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This review summarizes research on the electrochemical and photochemical reduction of CO₂ using a variety of iron and cobalt porphyrins, phthalocyanines and related complexes. Metalloporphyrins and metallophthalocyanines are visible light absorbers with extremely large extinction coefficients. However, yields of photochemically-generated active catalysts for CO₂ reduction are typically low owing to the requirement of a second photoinduced electron. This requirement is not relevant to the case of electrochemical CO₂ reduction. Recent progress on efficient and stable electrochemical systems includes the use of FeTPP catalysts that have prepositioned phenyl OH groups in their second coordination spheres. This has led to remarkable progress in carrying out coupled proton-electron transfer reactions for CO₂ reduction. Such ground-breaking research has to be continued in order to produce renewable fuels in an economically feasible manner.

A new family of pyrrole substituted metallophthalocyanine complexes, namely cobalt(II), iron(II), manganese(III), nickel(II) and zinc(II) tetrakis-4-(pyrrol-1-yl)phenoxy phthalocyanines (noted as M(TPhPyrPc), where M is the metallic cation) have been synthesized and fully characterized. In particular, the UV-visible spectra of the iron and nickel complexes showed extensive aggregation even at low concentrations. The cyclic voltammetry of the cobalt, iron and manganese complexes showed three to four redox couples assigned to metal and ring based processes. Spectroelectrochemistry of the manganese derivative confirmed that the synthesized complex is Mn^III(TPhPyrPc^-2) and that the reduction of Mn^II(TPhPyrPc^-2) to be centred on the ring and rather than on the metal, forming the Mn^II(TPhPyrPc^-4) species. Also, the electrochemical polymerization of these newly synthesized pyrrole-substituted phthalocyanines has been demonstrated in the case of the cobalt complex and the electrocatalytic activity of the obtained film has been tested towards the oxidation of L-cysteine.

Two iron phthalocyanines peripherally octasubstituted either with electron-withdrawing isobutylsulfonyl moities or electron-donating isobutoxy moieties were designed to investigate the effect of the substitution pattern on their oxidation catalytic activity, and were then tested in oxidation of cyclohexene as a reaction model. For both catalysts, the main product of oxidation was 2-cyclohexen-1-ol which is an allylic oxidation product. The electron-withdrawing isobutylsulfonyl substituted iron phthalocyanine 1 exhibited better catalytic activities than the electron-donating isobutoxy substituted iron phthalocyanine 2.

Ferrochelatase (also known as PPIX ferrochelatase; Enzyme Commission number 4.9.9.1.1) catalyzes the insertion of ferrous iron into PPIX to form heme. This reaction unites the biochemically synchronized pathways of porphyrin synthesis and iron transport in nearly all living organisms. The ferrochelatases are an evolutionarily diverse family of enzymes with no more than six active site residues known to be perfectly conserved. The availability of over thirty different crystal structures, including many with bound metal ions or porphyrins, has added tremendously to our understanding of ferrochelatase structure and function. It is generally believed that ferrous iron is directly channeled to ferrochelatase in vivo, but the identity of the suspected chaperone remains uncertain despite much recent progress in this area. Identification of a conserved metal ion binding site at the base of the active site cleft may be an important clue as to how ferrochelatases acquire iron, and catalyze desolvation during transport to the catalytic site to complete heme synthesis.

The iron complexes of 5,10,15-tris(4-nitrophenyl)corrole have been prepared and characterized by various spectroscopic techniques. The (nitrosyl)iron complex is diamagnetic and its X-ray structure reveals an almost perfectly linear Fe–N–O bond. EPR spectroscopy in conjunction with ¹⁵N labelling were used to deduce the redox centre of the one-electron reduction and oxidation products of the (nitrosyl)iron corrole.

Effective systems for the catalytic oxygenation of hydrocarbons have been developed based on metalloporphyrins containing iron, manganese and ruthenium. These metalloporphyrin catalysts were inspired by studies of the mechanism of the heme oxygenase cytochrome P450 and related enzymes. Oxometalloporphyrins, which have now been spectroscopically characterized, have very high reactivity as oxygen transfer agents. A combination of experimental and computational methods has begun to provide an understanding of the structure and reactivity of these oxometalloporphyrin complexes and the mechanisms of oxygen transfer reactions they catalyze.

Synchrotron radiation X-ray fluorescence (SR-XRF) using high energy incident X-rays was combined with micro-PIXE to analyze the renal distribution of Rb and essential elements in immature rats. The Rb concentrations in the kidneys of newborn (1 week old) and young (3 weeks old) rats were 4.19 ± 0.71 and 4.13 ± 0.30 µg/g, respectively, similar to those of adult rats. Rubidium as well as Zn was detected more in the cortex than the medulla, while Fe was concentrated in the outermost areas of the medulla of newborn rats. The renal structures of young rats achieved adult zonation into the cortex, the outer medulla and the inner medulla. Rubidium was high in the outer stripe of the outer medulla. Further analysis at higher resolution revealed Rb in the proximal tubules in the innermost part of the cortex. These results indicated that Rb was distributed downstream of the proximal tubules. This profile was similar to that of potassium, an Rb congener.

Gupta and Density Functional Theory (DFT) calculations were performed to investigate of structural and magnetic behaviors of 19 atom Fe_nRh${}_{19\text{-}n}$ ($n=0$–19) nanoalloys. A double icosahedron structure was considered for Fe_nRh${}_{19\text{-}n}$ ($n=0$–19) nanoalloys. Significantly, the effects of Fe atom addition on the chemical ordering, stability and total magnetic moments of the nanoalloys were investigated. Local optimization results at the Gupta level show that the Fe atoms are located in the center of the double icosahedron structure and finally in the equatorial region on the surface. The mixing energy analysis obtained that Fe${}_{12}$Rh₇ and Fe₄Rh${}_{15}$ nanoalloys are the most stable compositions at Gupta and DFT levels, respectively. It was found that Fe_nRh${}_{19\text{-}n}$ ($n=0$–19) nanoalloys are energetically suitable for mixing at both Gupta and DFT levels. Also, the bond order parameter result is compatible with the mixing energy analysis result. The total magnetic moments of the Fe_nRh${}_{19\text{-}n}$ ($n=0$–19) nanoalloys increase with the addition of the Fe atom, which is a ferromagnetic metal.

The interaction between iron(II) tetrasulfophthalocyanine ([Fe^IITSPc]⁴⁺) and histamine results in the oxidation of the central metal by oxygen in the former, with the formation of a complex denoted as [(His)Fe^IIITSPc]³⁻ (where His = histamine). The rate constant for the formation of the complex is k_f = 2.41 × 10⁻²dm³.mol⁻¹.s⁻¹ and an equilibrium constant of 6.3 dm³.mol^-1 was obtained. The oxidation state of the central metal of [Fe^IITSPc]⁴⁻ before and after the coordination of histamine is confirmed by spectroelectrochemistry. Further electrochemical oxidation of this [(His)Fe^IIITsPc]³⁻ derivative results in a metal-based process proposed to involve an Fe^IV phthalocyanine species.

Coupled oxidation of iron tetraphenylporphyrins bearing either a OMe, Me, F, Cl, COOMe, CF₃ or CN group in the para-position of the phenyl groups gave tetraarylbiladien-ab-1-one and triarylbilindione. The ratios of the yields of the former to those of the latter were linearly correlated with the Hammett substituent constants σ_p⁺, with a positive slope (Δρ = 0.64). The Hammett plot of the oxidation rate vs. the substituent constant σ_p also showed a positive slope (ρ = 0.30). These substituent effects suggest that a nucleophilic step is included in the formation of bilindione. Coupled oxidation of an A3B type tetraarylporphyrin having an electron withdrawing nitro group in one of the phenyl groups indicated that the oxidation leading to biladienone occurred rather statistically in any of the meso-positions, while the oxidation leading to bilindione occurred preferentially in the meso-position bearing the 4-nitrophenyl group.

We report the fast discharge–charge cycle of micro-sized FePS₃ electrode particles in all-solid-state batteries (ASSBs) using sulfide electrolytes at 80^∘C. At a current density of 2.04 mA cm${}^{-2}$, corresponding to approximately 1 C, the capacity of the FePS₃ electrodes reached $\sim$180 mAh g${}^{-1}$ without any electron or lithium-ion conductive additives. Galvanostatic intermittent titration technique (GITT) measurements showed a stable diffusion path of FePS₃ represented by the product of the diffusion coefficient and square of the surface area. These electrochemical properties were compared with those of FeS, whose capacity was lower because of its unstable diffusion path.

Disrupted iron homeostasis is associated with several neurodegenerative diseases, including Alzheimer’s disease (AD), and may be partially modulated by genetic risk factors. Here we evaluated whether subcortical iron deposition is associated with ApoE genotype, which substantially affects risk for late-onset AD. We evaluated differences in subcortical quantitative susceptibility mapping (QSM), a type of MRI sensitive to cerebral iron deposition, between either ApoE4 (E3E4+E4E4) or ApoE2 (E2E3+E2E2) carriers and E3 homozygotes (E3E3) in 27,535 participants from the UK Biobank (age: 45-82 years). We found that ApoE4 carriers had higher hippocampal (d=0.036; p=0.012) and amygdalar (d=0.035; p=0.013) magnetic susceptibility, particularly individuals aged 65 years or older, while those carrying ApoE2 (which protects against AD) had higher QSM only in the hippocampus (d=0.05; p=0.006), particularly those under age 65. Secondary diffusion MRI microstructural associations in these regions revealed greater diffusivity and less diffusion restriction in E4 carriers, however no differences were detected in E2 carriers. Disease risk conferred by ApoE4 may be linked with higher subcortical iron burden in conjunction with inflammation or neuronal loss in aging individuals, while ApoE2 associations may not necessarily reflect unhealthy iron deposits earlier in life.

The hard tissues of cephalopod, namely statoliths were analyzed with PIXE for the Japanese common squid Todarodes pacificus of the Sea of Japan origin in order to examine the relationship between the amount of trace elements in statoliths and environmental temperature of the squid habitat. Calcium, iron, zinc. copper and strontium were detected in the statoliths. Negative relationship was observed between Sr concentration in statoliths and environmental temperature. On the contrary to Sr, Fe and Zn concentration in statoliths related positively with environmental temperature. These observations revealed that the statoliths would be a useful thermometer for reconstructing the environmental temperature of cephalopod habitat as seen in the hard tissues of other marine organisms.

The growth and structure of ultrathin Rh films on Fe(100) are studied by grazing scattering of 50 keV He projectiles, incident along "random" and low index surface lattice directions. Oscillations in the specular intensity for scattered ions indicate initial layer-by-layer growth, followed by multilayer growth on top of the two-monolayer film. Growth temperatures below about 400 K result in a persistent though rough layer growth up to higher coverages. From distinct maxima in the target current as a function of the azimuthal incidence angle, we deduce that growth is epitaxial and pseudomorphic.

We have investigated the adsorption sites and the electronic structure correlated with the magnetic properties of ultrathin Fe films on W(110) system using spin-polarized calculations within the density-functional approach with generalized gradient approximation by the pseudopotential plane-wave code. For one Fe monolayer (ML) on W(110) system the Fe atoms prefer to bind on the bridge adsorption sites of the W(110) surface, with an inward relaxation of $-$12.68%. The top and diagonal bridge sites investigated are energetically less favorable. We have shown that intermixing between Fe and W is unlikely: the surface ordered Fe–W alloy is unstable against the 1-ML Fe on W(110). While the control of oxygen element is known to be an important key to a perfect growth of Fe on W(110), its possible contamination is checked. Performing spin polarized calculations with the optimized geometry, the induced magnetic moments on W subsurface are obtained: the W atoms are always antiferromagnetically coupled to the Fe atoms, one exception being the case of the antiferromagnetic Fe surface where, due to frustration, the induced polarization on the W atoms is zero. The bridge site is the lower adsorption energy one for O₂ molecular bonding perpendicular to the surface. In the case of O₂ bonding parallel and oblique to the surface, it is always dissociated into two O atoms on Fe/W(110) surface through geometry optimization, for all considered sites.

Novel chiral systems for the catalytic asymmetric oxidation and cyclopropanation of olefins based on metalloporphyrins containing iron, ruthenium and manganese, have been recently introduced. High catalyst turnover numbers and sometimes high enantiomeric excess were observed. New catalytic reactions with metalloporphyrins have recently been reported; these are the olefination of aldehydes and cyclotrimerization of terminal alkynes. Dendrimers and polymers containing metalloporphyrins, have also been found to be efficient catalysts for oxidation and carbene transfer.

The chlorido iron(III) complex of octaethyl-2,2′-bidipyrrin has been transformed to a series of pseudohalide complexes by ligand exchange reactions with azide, cyanate, thiocyanate and selenocyanate anions. All new complexes show the expected N-coordination of the axial ligand to the iron(III) center. In the solid state, all four species display an intermediate spin (S = 3/2) ground state, with a gradual increase of a high spin (S = 5/2) contribution at elevated temperatures for the members with the smallest ligand field strengths, i.e. the cyanato and the azido derivatives. In solution, proton NMR, and in particular IR spectroscopic studies support the interpretation of a high-spin state at ambient temperature throughout the series. The dependency of the spin state on the crystalline or dissolved state thus resembles that found for a similar series of halide derivatives before. In dichloromethane solution, the thiocyanato and selenocyanato complexes are very sensitive to aerial oxidation, forming oxacorrole and thiacorrole complexes as the only isolated products. These complexes show a S = 3/2 spin state in the solid as well as in solution, and their structural analyses prove the expected strong π-binding of the linear pseudohalide ion to the iron(III) central metal.

Recent experimental studies of Liu and Groves (J. Am. Chem. Soc. 2010; 132: 12847) on dioxomanganese(V) porphyrin complexes implicated substrate halogenation in good yield. Currently, little is known of this unique mechanism, therefore to gain understanding on the halogenation mechanism and the chemical features of this oxidant we decided to do a computational (density functional theory) study. We show that the dioxomanganese(V) complex has considerably different molecular (valence) orbitals as compared to monooxomanganese(V) porphyrin due to mixing of the metal 3d orbitals with 2p orbitals on both oxygen atoms. This results in a set of three pairs of orbitals of which the bonding and nonbonding pairs are doubly occupied and the antibonding orbitals are vacant. As a consequence, the bonding character along the Mn–O bond is less in dioxomanganese(V) as compared to monooxomanganese(V) complexes and therefore this bond can formally be described as a double bond rather than a triple bond. The differences in orbital interactions and orbital energies also affect the intrinsic chemical properties of the oxidants, such as the electron affinity and pK_a values, which result in enhanced catalytic potential for dioxomanganese(V) porphyrin. Our calculations predict a halogenation mechanism in line with that proposed by experiment with an initial hydrogen atom abstraction followed by ligand exchange and halogen transfer.

The catalytic functionalization of C–H, C–OH and C–C bonds belongs to the most important processes in nature and the industry. In nature, this process occurs via involvement of enzymes, effectively and selectively, usually with very high turnover numbers. The pivotal role in enzymatic activity is played by the metal center cofactors, which involve several bioavailable transition metals, such as, iron, copper, manganese and zinc. In the industry, bond functionalization requires the presence of metal catalysts; therefore, a bio-inspired design of metal catalysts is a challenging approach. The recent advances in the catalysis of industrially important reactions, namely the oxidation and hydrocarboxylation of alkanes, the oxidation of alcohols and C–C coupling are reported. Convenient, environmentally friendly methods are presented, and the role and efficacy of the various transition-metal (iron, copper, zinc, manganese, nickel, vanadium, palladium and cobalt) catalysts are explored.

Oxidative damage and response are major features of Alzheimer's disease and other neurodegenerative diseases. Metal-catalyzed oxidative events are at the center of radical formation and abnormalities in iron and copper have been noted. In this review, we consider the evidence implicating the central role of metals.