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

Sweet, J. A., Cavallari, J. M., Price, W. A., Ziller, J. W., & McGrath, D. V. (1997). Synthesis and characterization of new amine-imine ligands based on trans-2,5-disubstituted pyrrolidines. Tetrahedron Asymmetry, 8(2), 207-211.

Abstract:

We present a modular synthesis of a new class of chiral N,N-chelating ligands containing the C2-symmetric trans-2,5-disubstituted pyrrolidine moiety linked to a pyridine ring. (-)-2-[(2R,5R)-2,5-Dimethylpyrrolidin-1-ylmethyl]pyridine (11, (R,R)-MePMP), (-)-2-[2((2R,5R)-2,5-dimethylpyrrolidin- (12, (R,R)-MePEP), and (+)-2-[(2R,5R)-2,5-diphenylpyrrolidin-1-ylmethyl]pyridine (13, (R,R)-PhPMP) have been prepared. The X-ray structure of the (Λ3-allyl)Pd complex of (R,R)-MePMP (11) is reported.

Ashton, J. H., Mertz, J. A., Harper, J. L., Slepian, M. J., Mills, J. L., McGrath, D. V., & Vande Geest, J. P. (2010). Polymeric Endoaortic Paving (PEAP): Thermomechanical and Degradation Properties of Polycaprolactone/Polyurethane Blends for Cardiovascular Applications," Ashton, J.H.; Mertz, J.A.; Harper, J.L.; Slepian, M.J.; Mills, J.L.; McGrath, D.V.; Vande Geest,† J.P.. Acta Biomaterialia, 7, 287-294. doi:http://doi.org/10.1016/j.actbio.2010.09.004
Plata, R. E., Rogers, H. R., Banister, M., Vohnout, S., & McGrath, D. V. (2007). EAP hydrogels for pulse-actuated cell system (PACS) architectures. Proc. SPIE 6524, Electroactive Polymer Actuators and Devices (EAPAD), 6524, 65241T. doi:http://doi.org/10.1117/12.716107

Abstract:

Electroactuated polymer (EAP) hydrogels based on JEFFAMINE® T-403 and ethylene glycol glycidyl ether (EGDGE) are used in an infusion pump based on the proprietary Pulse Actuated Cell System (PACS) architecture in development at Medipacs LLC. We report here significant progress in optimizing the formulation of the EAP hydrogels to dramatically increase hydrolytic stability and reproducibility of actuation response. By adjusting the mole fraction of reactive components of the formulation and substituting higher molecular weight monomers, we eliminated a large degree of the hydrolytic instability of the hydrogels, decreased the brittleness of the gel, and increased the equilibrium swelling ratio. The combination of these two modifications to the formulation resulted in hydrogels that exhibited reproducible swelling and deswelling in response to pH for a total period of 10-15 hours.

McGrath, D. V., Grubbs, R. H., & Ziller, J. W. (1991). Aqueous ruthenium(II) complexes of functionalized olefins: The X-ray structure of Ru(H2O)21(O):η 2(C,C′)-OCOCH2CH=CHCH3)2. Journal of the American Chemical Society, 113(9), 3611-3613.
Junge, D. M., & McGrath, D. V. (1998). Synthesis of optically active chiral shell dendrons. Tetrahedron Letters, 39(13), 1701-1704.

Abstract:

We present the preparation of a series of chiral dendrons, in which chiral subunits are placed in individual generational shells at increasing distances from the focal point, by a combination of convergent and divergent dendrimer synthesis methods. Analysis of chiroptical data suggests that these dendrons do not possess conformational order in solution.