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Antibacterial photodynamic therapy (a‐PDT) has emerged as a promising non‐invasive therapeutic modality that utilizes the combination of a photosensitive agent, molecular oxygen, and excitation light to generate reactive oxygen species (ROS), demonstrating remarkable activity against multidrug‐resistant bacterial infections. However, the effective use of conventional photosensitizers is significantly limited by a number of their shortcomings, namely, poor water solubility and low selectivity. Herein, we present a novel biocompatible water‐soluble nanocomposite based on hydrophobic tetraphenylporphyrin (TPP) molecules and hydrophilic ternary AgInS2/ZnS quantum dots incorporated into a chitosan matrix as an improved photosensitizer for a‐PDT. We demonstrated that TPP molecules could be successfully transferred into chitosan solution while remaining primarily in the form of monomers, which are capable of singlet oxygen generation. We performed a detailed analysis of the Förster resonance energy transfer (FRET) between quantum dots and TPP molecules within the nanocomposite and proposed the mechanism of the singlet oxygen efficiency enhancement via FRET. [ABSTRACT FROM AUTHOR]

To achieve carbon neutrality, the development of effective and durable electrodes for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of utmost importance. Herein, the Ru 3.4 -PMOF/NF electrode was successfully prepared by immobilizing Ru nanoparticles on porphyrinic metal-organic framework/nickel foam (PMOF/NF), effectively driving both the OER and the HER in an alkaline electrolyte. To achieve 10 mA cm−2, the Ru 3.4 -PMOF/NF electrode only required overpotentials of 19 and 215 mV for HER and OER, respectively. For overall water splitting, an ultra-low cell voltage of 1.468 V was required to drive 10 mA cm−2, surpassing the performance of the integrated Pt/C and RuO 2 couple electrode (1.6627 V). The outperformed electrocatalytic activity could be ascribed to the well-dispersed Ru nanoparticles, the self-reconstruction of PMOF, the synergistic effect, and the lamellar morphology. This study offers a promising approach for the development of ruthenium-doped electrodes that can enhance the efficiency of electrocatalytic water splitting. • The self-supporting electrode was prepared by immobilizing Ru on PMOF/NF. • The Ru 3.4 -PMOF/NF exhibited better HER and OER performance than Pt/C and RuO 2. • The Ru 3.4 -PMOF/NF couple could achieve a low cell voltage for water splitting. • The reasons for the improvement of electrocatalytic performance were summarized. [ABSTRACT FROM AUTHOR]

The fossil record demonstrates the preservation of porphyrins (e.g., heme) in organic sediments and the fossilized remains of animals. These molecules are essential components in modern metabolic processes, such as electron transport (cytochromes) and oxygen transport (hemoglobin), and likely originated before the emergence of life. The integration and adaptation of porphyrins and structurally similar molecules (e.g., chlorophylls) are key aspects in the evolution of energy production (i.e., aerobic respiration and photosynthesis) and complex life (i.e., eukaryotes and multicellularity). Here, we discuss the evolution and functional diversity of heme-bound hemoglobin proteins in vertebrates, along with the preservation of these molecules in the fossil record. By elucidating the pivotal role of these molecules in the evolution of life, this review lays the groundwork necessary to explore hemoglobin as a means to investigate the paleobiology of extinct taxa, including non-avian dinosaurs. [ABSTRACT FROM AUTHOR]

The efficient synthesis of nanosheets containing two metal ions is currently a formidable challenge. Here, we attempted to dope lanthanide-based bimetals into porphyrin-based metal-organic skeleton materials (MOFs) by microwave-assisted heating. The results of the EDX, ICP, and XPS tests show that we have successfully synthesized porphyrin-based lanthanide bimetallic nanosheets (Tb-Eu-TCPP) using a household microwave oven. In addition, it is tested and experimentally evident that these nanosheets have a thinner thickness, a larger BET surface area, and higher photogenerated carrier separation efficiency than bulk porphyrin-based bimetallic materials, thus exhibiting enhanced photocatalytic activity and n-type semiconductor properties. Furthermore, the prepared Tb-Eu-TCPP nanomaterials are more efficient in generating single-linear state oxygen under visible light irradiation compared to pristine monometallic nanosheets due to the generation of bimetallic nodes. The significant increase in catalytic activity is attributed to the improved separation and transfer efficiency of photogenerated carriers. This study not only deepens our understanding of lanthanide bimetallic nanosheet materials but also introduces an innovative approach to improve the photocatalytic performance of MOFs. [ABSTRACT FROM AUTHOR]

Self-organized, well-defined porphyrin-based nanostructures with controllable sizes and morphologies are in high demand for the photodegradation of hazardous contaminants under sunlight. From this perspective, this review summarizes the development progress in the fabrication of porphyrin-based nanostructures by changing their synthetic strategies and designs. Porphyrin-based nanostructures can be fabricated using several methods, including ionic self-assembly, metal–ligand coordination, reprecipitation, and surfactant-assisted methods. The synthetic utility of porphyrins permits the organization of porphyrin building blocks into nanostructures, which can remarkably improve their light-harvesting properties and photostability. The tunable functionalization and distinctive structures of porphyrin nanomaterials trigger the junction of the charge-transfer mechanism and facilitate the photodegradation of pollutant dyes. Finally, porphyrin nanomaterials or porphyrin/metal nanohybrids are explored to amplify their photocatalytic efficiency. [ABSTRACT FROM AUTHOR]

A new family of macrocyclic host molecules that possess two bisporphyrin clefts was synthesized. The tetrameric porphyrin macrocycle provides the two guest binding sites in which two electron‐deficient aromatic molecules are encapsulated through donor‐acceptor and π‐π stacking interactions. The tetrameric porphyrin macrocycle showed positive cooperativity, whereas the nonmacrocyclic analog did not. The preorganization concept drives positive cooperativity, which is directed by the entropy benefit to macrocyclization. [ABSTRACT FROM AUTHOR]

We present the fabrication of a novel Starfruit‐shaped metal‐organic framework (SMOF) composed of zirconium and Tetra(4‐carboxyphenyl)porphine linkers. The SMOF exhibits a unique morphology with edge‐sharing two‐dimensional (2D) nanosheet petals. Our investigation unravels a captivating transformation process, wherein three‐dimensional (3D) shuttle‐shaped MOFs form initially and subsequently evolve into 2D nanosheet‐based SMOF structures. The distinct morphology of SMOF showcases superior catalytic activity in detoxifying G‐type nerve agent and blister agent simulants, surpassing that of its 3D counterparts. This discovery of the 3D‐to‐2D transition growth pathway unlocks exciting opportunities for exploring novel strategies in advanced MOF nanostructure development, not only for catalysis but also for various other applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cobalt protoporphyrin (CoPpIX) grafted MIL-101(Cr)–NH 2 was constructed through facile post-synthetic modification. • The porphyrins are covalently linked to amino groups of the parent MOF without impairing its well-defined porous framework. • The parent MOF with superior CO 2 capture ability exposes Co porphyrins to elevated local CO 2 concentration by CO 2 enrichment. • A remarkably high CO Faradaic efficiency of 97.1% and a turnover frequency up to 0.63 s−1 are achieved. Electrocatalytic carbon dioxide reduction reaction (CO 2 RR) presents a sustainable route to address energy crisis and environmental issues, where the rational design of catalysts remains crucial. Metal–organic frameworks (MOFs) with high CO 2 capture capacities have immense potential as CO 2 RR electrocatalysts but suffer from poor activity. Herein we report a redox-active cobalt protoporphyrin grafted MIL-101(Cr)–NH 2 for CO 2 electroreduction. Material characterizations reveal that porphyrin molecules are covalently attached to uncoordinated amino groups of the parent MOF without compromising its well-defined porous structure. Furthermore, in situ spectroscopic techniques suggest inherited CO 2 concentrate ability and more abundant adsorbed carbonate species on the modified MOF. As a result, a maximum CO Faradaic efficiency (FE CO) up to 97.1% and a turnover frequency of 0.63 s−1 are achieved, together with FE CO above 90% within a wide potential window of 300 mV. This work sheds new light on the coupling of MOFs with molecular catalysts to enhance catalytic performances. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) are a novel category of porous crystalline materials with an exceptionally high surface area and adjustable pore structure. They possess a designable composition and can be easily functionalized with different units. Porphyrins with conjugated tetrapyrrole macrocyclic structures can absorb light from ultraviolet to visible light regions, and their structures and properties can be facilely regulated by altering their peripheral groups or central metal ions. Porphyrin-based MOFs constructed from porphyrin ligands and metal nodes combine the unique features of porphyrins and MOFs as well as overcoming their respective limitations. This paper reviewed the design and construction, light absorption and charge transfer pathways, and strategy for improving the photocatalytic performance of porphyrin-based MOFs, and highlighted the recent progress in the field of CO2 reduction, hydrogen evolution, organic synthesis, organic pollutant removal, and nitrogen fixation. The intrinsic relationships between the structure and the property of porphyrin-based MOFs received special attention, especially the relationships between the arrangements of porphyrin ligands and metal nods and the charge transfer mechanism. We attempted to provide more valuable information for the design and construction of advanced photocatalysts in the future. Finally, the challenges and future perspectives of the porphyrin-based MOFs are also discussed. [ABSTRACT FROM AUTHOR]

The development of nanotools for chemical sensing and macromolecular modifications is a new challenge in the biomedical field, with emphasis on artificial peptidases designed to cleave peptide bonds at specific sites. In this landscape, metal porphyrins are attractive due to their ability to form stable complexes with amino acids and to generate reactive oxygen species when irradiated by light of appropriate wavelengths. The issues of hydrophobic behavior and aggregation in aqueous environments of porphyrins can be solved by using its PEGylated derivatives. This work proposes the design of an artificial photo-protease agent based on a PEGylated mercury porphyrin, able to form a stable complex with l-Tryptophan, an amino acid present also in the lysozyme structure (a well-known protein model). The sensing and photodegradation features of PEGylated mercury porphyrin were exploited to detect and degrade both l-Trp and lysozyme using ROS, generated under green (532 nm) and red (650 nm) light lasers. The obtained system (Star3600_Hg) and its behavior as a photo-protease agent were studied by means of several spectroscopies (UV-Vis, fluorescence and circular dichroism), and MALDI-TOF mass spectrometry, showing the cleavage of lysozyme and the appearance of several short-chain residues. The approach of this study paves the way for potential applications in theranostics and targeted bio-medical therapies. [ABSTRACT FROM AUTHOR]

The replacement of palladium catalysts for Wacker‐type oxidation of olefins into ketones by first‐row transition metals is a relevant approach for searching more sustainable protocols. Besides highly sophisticated iron catalysts, all the other first‐row transition metal complexes have only led to poor activities and selectivities. Herein, we show that the cobalt‐tetraphenylporphyrin complex is a competent catalyst for the aerobic oxidation of styrenes into ketones with silanes as the hydrogen sources. Remarkably, under room temperature and air atmosphere, the reactions were exceedingly fast (up to 10 minutes) with a low catalyst loading (1 mol %) while keeping an excellent chemo‐ and Markovnikov‐selectivity (up to 99 % of ketone). Unprecedently high TOF (864 h−1) and TON (5,800) were reached for the oxidation of aromatic olefins under these benign conditions. Mechanistic studies suggest a reaction mechanism similar to the Mukaiyama‐type hydration of olefins with a change in the last fundamental step, which controls the chemoselectivity, thanks to a unique hydrogen bonding network between the ethanol solvent and the cobalt peroxo intermediate. [ABSTRACT FROM AUTHOR]

In this work, we present Zn, CoII, and MnIII metalated meso‐tetra‐[4‐(methylthio) phenyl] porphyrin ([Zn(TMtPP)], [CoII(TMtPP], and [MnIII(TMtPP)Cl]) as electrocatalysts and photoelectrocatalysts for electrochemical detection and photoelectrocatalytic degradation of pentachlorophenol (PCP). The complexes were characterized using UV‐visible spectroscopy, mass spectroscopy, and elemental analysis. Proton nuclear magnetic resonance (1H NMR) studies were only conducted for the Zn derivative. The electrochemical detection of PCP was carried out using cyclic voltammetry and chronoamperometry. [CoII(TMtPP)] showed better detection limit. For photoelectrocatalytic (PEC) degradation studies of PCP, linear sweep voltammetry and UV‐visible spectra were employed. [Zn(TMtPP)] showed better removal efficiency. The main species responsible for the PEC degradation were found to be superoxide radicals (⋅O2) and electron holes (h+). [ABSTRACT FROM AUTHOR]

Highlights: Strain induces coupling in Bi12O17Br2 and Cu porphyrin-based monoatomic layer (PML-Cu), constructing Bi–O bonding interface in PML-Cu/BOB (PBOB). Surface interface dual polarization boosts internal electric field, promoting electron transfer. PML-Cu provides high density of dispersed active Cu sites in PBOB, enhancing CO2 photoreduction. The insufficient active sites and slow interfacial charge transfer of photocatalysts restrict the efficiency of CO2 photoreduction. The synchronized modulation of the above key issues is demanding and challenging. Herein, strain-induced strategy is developed to construct the Bi–O-bonded interface in Cu porphyrin-based monoatomic layer (PML-Cu) and Bi12O17Br2 (BOB), which triggers the surface interface dual polarization of PML-Cu/BOB (PBOB). In this multi-step polarization, the built-in electric field formed between the interfaces induces the electron transfer from conduction band (CB) of BOB to CB of PML-Cu and suppresses its reverse migration. Moreover, the surface polarization of PML-Cu further promotes the electron converge in Cu atoms. The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB, significantly promoting the adsorption and activation of CO2 and CO desorption. The conversion rate of CO2 photoreduction to CO for PBOB can reach 584.3 μmol g−1, which is 7.83 times higher than BOB and 20.01 times than PML-Cu. This work offers valuable insights into multi-step polarization regulation and active site design for catalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] • Porphyrin-based POPs with different heteroatoms were constructed. • N and S heteroatoms were embed into the backbone structure. • PS 2 F showed high Hg2+ capacity of 1049 mg/g. • Functional groups play more important role in heavy metal adsorption. Development of novel sulf-functionalized porous organic polymers (POPs) for Mercury (II) (Hg2+) removal is of great significant, but the adsorbents always suffered by the low adsorption capacity, stability, and efficiency for the reason that the common construction of functionalized POPs from the functionalized monomers or post-functionalization of the POPs always sacrifice the porosity. In this paper, porphyrin-based POPs with different heteroatoms were constructed through the aldehyde monomer (benzene, 2,5-thiophenedicarboxaldehyde and thieno[3,2- b ]thiophene-2,5-dicarboxaldehyde) and pyrrole according to the Adler-Longo method. In this way, nitrogen (N) in pyrrole and sulfur (S) in thiophene structures were embed into the backbone structure of the polymers. The functional structures not only act as the linking building block into the stable cross-linking structure, but also offer abundant uncovered functional sites for Hg2+ adsorption, resulting the porphyrin-based POPs high Hg2+ capacity (1049 mg/g), removal efficiency (more than 99.9%), good reusability and selectivity for its highest heteroatoms contents. The adsorption mechanism confirmed the cooperative coordination of N in porphyrin and S in thiophene with Hg2+. This work confirmed the functional groups play more important role in heavy metal adsorption, and the embedded functional sites into backbone also promotes the stability and the adsorption performance. [ABSTRACT FROM AUTHOR]

In this study, FeTOMPP (Tetrakis(4-methoxyphenyl) phenylporphyrinatoiron(III)) was synthesized and investigated for its peroxidase-like activity. The catalytic performance of FeTOMPP as a peroxidase mimic was explored by utilizing the colorless peroxidase substrate, 3,3',5,5'-tetramethylbenzidine (TMB), in the presence of hydrogen peroxide (H2O2). The oxidation of TMB by FeTOMPP resulted in the formation of its blue oxidized state. This enzymatic reaction was employed for the quantitative detection of H2O2, with a linear detection range spanning from 1.0 to 100 µM. The detection limit achieved using FeTOMPP as the catalyst was determined to be 2.4 µM. Furthermore, kinetic studies were conducted to investigate the interaction between FeTOMPP and H2O2. The results indicated that FeTOMPP exhibited favorable affinity towards H2O2, further highlighting its potential as a peroxidase mimic. In addition to its peroxidase-like activity, a simple and sensitive visual and colorimetric method was developed for the detection of ethanol by combining FeTOMPP with alcohol oxidase. The method relied on the use of TMB as the substrate. Ethanol-containing samples were subjected to the enzymatic reaction, resulting in the generation of a color change. The detection of ethanol was achieved with a minimum detection limit of 0.95 % v/v, and the linear range for quantification extended from 0 to 15 % v/v. This study demonstrates the potential application of FeTOMPP as a peroxidase mimic for the sensitive detection of H2O2 and the development of a colorimetric method for ethanol detection. The findings highlight the versatility and promising capabilities of FeTOMPP in various analytical and diagnostic applications. [ABSTRACT FROM AUTHOR]

In the current study, a chemiresistive SO2 sensor based on a composite of reduced graphene oxide (rGO) and 5, 10, 15, 20-tetra-p-tolyl-21H, 23H-porphine (TPTP) was developed and extensively studied. Improved Hummers methods were used to synthesize graphene oxide (GO), and a thermally heating bottom-up approach was used to reduce GO to rGO. Gold electrodes were thermally coated on the transparent sheet using a thermal evaporator. The composite of rGO/TPTP was synthesized using a simple chemical method. Structural, morphological, spectroscopic, electrical, and optical studies were carried out using X-ray diffraction, atomic force microscopy, field emission scanning electron microscopy, Fourier-transfer infrared spectroscopy, Raman spectroscopy, current–voltage, and UV–vis spectroscopy, respectively. The sensing response of rGO/TPTP for various concentrations of sulfur dioxide (SO2) was investigated in chemiresistive modality. The rGO/TPTP composite chemiresistive sensor displayed exceptional performance, with a consistent response spanning 1 ppm to 10 ppm. It exhibited outstanding repeatability, linearity, stability, and boasted an impressive limit of detection (LOD) of 1 ppm. This LOD is significantly lower than the recommended permissible exposure limit (PEL) of 5 ppm set by OSHA (Occupational Safety and Health Administration), USA. The sensor based on the rGO/TPTP composite exhibited a very fast response and recovery time of 33 s. and 27 s. respectively. [ABSTRACT FROM AUTHOR]

Exposure to certain metal ions can lead to many diseases including cardiovascular, reproductive, and kidney disorders. Certain inorganic anions and organic species can also adversely affect living organisms as well as pose a severe threat to the environment. Detection and determination of biological analytes or biomarkers can help in the early diagnosis and treatment of several human diseases. Accordingly, great efforts have been devoted to the development of fluorescent and colorimetric sensors. Compared to many other detection techniques, the optical sensor stands unique. Porphyrins are excellent fluorophores with strong absorption and emission in the visible region. This highly conjugated macrocycle can be tuned to desirable properties with proper substituents at the periphery and complex formation with a vast number of metal ions. This detailed review discusses optical sensors that encompass both colorimetric and fluorescence sensors based on porphyrin/metalloporphyrin and their various forms for sensing metal ions, inorganic anions, organic moieties, and biologically significant molecules. In the presence of the concerned analyte, rearrangement of energy level of optical probe occurs and further facilitates interaction with the analyte which is mainly operated through various mechanisms like FRET, PET, ground state complex formation, intramolecular charge transfer, exciplex formation, etc. [ABSTRACT FROM AUTHOR]

Molecular layer deposition (MLD) is an incredibly powerful and flexible tool for designing completely new materials with novel and unique properties. The low temperature layer‐by‐layer approach and the use of highly reactive reactants allows one to combine vastly different organic and inorganic species and construct nanostructures with subnanometer precision. If not limited by the volatility of the reactants involved, the possibilities will be endless. This is most notable for the organic building blocks where an overall low volatility severely limits the toolbox of large molecules with interesting optical and electrical properties such as red‐ox activity and optical conversion. In this work, different strategies for molecular design of large molecules are investigated that allow vaporization while still having the necessary reactivity for MLD growth. Using these strategies, film growth with perylene and porphyrin derivatives, both molecules well known for their functional and optical properties are successfully achieved. With this knowledge, there is an opening to include much larger and more complex organic molecules into the world of vapor phase chemistry. [ABSTRACT FROM AUTHOR]

In the continuation of our sustained interest in porphyrin-based dendrimers and their use as luminescent photosensitizers for two-photon photodynamic therapy (2P-PDT), we wondered about the effect of changing the connectors in our macromolecular structures. We also wanted to initiate preliminary studies on meso-tetraarylporphyrins decorated with more electron-releasing arms. Thus, various meso-tetrafluorenylporphyrin-cored star-shaped and dendrimeric derivatives have been synthesized and characterized, as well as their zinc(II) complexes. In the new dendrimeric derivatives, the peripheral fluorenyl units of the dendrons are linked to the inner core either by N-phenylcarbazole (CCbz) or triphenylamine (CTpa) connectors instead of the more classic 1,3,5-phenylene (CPh) linkers previously used by us. Selected linear and non-linear optical (LO and NLO) properties were then determined for these compounds via absorption or emission studies and by two-photon excited fluorescence (TPEF) measurements. It was found that the CCbz-containing dendrimer, which has the most rigid structure, exhibits a significantly lower two-photon absorption (2PA) cross-section than its CTpa analog, presenting a more flexible structure while rather similar luminescence and singlet oxygen activation quantum yields are found for both. The origin of this unexpected discrepancy is briefly discussed based on our photophysical data. It is then demonstrated that the latter dendrimer also outperforms several closely related dendrimers in terms of 2PA action cross-section and 2PA-oxygen sensitization, making its molecular architecture quite appealing for developing new 2PA photosensitizers suited to theranostic uses.

Thanks to its very high genome-editing efficiency, CRISPR-Cas9 technology could be a promising anticancer weapon. Clinical trials using CRISPR-Cas9 nuclease to ex vivo edit and alter immune cells are ongoing. However, to date, this strategy still has not been applied in clinical practice to directly target cancer cells. Targeting a canonical metabolic pathway essential to good functioning of cells without potential escape would represent an attractive strategy. We propose to mimic a genetic metabolic disorder in cancer cells to weaken cancer cells, independent of their genomic abnormalities. Mutations affecting the heme biosynthesis pathway are responsible for porphyria, and most of them are characterized by an accumulation of toxic photoreactive porphyrins. This study aimed to mimic porphyria by using CRISPR-Cas9 to inactivate UROS, leading to porphyrin accumulation in a prostate cancer model. Prostate cancer is the leading cancer in men and has a high mortality rate despite therapeutic progress, with a primary tumor accessible to light. By combining light with gene therapy, we obtained high efficiency in vitro and in vivo, with considerable improvement in the survival of mice. Finally, we achieved the preclinical proof-of-principle of performing cancer CRISPR gene therapy.

Abstract In this manuscript, the development of an experimental and mathematical toolset is reported that allows for improved in vivo measurements of optical transcutaneous oxygen tension measurements (TCOM) wearable technology in humans. In addition to optimizing O2‐sensing films for higher sensitivity oxygen detection, calibration algorithms are additionally developed to account for excitation source leakage, as well as algorithms to combine readings of partial pressure of oxygen (pO2), derived from phosphorescence intensity and lifetime, into a single metric. This new iteration of the TCOM wearable device is then tested in a pilot human study. By implementing characterization and calibration algorithms, the data from the pilot study demonstrates the ability to obtain reliable transcutaneous pO2 readings with a TCOM sensor regardless of size and without the need for strict conditions of constant temperature, humidity, or motion that have limited the range of applications of this technology in the past.

The global energy crisis and environmental pollution issues caused by the continuous consumption of fossil fuels are increasingly becoming severe. Developing clean and sustainable hydrogen (H2) energy and corresponding storage and conversion devices have attracted increasing attention. The utilization of H2 energy highly depends on the fuel cell (FC). However, the slow kinetics of oxygen reduction reaction (ORR) on the cathode of FC cannot be improved without efficient catalysts. Currently, precious metal platinum (Pt) and its alloys are commonly used catalysts for ORR process. However, the scarcity and high cost of Pt hinder their large-scale practical application. To replace typical Pt-based catalysts, non-precious metal electrocatalysts have been investigated for ORR. Inspired by the catalytic ORR active center Fe porphyrin of cytochrome c oxidase in nature, metalloporphyrin-based frameworks and their derivatives have become promising electrocatalysts due to their abundant conjugated electronic structure, tunable functional groups, and large specific surface area. First, this review briefly introduces porphyrins and catalytic ORR mechanisms. Second, recent progress on porphyrin-based ORR catalysts including porphyrin-based frameworks, framework@substrate composites, and framework-based derivatives was summarized. Porphyrin-based frameworks mainly include metal-organic frameworks (MOFs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and polymers constructed with porphyrin building blocks. Porphyrin-based framework@substrate composites were usually assembled and constructed to improve the electron transfer rate of frameworks. To further improve the conductivity, framework-based derivatives, usually named metal, nitrogen-doped carbon (M-N-C) materials, were synthesized through pyrolyzing frameworks at high temperatures. Finally, research challenges and directions of porphyrin-based electrocatalysts for ORR were discussed. This review is meaningful and enlightening for designing and developing other porphyrin-based electrocatalysts for ORR.

Background: Our group focused on a meso‑aryl substituted porphyrin molecule for its photodynamic anti-inflammatory activities on the mammalian macrophages. Materials and methods: The porphyrine derivative previously synthesized in this study was synthesized and characterized by 1H NMR. We then examined their immunomodulatory activities based on the changes in the pro-inflammatory cytokine production levels after LPS stimulation in dark and light activated conditions. Results: Our results suggest that porphyrin derivative had anti-inflammatory photodynamic activity in vitro at subtoxic concentrations. Our study aims to pave a way for anti-inflammatory photodynamic therapy application in the inflammatory and autoimmune disorders. Most of the studies either focus on photodynamic cytotoxicity of the porphyrin derivatives to suppress the inflammation or porphyrin derivatives’ anti-inflammatory activity without the photodynamic activation. Conclusion: Our future studies will focus on the generation and in vitro as well as in vivo characterization of the porphyrin derivatives with anti-inflammatory photodynamic therapy applications. In this way, novel drug candidates that would have lower side effects can be generated for the patients.

Abstract Molecular layer deposition (MLD) is an incredibly powerful and flexible tool for designing completely new materials with novel and unique properties. The low temperature layer‐by‐layer approach and the use of highly reactive reactants allows one to combine vastly different organic and inorganic species and construct nanostructures with subnanometer precision. If not limited by the volatility of the reactants involved, the possibilities will be endless. This is most notable for the organic building blocks where an overall low volatility severely limits the toolbox of large molecules with interesting optical and electrical properties such as red‐ox activity and optical conversion. In this work, different strategies for molecular design of large molecules are investigated that allow vaporization while still having the necessary reactivity for MLD growth. Using these strategies, film growth with perylene and porphyrin derivatives, both molecules well known for their functional and optical properties are successfully achieved. With this knowledge, there is an opening to include much larger and more complex organic molecules into the world of vapor phase chemistry.

Abstract In this work, we present Zn, CoII, and MnIII metalated meso‐tetra‐[4‐(methylthio) phenyl] porphyrin ([Zn(TMtPP)], [CoII(TMtPP], and [MnIII(TMtPP)Cl]) as electrocatalysts and photoelectrocatalysts for electrochemical detection and photoelectrocatalytic degradation of pentachlorophenol (PCP). The complexes were characterized using UV‐visible spectroscopy, mass spectroscopy, and elemental analysis. Proton nuclear magnetic resonance (1H NMR) studies were only conducted for the Zn derivative. The electrochemical detection of PCP was carried out using cyclic voltammetry and chronoamperometry. [CoII(TMtPP)] showed better detection limit. For photoelectrocatalytic (PEC) degradation studies of PCP, linear sweep voltammetry and UV‐visible spectra were employed. [Zn(TMtPP)] showed better removal efficiency. The main species responsible for the PEC degradation were found to be superoxide radicals (⋅O2) and electron holes (h+).

Locking nonequilibrium shapes of liquids into targeted architectures by interfacial jamming of nanoparticles is an emerging area in material science. 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (H6 TPPS) shows three different aggregation states that present an absorption imaging platform to monitor the assembly and jamming of supramolecular polymer surfactants (SPSs) at the liquid/liquid interface. The interfacial interconversion of H6 TPPS, specifically H4 TPPS2- dissolved in water, from J- to an H-aggregation was induced by strong electrostatic interactions with amine-terminated polystyrene dissolved in toluene at the water/toluene interface. This resulted in color-tunable liquids due to interfacial jamming of the SPSs formed between H4 TPPS2- and amine-terminated polystyrene. However, the formed SPSs cannot lock in nonequilibrium shapes of liquids. In addition, a self-wrinkling behavior was observed when amphiphilic triblock copolymers of PS-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) were used to interact with H4 TPPS2- . Subsequently, the SPSs formed can lock in nonequilibrium shapes of liquids.

[Display omitted] • The nitrogen vacancies-zinc porphyrin (NVs-ZnTCPP) ultrathin nanosheets was fabricated through a simple surface N 2 plasma treatment. • The optimized NVs-ZnTCPP exhibits superior photocatalytic carbon dioxide (CO 2) reduction activity and selectivity to carbon monoxide (CO). • The promoted photocatalytic performance of NVs-ZnTCPP could be mainly attributed to nitrogen vacancy-induced spin polarization. Metalloporphyrin compounds have excellent electron transfer and visible light absorption ability, demonstrating broad application prospects in the field of photocatalysis. In this work, the nitrogen vacancies (NVs) were successfully introduced into zinc porphyrin (ZnTCPP) ultrathin nanosheets through surface N 2 plasma treatment, which is environmentally friendly and can react in low temperatures. Furthermore, the prepared nitrogen vacancies-zinc porphyrin (NVs-ZnTCPP) materials exhibited excellent photocatalytic CO 2 reduction activity and selectivity, specifically, the CO production rate of ZnTCPP-1 (N 2 plasma treatment, 1 min) achieved as high as 12.5 µmol g–1h−1, which is about 2.7 times greater than that of untreated ZnTCPP. Based on the experimental and density functional theory calculation (DFT) results, it is found that the promoted photocatalytic performance of NVs-ZnTCPP could be mainly attributed to nitrogen vacancy-induced spin polarization by reducing the reaction barriers and inhibiting the recombination of photoexcited carriers. This work provides a new perspective for the construction of vacancy-based metalloporphyrin, and further explores the intrinsic mechanism between the electron spin property and the performance of the photocatalyst. [ABSTRACT FROM AUTHOR]

This study investigated the adsorption of CO[sub 2] molecules on transition metal ions (TM) porphyrins induced carbon nanocone (TM-PICNC) (TM = Sc[sup 2+], Ti[sup 2+], V[sup 2+], Cr[sup 2+], Fe[sup 2+], Co[sup 2+], Ni[sup 2+], Cu[sup 2+], and Zn[sup 2+]) using density functional theory (DFT) to determine the stabilities, energetic, structural, and electronic properties. The results showed that the CO2 molecule is adsorbed on TM-PICNC with adsorption energies ranging from 0.03 to -12.12 kcal/mol. The weak interactions of CO2 gas with Cr, Ni, Cu, and Zn-PICNC were observed, while strong adsorption was found on Sc, Ti, and V-PICNC. The Ti, V, and Cr-PCNC structures were shown to have a suitable energy gap (Eg) for sensing ability because of the effective and physical interaction between these structures and CO2 gas, leading to a short recovery time. DFT calculations also revealed that V-PCNC had a high %ΔEg (about %56.79) and hence high sensitivity to CO2 gas, making it a promising candidate for having good sensing ability to CO2 gas in presence of O2 and H2O gas. [ABSTRACT FROM AUTHOR]

Acidithiobacillus ferrooxidans are beneficial bacteria for bioleaching in the mining industry to extract useful fractions from tons of waste. These bacteria are able to oxidize ferrous iron (Fe2+) to ferric iron (Fe3+) and use the released energy to assimilate carbon from carbon dioxide or carbonates, and can be used in the desulfurization of coal and gas. In this regard, activators of the growth of these bacteria may be useful. During the experiments on these bacterial strains, an unexpected effect of growth activation was revealed. This gives rise to further research in this direction and the identification of patterns of "structure‐activity" derivatives of ferrocene and porphyrins in relation to A. ferrooxidans. [ABSTRACT FROM AUTHOR]

Novel hybrid TiO2-based materials were obtained by adsorption of two different porphyrins on the surface of nanoparticles—commercially available 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and properly modified metalloporphyrin—5,10,15,20-tetrakis(2,6-difluoro-3-sulfophenyl)porphyrin palladium(II) (PdF2POH). The immobilization of porphyrins on the surface of TiO2 was possible due to the presence of sulfonyl groups. To further elevate the adsorption of porphyrin, an anchoring linker—4-hydroxybenzoic acid (PHBA)—was used. The synthesis of hybrid materials was proven by electronic absorption spectroscopy, dynamic light scattering (DLS), and photoelectrochemistry. Results prove the successful photosensitization of TiO2 to visible light by both porphyrins. However, the presence of the palladium ion in the modifier structure played a key role in strong adsorption, enhanced charge separation, and thus effective photosensitization. The incorporation of halogenated metalloporphyrins into TiO2 facilitates the enhancement of the comprehensive characteristics of the investigated materials and enables the evaluation of their performance under visible light. The effectiveness of reactive oxygen species (ROS) generation was also determined. Porphyrin-based materials with the addition of PHBA seemed to generate ROS more effectively than other composites. Interestingly, modifications influenced the generation of singlet oxygen for TPPS but not hydroxyl radical, in contrast to PdF2POH, where singlet oxygen generation was not influenced but hydroxyl radical generation was increased. Palladium (II) porphyrin-modified materials were characterized by higher photostability than TPPS-based nanostructures, as TPPS@PHBA-P25 materials showed the highest singlet oxygen generation and may be oxidized during light exposure. Photocatalytic activity tests with two model pollutants—methylene blue (MB) and the opioid drug tramadol (TRML)—confirmed the light dose-dependent degradation of those two compounds, especially PdF2POH@P25, which led to the virtually complete degradation of MB. [ABSTRACT FROM AUTHOR]

Treatment regimens are regularly evolving alongside novel therapies and drugs. Such evolution is necessary to circumvent resistance mechanisms and to give patients the best possible health care. When dealing with cancer, most regimens involve multiple treatments (surgery, radiation therapy, chemotherapy, immunotherapy, etc.). The purpose of this study was to associate in a single compound metal-based drugs and photosensitizers to combine chemotherapy and photodynamic therapy. Two arene–ruthenium tetrapyridylporphyrin compounds (2H-TPyP-arene-Ru and Zn-TPyP-arene-Ru) have been synthesized and evaluated on two colorectal cancer cell lines (HCT116 and HT-29). Their cytotoxicity and phototoxicity have been evaluated. In addition, the anticancer mechanism and the cell death process mediated by the two compounds were studied. The results showed that the two arene–ruthenium photosensitizer-containing complexes have a strong phototoxic effect after photoactivation. The 2H-TPyP-arene-Ru complex induced outstanding cytotoxicity when compared to the Zn-TPyP-arene-Ru analogue. Moreover, under light, these two arene–ruthenium photosensitizers induce an apoptotic process in human colorectal cancer cell lines. [ABSTRACT FROM AUTHOR]

[Display omitted] • Minor structural differences of hydrophobic porphyrins can distinctly influence their release properties from liposomes. • mTHPP (meta OH) redistributes much slower than pTHPP (para OH) from liposomal membranes. • Reversed-phase HPLC experiments indicate a higher partition coefficient for mTHPP. • In MD simulations, mTHPP has a higher tendency for hydrogen bonding, a larger tilt angle and locates deeper in the membrane. • Both HPLC and MD simulation results support the observed differences in release and redistribution of mTHPP and pTHPP from liposomal membranes. The release of hydrophobic compounds from liposomal membranes occurs by partitioning and is thus determined by the physicochemical properties (e.g. logP and water solubility) of the drug. We postulate that even minor structural differences, e.g. the position of the phenolic OH-group of the hydrophobic porphyrins mTHPP and pTHPP (meta vs. para substitution), distinctly affect their partitioning and release behavior from liposomes. The release and redistribution of mTHPP and pTHPP from lecithin or POPC/POPG liposomes to different acceptor particles (DSPE-mPEG micelles and liposomes) was studied by asymmetrical flow field-flow fractionation to separate donor and acceptor particles. Reversed phase HPLC was applied to detect differences in partitioning. Molecular dynamics (MD) simulations were carried out to obtain molecular insight in the different behavior of the two compounds inside a lipid bilayer. Despite the minor differences in chemical structure, mTHPP is more hydrophobic and redistributes much slower to both acceptor phases than pTHPP. MD simulations indicate that compared to pTHPP, mTHPP makes stronger hydrogen bonds with the lipid head groups, is oriented more parallel to the lipid tails and is embedded slightly deeper in the membrane. [ABSTRACT FROM AUTHOR]

The harmful pollutant perfluorooctane sulfonate (PFOS) is difficult to detect without extensive laboratory equipment used by trained personnel. Herein, we report the use of a micelle-encapsulated porphyrin host molecule as a rapid colorimetric indicator for PFOS and its anionic salts. A range of common commercially available surfactants were tested and optimised to encapsulate the hydrophobic highly pigmented porphyrin sensor molecule. This method was used for the detection of PFOS in aqueous solutions at concentrations as low as 3 ppm. Colour space RGB information was extracted from a mobile phone photograph and parameterised, allowing for threshold PFOS detection, demonstrating the applicability of this method as an easily accessible approach to inform an untrained user. A proof-of-concept method has been developed to detect perfluorooctanesulfonate (PFOS). A coloured porphyrin host molecule suspended in micelles changes colour when it encounters PFOS. Photographs of the coloured solutions were analysed allowing for the detection of PFOS in water at concentrations as low as 3 ppm. CH23061_TOC.jpg [ABSTRACT FROM AUTHOR]

Pollutant degradation has been a very important topic in environmental research. The present paper presents an approach to degrade atrazine, an environmentally harmful herbicide that has been widely used in the agriculture industry. Ti/TiO2 nanotube electrodes modified by porphyrins were prepared for photolysis, photocatalysis, and photoelectrocatalysis (PEC) applications. Manganese- and free base porphyrin were studied, and it was possible to verify the kinetic model more suitable for each system. Unfortunately, Mn-porphyrins had an inhibitory effect on the ATZ degradation activity by Ti/TiO2 nanotube electrodes. Although the Ti/TiO2-free base porphyrin under the PEC experiment (using surface water from a Brazilian river) did not lead to the best degradation system, we could verify the formed products, which have been not described for other porphyrin-mediated atrazine degradation, are equal or more toxic than the original atrazine. We highlight the importance of verifying the products formed in the degradation systems and determining their toxicities. [ABSTRACT FROM AUTHOR]

Photosensitization of proteins mediated by chromophores is a mechanism commonly employed by nature and mimicked in a broad array of laboratory research and applications. Nature has evolved specialized complexes of proteins and photosensitizers (PS) that assemble to form photoreceptor proteins (PRP). These are used by many organisms in diverse processes, such as energy conversion, protection against photodamage, etc. The same concept has been used in laboratory settings for many applications, such as the stimulation of neurons or the selective depletion of proteins in a signaling pathway. A key issue in laboratory settings has been the relationship between the photooxidation of proteins and conformational changes in host proteins. For several years, we have been interested in creating non-native PRP using porphyrin PS. In this study, we investigated the self-assembled complex between zinc protoporphyrin IX (ZnPPIX) and bovine β-lactoglobulin (BLG) as a model of non-native PRP. Since BLG undergoes a significant conformational transition near physiological pH, the study was carried out at acidic (pH 5) and alkaline (pH 9) conditions where the two conformations are respectively prevalent. We employed a series of steady-state and time-resolved optical spectroscopies as well as gel electrophoresis to experimentally characterize the photosensitization mechanisms and their effect on the host protein. Our results show that ZnPPIX prompts light-dependent modifications of BLG, which appear to be much more significant at alkaline pH. The modifications seem to be driven by photooxidation of amino acid residues that do not lead to the formation of cross-links or protein fragmentation. [ABSTRACT FROM AUTHOR]

The emergence of toxic pollutants due to heavy human intervention in the ecosystem causes serious environmental problems. Therefore, sensors based on material having a strong affinity towards specific environmental gaseous pollutants are urgently needed. The present study deals with chemiresistive gas sensors for the detection of sulfur dioxide (SO2) based on a composite of reduced graphene oxide (rGO) and 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP). The improved Hummers method was used to synthesize graphene oxide (GO); it was further thermally reduced to rGO. The pattern of the copper electrode was coated on glass slides with a shadow mask using thermal evaporation. Then, GO was drop-cast between the two copper electrodes, thermally reduced to obtain rGO, and then modified by TAPP. The spectroscopic, structural, morphological, electrical, and optical studies were carried out using Fourier transform infrared spectroscopy, x-ray diffraction, Raman spectroscopy, atomic force microscopy, field emission scanning electron microscopy, current–voltage (I–V) and UV–visible spectroscopy, respectively. The developed sensor shows high selectivity towards SO2 gas analytes among exposed gaseous analytes. It exhibited reproducible response from 50 ppm to 200 ppm with enhanced repeatability at 50 ppm. The rGO/TAPP sensor exhibited a significant response (57 s) and recovery time (61 s), with a 5 ppm limit of detection. [ABSTRACT FROM AUTHOR]

The interaction of cationic porphyrin with gold nanoparticles (GNPs) coated with polymer shells with positive and negative surface potentials in an aqueous solution is studied. The criteria for the formation of hybrid molecular-plasmon nanostructures based on the determination of the luminescence quenching mechanism according to the Stern–Volmer equation and the change in the shape of the porphyrin luminescence spectrum are established. The effect of the sign of the zeta potential of GNPs on the formation of hybrid molecular-plasmon nanostructures due to electrostatic interaction is established. [ABSTRACT FROM AUTHOR]

The aim of this study was to investigate whether antimicrobial blue light (aBL) can cause the death of Aggregatibacter actinomycetemcomitans (A.a) and to determine the influence of different culture media, specifically brain heart infusion and blood agar, on bacterial survival fraction. An LED emitting at 403 ± 15 nm, with a radiant power of 1W, irradiance of 588.2 mW/cm2, and an irradiation time of 0 min, 1 min, 5 min, 10 min, 30 min, and 60 min, was used. The plates were incubated in microaerophilic conditions at 37 °C for 48 h, and the colony-forming units were counted. The photosensitizers were investigated using spectroscopy and fluorescence microscopy. There was no significant difference between the culture media (p > 0.05). However, a statistical reduction in both media was observed at 30 min (1058 J/cm2) (p < 0.05). The findings of this study suggest that aBL has the potential to kill bacteria regardless of the culture media used. Light therapy could be a promising and cost-effective strategy for preventing periodontal disease when used in combination with mechanical plaque control. [ABSTRACT FROM AUTHOR]

Graphene oxide (GO) as a coating material for gold nanorods (AuNRs) has gained interest in reducing toxicity and improving the photothermal profiling of AuNRs. However, there is still a challenge regarding the storage of colloidal suspensions of GO-coated AuNRs (GO@AuNRs). Hence, the conjugation of GO@AuNRs to meso-tetra-(4-sulfonatophenyl)porphyrin (TPPS4), an anionic water-soluble porphyrin, has been reported to enhance their re-dispensability and improve their phototherapeutic properties. The AuNRs and GO were synthesised using seed-mediated and Hummers' methods, respectively. The GO@AuNRs were conjugated to TPPS4 and characterised using ultraviolet–visible–near-infrared (UV-Vis-NIR) spectroscopy, zeta analyser, dynamic light scattering (DLS), photoluminescence spectroscopy (PL), x-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and Fourier-transform infrared spectroscopy (FTIR) before freeze-drying. The results showed that the AuNRs were sandwiched between GO and TPPS4. After freeze-drying, the freeze-dried conjugate was dispensed in deionised water without adding cryoprotectants and its properties were compared to those of the unfreeze-dried conjugate. The results showed that the freeze-dried conjugate contained similar optical properties to the unfreeze-dried conjugate. However, the bare GO@AuNRs showed a change in the optical properties after freeze-drying. These results revealed that porphyrin is an excellent additive to reduce the freeze-drying stress tolerance of GO@AuNRs. The freeze-dried conjugate also showed both singlet oxygen and photothermal properties of GO@AuNRs and porphyrin. These results indicated that the freeze-dried conjugate is a promising dual photodynamic and photothermal agent, and porphyrin can act as a cryoprotectant. [ABSTRACT FROM AUTHOR]

Bacterial resistance to antibiotics is a critical global health issue and the development of alternatives to conventional antibiotics is of the upmost relevance. Antimicrobial photodynamic therapy (aPDT) is considered a promising and innovative approach for the photoinactivation of microorganisms, particularly in cases where traditional antibiotics may be less effective due to resistance or other limitations. In this study, two β-modified monocharged porphyrin-imidazolium derivatives were efficiently incorporated into polyvinylpyrrolidone (PVP) formulations and supported into graphitic carbon nitride materials. Both porphyrin-imidazolium derivatives displayed remarkable photostability and the ability to generate cytotoxic singlet oxygen. These properties, which have an important impact on achieving an efficient photodynamic effect, were not compromised after incorporation/immobilization. The prepared PVP-porphyrin formulations and the graphitic carbon nitride-based materials displayed excellent performance as photosensitizers to photoinactivate methicillin-resistant Staphylococcus aureus (MRSA) (99.9999% of bacteria) throughout the antimicrobial photodynamic therapy. In each matrix, the most rapid action against S. aureus was observed when using PS 2. The PVP-2 formulation needed 10 min of exposure to white light at 5.0 µm, while the graphitic carbon nitride hybrid GCNM-2 required 20 min at 25.0 µm to achieve a similar level of response. These findings suggest the potential of graphitic carbon nitride-porphyrinic hybrids to be used in the environmental or clinical fields, avoiding the use of organic solvents, and might allow for their recovery after treatment, improving their applicability for bacteria photoinactivation. [ABSTRACT FROM AUTHOR]

Porphyrin‐based porous organic polymers (Por‐POPs) are attracting increasing attention because of their potential in visible light photocatalysis. The distinctive attributes of Por‐POPs have been elucidated by investigating their response to specific reactions, such as the aerobic oxidation of sulfides. However, most researchers choose porphyrin molecules with relatively short peripheral substituent chains and strong stiffness to construct porphyrin‐based materials, especially Por‐POPS. Herein, we designed and prepared a flexible POP material H2Pp‐TAPM by incorporating extra π‐conjugated rigid units TAPM into a relatively flexible porphyrin monomer H2Pp through imine linkages. The POP synthesized in this study has demonstrated the ability to facilitate the transfer and dissociation of photogenerated electron–hole pairs, leading to the production of singlet oxygen 1O2 and superoxide radical anions O2˙−. These anions act as effective mediators for the selective aerobic oxidation of sulfides, resulting in the conversion of 99% and the selectivity more than 99%. Furthermore, the H2Pp‐TAPM has excellent stability and recyclability, indicating its attractiveness as heterogeneous photocatalyst for the transformation of organic compounds. This makes it a promising candidate for visible‐light‐driven reactions. [ABSTRACT FROM AUTHOR]

Results are presented from investigating the dependence of the ratio of the intensity of these bands on temperature in the range of 25–75°C for nonmetalated and zinc metalated porphyrins, along with porphyrin dyads in solutions of 1,2-dichloroethane. A comparative analysis of the thermometric parameters of these molecules is performed. [ABSTRACT FROM AUTHOR]

Gold nanoparticles are widely used as local heaters under optical excitation. Hybrid molecular-plasmon nanostructures based on gold nanoparticles and water-soluble porphyrin have been developed. A colloidal solution of gold nanoparticles was obtained by laser ablation of metallic gold in water, ensuring its highest chemical purity. The hybrid nanostructures formation was performed due to the Coulomb interaction of cationic porphyrin and gold nanoparticles. The revealed functional properties of hybrid nanostructures make them promising for controllable nano-heater applications (for example, photothermal therapy). Gold nanoparticles act as heaters, whereas porphyrin serves as a fluorescent thermometer with a single optical excitation. [ABSTRACT FROM AUTHOR]

Ferrocenyl‐substituted nickel(II) norcorrole and nickel(II) porphyrin (Fc2NiNc and Fc2NiPor, respectively) are prepared as active electrode materials for dual‐ion batteries, which enables the systematically study of aromaticity and antiaromaticity for organic electrode materials. Intrinsically, Fc2NiNc and Fc2NiPor electrodes have excellent electrochemical behaviors with dual ion interaction with Li cations and bis(fluorosulfonyl)amide [FSA]– inorganic anions from the ionic liquid electrolyte, inducing high capacities (259 mAh g−1 for Fc2NiNc and 200 mAh g−1 for Fc2NiPor). The dominance of pseudocapacitive charge storage is exhibited by the Fc2NiNc and Fc2NiPor electrodes giving rise to rapid charge‐discharge processes. Computational calculation conclusively demonstrates the mechanism of multi‐electron redox reaction resulting in high discharge capacities and aromatic stabilization energy toward achieving a stable long‐term cyclability over 1000 cycles at high current density. Furthermore, Li4Ti5O12/IL/Fc2NiNc cells exhibit high power and energy densities (234 Wh kg−1 at 118 W kg−1) and accomplish outstanding cyclability over 10 000 cycles. This work provides a strategy for designing robust organic electrode materials for dual‐ion batteries. [ABSTRACT FROM AUTHOR]

Heterogeneous photocatalysts have attracted extensive attention in photo‐induced electron transfer‐reversible addition–fragmentation chain transfer (PET‐RAFT) polymerization due to their remarkable advantages such as easy preparation, tunable photoelectric properties, and recyclability. In this study, zinc (II) 5,10,15,20‐tetrakis(4‐aminophenyl)porphyrin (ZnTAPP)‐based poly‐porphyrin nanoparticles (PTAPP‐Zn) are constructed by an emulsion‐directed approach. It is investigated as a heterogeneous photocatalyst for PET‐RAFT polymerization of various methacrylate monomers under visible light exposure, and the reactions show refined polymerization control with high monomer conversions. Furthermore, it is demonstrated that the PTAPP‐Zn nanoparticles with the larger pore size enhance photocatalytic activity in PET‐RAFT polymerization. In addition, the capabilities of oxygen tolerance and temporal control are demonstrated and PTAPP‐Zn particles can be easily recycled and reused without an obvious decrease in catalytic efficiency. [ABSTRACT FROM AUTHOR]