Search Results (6)

An efficient protocol was developed for the microwave-mediated metallation of 5-(4-methoxycarbonylphenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (P1) with bis(benzonitrile)platinum dichloride salt and subsequent 1,3-dipolar cycloaddition of the resulting PtP1 with an azomethine ylide to give two isomeric metallochlorins: PtC1 (main isomer) and PtC3. The methyl ester group of metalloporphyrin PtP1 and metallochlorin PtC1 was successfully hydrolysed in an alkaline medium to yield the corresponding derivatives PtP2 and PtC2 in moderate-to-good yields. As a proof of concept of the reactivity of the carboxy group in PtP2 and PtC2, these compounds were conjugated with a hydroxylated derivative of indomethacin, a known potent non-steroidal anti-inflammatory, obtaining the conjugates PtP2-Ind and PtC2-Ind. The obtained platinum(II) porphyrins and chlorins were characterized by UV-Vis, NMR spectroscopy and mass spectrometry. The structure of PtP1 was also confirmed by X-ray crystallography. Singlet oxygen generation studies were carried out, as well as theoretical calculations, which demonstrated that the prepared Pt(II) complexes can be considered potential photosensitizers for PDT. Full article

Metalloporphyrins are highly recognized for their capacity to act as sensitive substances used in formulation of optical, fluorescent, and electrochemical sensors. A novel compound, namely Pt(II)-5,10,15,20-tetra-(4-allyloxy-phenyl) porphyrin, was synthesized by metalation with PtCl₂(PhCN)₂ of the corresponding porphyrin base and was fully characterized by UV-vis, fluorimetry, FT-IR, ¹H-NMR, and ¹³C-NMR methods. The fluorescence response of this Pt-porphyrin in the presence of different concentrations of hydrogen peroxide was investigated. Besides, modified glassy carbon electrodes with this Pt-porphyrin (Pt-Porf-GCE) were realized and several electrochemical characterizations were comparatively performed with bare glassy carbon electrodes (GCE), in the absence or presence of hydrogen peroxide. The Pt-porphyrin demonstrated to be a successful sensitive material for the detection of hydrogen peroxide both by fluorimetric method in a concentration range relevant for biological samples (1.05–3.9 × 10⁻⁷ M) and by electrochemical method, in a larger concentration range from 1 × 10⁻⁶ M to 5 × 10⁻⁵ M. Based on different methods, this Pt-porphyrin can cover detection in diverse fields, from medical tests to food and agricultural monitoring, proving high accuracy (correlation coefficients over 99%) in both fluorimetric and electrochemical measurements. Full article

Bromide ions are present in many environments, such as sedative drugs, methyl-bromide-treated vegetables and seawater. Excess bromide in humans interferes with iodide metabolism and is considered toxic. The need for fast and inexpensive methods for bromide detection is of interest. Spectrophotometric detection methods provide accurate and sensitive results. The well-known ability of metalloporphyrins to bind anionic ligands to the central metal ion has been exploited. The changes in the optical properties of Pt(II) 5,10,15,20-tetra(4-methoxy-phenyl)-porphyrin (PtTMeOPP) under the influence of bromide ions allowed us to achieve a fast, simple and reliable UV-vis spectrophotometric method of detection with a detection limit of 2.5 × 10⁻⁸ M and a good confidence coefficient: 99.05%. The potential interfering ions, such as Cl⁻, I⁻, NO₂⁻, NO₃⁻, SCN⁻, SO₃²⁻, SO₄²⁻ and PO₄³⁻ of 100-fold higher and Cl⁻ and R-S⁻ of 1000-fold higher concentrations in the mixture as compared to the determined concentration of bromide ions (c = 10⁻⁵ M), were tested and did not influence the results. The behavior of the sensitive porphyrin in various pH media was investigated in order to determine their influence upon the bromide detection capacity. Full article

The development of UV–vis spectrophotometric methods based on metalloporphyrins for fast, highly sensitive and selective anion detection, which avoids several of the practical challenges associated with other detection methods, is of tremendous importance in analytical chemistry. In this study, we focused on achieving a selective optical sensor for triiodide ion detection in traces based on a novel hybrid material comprised of Pt(II) 5,10,15,20-tetra(4-methoxy-phenyl)-porphyrin (PtTMeOPP) and gold nanoparticles (AuNPs). This sensor has high relevance in medical physiological tests. The structure of PtTMeOPP was investigated by single crystal X-ray diffraction in order to understand the metal surroundings and the molecule conformation and to assess if it qualifies as a potential sensitive material. It was proven that the Pt-porphyrin generated 1D H-bond supramolecular chains due to the weak C-H···O intermolecular hydrogen bonding. The presence of ordered voids in the crystal encouraged us to use PtTMeOPP as the sensing material for triiodide ion and to enhance its potential in a novel AuNPs/PtTMeOPP hybrid by the synergistic effects provided by the plasmonic gold nanoparticles. The spectrophotometric sensor is characterized by a detection limit of 1.5 × 10⁻⁹ M triiodide ion concentration and a remarkable confidence coefficient of 99.98%. Full article

Pt(II) 5,10,15,20-tetra(4-methoxy-phenyl)-porphyrin (PtTMeOPP) was used in the construction of new ion-selective sensors. The potentiometric response characteristics (slope and selectivity) of iodide and bromide-selective electrodes based on (PtTMeOPP) metalloporphyrin in o-nitrophenyloctylether (NPOE), dioctylphtalate (DOP) and dioctylsebacate (DOS) plasticized poly(vinyl chloride) membranes are compared. The best results were obtained for the membranes plasticized with DOP and NPOE. The sensors have linear responses with near-Nernstian slopes toward bromide and iodide ions and good selectivity. The membrane plasticized with NPOE was electrochemically characterized using the EIS method to determine its water absorption and the diffusion coefficient into the membrane. Full article

This paper presents a gaseous oxygen detection system based on time-resolved phosphorimetry (time-domain), which is used to investigate O${}_2$ optical transducers. The primary sensing elements were formed by incorporating iridium(III) and palladium(II) meso-tetrakis(pentafluorophenyl)porphyrin complexes (IrTFPP-CO-Cl and PdTFPP) in polystyrene (PS) solid matrices. Probe excitation was obtained using a violet light-emitting diode (LED) (low power), and the resulting phosphorescence was detected by a high-sensitivity compact photomultiplier tube. The detection system performance and the preparation of the transducers are presented along with their optical properties, phosphorescence lifetimes, calibration curves and photostability. The developed lifetime measuring system showed a good signal-to-noise ratio, and reliable results were obtained from the optodes, even when exposed to moderate levels of O${}_2$. The new IrTFPP-CO-Cl membranes exhibited room temperature phosphorescence and moderate sensitivity: <${\tau }_0$>/<${\tau }_{21\%}$> ratio of ≈6. A typically high degree of dynamic phosphorescence quenching was observed for the traditional indicator PdTFPP: <${\tau }_0$>/<${\tau }_{21\%}$> ratio of ≈36. Pulsed-source time-resolved phosphorimetry combined with a high-sensitivity photodetector can offer potential advantages such as: (i) major dynamic range, (ii) extended temporal resolution ($\Delta$$\tau$/$\Delta$[O${}_2$]) and (iii) high operational stability. IrTFPP-CO-Cl immobilized in polystyrene is a promising alternative for O${}_2$ detection, offering adequate photostability and potentially mid-range sensitivity over Pt(II) and Pd(II) metalloporphyrins. Full article