Search Results (30)

The use of pressure-sensitive paints (PSPs), an optical oxygen sensing technique, to visualise and measure the surface pressure on vehicle models in wind tunnel testing is becoming increasingly prevalent. Porphyrins have long been the standard luminophore for PSP formulations, with the majority employing the red-emitting platinum(II)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorphenyl)-porphyrin. nIR-emitting luminophores, such as Pt(II) tetraphenyl tetrabenzoporphyrins, possess distinct advantages over visible emitting luminophores. In particular, they have wider spectrally useful ‘windows’, facilitating the insertion of a secondary visible emitting temperature-sensitive luminophore to be used for internal calibration without spectral crosstalk that detrimentally impacts PSP performance. In this work, we explore the effect of changing the loading quantity of an nIR-emitting para-CF₃ Pt(II) benzoporphyrin luminophore on the performance of PSP formulations. An optimal luminophore loading of 1.28% wt/wt benzoporphyrin luminophore to polystyrene binder was identified, resulting in a low temperature sensitivity at 100 kPa of 0.61%/K and a large pressure sensitivity at 293 K of 0.740%/kPa. These strong performance metrics, for a polystyrene-based PSP, demonstrate the efficacy of benzoporphyrin luminophores as an attractive luminophore option for the development of a new generation of high-performance PSP formulations that outperform current commercially available ones. Full article

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

The popular method of micro-respirometry (μR) for measuring total viable (aerobic) count (TVC) utilises luminescence-based O₂ sensors that are difficult to fabricate and therefore expensive. A simple method is described for making inexpensive, ink-based potential substitutes that utilise the same O₂-sensitive dyes. The sensitivity of such inks is readily increased by using dyes with a long lifetime in the absence of O₂, τ_o, and/or an ink resin/polymer with a high O₂ permeability, P_m(O₂). Response modelling of the μR-based TVC system and subsequent testing using a range of O₂ sensors of different sensitivity show that there is little to be gained by making the O₂ sensor either very sensitive or insensitive, and that the best O₂ sensors are dyes such as Pt(II) tetraphenyltetrabenzoporphyrin (PtBP), with τ_o = ca. 40–50 μs. Further work shows that a simple-to-make PtBP ink can be used as a direct replacement for the expensive O₂ sensor used in commercial instruments for measuring TVC based on μR. In addition, the PtBP can be replaced by an even less expensive O₂-sensitive dye, Pt(II) meso-tetra(pentafluorophenyl)porphyrin (PtTFPP). The potential use of inexpensive O₂-sensitive inks as an alternative to any expensive commercial counterpart based on the same O₂-sensitive dye is discussed briefly. Full article

The interaction of a series of metal derivatives of 5, 10, 15, 20-tetrakis(4-sulfonato-phenyl)porphyrin (MTPPS₄, M = Cu(II), Pt(II), Ni(II), Zn(II) and Co(II)), including the metal free porphyrin (TPPS₄), with the aromatic amino acids L-tryptophan (L-Trp), L-and D-phenylalanine (L-and D-Phe) and L-histidine (L-His) have been investigated through UV/Vis spectroscopy. The amino acid L-serine (L-Ser) has been included as reference compound. The spectroscopic changes induced by adding the amino acids have been exploited to evaluate the extent of interaction between the molecular components in the supramolecular adducts. The binding constants have been estimated for most of the investigated systems, assuming a simple 1:1 equilibrium. The bathochromic shifts of the B-bands, the extent of hypochromicity and the binding constants have been analyzed through two chemical descriptors. All the data point to the important role played by the steric hindrance introduced by axial ligands coordinated to the metal ions and to the degree of hydrophobicity and size of the aromatic moiety in the amino acids. Full article

This work presents a new optical dual sensor based on PtTFPP-containing electrospun fibers and CsPbBr₃ perovskite quantum dots (PQDs) for simultaneous detection of oxygen (O₂) and nitric oxide (NO) gases, wherein PtTFPP-containing electrospun fibers for O₂ sensing was based on electrospinning process fabricated by platinum(II) meso-tetrakis (pentafluorophenyl) porphyrin (PtTFPP) complex immobilized in cellulose acetate (CA) matrix. CsPbBr₃ PQDs were used as NO-sensitive material and coated on the surface of PtTFPP-containing electrospun fibers. Both materials were excited by a UV LED with a central wavelength of 380 nm, and the fluorescence intensities of sensing materials were recorded and analyzed with a spectrometer. The experiment results show that the optical NO and O₂ sensors have linear Stern–Volmer plots, and the sensitivities are around 2.7 and 10.7, respectively. The response and recovery times of the optical NO sensor are 71 and 109 s, respectively. For optical O₂, response and recovery times are 60 and 65 s, respectively. The optical dual sensor with a new method based on fluorescent dye containing electrospun fibers and coated with CsPbBr₃ PQDs has been successfully developed to detect NO and O₂ gases simultaneously. The optical dual gas sensor provides great potential for practical applications with low cost and ease of fabrication. Full article

We report the DNA-binding properties of three porphyrins with peripheral thienyl substituents (TThPor, PdTThPor and PtTThPor). The binding capacity of each porphyrin with DNA was determined by UV-Vis and steady-state fluorescence emission spectroscopy combined with molecular docking calculations. The results suggest that the interaction of these compounds probably occurs via secondary interactions via external grooves (minor grooves) around the DNA macromolecule. Moreover, porphyrins containing peripheral Pd(II) or Pt(II) complexes (PdTThPor and PtTThPor) were able to promote photo-damage in the DNA. Full article

Onychomycosis is a prevalent nail fungal infection, and Candida albicans is one of the most common microorganisms associated with it. One alternative therapy to the conventional treatment of onychomycosis is antimicrobial photoinactivation. This study aimed to evaluate for the first time the in vitro activity of cationic porphyrins with platinum(II) complexes 4PtTPyP and 3PtTPyP against C. albicans. The minimum inhibitory concentration of porphyrins and reactive oxygen species was evaluated by broth microdilution. The yeast eradication time was evaluated using a time-kill assay, and a checkerboard assay assessed the synergism in combination with commercial treatments. In vitro biofilm formation and destruction were observed using the crystal violet technique. The morphology of the samples was evaluated by atomic force microscopy, and the MTT technique was used to evaluate the cytotoxicity of the studied porphyrins in keratinocyte and fibroblast cell lines. The porphyrin 3PtTPyP showed excellent in vitro antifungal activity against the tested C. albicans strains. After white-light irradiation, 3PtTPyP eradicated fungal growth in 30 and 60 min. The possible mechanism of action was mixed by ROS generation, and the combined treatment with commercial drugs was indifferent. The 3PtTPyP significantly reduced the preformed biofilm in vitro. Lastly, the atomic force microscopy showed cellular damage in the tested samples, and 3PtTPyP did not show cytotoxicity against the tested cell lines. We conclude that 3PtTPyP is an excellent photosensitizer with promising in vitro results against C. albicans strains. Full article

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. Full article

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. Full article

Monitoring O₂ and pH has excellent potential in different sensing applications, especially in biological and clinical applications. This report presents a protocol for synthesizing an optical dual nanosensor for those two parameters. The organically modified silica (ormosil) nanoparticles were prepared based on phenytrimethoxysilane in an aqueous solution using an acid-base one-pot strategy. Ormosil was selected as a lipophilic matrix for loading fluorescent O₂-sensitive dye platinum(II)-tetrakis-(pentafluorophenyl) porphyrin (Pt-TPFPP), which was quenched in the presence of O₂ gas and exhibited a considerable detection proficiency within a percentage range of (0–100%) O₂. Commercially available drug ingredient salicylamide was labeled on the surface of the nanoparticles using a coupling agent (3-glycidoxypropyl) trimethoxysilane (GPTMS). For measuring pH, salicylamide acted for the first time as a pH-sensitive probe based on a turn-on process with increasing pH. The nanosensor displayed a significant pH detection efficiency in the range of (pH = 6–10). Salicylamide turn-on fluorescence was attributed to the excited state intramolecular transfer (ESIPT) process followed by the inter charge transfer (ICT). The presented dual nanosensor opens new opportunities as a promising candidate material for industrial systems and medical applications. Full article

Sensitivity is one of the crucial factors in determining the quality of a fluorescence/phosphorescence-based gas sensor, and is estimated from the measurement of responses (I₀/I, where I₀ and I refer to the measured optical intensity of a sensor in absence and presence of analyte molecules) at various concentrations of analytes. In this work, we demonstrate phosphorescence-based optical oxygen sensors fabricated on highly porous anodic aluminum oxide (AAO) membranes showing dramatically high response. These sensors exploit the enormous surface area of the AAO to facilitate the effective interaction between the sensing molecules and the analytes. We spin-coat an AAO membrane (200 nm pore diameter) with a platinum-based oxygen sensing porphyrin dye, platinum(II) meso-tetrakis (pentafluorophenyl) porphyrin (PtTFPP), to fabricate a sensor exhibiting I₀/I ~400 at 100% oxygen atmosphere. To address the generality of the AAO membrane, we fabricate a separate sensor with another porphyrin dye, platinum octaethylporphyrin (PtOEP), which exhibits an even higher I₀/I of ~500. Both of these sensors offer the highest responses as an optical oxygen sensor hitherto reported. SEM and EDS analysis are performed to realize the effect of the increased surface area of the AAO membrane on the enhanced sensitivity. Full article

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. Full article

Triplet-triplet annihilation upconversion (TTA-UC) nanoparticles (NPs) have emerged as imaging probes and therapeutic probes in recent years due to their excellent optical properties. In contrast to lanthanide ion-doped inorganic materials, highly efficient TTA-UC can be generated by low excitation power density, which makes it suitable for clinical applications. In the present study, we used biodegradable poly(lactic-co-glycolic acid) (PLGA)-NPs as a delivery vehicle for TTA-UC based on the heavy metal porphyrin Platinum(II) octaethylporphyrin (PtOEP) and the polycyclic aromatic hydrocarbon 9,10-diphenylanthracene (DPA) as a photosensitizer/emitter pair. TTA-UC-PLGA-NPs were successfully synthesized according to an oil-in-water emulsion and solvent evaporation method. After physicochemical characterization, UC-efficacy of TTA-UC-PLGA-NPs was assessed in vitro and ex vivo. TTA-UC could be detected in the tumour area 96 h after in vivo administration of TTA-UC-PLGA-NPs, confirming the integrity and suitability of PLGA-NPs as a TTA-UC in vivo delivery system. Thus, this study provides proof-of-concept that the advantageous properties of PLGA can be combined with the unique optical properties of TTA-UC for the development of advanced nanocarriers for simultaneous in vivo molecular imaging and drug delivery. Full article

Real-time monitoring of dissolved oxygen (DO) and pH is of great significance for understanding cellular metabolism. Herein, a dual optical pH/O₂ sensing membrane was prepared by the electrospinning method. Cellulose acetate (CA) and poly(ε-caprolactone) (PCL) nanofiber membrane blended with platinum (II)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)-porphyrin (PtTFPP) was used as the DO sensing matrix, upon which electrospun nanofiber membrane of chitosan (CS) coupled with fluorescein 5-isothiocyanate (FITC) was used as the pH sensing matrix. The electrospun sensing film prepared from biocompatible biomaterials presented good response to a wide range of DO concentrations and physiological pH. We used it to monitor the exracellular acidification and oxygen consumption levels of cells and bacteria. This sensing film can provide a luminescence signal change as the DO and pH change in the growth microenvironment. Due to its advantages of good biocompatibility and high stability, we believe that the dual functional film has a high value in the field of biotechnology research. Full article

Degradation of fast response pressure-sensitive paints (PSP) above room temperature is a serious problem for PSP measurements in high-temperature environments. A standard polymer-ceramic PSP (PC-PSP) composed of platinum(II)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorphenyl)-porphyrin (PtTFPP), titania particles and poly(isobutyl methacrylate) (polyIBM) was characterized to elucidate the degradation mechanism. Applying a two-gate lifetime-based method, the PC-PSP has sufficient pressure and temperature sensitivities even at 100 °C, while the luminescence intensity significantly decreases during the test. Subsequent measurements on thermal and photostability as well as luminescence spectra reveal that the main cause of the degradation is the photodegradation of PtTFPP due to direct exposure of the dye molecules to the atmosphere. In order to suppress such degradation, a small amount of urethane resin is added to the dye solution as a simple additional step in the preparation of PC-PSP. The addition of the urethane resin significantly reduces the degradation of the PSP, although its time response is slightly slower than that of the standard PC-PSP. Full article