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
Abstract:The synthetic versatility and the potential applications of porphyrins and analogues in different fields have aroused special interest in their study, especially to mimic biological systems, such as cytochrome P-450. The ability of the porphyrin tetrapyrrolic core to accommodate metal ions of varying charges can modulate the type of application of these compounds. As a contribution, in this special number in honor to the Brazilian women who have devoted their lives to the growth and dissemination of chemistry … Show more
“…The chemical structures of a cellulose molecule and the porphyrin-type molecules used as analytes are shown in Figure a,b, respectively. In the study, we used a wide variety of porphyrins, including neutral hydrophobic tetraphenyl porphyrin (TPP), as well as water-soluble molecules: two cationic species (TMPyP neutralized by Cl – ions and TMAP with p -toluenesulfonic acid used as counterion) and two anionic species (TPPS neutralized by Na + and TCPP neutralized by H + ). , The cellulose nanofiber (CNF) platform was prepared by drop-casting a nanofiber dispersion on a silicon piece and drying out the solvent. Figure c shows a scanning electron microscopy (SEM) image of the substrate fabricated using a highly concentrated (1 wt %) cellulose dispersion showing a thick layer of randomly distributed nanofibers.…”
The detection of analytes using spectroscopy methods, such as surface-enhanced Raman spectroscopy (SERS), is crucial in the fields of medical diagnostics, forensics, security, and environmental monitoring. In recent years, a lot of focus has been directed toward organic polymer material-based SERS platforms due to their lower cost, controllable synthesis and fabrication, structural versatility, as well as biocompatibility and biodegradability. Here, we report that cellulose nanofiber-based substrates can be used as a metal-free SERS platform for the detection of porphyrin-type molecules. We report SERS signal enhancement for five different porphyrin molecules with exceptional 2 orders of magnitude peak intensity enhancement observed resulting in a detection limit of 10 −5 M. We show that the cellulose-based platform is more suitable for porphyrin molecule detection than traditionally used semiconductor materials like graphene oxide. The observed enhancement is attributed to the disturbed growth of self-assembled structures on the cellulose nanofibers and the generation of disordered 3D clusters of porphyrin molecules.
“…The chemical structures of a cellulose molecule and the porphyrin-type molecules used as analytes are shown in Figure a,b, respectively. In the study, we used a wide variety of porphyrins, including neutral hydrophobic tetraphenyl porphyrin (TPP), as well as water-soluble molecules: two cationic species (TMPyP neutralized by Cl – ions and TMAP with p -toluenesulfonic acid used as counterion) and two anionic species (TPPS neutralized by Na + and TCPP neutralized by H + ). , The cellulose nanofiber (CNF) platform was prepared by drop-casting a nanofiber dispersion on a silicon piece and drying out the solvent. Figure c shows a scanning electron microscopy (SEM) image of the substrate fabricated using a highly concentrated (1 wt %) cellulose dispersion showing a thick layer of randomly distributed nanofibers.…”
The detection of analytes using spectroscopy methods, such as surface-enhanced Raman spectroscopy (SERS), is crucial in the fields of medical diagnostics, forensics, security, and environmental monitoring. In recent years, a lot of focus has been directed toward organic polymer material-based SERS platforms due to their lower cost, controllable synthesis and fabrication, structural versatility, as well as biocompatibility and biodegradability. Here, we report that cellulose nanofiber-based substrates can be used as a metal-free SERS platform for the detection of porphyrin-type molecules. We report SERS signal enhancement for five different porphyrin molecules with exceptional 2 orders of magnitude peak intensity enhancement observed resulting in a detection limit of 10 −5 M. We show that the cellulose-based platform is more suitable for porphyrin molecule detection than traditionally used semiconductor materials like graphene oxide. The observed enhancement is attributed to the disturbed growth of self-assembled structures on the cellulose nanofibers and the generation of disordered 3D clusters of porphyrin molecules.
“…11 Since then, different strategies have been implemented by the scientific community to increase the efficiency of these catalytic systems, such as the introduction of functional groups on the periphery of the porphyrin macrocycle, 8 the use of additives such as imidazole and water 12,13 and immobilization on different inorganic and/ or organic supports. 14 The immobilization of metalloporphyrins on chemical supports and their use in heterogeneous catalytic processes appears as an alternative to overcome the limitations inherent to homogeneous systems. 15−21 A variety of supports, both organic and inorganic, have been used to anchor (immobilize and support) metalloporphyrins.…”
Section: Introductionmentioning
confidence: 99%
“…The use of metalloporphyrins as CYP biomimetic catalysts has been carried out since the 1980s . Since then, different strategies have been implemented by the scientific community to increase the efficiency of these catalytic systems, such as the introduction of functional groups on the periphery of the porphyrin macrocycle, the use of additives such as imidazole and water , and immobilization on different inorganic and/or organic supports …”
A heterogenized Mn(III) porphyrin-based catalyst was prepared for dye degradation. The new Mn(III) complex of 5,15-bis(4-aminophenyl)-10,20-diphenylporphyrin was immobilized, via covalent bond, in chloropropyl silica gel, generating the material (Sil-Cl@MnP) with a loading of 23 μmol manganese porphyrin (MnP) per gram of Sil-Cl. This material was used as a catalyst in degradation reactions of model dyes, a cationic dye [methylene blue (MB)] and an anionic dye (reactive red 120, RR120), using PhI(OAc) 2 and H 2 O 2 as oxidants. The oxidation reactions were carried out after the dye reached adsorption/ desorption equilibrium with the catalytic material, with a much higher percentage of adsorption being observed for the cationic MB dye (20%) than for the anionic RR120 dye (3%), which may be associated with electrostatic attraction or repulsion effects, respectively, with the negatively charged surface of the silica (zeta potential measurement for Sil-Cl@MnP, ζ = −19.2 mV). In general, there was a higher degradation percentage for MB than for RR120, probably because the size and charge of RR120 would hinder its approach to the MnP active species on the silica surface. With respect to the oxidant, the PhI(OAc) 2 -based systems showed a higher degradation percentage than those of H 2 O 2 . It was observed that the increase in the oxidant concentration promoted a significant increase in the degradation of MB, with a degradation of approximately 65%. The efficiency of the catalyst was also evaluated after successive additions of the oxidant every 2 h, and it can be seen that the catalyst had no loss of efficiency, with a degradation percentage greater than 80% being observed after 8 h of reaction. The phytotoxicity of the products formed in the system was evaluated in a 1:23.5:188 molar ratio Sil-Cl@MnP: MB:PhI(OAc) 2 was used. In these studies, phytotoxicity was found for the germination of lettuce seeds when the original solution was used without dilution; however, when diluted (10% V/V), the results were close to the positive and negative controls. Thus, the material obtained proved to be a potential candidate for application in the degradation reactions of environmental pollutants.
“…Metalloporphyrins and analogues have already proved their efficiency as catalysts, namely for oxidative reactions [11][12][13][14][15][16][17][18][19][20]. Porphyrins are also efficient producers of reactive oxygen species (ROS) in the presence of light, such as singlet oxygen ( 1 O2) [21][22][23][24], thus inducing many photocatalytic reactions [25,26].…”
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