Polymers Containing Hydroxamate Groups: Nanoreactors For Hydrolysis Of Phosphoryl Esters

A polyhydroxamicalkanoate (PHA) polymer containing the functional groups hydroxamic acid and carboxylic acid with the ability to accelerate dephosphorylation reactions is proposed. The methodology used to prepare this polymer favored the position of the two functional groups next to each other, which allows for the cooperativity between these groups. This cooperative effect has an important role when one wants to mimic enzymes. The catalytic effect promoted by the polymer was evaluated on the cleavage of the bis(2,4-dinitrophenyl) phosphate (BDNPP) and diethyl 2,4-dinitrophenyl phosphate (DEDNPP) esters. Indeed, PHA was very efficient and promiscuous because it increased the rate of both reactions by a factor of up to 10 6-fold. Isothermal titration calorimetry (ITC) experiments showed that the presence of PHA aids the formation of cetyltrimethylammonium bromide (CTABr) micelles. Thus, the effect of the cationic surfactant CTABr on the dephosphorylation of BDNPP by PHA was also investigated, and it was observed that, when CTABr is added to PHA, the reaction is ca. 15-fold faster compared to the reaction when only PHA is present. © 2011 American Chemical Society.27241511215119Liang, C., Fréchet, J.M.J., (2005) Prog. Polym. Sci., 30, p. 385Kamerlin, S.C.L., Warshel, A., (2010) Proteins, 78, p. 1339Orth, E.S., Da Silva, P.L.F., Mello, R.S., Bunton, C.A., Milagre, H.M.S., Eberlin, M.N., Fiedler, H.D., Nome, F., (2009) J. Org. Chem., 74, p. 5011Dong, S.D., Breslow, R., (1998) Tetrahedron Lett., 39, p. 9343Liu, L., Breslow, R., (2002) J. Am. Chem. Soc., 124, p. 4978Faria, A.C., Mello, R.S., Orth, E.S., Nome, F., (2008) J. Mol. Catal. A, 289, p. 106Motherwell, W.B., Bingham, M.J., Six, Y., (2001) Tetrahedron, 57, p. 4663Klotz, I.M., Royer, G.P., Scarpa, I.S., (1971) Proc. Natl. Acad. Sci. U.S.A., 68, p. 263Berlamino, A.T.N., Orth, E.S., Mello, R.S., Medeiros, M., Nome, F., (2010) J. Mol. Catal. A: Chem., 332, p. 7Kirby, A.J., Davies, J.E., Brandao, T.A.S., Da Silva, P.F., Rocha, W.R., Nome, F., (2006) J. Am. Chem. Soc., 128, p. 12374Domingos, J.B., Longhinotti, E., Bunton, C.A., Nome, F., (2003) J. Org. Chem., 68, p. 7051Domingos, J.B., Longhinotti, E., Brandao, T.A.S., Santos, L.S., Eberlin, M.N., Bunton, C.A., Nome, F., (2004) J. Org. Chem., 69, p. 7898Silva, M., Mello, R.S., Farrukh, M.A., Venturini, J., Bunton, C.A., Milagre, H.M.S., Eberlin, M.N., Nome, F., (2009) J. Org. Chem., 74, p. 8254Bunton, C.A., Gillitt, N.D., Foroudian, H.J., (1998) Langmuir, 14, p. 4415Buncel, E., Um, I., (2004) Tetrahedron, 60, p. 7801Rappoport, Z., Liebman, J.F., (2009) The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids, , Wiley: Chichester, U.KKirby, A.J., Souza, B.S., Medeiros, M., Priebe, J.P., Manfredi, A.M., Nome, F., (2008) Chem. Commun., p. 4428Bunton, C.A., Farber, S.J., (1969) J. Org. Chem., 34, p. 767Domb, A.J., Cravalho, E.G., Langer, R., (1988) J. Polym. Sci., Part A: Polym. Chem., 26, p. 2623Martell, A.E., Hancock, R.D., (1996) Metal Complexes in Aqueous Solutions, , Plenum Press: New YorkBlodgett, J.K., Loudon, G.M., Collins, K.D., (1985) J. Am. Chem. Soc., 107, p. 4305Laguecir, A., Ulrich, S., Labille, J., Fatin-Rouge, N., Stoll, S., Buffle, J., (2006) Eur. Polym. J., 42, p. 1135Wise, W.M., Brandt, W.W., (1955) J. Am. Chem. Soc., 77, p. 1058Olofsson, G., Loh, W., (2009) J. Braz. Chem. Soc., 20, p. 577Niemiec, A., Loh, W., (2008) J. Phys. Chem. B, 112, p. 727Ghosh, K.K., Satnami, M.L., Daliya Sinha, D., (2004) Tetrahedron Lett., 45, p. 910

Susan Lynn Williams: The Life of an Exceptional Scholar, Leader, and Friend (1951–2018)

Susan Lynn Williams (1951–2018) was an exceptional marine ecologist whose research focused broadly on the ecology of benthic nearshore environments dominated by seagrasses, seaweeds, and coral reefs. She took an empirical approach founded in techniques of physiological ecology. Susan was committed to applying her research results to ocean management through outreach to decision-makers and resource managers. Susan’s career included research throughout the USA in tropical, temperate, and polar regions, but she specialized in tropical marine ecology. Susan’s scholarship, leadership, and friendship touched many people, leading to this multi-authored paper. Susan’s scholarship was multi-faceted, and she excelled in scientific discovery, integration of scientific results, application of science for conservation, and teaching, especially as a mentor to undergraduate and graduate students and postdoctoral scholars. Susan served in a variety of leadership positions throughout her career. She embodied all facets of leadership; leading by example, listening to others, committing to the “long haul,” maintaining trust, and creating a platform for all to shine. Susan was an important role model for women in science. Susan was also a loyal friend, maintaining friendships for many decades. Susan loved cooking and entertaining with friends. This paper provides an overview of the accomplishments of Susan in the broad categories of scholarship, leadership, and friendship