Metal Porphyrins Research Articles

COMPARANDO O DESEMPENHO DE DOIS ANALISADORES DE MASSAS (FT-ICR MS & LTQ MS): UMA AULA EXPERIMENTAL SOBRE ANÁLISE DE COMPOSTOS ORGÂNICOS

COMPARING THE PERFORMANCE OF TWO MASS ANALYZERS (FT-ICR MS & LTQ MS): AN EXPERIMENTAL CLASS ON ANALYSIS OF ORGANIC COMPOUNDS. Mass spectrometry (MS) is a high-performance analytical technique that allows a measurement of the mass/charge (m/z) ratio of compounds present in a sample. MS is able to separate two m/z ions with determined values (mass resolution), being an important characteristic, especially in the analysis of biochemical components and complex mixtures. Mass analyzers define the resolving power and accuracy of different types of mass spectrometers. Herein, the performance of two mass analyzers (Fourier Transform Ion Cyclotronic Resonance (FT-ICR) and quadrupole ion trap (LTQ)) was tested on low (Mw = 165-679 Da) and high (Mw = 783-8.58 kDa) molecular weight molecules (Phenacetin, Procaine, Benzocaine, Caffeine anhydrous, Lidocaine, two metal porphyrin standards, the first cobalt and the second vanadium, and two protein standards, Ubiquitin and Beauvericin), and finally, for an oil sample. LTQ-MS and FT-ICR-MS had similar performance and high reproducibility. However, the mass accuracy and resolution power of the FT-ICR (error lower than 5 ppm and RP higher than 400,000) was higher, being therefore, it was more suitable for the analysis of proteins and oil, for instance. On the other hand, the CID analysis via LTQ demonstrated its applicability in fragmentation experiments, being able to determinate the chemical connectivity of organic compounds in non-complex mixtures.

Defect-engineered porphyrinic metal-organic framework nanoparticles for targeted multimodal cancer phototheranostics.

Defect-engineered porphyrinic MOF nanoparticles were fabricated with an in situ one-pot protocol using cypate as the co-ligand and modulator. This multifunctional nanoplatform integrated the photothermal and multimodal imaging properties of cypate with the photodynamic effects of porphyrins, thus achieving targeted multimodal cancer phototheranostics after folic acid modification.

A versatile nanoplatform based on multivariate porphyrinic metal-organic frameworks for catalytic cascade-enhanced photodynamic therapy.

In recent years, the antitumor application of photodynamic therapy (PDT) has gained widespread interest in treating solid tumors. Due to the hypoxic environment in tumors, the major limit of PDT seems to be the source of oxygen. In this work, we attempted to relieve hypoxia and enhance photodynamic therapy, and therefore, designed and assembled a catalytic cascade-enhanced PDT multifunctional nanoplatform. The mentioned platform termed UIO@Ca-Pt is based on porphyrinic metal-organic framework (UIO) combination, which is simultaneously loaded by CaO2 NPs with polydopamine (PDA) and then the Pt raw material to further improve biocompatibility and efficiency. In a tumor microenvironment, CaO2 could react with water to generate calcium hydroxide and hydrogen peroxide, which was further decomposed by Pt nanoparticles to form oxygen, thereby facilitating the generation of cytotoxic singlet oxygen by photosensitizer TCPP under laser irradiation. Both in vitro and in vivo experiment results confirmed the excellent oxygen production capacity and enhanced PDT effect of UIO@Ca-Pt. With guaranteed safety in PDT, the oxygen-supplying strategy might stimulate considerable interest in the development of various metal-organic materials with multifunctionality for tumor diagnosis and therapy.

Proton conductivity as a function of the metal center in porphyrinylphosphonate-based MOFs.

The rational design of metal-organic frameworks (MOFs) is highly important for the development of new proton conductors. Porphyrinylphosphonate-based MOFs, providing the directed tuning of physical and chemical properties of materials through the modification of a macrocycle, are potentially high-conducting systems. In this work the synthesis and characterization of novel anionic Zn-containing MOF based on palladium(ii) meso-tetrakis(3-(phosphonatophenyl))porphyrinate, IPCE-2Pd, are reported. Moreover, the proton-conductive properties and structures of two anionic Zn-containing MOFs based on previously described nickel(ii) and novel palladium(ii) porphyrinylphosphonates, IPCE-2M (M = Ni(ii) or Pd(ii)), are compared in details. The high proton conductivity of 1.0 × 10-2 S cm-1 at 75 °C and 95% relative humidity (RH) is revealed for IPCE-2Ni, while IPCE-2Pd exhibits higher hydrolytic and thermal stability of the material (up to 420 °C) simultaneously maintaining a comparable value of conductivity (8.11 × 10-3 S cm-1 at 95 °C and 95% RH). The nature of the porphyrin metal center is responsible for the features of crystal structure of materials, obtained under identical reaction conditions. The structures of IPCE-2Pd and its dehydrated derivative IPCE-2Pd-HT are determined from the synchrotron powder diffraction data. The presence of phosphonic groups in compared materials IPCE-2M affords a high concentration of proton carriers that together with the sorption of water molecules leads to a high proton conductivity.

PCN-222@g-C3N4 cathodic materials for "signal-off" photoelectrochemical sensing of kanamycin sulfate.

A novel cathodic photoelectrochemical (PEC) sensor was developed for the ultrasensitive detection of kanamycin sulfate (KAM) based on the g-C3N4 coupled zirconium-based porphyrinic metal–organic framework (PCN-222). Photocathodes made by double n-type semiconductors, which was attributed to the transfer of electrons and holes from g-C3N4 broad band to PCN-222 with narrow band gap. The photocurrent decreased when KAM was added, which was conducive to the construction of the PEC sensor. Then, the PCN-222@g-C3N4 was used as a photosensitive platform to construct a label-free strategy and ultrasensitive detection of KAM with wide linear range from 1 to 1000 nM and a low detection limit of 0.127 nM. Moreover, this sensing platform shows good selectivity, favourable reproducibility and brilliant stability. The reported sensors provided great potential for the detection of KAM in actual samples.

Effect of porphyrin metal center on synthesis, structure, morphology and oxygen reduction properties of porphyrin encapsulated metal organic frameworks

A series of different metal centered 5,15-Bis(4-aminophenyl)-10,20-bis(4-bromophenyl)porphyrins (PorM) where M = H2, MnOAc, FeCl, Co or Zn were synthesized, and then encapsulated in zeolite imidazole framework-8 (ZIF-8) by typical template directed strategy to generate PorM@ZIF-8 metal organic frameworks (MOFs). These composites were characterized by UV-vis, FTIR, XRD, FESEM and HRTEM methods. Each prepared PorM@ZIF-8 MOF retained the molecular structure of porphyrin and crystal structure of ZIF-8. It is clearly shown that porphyrin centered metal ions will affect MOFs morphology. Both PorH2@ZIF-8 and PorZn@ZIF-8 gave a rhombic dodecahedron, PorMnOAc@ZIF-8 gave a truncated hexagonal prism-like structure, while no specific structures were obtained for PorFeCl@ZIF-8 and PorCo@ZIF-8 due to aggregation as characterized by FESEM spectrum. Oxygen reduction catalytic ability of ZIF-8, PorM and PorM@ZIF-8 were measured in alkaline condition (0.1 M KOH) with the number of electrons transferred being [Formula: see text] = 2.20–2.60 and generating HO[Formula: see text] as the oxygen reduction product. The catalytic property slightly increased after the porphyrin was encapsulated, due possibly to the capacity limit, inappropriate molecular distance or the direction of encapsulated porphyrin molecular.

Enhanced CO2 Adsorption by Insertion Reaction in the Nanospace of a Porphyrin-based MOF

Abstract Here we report enhanced CO2 molecular recognition ability by incorporating insertion reaction into a metal porphyrin complex in a metal-organic framework (MOF). PCN-222(Cu)-INA was synthesized by the reaction of PCN-222(Cu) [Zr6O8(H2O)8(Cu-TCPP)2], where Cu-TCPP = Cu(II) tetrakis(4-carboxyphenyl)porphyrin, and isonicotinic acid (INA). PCN-222(Cu)-INA exhibited a 1.5 times larger CO2 adsorption amount than PCN-222(Cu) at 298 K and 1 bar. The mechanism involving insertion reaction of CO2 into Cu–N bonds enhanced the adsorption, which was revealed by in situ IR spectroscopy and theoretical calculations.

SNAr Reaction Toward the Synthesis of Fluorinated Quinolino[2,3,4‐at]porphyrins

AbstractAn intramolecular SNAr displacement of one o‐fluorine atom of a meso‐pentafluorophenyl‐substituted porphyrin metal complex by a neighboring β‐amino functionality generated the corresponding meso‐fluorophenyl‐substituted metallo‐quinolino[2,3,4‐at]porphyrins that are not accessible using established quinoline‐annulation methodologies. The Cu(II), Ni(II), and Zn(II) complexes were thus prepared. The parent free base quinolino[2,3,4‐at]porphyrin is accessible only by demetallation of the copper or zinc complexes. A strong through‐space NMR‐spectroscopic coupling between the remaining o‐fluorine atoms on the annulated meso‐aryl group and the β‐hydrogen atom on the adjacent pyrrole moiety provide a clear spectroscopic signature for the annulation. Quinoline‐annulation alters the optical properties significantly. On account of the presence of the β‐amino functionality, all quinoline‐annulated porphyrins show strong halochromic responses with Brønsted acids and bases, the prerequisite for their potential use in chemosensing applications.

Topological Strain-Induced Regioselective Linker Elimination in a Chiral Zr(IV)-Based Metal-Organic Framework

Summary Zr-carboxylate metal-organic frameworks (MOFs) are structurally robust materials, in part due to their strong coordination bonds. The regioselective Zr–O bond cleavage and formation between 3D architectures are thus challenging and are heretofore unexplored. In this work, by introducing highly flexible 18-crown-6-ether functionalities into a homochiral Zr-MOF, we report an unprecedented topology transition in which a 4,10-connected framework undergoes a rapid solid-state transition into a thermodynamically more stable 4,8-connected analog by a regioselective-linker-elimination under ambient conditions. The transition process was unambiguously unraveled by single-crystal and powder X-ray diffraction studies, and we proposed a possible transition mechanism based on various control experiments and theoretical calculations. The excellent chemical stability and substantially expanded porosity and pore apertures endowed the transformed chiral MOF with an exceptional capacity for the enantioadsorptive and solid-phase extractive separation of the racemic drug molecule of lansoprazole with 98% ee and 93% ee, respectively.

Protein-Embedded Metalloporphyrin Arrays Templated by Circularly Permuted Tobacco Mosaic Virus Coat Proteins.

Bioenergetic processes in nature have relied on networks of cofactors for harvesting, storing, and transforming the energy from sunlight into chemical bonds. Models mimicking the structural arrangement and functional crosstalk of the cofactor arrays are important tools to understand the basic science of natural systems and to provide guidance for non-natural functional biomaterials. Here, we report an artificial multiheme system based on a circular permutant of the tobacco mosaic virus coat protein (cpTMV). The double disk assembly of cpTMV presents a gap region sandwiched by the two C2-symmetrically related disks. Non-native bis-his coordination sites formed by the mutation of the residues in this gap region were computationally screened and experimentally tested. A cpTMV mutant Q101H was identified to create a circular assembly of 17 protein-embedded hemes. Biophysical characterization using X-ray crystallography, cyclic voltammetry, and electron paramagnetic resonance (EPR) suggested both structural and functional similarity to natural multiheme cytochrome c proteins. This protein framework offers many further engineering opportunities for tuning the redox properties of the cofactors and incorporating non-native components bearing varied porphyrin structures and metal centers. Emulating the electron transfer pathways in nature using a tunable artificial system can contribute to the development of photocatalytic materials and bioelectronics.

Self-assembled supramolecular nanostructure photosensitizers for photocatalytic hydrogen evolution

Supramolecular self-assembly as a breakthrough methodology in the nanoscience and nanotechnology fields has attracted increasing attention. Highly ordered self-assembled supramolecular nanostructures aim to emulate natural light-harvesting and energy transfer and electron transfer processes, which have been an active and rapidly developing field for visible-light-driven photocatalytic applications. This Research Update aims to present the recent progress of the self-assembly of π-conjugated molecules, including perylene diimides (PDIs), porphyrin, and co-assembly of peptide–porphyrin as well as the shape-defined functional hierarchical structures. First, the basic principles of π-conjugated molecular structure design are described. The two nitrogen positions and the bay positions of PDIs can effectively regulate their electronic properties and geometric skeleton, and the functional groups and the good solvents of porphyrin effectively determine the choice of self-assembly methods. Then, the key morphology dependent optoelectronic properties and charge-transport and energy-transport functionalities are also discussed. These self-assembled supramolecular nanostructures’ inherent optoelectronic properties correlated with applications in photocatalytic water splitting into hydrogen evolution are overviewed. By now, the self-assembled In(III) meso-tetraphenylporphine (InTPP) porphyrin nanostructures exhibited the highest photocatalytic hydrogen generation activity among the reported supramolecular nanostructures owing to the central metal of porphyrin and small size of the InTPP nanostructure. Finally, perspectives on the crucial issues and potential future research directions are addressed. This Research Update will provide a new reference for building high performance, stable, and durable photosensitizers based on the supramolecular assembly.

DFT and Empirical Considerations on Electrocatalytic Water/Carbon Dioxide Reduction by CoTMPyP in Neutral Aqueous Solutions*.

A combined experimental and density functional theory (DFT) investigation was employed in order to examine the mechanism of electrochemical CO2 reduction and H2 formation from water reduction in neutral aqueous solutions. A water soluble cobalt porphyrin, cobalt [5,10,15,20-(tetra-N-methyl-4-pyridyl)porphyrin], (CoTMPyP), was used as catalyst. The possible attachment of different axial ligands as well as their effect on the electrocatalytic cycles were examined. A cobalt porphyrin hydride is a key intermediate which is generated after the initial reduction of the catalyst. The hydride is involved in the formation of H2 and formate and acts as an indirect proton source for the formation of CO in these H+ -starving conditions. The experimental results are in agreement with the computations and give new insights into electrocatalytic mechanisms involving water soluble metalloporphyrins. We conclude that in addition to the porphyrin's structure and metal ion center, the electrolyte surroundings play a key role in dictating the products of CO2 /H2 O reduction.

Silicon Phthalocyanine Modified Multi-Walled Carbon Nanotubes As a Novel Metal-Free Catalyst for the Oxygen Electroreduction

Finding an alternative catalysts for the oxygen reduction reaction (ORR) has been a key issue in modern electrocatalysis. Traditional platinum-based catalysts are not viable in the long term and thus much effort has been focused on non-precious metal catalysts. Heteroatom doped and metal-heteroatom co-doped carbon materials have emerged as the main candidate for replacing the platinum-based catalysts. Different MN4 macrocycles, such as metal phthalocyanines and porphyrins, have been studied as promising materials to prepare electrocatalysts for ORR in alkaline media [1]. While the development of non-precious metal and non-metal carbon catalysts has gained a lot of attention recently, non-metal phthalocyanines are a less studied topic [2].In this work a novel catalyst material including multi-walled carbon nanotubes (MWCNT) and silicon phthalocyanine dichloride (SiPcCl2) was synthesised and the electrochemical activity towards the oxygen reduction reaction (ORR) in alkaline media was studied. Different ratios of phthalocyanine-to-nanotubes were pyrolysed at 800 °C. After optimising the ratio of phthalocyanine-to-nanotubes, the pyrolysis process was also carried out at different temperatures, but the results showed that the best temperature for pyrolysis is still 800 °C. ORR activity on SiPc/MWCNT catalyst was studied in 0.1 M KOH by employing rotating disc electrode method. Physical characterisation was carried out with X-ray photoelectron spectroscopy and transmission electron microscopy. The results showed successful incorporation of silicon and nitrogen into the carbon framework. We show that doping MWCNTs with a non-metal phthalocyanine creates a highly active ORR catalyst rivaling the activity of metal-based catalysts in alkaline conditions. This work clearly demonstrates that non-metal macrocyclic compound modified carbons, similar to the the SiPc/MWCNT can be used as alternative cathode catalysts for the metal-air batteries and alkaline membrane fuel cells.[1] Y. Liu, X. Yue, K. Li, J. Qiao, D.P. Wilkinson, J. Zhang, PEM fuel cell electrocatalysts based on transition metal macrocyclic compounds, Coord Chem Rev. 315 (2016) 153-177.[2] K.-K. Türk, K. Kaare, I. Kruusenberg, M. Merisalu, U. Joost, L. Matisen, V. Sammelselg, J.H. Zagal, K. Tammeveski, Oxygen electroreduction on zinc and dilithium phthalocyanine modified multiwalled carbon nanotubes in alkaline media, J. Electrochem. Soc. 164 (2017) H338-H344.

Open versus Interpenetrated: Switchable Supramolecular Trajectories in Mechanosynthesis of a Halogen-Bonded Borromean Network

Summary Precise control over topologically intricate molecular architectures remains an open challenge for chemists due to their inherent structural complexity. We report a simple solvent-free strategy to selectively prepare two multi-component supramolecular crystalline systems based on the halogen bond, endowed with either an unknot topology or a Borromean-type entanglement. Real-time in situ monitoring of the solvent-free mechanochemical synthesis of these three-component halogen-bonded ionic co-crystals reveals that the choice of milling conditions leads to a switch in the supramolecular reaction trajectory, resulting in the selective formation of an open halogen-bonded network or a halogen-bonded Borromean-type assembly.

Cover Feature: A Mixed‐Metal Porphyrinic Framework Promoting Gas‐Phase CO2 Photoreduction without Organic Sacrificial Agents (ChemSusChem 23/2020)

The Cover Feature shows how, serving as an artificial photosynthesis system, the rationally designed Ti/Zr porphyrinic metal–organic framework demonstrates gas-phase water oxidation-assisted selective photoreduction of CO2 under visible-light irradiation. More information can be found in the Communication by W.-Y. Gao, H. T. Ngo, et al.

Rugby-ball like Ag modified zirconium porphyrin metal–organic frameworks nanohybrid for antimicrobial activity: Synergistic effect for significantly enhancing photoactivation capacity

Despite of the current advancement in antibacterial material, the bacterial issues are still great challenges in health problems worldwide. Herein, Ag nanoparticles doped to zirconium porphyrin metal–organic frameworks (ZPM@Ag) were synthesized for antibacterial activity. The effect of different dosage of Ag nanoparticles on the antibacterial activity was also investigated. The morphology, porous microstructure, and composition of the prepared nanohybrids were characterized by SEM, TEM, XRD, FT-IR, XPS and BET analysis. The results revealed that the optimized antimicrobial efficiency was ZPM@Ag(2). The reactive oxygen species (ROS) production of ZPM@Ag(2) under visible light was obviously abundant than that in the dark, and moreover, the nanohybrid exhibited high antimicrobial efficacy. Furthermore, the antimicrobial mechanism of the prepared sample was also carefully investigated. The enhanced photoactivation antimicrobial activity could be ascribed to the synergistic effect between zirconium porphyrin MOFs (ZPM) and Ag nanoparticles, which possesses high specific surface area and abundant active sites due to the uniform rugby-ball like shape. ZPM@Ag(2) nanohybrid was demonstrated excellent stability even after five cycles. The antimicrobial Ag nanoparticles immobilized in photocatalytic antibacterial porous MOFs are expected to provide a guideline to broaden the applications of MOFs and design novel metal-based antibacterial nanomaterials.

First-row transition metal porphyrins for electrocatalytic hydrogen evolution — a SPP/JPP Young Investigator Award paper

A series of first-row transition metal complexes of tetrakis(pentafluorophenyl)porphyrin (1), denoted as 1-M (M [Formula: see text] Mn, Fe, Co, Ni, Cu, and Zn), were synthesized and examined as electrocatalysts for the hydrogen evolution reaction (HER). All these transition metal porphyrins were shown to be active for HER in acetonitrile using trifluoroacetic acid (TFA) as the proton source. The molecular nature and the stability of these metal porphyrins when functioning as HER catalysts were confirmed, and all catalysts gave Faradaic efficiency of >97% for H2generation during bulk electrolysis. Importantly, by using 1-Cu, a remarkably high turnover frequency (TOF) of 48500 s[Formula: see text] 1-Cu the most efficient among this series of metal porphyrin catalysts. This TOF value also represents one of the highest values reported in the literature. In addition, electrochemical analysis demonstrated that catalytic HER mechanisms with these 1-M complexes are different. These results show that with the same porphyrin ligand, the change of metal ions will have significant impact on both catalytic efficiency and mechanism. This work for the first time provides direct comparison of electrocatalytic HER features of transition metal complexes of tetrakis(pentafluorophenyl)porphyrin under identical conditions, and will be valuable for future design and development of more efficient HER electrocatalysts of this series.

Palladium Nanocrystals‐Engineered Metal–Organic Frameworks for Enhanced Tumor Inhibition by Synergistic Hydrogen/Photodynamic Therapy

AbstractHydrogen therapy, as a star therapeutic modality, has recently acquired much attention in the field of anticancer medicine. Evidence suggests that hydrogen can selectively reduce intratumoral overexpressed hydroxyl radicals (•OH) to break the redox homoeostasis and thereby result in redox stress and cell damage. As a reactive oxygen species‐related noninvasive modality, photodynamic therapy (PDT) has been approved for varied tumor treatments clinically. For implementing tumor therapy with enhanced anticancer efficacy and attenuated side effects, here a biocompatible palladium nanocrystals‐integrated nanoscale porphyrinic metal–organic framework (NPMOF) is designed to develop a novel combined therapy modality, that is, synergistic hydrogen/photodynamic therapy. The NPMOF is employed simultaneously as the photosensitizer for PDT and as the nanocarrier to support palladium nanocrystals, which is further used as the hydrogen vehicle. The final hydrogen‐containing nanosystems exhibit a persistent reductive hydrogen release behavior and considerable light‐activated singlet oxygen (1O2) generation without mutual interference, contributing to the adequate disturbance of tumor microenvironment redox steady‐state for synergistically inducing tumor cell death. Ultimately, by coupling of tumor‐selective hydrogen therapy and PDT, the designed nanosystems realize the augmented therapeutic outcome with minimal side effects, providing a safe and efficient tumor treatment for future clinical translation.

Platinic metal porphyrins and hybrid nanomaterials embedding them as catalysts in chemical transformations

Platinic metal porphyrins and hybrid nanomaterials embedding them as catalysts in chemical transformations

Tumor targeted self-synergistic nanoplatforms for arsenic-sensitized photodynamic therapy

Development of antitumor agents with high efficiency and low toxicity is one of the most important goals for biomedical research. However, most traditional therapeutic strategies were limited due to their non-specificity and abnormal tumor microenvironments, causing a poor therapeutic efficiency and severe side effects. In this paper, a tumor targeted self-synergistic nanoplatform (designated as PAO@PCN@HA) was developed for chemotherapy sensitized photodynamic therapy (PDT) against hypoxic tumors. The efficient drug loading of phenylarsine oxide (PAO) in porphyrinic metal organic framework of PCN-224 as well as the surface modification of hyaluronic acid (HA) improved the targeted drug delivery and reduced the side effects of PAO at the therapeutic dose. Particularly, PAO as an arsenical-based chemotherapeutic agent could not only induce cell apoptosis by generating reactive oxygen species (ROS), but also regulate tumor microenvironments to improve the PDT effect of PCN-224 by mitigating hypoxia and consuming cellular GSH. Both in vitro and in vivo investigations confirmed an effective self-synergy of PAO@PCN@HA in hypoxic tumor therapy with a low systemic toxicity. This integration of microenvironment adjustment with tumor targeted self-synergistic mechanism might provide a new insight for the development of arsenic-based antitumor strategy for clinical applications.