Search Results (49)

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

Photocatalytic H₂ production is one of the most promising approaches for sustainable energy. The literature presents a plethora of carefully designed systems aimed at harnessing solar energy and converting it into chemical energy. However, the main drawback of the reported photocatalysts is their stability. Thus, the development of a cost-effective and stable photocatalyst, suitable for real-world applications remains a challenge. An ideal photocatalyst for H₂ production must possess appropriate band-edge energy positions, an effective sacrificial agent, and a suitable cocatalyst. Among the various photocatalysts studied, TiO₂ stands out due to its stability, abundance, and non-toxicity. However, its efficiency in the visible spectrum is limited by its wide bandgap. Metal doping is an effective strategy to enhance electron–hole separation and improve light absorption efficiency, thereby boosting H₂ synthesis. Common metal cocatalysts used as TiO₂ dopants include platinum (Pt), gold (Au), copper (Cu), nickel (Ni), cobalt (Co), ruthenium (Ru), iron (Fe), and silver (Ag), as well as bimetallic combinations such as Ni-Fe, Ni-Cu, Nb-Ta, and Ni-Pt. In all cases, doped TiO₂ exhibits higher H₂ production performance compared to undoped TiO₂, as metals provide additional reaction sites and enhance charge separation. The use of bimetallic dopants further optimizes the hydrogen evolution reaction. Additionally, porphyrins, with their strong visible light absorption and efficient electron transfer properties, have demonstrated potential in TiO₂ photocatalysis. Their incorporation expands the photocatalyst’s light absorption range into the visible spectrum, enhancing H₂ production efficiency. This review paper explores the principles and advancements in metal- and porphyrin-doped TiO₂ photocatalysts, highlighting their potential for sustainable hydrogen production. Full article

The rising prevalence of skin lesions places a heavy burden on global health resources and necessitates an early and precise diagnosis for successful treatment. The diagnostic potential of recent multi-modal skin lesion detection algorithms is limited because they ignore dynamic interactions and information sharing across modalities at various feature scales. To address this, we propose a deep learning framework, Multi-Modal Skin-Imaging-based Information-Switching Network (MDSIS-Net), for end-to-end skin lesion recognition. MDSIS-Net extracts intra-modality features using transfer learning in a multi-scale fully shared convolutional neural network and introduces an innovative information-switching module. A cross-attention mechanism dynamically calibrates and integrates features across modalities to improve inter-modality associations and feature representation in this module. MDSIS-Net is tested on clinical disfiguring dermatosis data and the public Derm7pt melanoma dataset. A Visually Intelligent System for Image Analysis (VISIA) captures five modalities: spots, red marks, ultraviolet (UV) spots, porphyrins, and brown spots for disfiguring dermatosis. The model performs better than existing approaches with an mAP of 0.967, accuracy of 0.960, precision of 0.935, recall of 0.960, and f1-score of 0.947. Using clinical and dermoscopic pictures from the Derm7pt dataset, MDSIS-Net outperforms current benchmarks for melanoma, with an mAP of 0.877, accuracy of 0.907, precision of 0.911, recall of 0.815, and f1-score of 0.851. The model’s interpretability is proven by Grad-CAM heatmaps correlating with clinical diagnostic focus areas. In conclusion, our deep multi-modal information-switching model enhances skin lesion identification by capturing relationship features and fine-grained details across multi-modal images, improving both accuracy and interpretability. This work advances clinical decision making and lays a foundation for future developments in skin lesion diagnosis and treatment. 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

Photoactive artificial nanocatalysts that mimic natural photoenergy systems can yield clean and renewable energy. However, their poor photoabsorption capability and disfavored photogenic electron–hole recombination hinder their production. Herein, we designed two nanocatalysts with various microstructures by combining the tailored self-assembly of the meso-tetra(p-hydroxyphenyl) porphine photosensitizer with the growth of titanium dioxide (TiO₂). The porphyrin photoabsorption antenna efficiently extended the absorption range of TiO₂ in the visible region, while anatase TiO₂ promoted the efficient electron–hole separation of porphyrin. The photo-induced electrons were transferred to the surface of the Pt co-catalyst for the generation of hydrogen via water splitting, and the hole was utilized for the decomposition of methyl orange dye. The hybrid structure showed greatly increased photocatalytic performance compared to the core@shell structure due to massive active sites and increased photo-generated electron output. This controlled assembly regulation provides a new approach for the fabrication of advanced, structure-dependent photocatalysts. 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

Respirometric microbial assays are gaining popularity, but their uptake is limited by the availability of optimal O₂ sensing materials and the challenge of validating assays with complex real samples. We conducted a comparative evaluation of four different O₂-sensing probes based on Pt-porphyrin phosphors in respirometric bacterial assays performed on standard time-resolved fluorescence reader. The macromolecular MitoXpress, nanoparticle NanO2 and small molecule PtGlc₄ and PtPEG₄ probes were assessed with E. coli cells in five growth media: nutrient broth (NB), McConkey (MC), Rapid Coliform ChromoSelect (RCC), M-Lauryl lauryl sulfate (MLS), and Minerals-Modified Glutamate (MMG) media. Respiration profiles of the cells were recorded and analyzed, along with densitometry profiles and quenching studies of individual media components. This revealed several limiting factors and interferences impacting assay performance, which include probe quenched lifetime, instrument temporal resolution, inner filter effects (mainly by indicator dyes), probe binding to lipophilic components, and dynamic and static quenching by media components. The study allowed for the ranking of the probes based on their ruggedness, resilience to interferences and overall performance in respirometric bacterial assays. The ‘shielded’ probe NanO2 outperformed the established MitoXpress probe and the small molecule probes PtGlc₄ and PtPEG₄. 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

There is an urgent need to design and synthesize non-noble metal electrocatalysts (NNMEs) for the replacement of platinum-based electrocatalysts to enhance the sluggish oxygen reduction reaction (ORR) for Zn–air batteries and fuel cells. Herein, Fe-N,S-C materials were fabricated through two steps: first, reprecipitating hemin by adjusting the pH and, then, decorating it with melamine and cysteine in the presence of Zn²⁺. The resulting Fe-N,S-C-950 (Zn) was prepared after pyrolysis at 950 °C. Using this method, abundant iron-based active species with good dispersion were obtained. The fabrication of more micropores in Fe-N,S-C-950 (Zn) plays a positive role in the improvement of ORR activity. On comparison, Fe-N,S-C-950 (Zn) outperforms Fe-N,S-C-950 and Fe-N-C-950 (Zn) with respect to the ORR due to its larger specific surface area, porous structure, multiple iron-based active sites and N- and S-doped C. Fe-N,S-C-950 (Zn) achieves outstanding ORR performances, including a half-wave potential (E_1/2) of 0.844 V and 0.715 V versus a reversible hydrogen electrode (RHE) in 0.1 M KOH and 0.1 M HClO₄ solution, respectively. In addition, Fe-N,S-C-950 (Zn) shows an outstanding Zn–air battery performance with an open-circuit voltage (OCV) of 1.450 V and a peak power density of 121.9 mW cm⁻², which is higher than that of 20 wt% Pt/C. As a result, the as-prepared electrocatalyst in this work shows the development of the Zn-assisted strategy combined with the assembly of porphyrins as NNMEs for the enhancement of the ORR in both alkaline and acidic solutions. 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

Covalent organic frameworks (COFs) have emerged as promising electrocatalysts due to their controllable architectures, highly exposed molecular active sites, and ordered structures. In this study, a series of porphyrin-based COFs (TAPP-x-COF) with various transition metals (Co, Ni, Fe) were synthesized via a facile post-metallization strategy under solvothermal synthesis. The resulting porphyrin-based COFs showed oxygen reduction reaction (ORR) activity with a trend in Co > Fe > Ni. Among them, TAPP-Co-COF exhibited the best ORR activity (E_1/2 = 0.66 V and jL = 4.82 mA cm⁻²) in alkaline media, which is comparable to those of Pt/C under the same conditions. Furthermore, TAPP-Co-COF was employed as a cathode in a Zn-air battery, demonstrating a high power density of 103.73 mW cm^–2 and robust cycling stability. This work presents a simple method for using COFs as a smart platform to fabricate efficient electrocatalysts. 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

Photovoltaic solar cells have been extensively used for various applications and are considered one of the most efficient green energy sources. However, their 2D surface area solar harvesting has limitations, and there is an increasing need to explore the possibility of multiple layer solar harvest for enhanced energy density. To address this, we have developed spectral-selective transparent thin films based on porphyrin and iron oxide compounds that allow solar light to penetrate multiple layers, significantly increasing solar harvesting surface area and energy density. These thin films are designed as photovoltaic (PV) and photothermal (PT) panels that can convert photons into either electricity or thermal energy for various green energy applications, such as smart building skins and solar desalination. The advantages of this 3D solar harvesting system include enlarged solar light collecting surface area and increased energy density. The multilayer system transforms the current 2D to 3D solar harvesting, enabling efficient energy generation. This review discusses recent developments in the synthesis and characterization of PV and PT transparent thin films for solar harvesting and energy generation using multilayers. Major applications of the 3D solar harvesting system are reviewed, including thermal energy generation, multilayered DSSC PV system, and solar desalination. Some preliminary data on transparent multilayer DSSC PVs are presented. Full article

Photocatalysis is one of the most promising technologies to achieve efficient carbon dioxide reduction reaction (CO₂RR) under mild conditions. Herein, metalloporphyrin-based metal–organic frameworks (MOFs) with different metal centers, denoted as PCN-222, were utilized as visible-light photocatalysts for CO₂ reduction. Due to the combination of the conjugated planar macrocyclic structures of metalloporphyrins and the stable porous structures of MOFs, all PCN-222 materials exhibited excellent light-harvesting and CO₂-adsorbing abilities. Among the studied MOFs of varied metal centers (M = Pt, Fe, Cu, Zn, Mn), PCN-222(2H&Zn) exhibited the highest photocatalytic CO₂RR performance, with an average CO yield of 3.92 μmol g⁻¹ h⁻¹ without any organic solvent or sacrificial agent. Furthermore, this was three and seven times higher than that of PCN-222(Zn) (1.36 μmol g⁻¹ h⁻¹) and PCN-222(2H) (0.557 μmol g⁻¹ h⁻¹). The superior photocatalytic activity of PCN-222(2H&Zn) was attributed to its effective photoexcited electron–hole separation and transportation compared with other PCN-222(2H&M) materials. The obtained results indicate that Zn ions in the porphyrin’s center played an important role in the reaction of active sites for the adsorption–activation of CO₂. In addition, PCN-222(2H&Zn) showed the highest CO₂ selectivity (almost 100%) and stability. This work provides a clear guide for the design of efficient photocatalysts. Full article