A new heterobinuclear FeIIICuII complex with a single terminal FeIII–O(phenolate) bond. Relevance to purple acid phosphatases and nucleases

JBIC Journal of Biological Inorganic Chemistry - Tập 10 - Trang 319-332 - 2005
Mauricio Lanznaster1, Ademir Neves1, Adailton J. Bortoluzzi1, Veronika V. E. Aires1, Bruno Szpoganicz1, Hernán Terenzi2, Patricia Cardoso Severino2, Julie M. Fuller3, Simon C. Drew4, Lawrence R. Gahan3, Graeme R. Hanson4, Mark J. Riley3, Gerhard Schenk3
1LABINC Laboratório de Bioinorgânica e Cristalografia, Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, Brazil
2Laboratório de Expressão Gênica, Departamento de Bioquímica, Universidade Federal de Santa Catarina, Florianópolis, Brazil
3Department of Chemistry, School of Molecular and Microbial Sciences, The University of Queensland, St. Lucia, Australia
4Centre for Magnetic Resonance, The University of Queensland, St Lucia, Australia

Tóm tắt

A novel heterobinuclear mixed valence complex [FeIIICuII(BPBPMP)(OAc)2]ClO4, 1, with the unsymmetrical N5O2 donor ligand 2-bis[{(2-pyridylmethyl)aminomethyl}-6-{(2-hydroxybenzyl)(2-pyridylmethyl)}aminomethyl]-4-methylphenol (H2BPBPMP) has been synthesized and characterized. A combination of data from mass spectrometry, potentiometric titrations, X-ray absorption and electron paramagnetic resonance spectroscopy, as well as kinetics measurements indicates that in ethanol/water solutions an [FeIII–(μ)OH–CuIIOH2]+ species is generated which is the likely catalyst for 2,4-bis(dinitrophenyl)phosphate and DNA hydrolysis. Insofar as the data are consistent with the presence of an FeIII-bound hydroxide acting as a nucleophile during catalysis, 1 presents a suitable mimic for the hydrolytic enzyme purple acid phosphatase. Notably, 1 is significantly more reactive than its isostructural homologues with different metal composition (FeIIIMII, where MII is ZnII, MnII, NiII, or FeII). Of particular interest is the observation that cleavage of double-stranded plasmid DNA occurs even at very low concentrations of 1 (2.5 μM), under physiological conditions (optimum pH of 7.0), with a rate enhancement of 2.7×107 over the uncatalyzed reaction. Thus, 1 is one of the most effective model complexes to date, mimicking the function of nucleases.

Tài liệu tham khảo

Schenk G, Ge Y, Carrington LE, Wynne CJ, Searle IR, Carroll BJ, Hamilton S, de Jersey J (1999) Arch Biochem Biophys 370:183–189 Klabunde T, Krebs B (1997) Struct Bond (Berlin) 1:177–198 Twitchett MB, Sykes AG (1999) Eur J Inorg Chem 12:2105–2115 Sträter N, Lipscomb WN, Klabunde T, Krebs B (1996) Angew Chem Int Ed 35:2024–2055 Merkx M, Averill BA (1998) Biochemistry 37:8490–8497 Campbell HD, Dionysius DA, Keough DT, Wilson BE, de Jersey J, Zerner B (1978) Biochem Biophys Res Commun 82:615–620 Marshall K, Nash K, Haussman G, Cassady I, Hume D, de Jersey J, Hamilton S (1997) Arch Biochem Biophys 345:230–236 Ljusberg J, Ek-Rylander B, Andersson G (1999) Biochem J 343:63–69 Ketcham CM, Roberts RM, Simmen RCM, Nick HS (1989) J Biol Chem 264:557–563 Halleen J, Hentunen TA, Hellman J, Väänänen HK (1996) J Bone Miner Res 11:1444–1452 Robinson DB, Glew RH (1980) J Biol Chem 255:5864–5870 Oddie GW, Schenk G, Angel NZ, Walsh N, Guddat LW, de Jersey J, Cassady AI, Hamilton SE, Hume DA (2000) Bone 27:575–584 Beck JL, McConaghie LA, Summors AC, Arnold WN, de Jersey J, Zerner B (1986) Biochim Biophys Acta 869:61–68 Durmus A, Eicken C, Sift BH, Kratel A, Kappl R, Hüttermann J, Krebs B (1999) Eur J Biochem 260:709–716 Kostrewa D, Wyss M, D’Arcy A, van Loon APGM (1999) J Mol Biol 288:965–974 Schenk G, Guddat LW, Ge Y, Carrington LE, Hume DA, Hamilton S, de Jersey J (2000) Gene 250:117–125 Schenk G, Korsinczky MLJ, Hume DA, Hamilton S, de Jersey J (2000) Gene 255:419–424 Guddat LW, McAlpine AS, Hume DA, Hamilton S, de Jersey J, Martin J (1999) Structure 7:757–767 Lindqvist Y, Johansson E, Kaija H, Vihko P, Schneider G (1999) J Mol Biol 291:135–147 Uppenberg J, Lindqvist F, Svensson C, Ek-Rylander B, Andersson G (1999) J Mol Biol 290:201–211 Sträter N, Klabunde T, Tucker P, Witzel H, Krebs B (1995) Science 268:1489–1492 Klabunde T, Sträter N, Fröhlich R, Witzel H, Krebs B (1996) J Mol Biol 259:737–748 Schenk G, Carrington LE, Hamilton SE, de Jersey J, Guddat LW (1999) Acta Cryst D55:2051–2052 Schenk G, Gahan LR, Carrington LE, Valizadeh M, Hamilton SE, de Jersey J, Guddat LW (2004) Proc Natl Acad Sci USA 102:273–278 Twitchett MB, Schenk G, Aquino MAS, Yiu DTY, Lau TC, Sykes AG (2002) Inorg Chem 41:5787–5794 Beck JL, Keough DT, de Jersey J, Zerner B (1984) Biochim Biophys Acta 791:357–363 Beck JL, McArthur MJ, de Jersey J, Zerner B (1988) Inorg Chim Acta 153:39–44 Beck JL, Durack MCA, Hamilton SE, de Jersey J (1999) Inorg Biochem 73:245–252 Merkx M, Averill BA (1999) J Am Chem Soc 121:6683–6689 Schenk G, Boutchard CL, Carrington LE, Noble CJ, Moubaraki B, Murray KS, de Jersey J, Hanson GR, Hamilton S (2001) J Biol Chem 276:19084–19088 Wilcox DE (1996) Chem Rev 96:2435–2458 Valizadeh M, Schenk G, Nash K, Oddie GW, Guddat LW, Hume DA, de Jersey J, Burke TR Jr, Hamilton S (2004) Arch Biochem Biophys 424:154–162 Batista SC, Neves A, Bortoluzzi AJ, Vencato I, Peralta RA, Szpoganicz B, Aires VVE, Terenzi H, Severino PC (2003) Inorg Chem Commun 6:1161–1165 Karsten P, Neves A, Bortoluzzi AJ, Lanznaster M, Drago V (2002) Inorg Chem 41:4624–4626 Karsten P, Neves A, Bortoluzzi AJ, Strähle J, Maichle-Mössmer C (2002) Inorg Chem Commun 5:434–438 Lanznaster M, Neves A, Bortoluzzi AJ, Szpoganicz B, Schwingel E (2002) Inorg Chem 41:5641–5643 Neves A, de Brito M, Vencato I, Drago V, Griesar K, Haase W (1996) Inorg Chem 35:2360–2368 Neves A, de Brito MA, Drago V, Griesar K, Haase W (1995) Inorg Chim Acta 237:131–135 Holman T, Andersen KA, Anderson OP, Hendrich MP, Juarez-Garcia C, Münck E, Que L Jr (1990) Angew Chem Int Ed 29:921–923 Belle C, Gautier-Luneau I, Gellon G, Pierre JL, Morgenstern-Badarau I, Saint-Aman E (1997) J Chem Soc Dalton Trans 3543–3546 Ghiladi M, McKenzie CJ, Meier A, Powell AK, Ulstrup J, Wocadlo S (1997) J Chem Soc Dalton Trans 21:4011–4018 Ghiladi M, Jensen KB, Jiang J, McKenzie CJ, Morup S, Sotofte I, Ulstrup J (1999) J Chem Soc Dalton Trans 2675–2681 Spek AL (1996) HELENA: CAD-4 data reduction program. University of Utrecht, The Netherlands Spek AL (1997) PLATON: molecular geometry and plotting program. University of Utrecht, The Netherlands Sheldrick GM (1990) SHELXS97: program for the solution of crystal structures. University of Göttingen, Germany Sheldrick GM (1997) SHELXL97: program for the refinement of crystal structures. University of Göttingen, Germany Zsolnai L (1997) ZORTEP: an interactive ORTEP program. University of Heidelberg, Germany Martell AE, Motekaits RJ (1992) Determination and use of Stability constants. VCH Publishers, New York Gagne RR, Koval CA, Lisensky GC (1980) Inorg Chem 19:2854–2855 Ravel B (2001) J Synchrotron Rad 8:314–316 Rehr JJ, Mustre de Leon J, Zabinsky SI, Albers RC (1991) J Am Chem Soc 113:5135–5140 Newville M (2001) J Synchrotron Rad 8:322–324 Hanson GR, Gates KE, Noble CJ, Griffin M, Mitchell A, Benson S (2004) J Inorg Biochem 98:903–916 Rossi LM, Neves A, Hörner R, Terenzi H, Szpoganicz B, Sugai J (2002) Inorg Chim Acta 337:366 Neves A, Terenzi H, Hörner R, Horn A Jr, Szpoganicz B, Sugai J (2001) Inorg Chem Commun 4:388–391 Scarpellini M, Neves A, Hörner R, Bortoluzzi AJ, Szpoganicz B, Zucco C, Silva RAN, Drago V, Mangrich AS, Ortiz WA, Passos WAC, Oliveira MCB, Terenzi H (2003) Inorg Chem 42:8353–8365 Lambert E, Chabut B, Chardon-Noblat S, Deronzier A, Chottard G, Bousseksou A, Tuchagues JP, Laugier J, Bardet M, Latour JM (1997) J Am Chem Soc 119:9424–9437 Westre TE, Kennepohl P, DeWitt JG, Hedman B, Hodgson KO, Solomon EI (1997) J Am Chem Soc 119:6297–6314 Roe AL, Schneider DJ, Mayer RJ, Pyrz JW, Widom J, Que L (1984) J Am Chem Soc 106:1676–1681 Juarez-Garcia C, Hendrich MP, Holma TR, Que L, Munck E (1991) J Am Chem Soc 113:518–525 Smith TD, Pilbrow JR (1974) Coord Chem Rev 13:173–278 Dessens SE, Merrill CL, Saxton RJ, Ilaria RL Jr, Lindsey JW, Wilson LJ (1982) J Am Chem Soc 104:4357–4361 Bunton CA, Farber SJ (1969) J Org Chem 34:767–772 Aquino MAS, Lim JS, Sykes AG (1994) J Chem Soc Dalton Trans 429–436 Smoukov SK, Quaroni L, Wang X, Doan PE, Hoffman BM, Que L Jr (2002) J Am Chem Soc 124:2595–2603 Sreedhara A, Freed JD, Cowan JA (2000) J Am Chem Soc 122:8814–8824 Cowan JA (2001) Curr Opin Chem Biol 5:634–642 Sreedhara A, Cowan JA (2001) J Biol Inorg Chem 6:337–347