Nanomaterials Based on 2,7,12,17-Tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphine Exhibiting Bifunctional Sensitivity for Monitoring Chloramphenicol and Co2.

Monitoring antibiotic retention in human body fluids after treatment and controlling heavy metal content in water are important requirements for a healthy society. Therefore, the approach proposed in this study is based on developing new optical sensors using porphyrin or its bifunctional hybrid materials made with AuNPs to accomplish the accurate detection of chloramphenicol and cobalt. To produce the new optical chloramphenicol sensors, 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphine (TBAP) was used, both alone in an acid medium and as a hybrid material with AuNPs in a water-DMSO acidified environment. The same hybrid material in the unchanged water-DMSO medium was the sensing material used for Co2+ monitoring. The best results of the hybrid materials were explained by the synergistic effects between the TBAP azaporphyrin and AuNPs. Chloramphenicol was accurately detected in the range of concentrations between 3.58 × 10-6 M and 3.37 × 10-5 M, and the same hybrid material quantified Co2+ in the concentration range of 8.92 × 10-5 M-1.77 × 10-4 M. In addition, we proved that AuNPs can be used for the detection of azaporphyrin (from 2.66 × 10-5 M to 3.29 × 10-4 M), making them a useful tool to monitor porphyrin retention after cancer imaging procedures or in porphyria disease. In conclusion, we harnessed the multifunctionality of this azaporphyrin and of its newly obtained AuNP plasmonic hybrids to detect chloramphenicol and Co2+ quickly, simply, and with high precision.

The Influence of the Nature of the Polymer Incorporating the Same A3B Multifunctional Porphyrin on the Optical or Electrical Capacity to Recognize Procaine.

The multifunctionality of an A3B mixed-substituted porphyrin, namely 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin (5-COOH-3MPP), was proven due to its capacity to detect procaine by different methods, depending on the polymer matrix in which it is incorporated. The hybrid nanomaterial containing k-carrageenan and AuNPs (5-COOH-3MPP-k-carrageenan-AuNPs) was able to optically detect procaine in the concentration range from 5.76 × 10-6 M to 2.75 × 10-7 M, with a limit of detection (LOD) of 1.33 × 10-7 M. This method for the detection of procaine gave complementary results to the potentiometric one, which uses 5-COOH-3MPP as an electroactive material incorporated in a polyvinylchloride (PVC) membrane plasticized with o-NPOE. The detected concentration range by this ion-selective membrane electrode is wider (enlarged in the field of higher concentrations from 10-2 to 10-6 M), linearly dependent with a 53.88 mV/decade slope, possesses a detection limit of 7 × 10-7 M, a response time of 60 s, and has a certified stability for a working period of six weeks.

Nanomaterials Based on Collaboration with Multiple Partners: Zn3Nb2O8 Doped with Eu3+ and/or Amino Substituted Porphyrin Incorporated in Silica Matrices for the Discoloration of Methyl Red.

Designing appropriate materials destined for the removal of dyes from waste waters represents a great challenge for achieving a sustainable society. Three partnerships were set up to obtain novel adsorbents with tailored optoelectronic properties using silica matrices, Zn3Nb2O8 oxide doped with Eu3+, and a symmetrical amino-substituted porphyrin. The pseudo-binary oxide with the formula Zn3Nb2O8 was obtained by the solid-state method. The doping of Zn3Nb2O8 with Eu3+ ions was intended in order to amplify the optical properties of the mixed oxide that are highly influenced by the coordination environment of Eu3+ ions, as confirmed by density functional theory (DFT) calculations. The first proposed silica material, based solely on tetraethyl orthosilicate (TEOS) with high specific surface areas of 518-726 m2/g, offered better performance as an adsorbent than the second one, which also contained 3-aminopropyltrimethoxysilane (APTMOS). The contribution of amino-substituted porphyrin incorporated into silica matrices resides both in providing anchoring groups for the methyl red dye and in increasing the optical properties of the whole nanomaterial. Two different types of methyl red adsorption mechanisms can be reported: one based on surface absorbance and one based on the dye entering the pores of the adsorbents due to their open groove shape network.

One A3B Porphyrin Structure-Three Successful Applications.

Porphyrins are versatile structures capable of acting in multiple ways. A mixed substituted A3B porphyrin, 5-(3-hydroxy-phenyl)-10,15,20-tris-(3-methoxy-phenyl)-porphyrin and its Pt(II) complex, were synthesised and fully characterised by 1H- and 13C-NMR, TLC, UV-Vis, FT-IR, fluorescence, AFM, TEM and SEM with EDX microscopy, both in organic solvents and in acidic mediums. The pure compounds were used, firstly, as sensitive materials for sensitive and selective optical and fluorescence detection of hydroquinone with the best results in the range 0.039-6.71 µM and a detection limit of 0.013 µM and, secondly, as corrosion inhibitors for carbon-steel (OL) in an acid medium giving a best performance of 88% in the case of coverings with Pt-porphyrin. Finally, the electrocatalytic activity for the hydrogen and oxygen evolution reactions (HER and OER) of the free-base and Pt-metalated A3B porphyrins was evaluated in strong alkaline and acidic electrolyte solutions. The best results were obtained for the electrode modified with the metalated porphyrin, drop-casted on a graphite substrate from an N,N-dimethylformamide solution. In the strong acidic medium, the electrode displayed an HER overpotential of 108 mV, at i = -10 mA/cm2 and a Tafel slope value of 205 mV/dec.

Efficient Decrease in Corrosion of Steel in 0.1 M HCl Medium Realized by a Coating with Thin Layers of MnTa2O6 and Porphyrins Using Suitable Laser-Type Approaches.

The purpose of this research is to meet current technical and ecological challenges by developing novel steel coating systems specifically designed for mechanical equipment used in aggressive acid conditions. Homogeneous sandwich-type layered films on the surface of steel electrodes were realized using a pseudo-binary oxide, MnTa2O6, and two different substituted porphyrin derivatives, namely: 5-(4-carboxy-phenyl)-10,15,20-tris (4-methyl-phenyl)-porphyrin and 5-(4-methyl-benzoate)-10,15,20-tris (4-methyl-phenyl)-porphyrin, which are novel investigated compound pairs. Two suitable laser strategies, pulsed laser deposition (PLD) and matrix-assisted pulsed laser evaporation (MAPLE), were applied in order to prevent porphyrin decomposition and to create smooth layers with low porosity that are extremely adherent to the surface of steel. The electrochemical measurements of corrosion-resistant coating performance revealed that in all cases in which the steel electrodes were protected, a significant value of corrosion inhibition efficiency was found, ranging from 65.6 to 83.7%, depending on the nature of the porphyrin and its position in the sandwich layer. The highest value (83.7%) was obtained for the MAPLE/PLD laser deposition of 5-(4-carboxy-phenyl)-10,15,20-tris (4-methyl-phenyl)-porphyrin/MnTa2O6(h), meaning that the inhibitors adsorbed and blocked the access of the acid to the active sites of the steel electrodes.

Hybrid Silica Materials Applied for Fuchsine B Color Removal from Wastewaters.

Hybrid materials, with applications in fuchsine B color removal from wastewaters, were obtained by in situ incorporation of platinum nanoparticles and/or Pt-porphyrin derivatives into silica matrices. The inorganic silica matrices were synthesized by the sol-gel method, conducted in acid-base catalysis in two steps and further characterized by Nitrogen porosimetry, Small Angle Neutron Scattering (SANS), Scanning electron microscopy, Atomic force microscopy and UV-vis spectroscopy. All of the investigated silica hybrid materials were 100% efficient in removing fuchsine B if concentrations were lower than 1 × 10-5 M. For higher concentrations, the silica matrices containing platinum, either modified with Pt-metalloporphyrin or with platinum nanoparticles (PtNPs), are the most efficient materials for fuchsine B adsorption from wastewaters. It can be concluded that the presence of the platinum facilitates chemical interactions with the dye molecule through its amine functional groups. An excellent performance of 197.28 mg fuchsine B/g adsorbent material, in good agreement with the best values mentioned in literature, was achieved by PtNPs-silica material, capable of removing the dye from solutions of 5 × 10-4 M, even in still conditions.

Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal.

Multifunctional hybrid materials with applications in gas sensing or dye removal from wastewaters were obtained by incorporation into silica matrices of either Pt(II)-5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (PtTAOPP) or platinum nanoparticles (PtNPs) alone or accompanied by 5,10,15,20-tetra-(4-allyloxy-phenyl)-porphyrin (TAOPP). The tetraethylorthosilicate (TEOS)-based silica matrices were obtained by using the sol-gel method performed in two step acid-base catalysis. Optical, structural and morphological properties of the hybrid materials were determined and compared by UV-vis, fluorescence and FT-IR spectroscopy techniques, by atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM) and by Brunauer-Emmett-Teller (BET) analysis. PtTAOPP-silica hybrid was the most efficient material both for CO2 adsorption (0.025 mol/g) and for methylene blue adsorption (7.26 mg/g) from wastewaters. These results were expected due to both the ink-bottle mesopores having large necks that exist in this hybrid material and to the presence of the porphyrin moiety that facilitates chemical interactions with either CO2 gas or the dye molecule. Kinetic studies concerning the mechanism of dye adsorption demonstrated a second order kinetic model, thus it might be attributed to both physical and chemical processes.