Mechanism for Copper(II)-Mediated Disaggregation of a Porphyrin J-Aggregate

Overview

Journal ACS Omega

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Aug 29

PMID 31458447

Citations 6

Authors

Mariachiara Trapani

Ilaria G Occhiuto

Roberto Zagami

Giovanna De Luca

Maria A Castriciano

Andrea Romeo

Luigi Monsu Scolaro

Robert F Pasternack

Affiliations

Soon will be listed here.

Abstract

J-aggregates of anionic -tetrakis(4-sulfonatophenyl)porphyrin form at intermediate pH (2.3-3.1) in the presence of NiSO or ZnSO (ionic strength, I.S. = 3.2 M). These aggregates convert to monomeric porphyrin units via metallation with copper(II) ions. The kinetics for the disassembly process, as monitored by UV/vis spectroscopy, exhibits zeroth-order behavior. The observed zeroth-order rate constants show a two-term dependence on copper(II) ion concentrations: linear and second order. Also observed is an inverse dependence on hydrogen ion concentration. Activation parameters have been determined for the disassembly process leading to Δ = (+163 ± 15) kJ·mol and Δ = (+136 ± 11) J·K. A mechanism is proposed in which copper(II) cation is in pre-equilibrium with a reactive site at the rim of the J-aggregate. An intermediate copper species is thus formed that eventually leads to the final metallated porphyrin either through an assisted attack of a second metal ion or through a direct insertion of the metal cation into the macrocycle core.

Citing Articles

Interaction of Aromatic Amino Acids with Metal Complexes of Tetrakis-(4-Sulfonatophenyl)Porphyrin.

Zagami R, Castriciano M, Trapani M, Romeo A, Monsu Scolaro L Molecules. 2024; 29(2).

PMID: 38257385 PMC: 10819004. DOI: 10.3390/molecules29020472.

Enhancement of the Rates for Insertion of Zinc(II) Ions into a Cationic Porphyrin Catalyzed by Poly(glutamate).

Zagami R, Castriciano M, Romeo A, Monsu Scolaro L Int J Mol Sci. 2023; 24(24).

PMID: 38139200 PMC: 10744324. DOI: 10.3390/ijms242417371.

Investigation of J-Aggregates of 2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl) Porphyrin in Aqueous Solutions.

Abdelaziz B, Sara M, Ayachi S, Zagami R, Patane S, Romeo A Nanomaterials (Basel). 2023; 13(21).

PMID: 37947678 PMC: 10649154. DOI: 10.3390/nano13212832.

Role of Cobalt(III) Cationic Complexes in the Self-Assembling Process of a Water Soluble Porphyrin.

Manganaro N, Zagami R, Trapani M, Castriciano M, Romeo A, Monsu Scolaro L Int J Mol Sci. 2020; 22(1).

PMID: 33375184 PMC: 7792976. DOI: 10.3390/ijms22010039.

Controlling J-Aggregates Formation and Chirality Induction through Demetallation of a Zinc(II) Water Soluble Porphyrin.

Occhiuto I, Castriciano M, Trapani M, Zagami R, Romeo A, Pasternack R Int J Mol Sci. 2020; 21(11).

PMID: 32503280 PMC: 7313071. DOI: 10.3390/ijms21114001.

References

Pasternack R, Fleming C, Herring S, Collings P, dePaula J, DECASTRO G . Aggregation kinetics of extended porphyrin and cyanine dye assemblies. Biophys J. 2000; 79(1):550-60. PMC: 1300958. DOI: 10.1016/S0006-3495(00)76316-8. View

Purrello R, Monsu Scolaro L, Bellacchio E, Gurrieri S, Romeo A . Chiral H- and J-Type Aggregates of meso-Tetrakis(4-sulfonatophenyl)porphine on alpha-Helical Polyglutamic Acid Induced by Cationic Porphyrins. Inorg Chem. 2001; 37(14):3647-3648. DOI: 10.1021/ic971432m. View

Pasternack R, Gibbs E, Bruzewicz D, Stewart D, Engstrom K . Kinetics of disassembly of a DNA-bound porphyrin supramolecular array. J Am Chem Soc. 2002; 124(14):3533-9. DOI: 10.1021/ja0124820. View

Gandini S, Gelamo E, Itri R, Tabak M . Small angle X-ray scattering study of meso-tetrakis (4-sulfonatophenyl) porphyrin in aqueous solution: a self-aggregation model. Biophys J. 2003; 85(2):1259-68. PMC: 1303243. DOI: 10.1016/S0006-3495(03)74561-5. View

Monsu Scolaro L, Romeo A, Castriciano M, Micali N . Unusual optical properties of porphyrin fractal J-aggregates. Chem Commun (Camb). 2005; (24):3018-20. DOI: 10.1039/b501083g. View

Micali N, Villari V, Castriciano M, Romeo A, Monsu Scolaro L . From fractal to nanorod porphyrin J-aggregates. Concentration-induced tuning of the aggregate size. J Phys Chem B. 2006; 110(16):8289-95. DOI: 10.1021/jp060730e. View

Collini E, Ferrante C, Bozio R . Strong enhancement of the two-photon absorption of tetrakis(4-sulfonatophenyl)porphyrin diacid in water upon aggregation. J Phys Chem B. 2006; 109(1):2-5. DOI: 10.1021/jp045652e. View

Wang Z, Li Z, Medforth C, Shelnutt J . Self-assembly and self-metallization of porphyrin nanosheets. J Am Chem Soc. 2007; 129(9):2440-1. DOI: 10.1021/ja068250o. View

Mohr A, Talbiersky P, Korth H, Sustmann R, Boese R, Blaser D . A new pyrene-based fluorescent probe for the determination of critical micelle concentrations. J Phys Chem B. 2007; 111(45):12985-92. DOI: 10.1021/jp0731497. View

10.

Watanabe K, Kano K . Time-dependent enzyme activity dominated by dissociation of J-aggregates bound to protein surface. Bioconjug Chem. 2010; 21(12):2332-8. DOI: 10.1021/bc100355v. View

11.

Castriciano M, Romeo A, Zagami R, Micali N, Monsu Scolaro L . Kinetic effects of tartaric acid on the growth of chiral J-aggregates of tetrakis(4-sulfonatophenyl)porphyrin. Chem Commun (Camb). 2012; 48(40):4872-4. DOI: 10.1039/c2cc00028h. View

12.

Occhiuto I, De Luca G, Trapani M, Monsu Scolaro L, Pasternack R . Peripheral stepwise degradation of a porphyrin J-aggregate. Inorg Chem. 2012; 51(19):10074-6. DOI: 10.1021/ic301570p. View

13.

Short J, Berriman J, Kubel C, El-Hachemi Z, Naubron J, Balaban T . Electron cryo-microscopy of TPPS4⋅2HCl tubes reveals a helical organisation explaining the origin of their chirality. Chemphyschem. 2013; 14(14):3209-14. PMC: 4281918. DOI: 10.1002/cphc.201300606. View

14.

Fuhrhop J . Porphyrin assemblies and their scaffolds. Langmuir. 2013; 30(1):1-12. DOI: 10.1021/la402228g. View

15.

Romeo A, Castriciano M, Occhiuto I, Zagami R, Pasternack R, Monsu Scolaro L . Kinetic control of chirality in porphyrin J-aggregates. J Am Chem Soc. 2013; 136(1):40-3. DOI: 10.1021/ja410514k. View

16.

Zhai D, Xu W, Zhang L, Chang Y . The role of "disaggregation" in optical probe development. Chem Soc Rev. 2014; 43(8):2402-11. DOI: 10.1039/c3cs60368g. View

17.

El-Hachemi Z, Balaban T, Campos J, Cespedes S, Crusats J, Escudero C . Effect of Hydrodynamic Forces on meso-(4-Sulfonatophenyl)-Substituted Porphyrin J-Aggregate Nanoparticles: Elasticity, Plasticity and Breaking. Chemistry. 2016; 22(28):9740-9. DOI: 10.1002/chem.201600874. View

18.

Occhiuto I, Zagami R, Trapani M, Bolzonello L, Romeo A, Castriciano M . The role of counter-anions in the kinetics and chirality of porphyrin J-aggregates. Chem Commun (Camb). 2016; 52(77):11520-11523. DOI: 10.1039/c6cc05768c. View

19.

Zagami R, Romeo A, Castriciano M, Monsu Scolaro L . Inverse Kinetic and Equilibrium Isotope Effects on Self-Assembly and Supramolecular Chirality of Porphyrin J-Aggregates. Chemistry. 2016; 23(1):70-74. DOI: 10.1002/chem.201604675. View

20.

Romeo A, Castriciano M, Zagami R, Pollicino G, Monsu Scolaro L, Pasternack R . Effect of zinc cations on the kinetics of supramolecular assembly and the chirality of porphyrin J-aggregates. Chem Sci. 2017; 8(2):961-967. PMC: 5354048. DOI: 10.1039/c6sc02686a. View