B.A., Reed College Ph.D., University of Wisconsin, Madison

Synthetic organic chemistry: new synthetic methodologies using free radicals; nitroxides, nitroxide mediated “living” polymerizations: design and functionalization of tailored polymers for biomedical applications and nanotechnology, profluorescent nitroxides as sensors, synthetically modified polymers, development of non-migratory plasticizers

Synthetic Organic Chemistry, Organic Free Radicals, Nitroxides, Nitroxide-Mediated Free Radical Polymerization, Development of Tailored Materials for Nanotechnology and Biomedical Applications, Nitroxide-based Sensors Our synthetic organic research group is focused on reactions involving free radical intermediates. Much of the work involves the synthesis and use of designed nitroxides for the preparation of specialized polymers for nanotechnology and biomedical applications, and as sensors via fluorescence quenching. We are engaged in the development of new synthetic methodologies, often via free radical intermediates. We are also involved in the synthesis of designed materials, such as non-migrating plasticizers.

C. L. Bailey, J. W. Clary, C. Tansakul, L. Klabunde, C. L. Anderson, A. Y. Joh, A. T. Lill, N. Peer, R. Braslau, and B. Singaram* “Reduction of Weinreb Amides to Aldehydes under Ambient Conditions with Magnesium Borohydride Reagents,” Tetrahedron Letters, 2015, 5, 5725-5733. doi:10.1016/j.tetlet.2014.12.066

C. Magee, A Earla, J. Petraitis, C. Higa, R. Braslau,* P. B. Zetterlund,* F. Aldabbagh* “Synthesis of Fluorinated Alkoxyamines and Alkoxyamine-Initiated Nitroxide-Mediated Precipitation Polymerizations of Styrene in Supercritical Carbon Dioxide,” Polymer Chemistry, 2014, 5, 5725-5733. doi: 10.1039/c4py00757c.

A. Earla, R. Braslau* “Covalently Linked Plasticizers: Triazole Analogues of Phthalate Plasticizers Prepared by mild Copper-free “Click” Reactions with Azide-functionalized PVC,” Macromolecular Rapid Communications, 2014, 35, 666-671. doi: 10.1002/marc.201300865.

R. Braslau,* F. Rivera, C. Tansakul “Reversible Crosslinking of Polymers bearing Pendant or Terminal Thiol Groups Prepared by Nitroxide-Mediated Radical Polymerization,” Reactive and Functional Polymers, 2013, 73, 624-632. \http://dx.doi.org/10.1016/j.reactfunctpolym.2013.01.009.

R. Braslau,* F. Schäffner, A. Earla “Polymeric phthalates: potential non-migratory macromolecular plasticizers,” Journal of Polymer Science Part A: Polymer Chemistry, 2013, 51, 1775-1184. doi: 10.1002/pola.26485.

R. Braslau,* F. Rivera, III, E. Lilie, and M. Cottman “Urushiol Detection using a Profluorescent Nitroxide,” J. Org. Chem. 2013, 78, 238-245. doi: \10.1021/jo301135m.

C. Tansakul and R. Braslau “Nitroxides in Synthetic Radical Chemistry” in Encyclopedia of Radicals in Chemistry, Biology and Materials, 2012, C. Chatgilialoglu and A. Studer (eds). John Wiley & Sons Ltd, Chichester, UK, pp 1095-1130.

C. Tansakul, E. Lilie, E. D. Walter, F. Rivera III, A. Wolcott, J. Z. Zhang, G. L. Millhauser, R. Braslau* “Distance-dependent Fluorescence Quenching and Binding of CdSe Quantum Dots by Functionalized Nitroxide Radicals,” J. Phys. Chem. C, 2010, 114, 7793-7805. doi: 10.1021/jp1005023.

J. Ruehl, N. Ningnuek, T. Thongpaisanwong, R. Braslau* “Cyclic Alkoxyamines for Nitroxide Mediated Radical Polymerization,” Journal of Polymer Science Part A: Polymer Chemistry, 2008, 49, 8049-8069. doi: 10.1002/pola.23103.

G. O'Bryan, N. Ningnuek, R. Braslau* “Cyclization of α, ω Heterotelechelic Polystyrene Prepared by Nitroxide-Mediated Radical Polymerization” Polymer 2008, 49, 5241-5248. doi:10.1016/j.polymer.2008.09.035.

J. Ruehl, C. Morimoto, D. J. Stevens, G. Millhauser, R. Braslau* “Carboxylic Acid and Hydroxy-Functionalized Alkoxyamine Initiators for Nitroxide Mediated Radical Polymerization,” Reactive & Functional Polymers 2008, 68, 1563-1577. doi:10.1016/j.reactfunctpolym.2008.08.010.

J. Ruehl, N. L. Hill, E. D. Walter, G. Millhauser, R. Braslau* “A Proximal Bisnitroxide Initiator: Studies in Low-temperature Nitroxide-Mediated Polymerizations” Macromolecules, 2008, 41, 1972-1982.doi: 10.1021/ma702358c http://tinyurl.com/cmbupv.

N. L. Hill, J. L. Jarvis, F. Pettersson, R. Braslau* ""Synthesis of Thiol-Derivatized Initiators for Nitroxide-Mediated Radical Polymerization: Reversible Disulfide Formation"" Reactive & Functional Polymers, 2008, 68, 361-368.

W. Chau; R. Turner; R. Braslau* “Ketone ω-Functionalization of Polymers Prepared by Nitroxide-Mediated Polymerization via Addition to a Benzyl Enol Ether”ull ” Reactive & Functional Polymers 2008, 68, 396-405.

G. O'Bryan, A. Nilsen, R. Braslau “Ketone Functionalized Nitroxides: Synthesis, Evaluation of N-Alkoxyamine Initiators, and Derivatization of Polymer Termini” Macromolecules, 2007, 40, 7848-7854.

J. Ruehl; A. Nilsen; S. Born; P. Thoniyot; L. Xu; S. Chen; R. Braslau* “Nitroxide-Mediated Polymerization to Form Symmetrical ABA Triblock Copolymers from a Bidirectional Alkoxyamine Initiator” Polymer 2007, 48(9), 2564-2571.

N. L. Hill; R. Braslau* “Synthesis of Arylethyl Functionalized N-Alkoxyamine Initiators and use in Nitroxide-Mediated Radical Polymerization” Journal of Polymer Science Part A: Polymer Chemistry, 2007, 45, 2341-2349.

J. Ruehl; R. Braslau* “A Bidirectional ATRP-NMRP Initiator: The Effect of Nitroxide Size on the Rate of Nitroxide-Mediated Polymerization” Journal of Polymer Science Part A: Polymer Chemistry, 2007, 45, 2015-2025. http://tinyurl.com/cjx4s4

J. Jiang, I. Kurnikov, N. A. Belikova, J. Xiao, Q. Zhao, I. L. Vlasova, A. A. Amoscato, R. Braslau, A. Studer, M. P. Fink, J. S. Greenberger, P. Wipf, V. E. Kagan* “Structural requirements for optimized delivery, inhibition of oxidative stress and anti-apoptotic activity of targeted nitroxides” J. Pharm. Exp. Therapeutics, 2007, 320, 1050-1060.

G. O'Bryan, R. Braslau* “Terminal Functionalization of Polymers via Single Electron Oxidation of N-Alkoxyamines,” Macromolecules, 2006, 39, 9010-9017.