Gold(III) Porphyrin-Metal-Polyphenolic Nanocomplexes: Breaking Intracellular Redox Environment for Enhancing Mild-Temperature Photothermal Therapy.

Photothermal therapy (PTT) is a promising clinical antitumor strategy. However, local hyperthermia inevitably induces heat damage to adjacent normal tissues, while alternative mild-temperature therapy (MPTT, T < 45 °C) is also inefficient due to the overexpressed hyperthermia-induced heat shock proteins (HSPs) by cancer cells. Therefore, developing PTT strategies with minimizing damage to healthy tissues with improved cellular temperature sensitivity is extremely valuable for clinical application. Herein, we proposed the strategy of disrupting the intracellular redox environment via destroying the ROS-defending systems to promote MPTT. The gold(III) porphyrin-Fe3+-tannic acid nanocomplexes (AuTPP@TA-Fe NPs) were achieved via interfacial cohesion and supramolecular assembly of bioadhesive species, which could trigger the Fenton reaction to produce ·OH radicals and downregulation of reductive TrxR enzyme and mitochondrial chaperone protein Hsp60. The aggravation of oxides and the inactivation of Hsp60 provide favorable pathways for impeding the heat shock-induced self-repair mechanism of cancer cells, which strengthens AuTPP@TA-Fe NPs mediated MPTT.

Zr-based metalloporphyrin MOF probe for electrochemical detection of parathion-methyl.

An electrochemical (EC) sensor based on metalloporphyrin metal-organic framework (MOF) for the detection of parathion-methyl (PM) has been developed. The prepared MOF-525(Fe) exhibits great signal enhancement toward the electrochemical detection of PM owing to its unique structural properties and electrochemical activities. Under optimal experimental conditions, the as-prepared MOF-525(Fe) based EC sensor exhibited excellent PM sensing performance with a wide linear detection range (0.1 µM-100 µM) and low limit of detection (LOD, 1.4 nM). Compared to its corresponding Fe metalloporphyrin (linker), MOF-525(Fe) exhibited a superior sensitivity (28.31 µA cm-2·µM-1), which is 3.7 times higher than the sensitivity of FeTCPP linker (7.56 µA cm-2·µM-1) towards PM. The improved performance is associated with the high specific surface area and the large pore channels of MOF-525(Fe) facilitating a better interaction between PM and the Fe metalloporphyrin active sites, especially in the lower concentration range. Moreover, a possible affinity of the PM molecules toward Zr6 clusters may also contribute to the selective enrichment of PM on MOF-525(Fe). This EC sensor further demonstrated high selectivity in the presence of interfering molecules. The recovery results further confirm accurate PM sensing in actual samples, which suggests promising applications for the rapid detection of environmental organophosphates by metalloporphyrin MOFs.

Photoelectrochemical immunoassay of cardiac troponin I based on ZnTCPP/CdIn2S4 type-II heterojunction and co-catalyzed precipitation biolabeling.

CdIn2S4 and zinc tetrakis(4-carboxyphenyl)porphyrin (ZnTCPP) were synthesized by hydrothermal method, and an organic dye-sensitized inorganic semiconductor ZnTCPP/CdIn2S4 type II heterojunction was constructed on a fluorine-doped tin oxide (FTO) substrate electrode. A sandwich immunostructure for signal-attenuation photoelectrochemical (PEC) detection of cardiac troponin I (cTnI) was constructed using the ZnTCPP/CdIn2S4/FTO photoanode and a horseradish peroxidase (HRP)-ZnFe2O4-Ab2-bovine serum albumin (BSA) immunolabeling complex. The bioenzyme HRP and the HRP-like nanozyme ZnFe2O4 can co-catalyze the oxidation of 4-chloro-1-naphthol (4-CN) by H2O2 to produce an insoluble precipitate on the photoanode, thus notably reducing the anodic photocurrent for quantitative determination of cTnI. Under the optimal conditions, the photocurrent at 0 V vs. SCE in 0.1 M phosphate buffer solution (pH 7.40) containing 0.1 M ascorbic acid was linear with the logarithm of cTnI concentration from 500 fg mL-1 to 50.0 ng mL-1, and the limit of detection (LOD, S/N = 3) is 0.15 pg mL-1. Spiked recoveries were 95.1% ~ 104% for assay of cTnI in human serum samples.

Using Metalloporphyrin Nanosensors for In Situ Monitoring and Measurement of Nitric Oxide and Peroxynitrite in a Single Human Neural Progenitor Cell.

Nitric oxide (NO) is an inorganic signaling molecule that plays a crucial role in the regulation of numerous physiological functions. An oxidation product of the cytoprotective NO is cytotoxic peroxynitrite (ONOO-). In biological systems, the concentrations of NO and ONOO- are typically transient, ranging from nanomolar to micromolar, and these increases are normally followed by a swift return to their basal levels due to their short life spans. To understand the vital physiological role of NO and ONOO- in vitro and in vivo, sensitive and selective methods are necessary for direct and continuous NO and ONOO- measurements in real time. Because electrochemical methods can be adjusted for selectivity, sensitivity, and biocompatibility in demanding biological environments, they are suitable for real-time monitoring of NO and ONOO- release. Metalloporphyrin nanosensors, described here, have been designed to measure the concentration of NO and ONOO- produced by a single human neural progenitor cell (hNPC) in real time. These nanosensors (200-300 nm in diameter) can be positioned accurately in the proximity of 4-5 ± 1 µm from an hNPC membrane. The response time of the sensors is better than a millisecond, while detection limits for NO and ONOO- are 1 × 10-9 and 3 × 10-9 mol/L, respectively, with a linear concentration response of up to about 1 µM. The application of these metalloporphyrin nanosensors for the efficient measurement of the concentrations of NO and ONOO- in hNPCs is demonstrated, providing an opportunity to observe in real time the molecular changes of the two signaling molecules in situ.

Soluble metal porphyrins - Zero-valent zinc system for effective reductive defluorination of branched per and polyfluoroalkyl substances (PFASs).

Nano zero-valent metals (nZVMs) have been extensively utilized for decades in the reductive remediation of groundwater contaminated with chlorinated organic compounds, owing to their robust reducing capabilities, simple application, and cost-effectiveness. Nevertheless, there remains a dearth of information regarding the efficient reductive defluorination of linear or branched per- and polyfluoroalkyl substances (PFASs) using nZVMs as reductants, largely due to the absence of appropriate catalysts. In this work, various soluble porphyrin ligands [[meso­tetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl·7H2O (CoTCPP), [[meso­tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H2O (CoTPPS), and [[meso­tetra(4-N-methylpyridyl) porphyrinato]cobalt(II)](I)4·4H2O (CoTMpyP) have been explored for defluorination of PFASs in the presence of the nZn0 as reductant. Among these, the cationic CoTMpyP showed best defluorination efficiencies for br-perfluorooctane sulfonate (PFOS) (94%), br-perfluorooctanoic acid (PFOA) (89%), and 3,7-Perfluorodecanoic acid (PFDA) (60%) after 1 day at 70 °C. The defluorination rate constant of this system (CoTMpyP-nZn0) is 88-164 times higher than the VB12-nZn0 system for the investigated br-PFASs. The CoTMpyP-nZn0 also performed effectively at room temperature (55% for br-PFOS, 55% for br-PFOA and 25% for 3,7-PFDA after 1day), demonstrating the great potential of in-situ application. The effect of various solubilizing substituents, electron transfer flow and corresponding PFASs defluorination pathways in the CoTMpyP-nZn0 system were investigated by both experiments and density functional theory (DFT) calculations. SYNOPSIS: Due to the unavailability of active catalysts, available information on reductive remediation of PFAS by zero-valent metals (ZVMs) is still inadequate. This study explores the effective defluorination of various branched PFASs using soluble porphyrin-ZVM systems and offers a systematic approach for designing the next generation of catalysts for PFAS remediation.

The effect of light irradiation on a nitro-ruthenium porphyrin complex in the induced death of lung cancer cells in two- and three-dimensional cultures: Insights into the effect of nitric oxide.

Efforts to find compounds selectively affecting cancer cells while sparing normal ones have continued to grow. Nitric oxide (NO) is critical in physiology and pathology, including cancer. It influences cellular processes like proliferation, apoptosis, and angiogenesis. The intricate interaction of NO with cancer cells offers innovative treatment possibilities, but its effects can vary by concentration and site. Ruthenium complexes capable of releasing NO upon stimulation show for this purpose. These versatile compounds can also enhance photodynamic therapy (PDT), a light-activated approach, which induces cellular damage. Ruthenium-based photosensitizers (PSs), delivering NO and producing reactive oxygen species (ROS), offer a novel strategy for improved cancer treatments. In this study, a nitro-ruthenium porphyrin conjugate: {TPyP[Ru(NO2)(bpy)2]4}(PF6)4, designated RuNO2TPyP, which releases NO upon irradiation, was investigated for its effects on lung cells (non-tumor MRC-5 and tumor A549) in 2D and 3D cell cultures. The findings suggest that this complex has potential for PDT treatment in lung cancer, as it exhibits photocytotoxicity at low concentrations without causing cytotoxicity to normal lung cells. Moreover, treatment of cells with RuNO2TPyP followed by light irradiation (4 J cm-2) can induce apoptosis, generate ROS, promote intracellular NO formation, and has anti-migratory effects. Additionally, the complex can modify tumor cell structures and induce photocytotoxicity and apoptosis in a 3D culture. These outcomes are attributed to the internalization of the complex and its subsequent activation upon light irradiation, resulting in NO release and singlet oxygen production.

Zeolitic imidazolate framework-encapsulated zinc porphyrin photoresponsive nanozyme for colorimetric/fluorescent dual-mode sensing of glyphosate.

A novel zeolitic imidazolate framework-encapsulated zinc porphyrin (ZnTCPP@ZIF-90) photoresponsive nanozyme is proposed for the colorimetric/fluorescent dual-mode visual sensing of glyphosate (Gly). ZnTCPP@ZIF-90 exhibits photoresponsive oxidase-like activity and fluorescence quenching behavior. Meanwhile, the outer ZIF-90 layer can be selectively destroyed by Gly, causing the release of free ZnTCPP, resulting in the enhanced enzyme-like activity as well as fluorescence emission. The constructed ZnTCPP@ZIF-90 was successfully used for the colorimetric/fluorescent dual-mode detection of Gly. Additionally, the colorimetric and fluorescent images information captured by the smartphone were converted to color intensity (HSV/RGB values), with limits of detection of 0.27 µg/mL and 0.19 µg/mL, respectively. The proposed dual-mode sensor exhibits excellent selectivity and reliability for detecting Gly, and can be successfully applied to the analysis of real samples such as tap water, lake water, and fruit washing water. The current research efforts are expected to provide new perspectives for designing highly active photoresponsive nanozymes and their stimuli-responsive sensing systems, paving the way for their applications in portable dual-mode chemical sensing and environmental monitoring.

Origin of Enantioselectivity in Engineered Cytochrome c-Catalyzed Carbon-Radical FePP Hydrolysis Revealed Using QM/MM (ABEEM Polarizable Force Field) and MD Simulations.

The origin of highly efficient asymmetric aminohydroxylation of styrene catalyzed by engineered cytochrome c is investigated by the developed Atom-Bond Electronegativity Equalization Method polarizable force field (ABEEM PFF), which is a combined outcome of electronic and steric effects. Model molecules were used to establish the charge parameters of the ABEEM PFF, for which the bond-stretching and angle-bending parameters were obtained by using a combination of modified Seminario and scan methods. The interactions between carbon-radical Fe-porphyrin (FePP) and waters are simulated by molecular dynamics, which shows a clear preference for the pre-R over the pre-S. This preference is attributed to the hydrogen-bond between the mutated 100S and 101P residues as well as van der Waals interactions, enforcing a specific conformation of the carbon-radical FePP complex within the binding pocket. Meanwhile, the hydrogen-bond between water and the nitrogen atom in the active intermediate dictates the stereochemical outcome. Quantum mechanics/molecular mechanics (QM/MM (ABEEM PFF)) and free-energy perturbation calculations elucidate that the 3RTS is characterized by sandwich-like structure among adjacent amino acid residues, which exhibits greater stability than crowed arrangement in 3STS and enables the R enantiomer to form more favorably. Thus, this study provides mechanistic insight into the catalytic reaction of hemoproteins.

Live Microscopy of Multicellular Spheroids with the Multimodal Near-Infrared Nanoparticles Reveals Differences in Oxygenation Gradients.

Assessment of hypoxia, nutrients, metabolite gradients, and other hallmarks of the tumor microenvironment within 3D multicellular spheroid and organoid models represents a challenging analytical task. Here, we report red/near-infrared (NIR) emitting cell staining with O2-sensitive nanoparticles, which enable measurements of spheroid oxygenation on a conventional fluorescence microscope. Nanosensor probes, termed "MMIR" (multimodal infrared), incorporate an NIR O2-sensitive metalloporphyrin (PtTPTBPF) and deep red aza-BODIPY reference dyes within a biocompatible polymer shell, allowing for oxygen gradient quantification via fluorescence ratio and phosphorescence lifetime readouts. We optimized staining techniques and evaluated the nanosensor probe characteristics and cytotoxicity. Subsequently, we applied nanosensors to the live spheroid models based on HCT116, DPSCs, and SKOV3 cells, at rest, and treated with drugs affecting cell respiration. We found that the growth medium viscosity, spheroid size, and formation method influenced spheroid oxygenation. Some spheroids produced from HCT116 and dental pulp stem cells exhibited "inverted" oxygenation gradients, with higher core oxygen levels than the periphery. This contrasted with the frequently encountered "normal" gradient of hypoxia toward the core caused by diffusion. Further microscopy analysis of spheroids with an "inverted" gradient demonstrated metabolic stratification of cells within spheroids: thus, autofluorescence FLIM of NAD(P)H indicated the formation of a glycolytic core and localization of OxPhos-active cells at the periphery. Collectively, we demonstrate a strong potential of NIR-emitting ratiometric nanosensors for advanced microscopy studies targeting live and quantitative real-time monitoring of cell metabolism and hypoxia in complex 3D tissue models.

4-Carboxyphenyl as efficient donor group in nano Zn-Porphyrin for dye sensitized solar cells.

Dye-sensitized solar cells, represent the alternate technology in solar research due to their cost effective, easy fabrication processes, higher efficiencies, and design flexibility. In this research, dual donor group modified zinc porphyrin dyes, have been synthesized for DSSCs. The complexes of zinc porphyrin functioned as acceptor or attaching groups within each mesophenyl ring and carboxylic acid. These complexes exhibited diverse alkyl substituents and sizable electron-donating substituents, contributing to their varied chemical structures and potential applications. The dual Donor-π bridge -Acceptor group sensitizers, Zn[5,15-diphenylcarbazole-10,20-(4-carboxyphenyl) Porphyrin] (KSR-1) and Zn [5,15-thiadiazole-10,20-(4-carboxyphenyl) Porphyrin] (KSR-2) have been synthesized and adopted for DSSCs implementation. The molar absorption coefficients (ε) of KSR-2 and KSR-1 Soret bands were 0.56 x 105 mol/L/cm and 0.47 x 105 mol/L/cm, respectively. The Q bands of the KSR-1 and KSR-2 dyes were 1.10 x 105 mol/L/cm and 1.0 x 105 mol/L/cm, respectively and the molar absorption coefficient of the KSR-1 dye was greater when compared to the KSR-2 dye. The molar absorption coefficient of 0.71 x 105 mol/L/cm was visible in the KSR -1 Q-band. DFT calculations and the electrochemical characteristics of the KSR-1 and KSR-2 dyes have been studied and discussed. The exploration involved in investigating the photophysical properties and photovoltaic performance which were affected by varying the length and number of the donor entities. The wall-plug efficiency of the KSR-1 based solar panel was Voc = 0.68 V, Jsc = 8.94 mA/m2, FF = 56 and Efficiency (µ) = 3.44%. The wall-plug efficiency of the KSR-2 based solar panel was Voc = 0.63 V, Jsc = 5.42 mA/m2, FF = 53 and Efficiency (µ) = 1.83%.

Artificial Cells and HepG2 Cells in 3D-Bioprinted Arrangements.

Artificial cells are engineered units with cell-like functions for different purposes including acting as supportive elements for mammalian cells. Artificial cells with minimal liver-like function are made of alginate and equipped with metalloporphyrins that mimic the enzyme activity of a member of the cytochrome P450 family namely CYP1A2. The artificial cells are employed to enhance the dealkylation activity within 3D bioprinted structures composed of HepG2 cells and these artificial cells. This enhancement is monitored through the conversion of resorufin ethyl ether to resorufin. HepG2 cell aggregates are 3D bioprinted using an alginate/gelatin methacryloyl ink, resulting in the successful proliferation of the HepG2 cells. The composite ink made of an alginate/gelatin liquid phase with an increasing amount of artificial cells is characterized. The CYP1A2-like activity of artificial cells is preserved over at least 35 days, where 6 nM resorufin is produced in 8 h. Composite inks made of artificial cells and HepG2 cell aggregates in a liquid phase are used for 3D bioprinting. The HepG2 cells proliferate over 35 days, and the structure has boosted CYP1A2 activity. The integration of artificial cells and their living counterparts into larger 3D semi-synthetic tissues is a step towards exploring bottom-up synthetic biology in tissue engineering.

Effect of the nature of the chelated metal on the photodynamic activity of metalloporphyrins.

Coordination of metal ions by the tetrapyrrolic macrocyclic ring of porphyrin-based photosensitizers (PSs) affects their photophysical properties and consequently, their photodynamic activity. Diamagnetic metals increase the singlet oxygen quantum yield while paramagnetic metals have the opposite effect. Since singlet oxygen is considered the main cell-damaging species in photodynamic therapy (PDT), the nature of the chelated cation would directly affect PDT efficacy. This expectation, however, is not always supported by experimental results and numerous exceptions have been reported. Understanding the effect of the chelated metal is hindered because different chelators were used. The aim of this work was to investigate the effect of the nature of chelated cation on the photophysical and photodynamic properties of metalloporphyrins, using the same tetrapyrrole core as a chelator of Ag(II), Cu(II), Fe(III), In(III), Mn(III), or Zn(II). Results demonstrated that with the exception of Ag(II), all paramagnetic metalloporphyrins were inefficient as generators of singlet oxygen and did not act as PSs. In contrast, the coordination of diamagnetic ions produced highly efficient PSs. The unexpected photodynamic activity of the Ag(II)-containing porphyrin was attributed to reduction of the chelated Ag(II) to Ag(I) or to demetallation of the complex, caused by cellular reductants and/or by exposure to light. Our results indicate that in biological systems, where PSs localize to various organelles and are subjected to the action of enzymes, reactive metabolites, and reducing or oxidizing agents, their physicochemical and photosensitizing properties change. Consequently, the photophysical properties alone cannot predict the anticancer efficacy of a PS.

Trajectory in biological metal-organic frameworks: Biosensing and sustainable strategies-perspectives and challenges.

The ligand attribute of biomolecules to form coordination bonds with metal ions led to the discovery of a novel class of materials called biomolecule-associated metal-organic frameworks (Bio-MOFs). These biomolecules coordinate in multiple ways and provide versatile applications. Far-spread bio-ligands include nucleobases, amino acids, peptides, cyclodextrins, saccharides, porphyrins/metalloporphyrin, proteins, etc. Low-toxicity, self-assembly, stability, designable and selectable porous size, the existence of rigid and flexible forms, bio-compatibility, and synergistic interactions between metal ions have led Bio-MOFs to be commercialized in industries such as sensors, food, pharma, and eco-sensing. The rapid growth and commercialization are stunted by absolute bio-compatibility issues, bulk morphology that makes it rigid to alter shape/porosity, longer reaction times, and inadequate research. This review elucidates the structural vitality, biocompatibility issues, and vital sensing applications, including challenges for incorporating bio-ligands into MOF. Critical innovations in Bio-MOFs' applicative spectrum, including sustainable food packaging, biosensing, insulin and phosphoprotein detection, gas sensing, CO2 capture, pesticide carriers, toxicant adsorptions, etc., have been elucidated. Emphasis is placed on biosensing and biomedical applications with biomimetic catalysis and sensitive sensor designing.

Dentifrícios branqueadores contendo Blue covarine: revisão de literatura / Bleaching dentifrices containing "Blue covarine" literature review

Introdução: O efeito branqueador dos dentifrícios contendo Blue covarine é fundamentado no seu mecanismo de ação, caracterizado pela sua deposição na superfície dentária, alterando a percepção da cor. Objetivo: Revisar a literatura e buscar evidência científica sobre o efeito branqueador do Blue Covarine em tecidos mineralizados e materiais restauradores estéticos. Materiais e métodos: Para a revisão da literatura foram feitas buscas nas bases de dados PubMed, LILACS, BBO, SciELO e MEDLINE para identificar estudos clínicos e laboratoriais que avaliassem a ação branqueadora do agente óptico Blue covarine. Como estratégia de busca foram utilizados os descritores "Blue covarine", "Blue covarine e pasta de dentes", "Blue covarine and toothpaste", "Blue covarine e dentifrícios", "Blue covarine and dentifrices", "Blue covarine e dentifrícios branqueadores", "Blue covarine and whitening dentifrices", "Blue covarine e dentifrícios clareadores", "Blue covarine and bleaching dentifrices", "Blue covarine e pasta de dentes branqueadoras", "Blue covarine and whitening toothpaste", "Blue covarine e pasta de dentes clareadoras", "Blue covarine and bleaching toothpaste". Resultados: Dois pesquisadores selecionaram e analisaram criticamente 31 artigos, sendo 2 revisões da literatura, 4 estudos clínicos e 25 estudos laboratoriais. Divergências quanto ao desenho de estudo, métodos, amostra, critérios clínicos e parâmetros laboratoriais foram observados, além de conflitos de interesse. Conclusão: O Blue Covarine presente nos dentifrícios branqueadores parece ser efetivo na promoção do branqueamento dentário apenas quando associado aos agentes abrasivos presentes nas formulações, evidenciando que ensaios clínicos e laboratoriais, com metodologias semelhantes, são necessários para se obter evidência científica conclusiva sobre o efeito deste agente branqueador.(AU)

Introduction: The whitening effect of dentifrices containing Blue Covarine is based on its mechanism of action, characterized by its deposition on the tooth surface, altering the perception of color. Objective: To review the literature and seek scientific evidence on the whitening effect of Blue Covarine on mineralized tissues and aesthetic restorative materials. Materials and methods: For the literature review, searches were carried out in the PubMed, LILACS, BBO, SciELO and MEDLINE databases, in order to identify clinical and laboratory studies that evaluated the whitening action of the optical agent Blue Covarine. As a search strategy, the descriptors "Blue Covarine", "Blue Covarine and toothpaste", "Blue Covarine and dentifrices", "Blue Covarine and whitening dentifrices", "Blue Covarine and bleaching dentifrices", "Blue Covarine and whitening toothpaste", "Blue Covarine and bleaching toothpaste". Results: Two researchers selected and critically analyzed 31 articles, including 2 literature reviews, 4 clinical studies and 25 laboratory studies. Differences in study design, methods, sample, clinical criteria and laboratory parameters were observed, in addition to conflicts of interest. Conclusion: Blue Covarine present in whitening dentifrices seems to be effective in promoting dental whitening only when associated with abrasive agents present in the formulations, showing that clinical and laboratory tests, with similar methodologies, are necessary to obtain conclusive scientific evidence on the effect of this bleaching agent.(AU)

Interactions of arylhydroxylamines and alkylaldoximes with a rhodium porphyrin.

Heme enzymes are involved in the binding and metabolism of hydroxylamine (RNHOH) and aldoxime (RCH=NOH) compounds (R = H, alkyl, aryl). We report the synthesis and X-ray crystal structure of a metalloporphyrin in complex with an arylhydroxylamine, namely that of (TPP)Rh(PhNHOH)(C6H4Cl) (TPP = tetraphenylpophryinato dianion). The crystal structure reveals, in addition to N-binding of PhNHOH to Rh, the presence of an intramolecular H-bond between the hydroxylamine -OH proton and a porphyrin N-atom. Results from density functional theory (DFT) calculations support the presence of this intramolecular H-bond in this global minimum structure, and a natural bond order (NBO) analysis reveals that this H-bond comprises a donor π N=C (porphyrin) to acceptor σ* O-H (hydroxylamine) interaction of 2.32 kcal/mol. While DFT calculations predict the presence of similar intramolecular H-bond interactions in the related aldoxime complexes (TPP)Rh(RCH=NOH)(C6H4Cl) in their global minima structures, the X-ray crystal structure obtained for the (TPP)Rh(CH3(CH2)2CH=NOH)(C6H4Cl) complex is consistent with the local (non-global) minima conformation that does not have this intramolecular H-bond interaction.

Kinetic Control via Binding Sites within the Confined Space of Metal Metalloporphyrin-Frameworks for Enhanced Shape-Selectivity Catalysis.

One striking feature of enzyme is its controllable ability to trap substrates via synergistic or cooperative binding in the enzymatic pocket, which renders the shape-selectivity of product by the confined spatial environment. The success of shape-selective catalysis relies on the ability of enzyme to tune the thermodynamics and kinetics for chemical reactions. In emulation of enzyme's ability, we showcase herein a targeting strategy with the substrate being anchored on the internal pore wall of metal-organic frameworks (MOFs), taking full advantage of the sterically kinetic control to achieve shape-selectivity for the reactions. For this purpose, a series of binding site-accessible metal metalloporphyrin-frameworks (MMPFs) have been investigated to shed light on the nature of enzyme-mimic catalysis. They exhibit a different density of binding sites that are well arranged into the nanospace with corresponding distances of opposite binding sites. Such a structural specificity results in a facile switch in selectivity from an exclusive formation of the thermodynamically stable product to the kinetic product. Thus, the proposed targeting strategy, based on the combination of porous materials and binding events, paves a new way to develop highly efficient heterogeneous catalysts for shifting selectivity.

Reactivity Factors in Catalytic Methanogenesis and Their Tuning upon Coenzyme F430 Biosynthesis.

Methyl-coenzyme M reductase, responsible for the biological production of methane by catalyzing the reaction between coenzymes B (CoBS-H) and M (H3C-SCoM), hosts in its core an F430 cofactor with the low-valent NiI ion. The critical methanogenic step involves F430-assisted reductive cleavage of the H3C-S bond in coenzyme M, yielding the transient CH3 radical capable of hydrogen atom abstraction from the S-H bond in coenzyme B. Here, we computationally explored whether and why F430 is unique for methanogenesis in comparison to four identified precursors formed consecutively during its biosynthesis. Indeed, all precursors are less proficient than the native F430, and catalytic competence improves at each biosynthetic step toward F430. Against the expectation that F430 is tuned to be the strongest possible reductant to expedite the rate-determining reductive cleavage of H3C-S by NiI, we discovered the opposite. The unfavorable increase in reduction potential along the F430 biosynthetic pathway is outweighed by strengthening of the Ni-S bond formed upon reductive cleavage of the H3C-S bond. We found that F430 is the weakest electron donor, compared to its precursors, giving rise to the most covalent Ni-S bond, which stabilizes the transition state and hence reduces the rate-determining barrier. In addition, the transition state displays high pro-reactive motion of the transient CH3 fragment toward the H-S bond, superior to its biosynthetic ancestors and likely preventing the formation of a deleterious radical intermediate. Thus, we show a plausible view of how the evolutionary driving force shaped the biocatalytic proficiency of F430 toward CH4 formation.

Electric field effect of positive and negative charges of substituents on electronic structure and reactivity of oxoiron(IV) porphyrin π-cation radical complex.

Electric field effect by the positive and negative changes near the active site is an important factor for controlling the reactivity of metalloenzymes. Previously, we reported that the positive charge of the N-methyl-2-pyridinium cation increases the reactivity of oxoiron(IV) porphyrin π-cation radical complex (Compound I), due to the attractive Coulomb interaction with electrons in Compound I. To further investigate the electric field effect, we study here the effect of the negative charge of the sulfonate group on the electronic structure and reactivity using Compound I of meso-tetrakis(2,4,6-trimethyl-3-sulfonatophenyl)porphyrin (TMPS-I). Although Compound I has been known as a very unstable complex, TMPS-I is very stable in 0.1 M acetate buffer at pH = 6. The half-life of TMPS-I is estimated to be 6.9 × 103 s, which is the longest in Compound I previously reported. The redox potential of TMPS-I is estimated to be 0.76 V vs SCE in phosphate buffer, pH = 10. Kinetic analysis with stopped-flow technique indicates TMPS-I is less reactive than Compounds I reported previously. However, 1H NMR and EPR spectra of TMPS-I are very close to those of Compounds I reported previously. The DFT calculations show that the orbital energy of Compound I is drastically altered by the positive and negative charges on the meso-phenyl group, suggesting the electric field effect. The difference of the reactivity of Compound I can be rationalized with the change of the orbital energy caused by the intramolecular electric field effect of the positive and negative charges.

Molecular Dipole Modulation of Porphyrins to Enhance Photocatalytic Oxidation Activity for Inactivation of Intracellular Bacteria.

The regulation of molecular structures of porphyrin-based photosensitizers is crucial for yielding the effective singlet oxygen as one of the efficient photocatalytic reactive oxidation species. Here, we select methoxy substitution as an electron donor to decorate the porphyrin rings. Introducing a series of metal ions into porphyrin centers further prepares the methoxy-substituted metalloporphyrins (MPs, M = Co, Ni, Cu, Zn), with the hope of modulating their molecular dipole moments and photocatalytic activity. The theoretical calculation analyses show that the metal-free porphyrin center possesses a higher transition dipole and more delocalized orbitals, leading to efficient charge transfer and improved photocatalytic activity. The metalloporphyrin samples are then polymerized by poly(D, l-lactide-co-glycolide) to be applied to in vitro sterilization experiments. As expected, metal-free porphyrin has good antibacterial ability and good biocompatibility. Moreover, the highly effective bacteriostatic metal-free porphyrin achieves satisfactory photodynamic therapeutic outcomes against intracellular pathogens in cancer cells. This work demonstrates that the molecular dipole modulation of porphyrins is critical for their photocatalytic oxidation and antibacterial ability.

Electronic, geometrical and photophysical facets of five coordinated porphyrin N-heterocyclic carbene transition metals complexes: A theoretical study.

In the realm of dye sensitized solar cells (DSSCs), the 3d transition metals as photosensitizers are scarcely studied. In the present work, electronic structures, FMO, MEP surfaces, NBO analysis, energetics and photophysical properties of earth abundant metals (Mn, Fe and Co) based metalloporphyrins coordinated with NHC-carbene have been explored by using DFT and TDDFT calculations. According to formation energies and energy decomposition analysis (EDA), the cobalt based metalloporphyrins species are found to be more stable while in contrast manganese based species are predicted as more reactive among all. Also, from the ligation point of view, the TPP (meso-tetraphenylporphyrin) ligand forms more steady and rigid coordination as compare to the TTP (meso-tetratolylporphyrin) ligand. FMO analysis also support these observations. NBO and SNO results support the electronic configurations as well as unveil the controversial bonding pattern of NHCcarbon and metal atom and found that there is σ-bonding present between the metal and the NHCcarbon by the overlapping of sp-hybridized orbitals of carbenecarbon and sp/d hybrid orbital of the metal atom. TDDFT results show that the highest light harvesting efficiency (LHE) of all the studied species is found under the range of 360 nm - 380 nm (λ) and this may due to the presence of longer π-conjugations. In-depth investigation of this work may help to design new robust energy harvesting systems for high energy conversion efficiency based on earth abundance metals. Our results are in well agreement with the available experimental findings.