Eugenia Fagadar-Cosma

The optical detection of thioacetamide was investigated using a metalated porphyrin, Mn(III)-5,10,15,20-tetrakis-(3,4-dimethoxyphenyl)-21H,23H-porphyrin chloride (Mn-3,4-diMeOPP), a gold colloid solution (AuNPs), and a complex formed between them (Mn-3,4-diMeOPP–AuNPs) in order to select the most sensitive material and to achieve complementarity between methods. Mn-3,4-diMeOPP, AuNPs, and their complex were synthesized and characterized by means of UV–Vis, FT-IR spectrometry, and AFM investigations. It could be concluded that Mn-3,4-diMeOPP could detect/quantify thioacetamide (TAA) in the range 3.13 × 10⁻⁸ M–7.67 × 10⁻⁷ M in a linear fashion, with a 99.85% confidence coefficient. The gold colloidal particles alone could detect TAA in an extremely narrow concentration domain of 2–9.8 × 10⁻⁷ M, slightly complementary with that of Mn-3,4-diMeOPP. The complex between Mn-3,4-diMeOPP and gold colloid proved to be able to quantify TAA in the trace domain with concentrations of 1.99 × 10⁻⁸ M–1.76 × 10⁻⁷ M in a polynomial fashion, with the method being more difficult. A potential mechanism for TAA detection based on Mn-3,4-diMeOPP is discussed based on computational modeling. The distorted porphyrin conformation and its electronic configuration favor the generation of a grid of electrostatic interactions between porphyrin and TAA.

A paramagnetic A₃B-type Mn(III)-porphyrin was synthesized and characterized by physical–chemical methods (UV-Vis, FT-IR, ¹H-NMR spectroscopy). The obtained compound was tested as a sensitive material for the spectrophotometric and potentiometric detection of iodine species. Using UV-Vis spectroscopy, the triiodide anions could be detected with high precision in the concentration interval of 1.02 × 10⁻⁵ to 2.3 × 10⁻⁵ M, with an LOD of 9.44 × 10⁻⁶ M. The PVC-based electrode using DOP as a plasticizer showed a sensitivity toward iodide in a wide concentration range of 1.0 × 10⁻⁵ to 1.0 × 10⁻¹ M, with an LOD of 8.0 × 10⁻⁶ M. Both methods are simple, low-cost, and efficient for the detection of iodine species in synthetic samples and pharmaceuticals.

In the context of water electrolysis being highlighted as a promising technology for the large-scale sustainable production of hydrogen, the water-splitting electrocatalytic properties of an asymmetrically functionalized A₃B zinc metalated porphyrin, namely, Zn(II) 5-(4-pyridyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin, were evaluated in a wide pH range. Two different electrode manufacturing procedures were employed to outline the porphyrin’s applicative potential for the O₂ and H₂ evolution reactions (OER and HER). The electrode, manufactured by coating the catalyst on a graphite support from a dimethylsulfoxide solution, displayed electrocatalytic activity for the OER in an acidic electrolyte. An overpotential value of 0.44 V (at i = 10 mA/cm²) and a Tafel slope of 0.135 V/dec were obtained. The modified electrode that resulted from applying a Zn(II)-porphyrin-containing catalyst ink onto the same substrate type was identified as a bifunctional water-splitting catalyst in a neutral medium. OER and HER overpotentials of 0.78 and 1.02 V and Tafel slopes of 0.39 and 0.249 V/dec were determined. This is the first Zn(II)-porphyrin to be reported as a heterogenous bifunctional water-splitting electrocatalyst in neutral aqueous electrolyte solution and is one of very few porphyrins behaving as such. The TEM analysis of the porphyrin’s self-assembly behavior revealed a wide variety of architectures.

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 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.

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.

Active and stable materials that utilize solar radiation for promoting different reactions are critical for emerging technologies. Two of the most common polymeric carbon nitrides were prepared by the thermal polycondensation of melamine. The scope of this work is to investigate possible structural degradation before and after photoelectrochemical testing. The materials were characterized using synchrotron radiation and lab-based techniques, and subsequently degraded photoelectrochemically, followed by post-mortem analysis. Post-mortem investigations reveal: (1) carbon atoms bonded to three nitrogen atoms change into carbon atoms bonded to two nitrogen atoms and (2) the presence of methylene terminals in post-mortem materials. The study concludes that polymeric carbon nitrides are susceptible to photoelectrochemical degradation via ring opening.

A new sensing material, Pt(II)-5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin (Pt(II)-COOH-TPOPP), was synthesized and characterized. Polymeric membranes containing the porphyrin and three different plasticizers were used as an electroactive material for a new anion-selective sensor. The best composition of the membrane was the one plasticized with dioctylsebacate (DOS), the obtained sensor being citrate-selective in a linear range of 5 × 10⁻⁷–1 × 10⁻¹ M citrate. The slope was Nernstian (19.73 mV/decade) with good selectivity towards a number of interfering anions and a lifetime of five weeks.

In response to the escalating global energy requests and the need to address them in a sustainable manner, researchers have identified hydrogen as an energy vector that provides a practical way to store and use energy from renewable sources. To make a step forward, the electrocatalytic properties for the hydrogen evolution reaction in an alkaline medium of graphite electrodes modified with combinations of nickel phosphite and free-base porphyrins were investigated voltammetrically. The sample obtained by combining the respective phosphite with 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin exhibited the highest catalytic activity, surpassing that observed for the specimens manufactured using the individual catalysts and thus providing enhanced water-splitting performance. The best electrode displayed an overpotential of 0.43 V (at i = −10 mA/cm²) and a Tafel slope of 0.14 V/dec. Since the catalytic activity of the compositions containing the metal salt and the porphyrins has not been previously studied, the investigation and its outcome constitute an original contribution to the growing water-splitting literature, providing new opportunities for obtaining better results than the ones reported for electrodes modified solely with the phosphite.

The combination of a metallated porphyrin, Pt(II)-5,10,15,20-tetrakis-(4-allyloxyphenyl)-porphyrin (Pt-allyloxyPP), and a water-soluble porphyrin, 5,10,15,20-tetrakis(4-sulfonatophenyl)-porphyrin (TSPP), leads to the formation of a porphyrin hetero-trimer. The hetero-trimer, consisting of two TSPP molecules linked via oxygen atoms axially to the platinum atom in the Pt-allyloxyPP molecule, was characterized by UV–Vis, FT-IR, fluorescence, and ¹H-NMR spectroscopy, and the proposed structure was confirmed. The new porphyrin hetero-trimer offers both the advantage of enhanced fluorescence and the presence of multiple sites for the detection of toluidine blue, due to its high affinity for acidic binding sites. This work brings attention to the purposely designed fluorescent sensor for toluidine blue, in the biologically relevant concentration domain of 1.9 × 10⁻⁶–6.39 × 10⁻⁵ M, with a very good accuracy.