The Research on Porphyrins and Analogues in Brazil: A Small Review Covering Catalytic and other Applications since the Beginning at Universidade de São Paulo in Ribeirão Preto until the Joint Venture between Brazilian Researchers and Colleagues from Universidade de Aveiro, Portugal

Nakagaki, Shirley; Castro, Kelly A. D. F.; Neves, Maria da Graça P. M. S.; Faustino, Maria do Amparo; Iamamoto, Yassuko

doi:10.21577/0103-5053.20190153

Shirley Nakagaki ^**e-mail: shirleyn@ufpr.br, gneves@ua.pt; yassuko.iamamoto@gmail.com

Laboratório de Bioinorgânica e Catálise, Departamento de Química, Centro Politécnico, Universidade Federal do Paraná (UFPR), Av. Cel. Francisco H. dos Santos, 100, Jardim das Américas, 81531-980 Curitiba-PR, Brazil

Shirley Nakagaki is Full Professor at the Chemistry Department of Universidade Federal do Paraná (UFPR). She graduated in Chemistry in 1985 at Universidade de São Paulo (FFCL-USP/RP). PhD Chemistry Institute UNESP/Araraquara-SP, under the supervision of Yassuko Iamamoto (1992). She is currently working on the preparation of solid catalysts efficient and selective for heterogeneous catalytic process based on metalloporphyrins. She has more than 100 publications and an H index of 30. She is CNPq researcher level 1C and has supervised 6 Post-doctoral researchers, 12 PhD thesis, 20 MSc dissertations and over more than 40 undergraduate projects (scientific initiation).

https://orcid.org/0000-0001-9562-7049

Kelly A. D. F. Castro

Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo (USP), Avenida do Café, s/nº, 14040-903 Ribeirão Preto-SP, Brazil

Kelly Aparecida Dias de Freitas Castro is graduated in Chemistry in 2008 at the Universidade Federal do Paraná (UFPR), Brazil, where she got her Master’s degree, in 2009. In 2013, she received a PhD degree in Chemistry at UFPR under the supervision of Prof Shirley Nakagaki. The work was developed partly at the University of Aveiro-Portugal (Chemistry Department/QOPNA Group). Pos-doctoral researcher at University of Aveiro in 2014. Presently, she is a Post-doctoral researcher in Brazil (School of Pharmaceutical Sciences of Ribeirão Preto/ FCFRP/USP). Has experience in Chemistry, focusing on Bioinorganic chemistry, acting on the following subjects: porphyrin, epoxidation, oxidation, catalysis, nonheme complexes, chlorins, metalloporphyrins, immobilization/encapsulation of porphyrin derivatives, catecholase, photocatalysis, photobiological and photophysical studies. She is the author/co-author of 29 papers published in international peer-reviewed journals and has an H factor of 16.

Maria da Graça P. M. S. Neves ^**e-mail: shirleyn@ufpr.br, gneves@ua.pt; yassuko.iamamoto@gmail.com

QOPNA & LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

Maria da Graça P. M. S. Neves is Associate Professor with Habilitation in the Department of Chemistry at the University of Aveiro, Portugal. She obtained her Habilitation and PhD degree both at the University of Aveiro, her MSc degree at UMIST, Manchester, Great Britain, and her BSc degree in Chemistry at the University of Lourenço Marques, Mozambique. Her research interests are centered on the synthesis, functionalization, and potential applications in different fields (e.g., catalysis, photocatalysis, photodynamic therapy, sensors, dye sensitized solar cells) of tetrapyrrolic macrocycles like porphyrins, corroles and phthalocyanines. She has been in charge of the supervision of more than 50 final works of BSc and interns; 16 MSc thesis concluded and 1 MSc under development; 21 PhD Thesis concluded and 3 PhD undergoing and several Post-doctoral fellowships. She published more than 316 publications, 8 book chapters, 4 patents and has an H factor of 42.

Maria do Amparo Faustino

QOPNA & LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

Maria do Amparo Faustino is since 2001 Assistant Professor at the Department of Chemistry (DQ) of the University of Aveiro (UA). She got her PhD in Chemistry (Organic Chemistry) in 1999 under the supervision of Prof José A. S. Cavaleiro and Prof Maria da Graça P. M. S. Neves, University of Aveiro. She has been in charge of the supervision of more than 70 undergraduate students, 8 PhD students (3 concluded and 5 undergoing) and 37 MSc. Over the last years, her work was focused essentially on the synthesis, reactivity and characterization of tetrapyrrolic macrocycles with structural features to be considered as dyes in solar cells (DSSC) and in medical and environmental applications (photodynamic therapy of neoplastic tissues, microorganisms photoinactivation, dermatologic formulations). She was inventor of 1 patent and published 17 book chapters and 139 scientific papers in ISI journals. These scientific papers were cited around 3000 times in the Scopus search, corresponding to an H factor of 32.

Yassuko Iamamoto ^**e-mail: shirleyn@ufpr.br, gneves@ua.pt; yassuko.iamamoto@gmail.com

Departamento de Química, Universidade de São Paulo, Av. Bandeirantes, 3900, 14040-901 Ribeirão Preto-SP, Brazil

Yassuko Iamamoto is full professor at USP/Ribeirão Preto-SP. Graduated in Farmacy and Biochemistry in 1968 at Universidade Federal do Mato Grosso do Sul and she obtained her PhD degree at the Instituto de Química da Universidade de São Paulo (analytical chemistry). Her first Post-doctoral was at University of California-San Diego, in the chemistry of porphyrins and biomimetic catalysis under the supervision of Prof T. G. Traylor (1981). Her research interests are centered on bioinorganic chemistry acting on porphyrins and metaloporphyrins (MeP), MeP immobilized on mesoporous silica, biomimetic catalysis, oxidative metabolism of drugs, bioactive molecules and pesticides and synthesis of porphyrin derivatives for application on PDT. She is also active in chemical education research and university pedagogical studies. She has about 90 publications with H factor of 26. She has been in charge of the supervision of more than 70 final works of scientific initiation, MSc, PhD thesis and Post-doctoral fellowships.

*e-mail: shirleyn@ufpr.br, gneves@ua.pt; yassuko.iamamoto@gmail.com

Shirley Nakagaki

is Full Professor at the Chemistry Department of Universidade Federal do Paraná (UFPR). She graduated in Chemistry in 1985 at Universidade de São Paulo (FFCL-USP/RP). PhD Chemistry Institute UNESP/Araraquara-SP, under the supervision of Yassuko Iamamoto (1992). She is currently working on the preparation of solid catalysts efficient and selective for heterogeneous catalytic process based on metalloporphyrins. She has more than 100 publications and an H index of 30. She is CNPq researcher level 1C and has supervised 6 Post-doctoral researchers, 12 PhD thesis, 20 MSc dissertations and over more than 40 undergraduate projects (scientific initiation).

Kelly Aparecida Dias de Freitas Castro

is graduated in Chemistry in 2008 at the Universidade Federal do Paraná (UFPR), Brazil, where she got her Master’s degree, in 2009. In 2013, she received a PhD degree in Chemistry at UFPR under the supervision of Prof Shirley Nakagaki. The work was developed partly at the University of Aveiro-Portugal (Chemistry Department/QOPNA Group). Pos-doctoral researcher at University of Aveiro in 2014. Presently, she is a Post-doctoral researcher in Brazil (School of Pharmaceutical Sciences of Ribeirão Preto/ FCFRP/USP). Has experience in Chemistry, focusing on Bioinorganic chemistry, acting on the following subjects: porphyrin, epoxidation, oxidation, catalysis, nonheme complexes, chlorins, metalloporphyrins, immobilization/encapsulation of porphyrin derivatives, catecholase, photocatalysis, photobiological and photophysical studies. She is the author/co-author of 29 papers published in international peer-reviewed journals and has an H factor of 16.

Maria da Graça P. M. S. Neves

is Associate Professor with Habilitation in the Department of Chemistry at the University of Aveiro, Portugal. She obtained her Habilitation and PhD degree both at the University of Aveiro, her MSc degree at UMIST, Manchester, Great Britain, and her BSc degree in Chemistry at the University of Lourenço Marques, Mozambique. Her research interests are centered on the synthesis, functionalization, and potential applications in different fields (e.g., catalysis, photocatalysis, photodynamic therapy, sensors, dye sensitized solar cells) of tetrapyrrolic macrocycles like porphyrins, corroles and phthalocyanines. She has been in charge of the supervision of more than 50 final works of BSc and interns; 16 MSc thesis concluded and 1 MSc under development; 21 PhD Thesis concluded and 3 PhD undergoing and several Post-doctoral fellowships. She published more than 316 publications, 8 book chapters, 4 patents and has an H factor of 42.

Maria do Amparo Faustino

is since 2001 Assistant Professor at the Department of Chemistry (DQ) of the University of Aveiro (UA). She got her PhD in Chemistry (Organic Chemistry) in 1999 under the supervision of Prof José A. S. Cavaleiro and Prof Maria da Graça P. M. S. Neves, University of Aveiro. She has been in charge of the supervision of more than 70 undergraduate students, 8 PhD students (3 concluded and 5 undergoing) and 37 MSc. Over the last years, her work was focused essentially on the synthesis, reactivity and characterization of tetrapyrrolic macrocycles with structural features to be considered as dyes in solar cells (DSSC) and in medical and environmental applications (photodynamic therapy of neoplastic tissues, microorganisms photoinactivation, dermatologic formulations). She was inventor of 1 patent and published 17 book chapters and 139 scientific papers in ISI journals. These scientific papers were cited around 3000 times in the Scopus search, corresponding to an H factor of 32.

Yassuko Iamamoto

is full professor at USP/Ribeirão Preto-SP. Graduated in Farmacy and Biochemistry in 1968 at Universidade Federal do Mato Grosso do Sul and she obtained her PhD degree at the Instituto de Química da Universidade de São Paulo (analytical chemistry). Her first Post-doctoral was at University of California-San Diego, in the chemistry of porphyrins and biomimetic catalysis under the supervision of Prof T. G. Traylor (1981). Her research interests are centered on bioinorganic chemistry acting on porphyrins and metaloporphyrins (MeP), MeP immobilized on mesoporous silica, biomimetic catalysis, oxidative metabolism of drugs, bioactive molecules and pesticides and synthesis of porphyrin derivatives for application on PDT. She is also active in chemical education research and university pedagogical studies. She has about 90 publications with H factor of 26. She has been in charge of the supervision of more than 70 final works of scientific initiation, MSc, PhD thesis and Post-doctoral fellowships.

Solid support	Detail	Reference
Silica	commercial	⁷⁹79 Iamamoto, Y.; Idemori, Y. M.; Nakagaki, S. J. Mol. Catal. A: Chem. 1995, 99, 187.
	amorphous silica prepared by sol-gel process	⁷⁶76 Ucoski, G. M.; Castro, K. A. D. F.; Ciuffi, K. J.; Ricci, G. P.; Marques, J. A.; Nunes, F. S.; Nakagaki, S.; Appl. Catal., A 2011, 404, 120., ⁸⁰80 Ferreira, G. K. B.; Castro, K. A. D. F. C.; Machado, G. S.; Ribeiro, R. R.; Ciuffi, K. J.; Ricci, G. P.; Marques, J. A.; Nakagaki, S.; J. Mol. Catal. A: Chem. 2013, 378, 263. 81 Papacídero, A. T.; Rocha, L. A.; Caetano, B. L.; Molina, E.; Sacco, H. C.; Nassar, E. J.; Martinelli, Y.; Mello, C.; Nakagaki, S.; Ciuffi, K.; Colloids Surf., A 2006, 275, 27. 82 Nakagaki, S.; Ferreira, G. K. B.; Marcalb, A. L.; Ciuffi, K. J.; Curr. Org. Synth. 2014, 11, 67. 83 Castro, K. A. D. F.; Halma, M.; Machado, G. S.; Ricci, G. P.; Ucoski, G. M.; Ciuffi, K. J.; Nakagaki, S.; J. Braz. Chem. Soc. 2010, 21, 1329.-⁸⁴84 Castro, K. A. D. F.; Pires, S. M. G.; Ribeiro, M. A.; Simões, M. M. Q.; Neves, M. G. P. M. S.; Schreiner, W. H.; Wypych, F.; Cavaleiro, J. A. S.; Nakagaki, S.; J. Colloid Interface Sci. 2015, 450, 339.
	mesoporous silica (SBA-15, HMS, MCM-41)	⁸⁵85 Pinto, V. H. A.; Rebouças, J. S.; Ucoski, G. M.; de Faria, E. H.; Ferreira, B. F.; Silva San Gil, R. A.; Nakagaki, S.; Appl. Catal., A 2016, 526, 9. 86 Ucoski, G. M.; Pinto, V. H. A.; DeFreitas-Silva, G.; Rebouças, J. S.; Mazzaro, I.; Nunes, F. S.; Nakagaki, S.; ChemistrySelect 2017, 2, 3703. 87 Ucoski, G. M.; Pinto, V. H. A.; DeFreitas-Silva, G.; Rebouças, J. S.; Marcos da Silva, R.; Mazzaro, I.; Nunes, F. S.; Nakagaki, S.; Microporous Mesoporous Mater. 2018, 265, 84. 88 Zanardi, F. B.; Barbosa, I. A.; de Sousa, P. C.; Zanatta, L. D.; da Silva, D. L.; Serra, O. A.; Iamamoto, Y.; Microporous Mesoporous Mater. 2016, 219, 161. 89 Bolzon, L. B.; Airoldi, H. R.; Zanardi, F. B.; Granado, J. G.; Iamamoto, Y.; Microporous Mesoporous Mater. 2013, 168, 37. 90 DeOliveira, E.; Neri, C. R.; Ribeiro, A. O.; Garcia, V. S.; Costa, L. L.; Moura, A. O.; Prado, A. G.; Serra, O. A.; Iamamoto, Y.; J. Colloid Interface Sci. 2008, 323, 98.-⁹¹91 Zanatta, L. D.; Barbosa, I. A.; Zanardi, F. B.; de Sousa Filho, P. C.; Bolzon, L. B.; Ramos, A. P.; Serra, O. A.; Iamamoto, Y.; RSC Adv. 2016, 6, 104886.
	magnetic (F₃O₄) mesoporous or amorphous silicas	⁸⁶86 Ucoski, G. M.; Pinto, V. H. A.; DeFreitas-Silva, G.; Rebouças, J. S.; Mazzaro, I.; Nunes, F. S.; Nakagaki, S.; ChemistrySelect 2017, 2, 3703., ⁸⁷87 Ucoski, G. M.; Pinto, V. H. A.; DeFreitas-Silva, G.; Rebouças, J. S.; Marcos da Silva, R.; Mazzaro, I.; Nunes, F. S.; Nakagaki, S.; Microporous Mesoporous Mater. 2018, 265, 84., ⁹²92 Ucoski, G. M.; Machado, G. S.; Silva, G. F.; Nunes, F. S.; Wypych, F.; Nakagaki, S.; J. Mol. Catal. A: Chem. 2015, 408, 123. 93 Henriques, C. A.; Fernandes, A.; Rossi, L. M.; Ribeiro, M. F.; Calvete, M. J. F.; Pereira, M. M.; Adv. Funct. Mater. 2016, 26, 3359.-⁹⁴94 Barbosa, I. A.; de Sousa Filho, P. C.; da Silva, D. L.; Zanardi, F. B.; Zanatta, L. D.; de Oliveira, A. J. A.; Serra, O. A.; Iamamoto, Y.; J. Colloid Interface Sci. 2016, 469, 296.
	modified amorphous or mesoporous silica functionalization	⁶¹61 Iamamoto, Y.; Prado, C. M. C.; Sacco, H. C.; Ciuffi, K. J.; Assis, M. D.; Maestrin, A. P. J.; Melo, A. J. B.; Baffa, O.; Nascimento, O. R.; J. Mol. Catal. A: Chem. 1997, 117, 259., ⁶⁴64 Faria, A. L.; Mac Leod, T. O. C.; Barros, V. P.; Assis, M. D.; J. Braz. Chem. Soc. 2009, 20, 895., ⁷⁹79 Iamamoto, Y.; Idemori, Y. M.; Nakagaki, S. J. Mol. Catal. A: Chem. 1995, 99, 187., ⁸⁵85 Pinto, V. H. A.; Rebouças, J. S.; Ucoski, G. M.; de Faria, E. H.; Ferreira, B. F.; Silva San Gil, R. A.; Nakagaki, S.; Appl. Catal., A 2016, 526, 9. 86 Ucoski, G. M.; Pinto, V. H. A.; DeFreitas-Silva, G.; Rebouças, J. S.; Mazzaro, I.; Nunes, F. S.; Nakagaki, S.; ChemistrySelect 2017, 2, 3703.-⁸⁷87 Ucoski, G. M.; Pinto, V. H. A.; DeFreitas-Silva, G.; Rebouças, J. S.; Marcos da Silva, R.; Mazzaro, I.; Nunes, F. S.; Nakagaki, S.; Microporous Mesoporous Mater. 2018, 265, 84., ⁹⁵95 Vinhado, F. S.; Martins, P. R.; Masson, A. P.; Abreu, D. G.; Vidoto, E. A.; Nascimento, O. R.; Iamamoto, Y.; J. Mol. Catal. A: Chem. 2002, 188, 141. 96 Schiavon, M. A.; Iamamoto, Y.; Nascimento, O. R.; Assis, M. D.; J. Mol. Catal. A: Chem. 2001, 174, 213. 97 Doro, F. G.; Smith, J. R. L.; Ferreira, A. G.; Assis, M. D.; J. Mol. Catal. A: Chem. 2000, 164, 97.-⁹⁸98 Iamamoto, Y.; Ciuffi, K. J.; Sacco, H. C.; Iwamoto, L. S.; Nascimento, O. R.; Prado, C. M. C.; J. Mol. Catal. A: Chem. 1997, 116, 405.
Zeolite	NaY	⁹⁹99 Nakagaki, S.; Xavier, C. R.; Wosniak, A. J.; Mangrich, A. S.; Wypych, F.; Cantão, M. P.; Denicoló, I.; Kubota, L. T.; Colloids Surf., A 2000, 168, 261. 100 Rosa, I. L. V.; Manso, C. M. C. P.; Serra, O. A.; Iamamoto, Y.; J. Mol. Catal. A: Chem. 2000, 160, 199.-¹⁰¹101 Skrobot, F. C.; Rosa, I. L. V.; Marques, A. P. A.; Martins, P. R.; Rocha, J.; Valente, A. A.; Iamamoto, Y.; J. Mol. Catal. A: Chem. 2005, 237, 86.
Porous glass	PVG (porous Vycor glass)	¹⁰²102 Nakagaki, S.; Ramos, A. R.; Benedito, F. L.; Peralta-Zamora, P. G.; Zarbin, A. J. G.; J. Mol. Catal. A: Chem. 2002, 185, 203.
Natural solids (clays)	montmorillonite clay	¹⁰³103 Machado, A. M.; Wypych, F.; Drechsel, S. M.; Nakagaki, S.; J. Colloid Interface Sci. 2002, 254, 158.
	kaolinite clay	¹⁰⁴104 Bizaia, N.; de Faria, E. H.; Ricci, G. P.; Calefi, P. S.; Nassar, E. J.; Castro, K. A. D. F.; Nakagaki, S.; Ciuffi, K. J.; Trujillano, R.; Vicente, M. A.; Gil, A.; Korili, S. A.; ACS Appl. Mater. Interfaces 2009, 1, 2667. 105 Lovo de Carvalho, A.; Ferreira, B. F.; Martins, C. H. G.; Nassar, E. J.; Nakagaki, S.; Machado, G. S.; Rives, V.; Trujillano, R.; Vicente, M. A.; Gil, A.; Korili, S. A.; de Faria, E. H.; Ciuffi, K. J.; J. Phys. Chem. C 2014, 118, 24562.-¹⁰⁶106 Nakagaki, S.; Benedito, F. L.; Wypych, F.; J. Mol. Catal. A: Chem. 2004, 217, 121.
	halloysite	¹⁰⁷107 Machado, G. S.; Ucoski, G. M.; Lima, O. J.; Ciuffi, K. J.; Wypych, F.; Nakagaki, S.; Appl. Catal., A 2013, 460-461, 124.,¹⁰⁸108 Machado, G. S.; Castro, K. A. D. F.; Wypych, F.; Nakagaki, S.; J. Mol. Catal. A: Chem. 2008, 283, 99.
	chrysotile	¹⁰⁹109 Nakagaki, S.; Castro, K. A. D. F.; Machado, G. S.; Halma, M.; Drechsel, S. M.; Wypych, F.; J. Braz. Chem. Soc. 2006, 17, 1672.
	modified natural clay (by exfoliation, intercalation/delamination, delamination, acid treatment, functionalization, etc.)	⁶⁴64 Faria, A. L.; Mac Leod, T. O. C.; Barros, V. P.; Assis, M. D.; J. Braz. Chem. Soc. 2009, 20, 895., ¹⁰⁵105 Lovo de Carvalho, A.; Ferreira, B. F.; Martins, C. H. G.; Nassar, E. J.; Nakagaki, S.; Machado, G. S.; Rives, V.; Trujillano, R.; Vicente, M. A.; Gil, A.; Korili, S. A.; de Faria, E. H.; Ciuffi, K. J.; J. Phys. Chem. C 2014, 118, 24562.,¹⁰⁶106 Nakagaki, S.; Benedito, F. L.; Wypych, F.; J. Mol. Catal. A: Chem. 2004, 217, 121.,¹¹⁰110 Machado, G. S.; Groszewicz, P. B.; Castro, K. A. D. F.; Wypych, F.; Nakagaki, S.; J. Colloid Interface Sci. 2012, 374, 278. 111 Machado, G. S.; Lima, O. J.; Ciuffi, K. J.; Wypych, F.; Nakagaki, S.; Catal. Sci. Technol. 2013, 3, 1094.-¹¹²112 Crepaldi, E. L.; Valim, J. B.; Quim. Nova 1998, 21, 300.
	talc-aminofunctionalyzed phyllosilicates	¹¹³113 de Faria, A. L.; Airoldi, C.; Doro, F. G.; Fonseca, M. G.; Assis, M. D.; Appl. Catal., A 2004, 268, 217.
Synthetic layered solids	layered MoS₂	¹¹⁴114 Nakagaki, S.; Mangrich, A. S.; Wypych, F.; Inorg. Chim. Acta 1997, 254, 213.
	layered double hydroxides (LDH)	⁶⁰60 Castro, K. A. D. F.; Simões, M. M. Q.; Neves, M. G. P. M. S.; Cavaleiro, J. A. S.; Wypych, F.; Nakagaki, S.; Catal. Sci. Technol. 2014, 4, 129., ¹¹⁵115 Nakagaki, S.; Mantovani, K. M.; Machado, G. S.; Castro, K. A. D. F.; Wypych, F.; Molecules 2016, 21, 291. 116 Halma, M.; Wypych, F.; Drechsel, S. M.; Nakagaki, S.; J. Porphyrins Phthalocyanines 2002, 6, 502. 117 Wypych, F.; Bubniak, G. A.; Halma, M.; Nakagaki, S.; J. Colloid Interface Sci. 2003, 264, 203. 118 Castro, K. A. D. F.; Wypych, F.; Antonangelo, A.; Mantovani, K. M.; Bail, A.; Ucoski, G. M.; Ciuffi, K. J.; Cintra, T. E.; Nakagaki, S.; J. Colloid Interface Sci. 2016, 478, 374. 119 Castro, K. A. D. F.; Bail, A.; Groszewicz, P. B.; Machado, G. S.; Schreiner, W. H.; Wypych, F.; Nakagaki, S.; Appl. Catal., A 2010, 386, 51.-¹²⁰120 Halma, M.; Castro, K. A. D. F.; Taviot-Gueho, C.; Prevot, V.; Forano, C.; Wypych, F.; Nakagaki, S.; J. Catal. 2008, 257, 233.
	layered hydroxide salts (LHS)	¹²¹121 Machado, G. S.; Arízaga, G. G. C.; Wypych, F.; Nakagaki, S.; J. Catal. 2010, 274, 130.,¹²²122 Machado, G. S.; Wypych, F.; Nakagaki, S.; Appl. Catal., A 2012, 413-414, 94.
	layered hydroxides + TiO₂	¹²³123 Mantovani, K. M.; Stival, J. F.; Wypych, F.; Bach, L.; Peralta Zamora, P. G.; Rocco, M. L.; Nakagaki, S.; J. Catal. 2017, 352, 442.
	lithium gordaite (layered hydroxide salt with cation exchange capacity)	¹²⁴124 Maruyama, S. A.; Westrup, K. C. M.; Nakagaki, S.; Wypych, F.; Appl. Clay Sci. 2017, 139, 108.
	modified synthetic layered solid (by exfoliation, temperature treatment, functionalization, preparation of macroporous layered solids, etc.)	¹¹⁷117 Wypych, F.; Bubniak, G. A.; Halma, M.; Nakagaki, S.; J. Colloid Interface Sci. 2003, 264, 203., ¹¹⁸118 Castro, K. A. D. F.; Wypych, F.; Antonangelo, A.; Mantovani, K. M.; Bail, A.; Ucoski, G. M.; Ciuffi, K. J.; Cintra, T. E.; Nakagaki, S.; J. Colloid Interface Sci. 2016, 478, 374., ¹¹⁹119 Castro, K. A. D. F.; Bail, A.; Groszewicz, P. B.; Machado, G. S.; Schreiner, W. H.; Wypych, F.; Nakagaki, S.; Appl. Catal., A 2010, 386, 51., ¹²⁵125 Halma, M.; Castro, K. A. D. F.; Prevot, V.; Forano, C.; Wypych, F.; Nakagaki, S.; J. Mol. Catal. A: Chem. 2009, 310, 42. 126 Nakagaki, S.; Castro, K. A. D. F.; Ucoski, G. M.; Halma, M.; Prevot, V.; Forano, C.; Wypych, F.; J. Braz. Chem. Soc. 2014, 25, 2329. 127 Nakagaki, S.; Halma, M.; Bail, A.; Arizaga, G. G.; Wypych, F.; J. Colloid Interface Sci. 2005, 281, 417. 128 Wypych, F.; Bail, A.; Halma, M.; Nakagaki, S.; J. Catal. 2005, 234, 431.-¹²⁹129 Mantovani, K. M.; Westrup, K. C. M.; da Silva Jr., R. M.; Jaerger, S.; Wypych, F.; Nakagaki, S.; Dalton Trans. 2018, 47, 3068.
Alumina	commercial	¹³⁰130 Saltarelli, M.; de Faria, E. H.; Ciuffi, K. J.; Nassar, E. J.; Trujillano, R.; Rives, V.; Vicente, M. A.; Mol. Catal. 2019, 462, 114.
Aluminosilicate	solid obtained by sol-gel process	¹³¹131 Machado, G. S.; Castro, K. A. D. F.; de Lima, O. J.; Nassar, E. J.; Ciuffi, K. J.; Nakagaki, S.; Colloids Surf., A 2009, 349, 162.
ZnO	nanostructures	¹³²132 Ribeiro, V. G. P.; Marcelo, A. M. P.; da Silva, K. T.; da Silva, F. L. F.; Mota, J. P. F.; do Nascimento, J. P. C.; Sombra, A. S. B.; Clemente, C. D. S.; Mele, G.; Carbone, L.; Mazzetto, S. E.; Materials 2017, 10, 1114.
ZnO	prepared by in situ thermal decomposition of LHS	¹³³133 Machado, G. S.; Wypych, F.; Nakagaki, S.; J. Colloid Interface Sci. 2012, 377, 379.
TiO₂	polycrystalline anatase phase	¹³⁴134 Vasapollo, G.; Mele, G.; Sole, R. D.; Pio, I.; Li, J.; Mazzetto, S. E.; Molecules 2011, 16, 5769.
Carbon nanotubes	multi-wall carbon nanotubes (MWCNT)	¹³⁵135 Wong, A.; Sotomayor, M. D. T.; Sens. Actuators, B 2013, 181, 332. 136 Safar, G. A. M.; Barros, W. P.; Idemori, Y. M.; CarvalhoDa-Silva, D.; Mendes, J. B. S.; Sinnecker, E. H. C. P.; Rebouças, J. S.; Stumpf, H. O.; J. Nanopart. Res. 2012, 14, 912.-¹³⁷137 Luz, R. C. S.; Damos, F. S.; Tanaka, A. A.; Kubota, L. T.; Gushikem, Y.; Talanta 2008, 76, 1097.
Polymeric membranes	polymeric film based on poly(dimethylsiloxane) (PDMS)	¹³⁸138 Gotardoa, M. C. A. F.; Guedes, A. A.; Schiavon, M. A.; José, N. A.; Valeria, I.; Yoshida, P.; Assis, M. D.; J. Mol. Catal. A: Chem. 2005, 229, 137.
Chitosan	film	¹³⁹139 Castro, K. A. D. F.; Moura, N. M. M.; Fernandes, A.; Faustino, M. A. F.; Simões, M. M. Q.; Cavaleiro, J. A. S.; Nakagaki, S.; Almeida, A.; Cunha, Â.; Silvestre, A. J. D.; Freire, C. S. R.; Pinto, R. J. B.; Neves, M. G. P. M. S.; Dyes Pigm. 2017, 137, 265.

Catalyst	Yield (darkness)^c,d / %		A + K^a a Reaction conditions:123 catalyst/oxidant/cyclohexane molar ratio of 1:50:5000. The reactions were carried out in a dichloromethane/acetonitrile mixture (1:1, v/v) at room temperature for 1 h. Homogeneous and heterogeneous catalysis reactions were performed using the same experimental conditions; total yield / %	A/K ratio	Yield (assisted by artificial radiation)^c c yields based on the amount of PhIO used in the reaction as oxidant; ,^d d A = cyclohexanol and K = cyclohexanone; / %		A + K total yield / %	A/K ratio
Catalyst	A	K		A/K ratio	A	K	A + K total yield / %	A/K ratio
MnP^b b homogeneous phase catalysis using FeP and MnP as catalysts;	14.2	2.84	17.0	5.0	4.21	3.80	8.01	1.1
FeP^b b homogeneous phase catalysis using FeP and MnP as catalysts;	3.00	1.00	4.00	3.0	8.10	5.90	14.0	1.4
MnP-C	18.3	2.33	20.6	7.8	50.3	13.8	64.1	3.6
FeP-C	14.9	0.53	15.4	26	25.4	17.6	43.0	1.5
FeP-MnP-C	20.0	0.93	20.9	21	80.2	19.7	100	4.1
C^e e control reactions in the absence of catalyst MP: C = solid C + substrate + PhIO and PhIO = substrate + PhIO.	1.19	0.95	2.14	1.2	20.8	17.4	38.2	1.2
PhIO^e e control reactions in the absence of catalyst MP: C = solid C + substrate + PhIO and PhIO = substrate + PhIO.	-	-	-	-	28.9	17.8	46.7	1.6

Catalyst^a a Reaction conditions: purged argon, catalyst/oxidant/heptane molar ratio = 1:10:1000; solvent mixture dichloromethane/acetonitrile 1:1 (v/v) at room temperature (yields obtained after 1 h of reaction based on starting PhIO);	time / h	Alcohol yield / %			Total yield / %
	time / h	1-ol^c	2-ol^d	3-ol^e	Alcohol^f f total alcohol yield;.	Ketone^g g total ketone (one) yield (4-heptanone). In this work, the alcohol in position 4 was not monitored.
[Fe(TDFSPP)]^b b homogeneous catalysis was carried out under identical conditions, in dichloromethane/acetonitrile 1:1 solvent mixture (v/v);	1	2	3	3	8	< 1
	24	3	4	3	10	< 1
[Fe(TDFSPP)]-3DM-MOXLDH	1	2	6	5	13	2
[Fe(TDFSPP)]-3DM-MOXLDH	24	12	4	4	20	2

Catalyst^a a Oxidation of n-hexane by PhIO catalyzed by MnP in homogeneous and heterogeneous systems. Reaction conditions: catalyst/oxidant/substrate molar ratio of 1:50:2500. The reactions were carried out in a solvent mixture of acetonitrile/dichloromethane (1:1, v/v), at room temperature, under argon for 1 h;	n-Hexane alcohol yield^c c yields based on the starting PhIO. All catalysts tested showed no detectable ketone production; / %			Alcohol total yield^c c yields based on the starting PhIO. All catalysts tested showed no detectable ketone production; / %
	1-ol^d	2-ol^e	3-ol^f
MnP1^b b homogeneous catalysis was performed under conditions identical to those employed for the heterogeneous catalysis;	-	0.3	0.7	1.0
MnP1-SBA-Si-Mag	-	1.5	2.5	4.0
MnP2^b b homogeneous catalysis was performed under conditions identical to those employed for the heterogeneous catalysis;	-	0.5	1.3	1.8
MnP2-SBA-Si-Mag	5.7	1.1	1.4	8.2

[1] *e-mail: shirleyn@ufpr.br, gneves@ua.pt; yassuko.iamamoto@gmail.com

Brasil

Brasil

The Research on Porphyrins and Analogues in Brazil: A Small Review Covering Catalytic and other Applications since the Beginning at Universidade de São Paulo in Ribeirão Preto until the Joint Venture between Brazilian Researchers and Colleagues from Universidade de Aveiro, Portugal