as followed by the evolution of p-nitrophenoxide reporter ion by UV-Visible spectroscopy. The rate and yield of disassembly was shown to depend on experimental conditions as well as length of the cleavage vector. © 2012 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

McGrath, D. V., Brabson, G. D., Sharpless, K. B., & Andrews, L. (1993). Reinvestigation of the infrared spectra of oxoosmium(VI) esters by isotopic labeling. Inorganic Chemistry, 32(19), 4164-4165.
Szalai, M. L., Sisk, D. T., Horst, M. J., & McGrath, D. V. (2008). Impact of click chemistry strategies on the synthesis of dendritic systems: Chromophore modification and disassembling systems. American Chemical Society, Polymer Preprints, Division of Polymer Chemistry, 49(1), 184-.
Warren, P. D., McGrath, D. V., & Vande Geest, J. P. (2010). Effect of Crosslinker Length and Composition on the Hydrophobicity and Thermomechanical Response of Acrylate-Based Shape-Memory Polymers. Macromolecular Materials and Engineering, 295(4), 386-396. doi:http://dx.doi.org/10.1002/mame.200900348
McGrath, D. V. (2005). Dendrimer disassembly as a new paradigm for the application of dendritic structures. Molecular Pharmaceutics, 2(4), 253-263. doi:10.1021/mp050047x

PMID: 16053328;Abstract:

We present an overview of an entirely new concept in nanotechnology, dendrimer disassembly. Dendrimer disassembly is a process that relies on a single triggering event to initiate multiple cleavages throughout a dendritic structure that result in release of individual dendrimer subunits or larger dendrimer fragments. The potential of this process lies in (1) the nature of dendrimers as covalent assemblages of active species, and using the chemistry of disassembly to release these species into a system; and (2) the role of dendritic components of a system in influencing solubility, energy harvesting, or insulating capabilities, etc., and using the chemistry of disassembly to reverse those contributions to a system. This is a powerful construct, in that dendrimers and dendritic structures can be made up of a wide variety of subunits, compatibilized with many different environments, and incorporated into countless systems. We anticipate that dendritic materials with disassembly capabilities will (a) be useful for traditional polymer degradation technologies and (b) have potential applications in nanotechnology, biomedicine, sensors, etc. © 2005 American Chemical Society.