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. 2010 Sep 15;13(6):877–918. doi: 10.1089/ars.2009.2876

FIG. 4.

FIG. 4.

Struture-activity relationships. (A) The very first structure–activity relationship between log kcat (O2·−) and E1/2 (MnIIIP/MnIIP) included porphyrins of different charge, different stericity, and different electrostatics for O2·− dismutation. (B) As the E1/2 increases, the Mn+2 oxidation state gets stabilized, and eventually oxidation of porphyrin becomes the rate-limiting step, and kcat starts to decrease again. Only water-soluble Mn(III) porphyrins are given in the left, linear section of the curve that obeys the Marcus equation, and data (circles) are from ref. 30: (1) MnIIITCPP3−, (2) MnIIIT(TMAP)5+, (3) MnIIIT(2,6-F2-3-SO3-P)P3−, (4) MnIIIT(TFTMAP)P5+, (5) MnIIIT(2,6-Cl2-3-SO3-P)P3−, (6) MnIIIBM-2-PyP3+, (7) MnIIITM-3-PyP5+, (8) MnIIITM-4-PyP5+, (9) MnIIITrM-2-PyP4+, (10) MnIIITM-2-PyP5+, and (11) MnIIITE-2-PyP5+. Data for EUK-8 are from ref. 302, and for MnCl2, from refs. 299 and 302; data for Mn(II) cyclic polyamine M40403 are from ref. 21. Data for SOD are from ref. 218. Data for MnIIICl1-4MnTE-2-PyP5+ (12–15) are from ref. 166, data for MnIIBr8TM-4-PyP4+ (16) are from ref. 33, and for MnIICl5TE-2-PyP4+ (#17), from ref. 165 (triangles). Data for MnIIITnBu-2-PyP5+ (a) are from ref. 37; MnIIITMOE-2-PyP5+ (b) from ref. 38; MnIIITD(M)E-2-ImP5+ (c, d) from refs. 38 and 167; MnIIITM,MOE-2-PyP5+ (e), and for MnIIITDMOE-2-ImP5+ (f ) from ref. 38 (squares). Data points 18 and 19 (diamonds) belong to MnTTEG-2-PyP5+ and MnTDTEG-2-ImP5+ and are from ref. 36.