A synthetic precedent for the [FeIV2(mu-O)2] diamond core proposed for methane monooxygenase intermediate Q

Intermediate Q, the methane-oxidizing species of soluble methane monooxygenase, is proposed to have an [Fe^IV₂(μ-O)₂] diamond core. In an effort to obtain a synthetic precedent for such a core, bulk electrolysis at 900 mV (versus Fc^+/0) has been performed in MeCN at −40°C on a valence-delocalized [Fe^IIIFe^IV(μ-O)₂(L^b)₂]³⁺ complex (1b) (E_1/2 = 760 mV versus Fc^+/0). Oxidation of 1b results in the near-quantitative formation of a deep red complex, designated 2b, that exhibits a visible spectrum with λ_max at 485 nm (9,800 M⁻¹·cm⁻¹) and 875 nm (2,200 M⁻¹·cm⁻¹). The 4.2 K Mössbauer spectrum of 2b exhibits a quadrupole doublet with δ = −0.04(1) mm·s⁻¹ and ΔE_Q = 2.09(2) mm·s⁻¹, parameters typical of an iron(IV) center. The Mössbauer patterns observed in strong applied fields show that 2b is an antiferromagnetically coupled diiron(IV) center. Resonance Raman studies reveal the diagnostic vibration mode of the [Fe₂(μ-O)₂] core at 674 cm⁻¹, downshifting 30 cm⁻¹ upon ¹⁸O labeling. Extended x-ray absorption fine structure (EXAFS) analysis shows two O/N scatterers at 1.78 Å and an Fe scatterer at 2.73 Å. Based on the accumulated spectroscopic evidence, 2b thus can be formulated as [Fe^IV₂(μ-O)₂(L^b)₂]⁴⁺, the first synthetic complex with an [Fe^IV₂(μ-O)₂] core. A comparison of 2b and its mononuclear analog [Fe^IV(O)(L^b)(NCMe)]²⁺ (4b) reveals that 4b is 100-fold more reactive than 2b in oxidizing weak CH bonds. This surprising observation may shed further light on how intermediate Q carries out the hydroxylation of methane.     

Direct Electrochemistry and Electrocatalysis of Horseradish Peroxidase Immobilized in a DNA/Chitosan-Fe3O4 Magnetic Nanoparticle Bio-Complex Film

A DNA/chitosan-Fe₃O₄ magnetic nanoparticle bio-complex film was constructed for the immobilization of horseradish peroxidase (HRP) on a glassy carbon electrode. HRP was simply mixed with DNA, chitosan and Fe₃O₄ nanoparticles, and then applied to the electrode surface to form an enzyme-incorporated polyion complex film. Scanning electron microscopy (SEM) was used to study the surface features of DNA/chitosan/Fe₃O₄/HRP layer. The results of electrochemical impedance spectroscopy (EIS) show that Fe₃O₄ and enzyme were successfully immobilized on the electrode surface by the DNA/chitosan bio-polyion complex membrane. Direct electron transfer (DET) and bioelectrocatalysis of HRP in the DNA/chitosan/Fe₃O₄ film were investigated by cyclic voltammetry (CV) and constant potential amperometry. The HRP-immobilized electrode was found to undergo DET and exhibited a fast electron transfer rate constant of 3.7 s⁻¹. The CV results showed that the modified electrode gave rise to well-defined peaks in phosphate buffer, corresponding to the electrochemical redox reaction between HRP(Fe^(III)) and HRP(Fe^(II)). The obtained electrode also displayed an electrocatalytic reduction behavior towards H₂O₂. The resulting DNA/chitosan/Fe₃O₄/HRP/glassy carbon electrode (GCE) shows a high sensitivity (20.8 A·cm⁻²·M⁻¹) toward H₂O₂. A linear response to H₂O₂ measurement was obtained over the range from 2 μM to 100 μM (R² = 0.99) and an amperometric detection limit of 1 μM (S/N = 3). The apparent Michaelis-Menten constant of HRP immobilized on the electrode was 0.28 mM. Furthermore, the electrode exhibits both good operational stability and storage stability.     

Mechanism of H+ dissociation–induced O–O bond formation via intramolecular coupling of vicinal hydroxo ligands on low-valent Ru(III) centers

The understanding of O–O bond formation is of great importance for revealing the mechanism of water oxidation in photosynthesis and for developing efficient catalysts for water oxidation in artificial photosynthesis. The chemical oxidation of the Ru^II₂(OH)(OH₂) core with the vicinal OH and OH₂ ligands was spectroscopically and theoretically investigated to provide a mechanistic insight into the O–O bond formation in the core. We demonstrate O–O bond formation at the low-valent Ru^III₂(OH) core with the vicinal OH ligands to form the Ru^II₂(μ-OOH) core with a μ-OOH bridge. The O–O bond formation is induced by deprotonation of one of the OH ligands of Ru^III₂(OH)₂ via intramolecular coupling of the OH and deprotonated O⁻ ligands, conjugated with two-electron transfer from two Ru^III centers to their ligands. The intersystem crossing between singlet and triple states of Ru^II₂(μ-OOH) is easily switched by exchange of H⁺ between the μ-OOH bridge and the auxiliary backbone ligand.

Water oxidation to produce O₂ (Eq. 1) is an important biological reaction in photosynthesis. The geometric structure of the active site with a manganese-oxo core (Mn₄CaO₅) for water oxidation, so called oxygen-evolving complex (OEC), has been characterized by recently advanced X-ray crystallographic analysis (1–5). The elucidation of the water oxidation mechanism at OEC on the basis of their geometric structure is a high-interest topic in photosynthesis studies. On the other hand, water oxidation is also a crucial process to use water as an electron source for the solar fuel production in artificial photosynthesis technology that is participated as a future solar energy conversion system (6–8). There has been a great deal of interest in developing active catalysts to promote water oxidation to establish efficient artificial photosynthesis systems (9–13). The elucidation of the water oxidation mechanism provides a key clue of the guideline for developing active catalysts for water oxidation.2H2O→O2+ 4H++ 4e−.[1]In a water oxidation process to produce O₂ (Eq. 1), formation of an O–O bond from two molecules of water is necessary with removal of either consecutive or concerted four electrons and four protons from the water (14–16). Commonly, the O–O bond formation is assisted by catalysts (OEC in photosynthesis) with one or two molecules of water bound on them to decrease thermodynamic energy for formation of the intermediate species. Two main classes of the mechanism for the O–O bond formation on metal centers of the catalysts have been reported: water nucleophilic attack (WNA) on metal-oxo centers (Mⁿ = O) (17–22) and interaction of two Mⁿ = O centers (I2M) (23–29). In the WNA mechanism (17–20), a water molecule nucleophilically attacks onto the Mⁿ = O center to generate a Mⁿ⁻²-OOH hydroperoxide intermediate. Therefore, the high-valent Mⁿ = O center (e.g., Ru^{IV or V}) with electrophilic properties is required. In the I2M mechanism (23–27), the coupling of either two Mⁿ⁻¹-O· oxyl radicals (formally Mⁿ = O) or coupling of one Mⁿ⁻¹-O· oxyl radical with another unit (e.g., Mⁿ = O) of nonradical character affords a Mⁿ⁻¹-OO-Mⁿ⁻¹ peroxide intermediate. For this mechanism, the high-valent Mnⁿ = O centers are not necessarily attained, in contrast to the required high-valent Mⁿ = O center in the WNA mechanism. However, O–O bond formation via coupling of relatively low-valent Mⁿ = O units (e.g., Ru^III) has not been demonstrated so far.proximal,proximal-[Ru₂(tpy)₂(pyan)(OH)(OH₂)]³⁺ (Ru^II₂(OH) (OH₂)) (tpy = 2,2′;6′,2″-terpyridine and pyan = 5-phenyl-2,8-di(2-pyridyl)-1,9,10-anthyridine) with the vicinal OH and OH₂ ligands in the Ru^II₂ core was reported to work efficiently for electrocatalytic water oxidation in a homogenous solution (26). The O–O bond formation via intramolecular coupling between the Ru^V = O units, derived from the Ru^II₂ core with the vicinal OH and OH₂ ligands, was suggested for O₂ production. Recently, we reported that O₂ is produced via the intramolecular coupling between the Ru^IV = O and Ru^IV-OH units for the proximal,proximal-[Ru₂(cptpy)₂(pyan)(OH)(OH₂)]⁺ (Hcptpy = 4′-(4-carboxyphenyl)-2,2′;6′,2″-terpyridine) derivative with 4-carboxyphenyl linkers adsorbed on the TiO₂ surface (27). However, the direct spectroscopic evidence has not yet been provided for the O–O bond formation via intramolecular coupling between the Ru^{IV or V} = O units. Herein, we spectroscopically and theoretically investigate chemical oxidation of Ru^II₂(OH)(OH₂) by a Na₂S₂O₈ oxidant in an aqueous solution to provide a mechanistic insight into the O–O bond formation in the unique Ru₂ core. We demonstrate that the O–O bond formation via intramolecular coupling of vicinal OH ligands on Ru^III-OH units is induced by dissociation of one proton of two OH ligands in the core. This is an observation of the O–O bond formation at the low-valent Ru^III centers. The mechanism of the O–O bond formation is revealed to propose the important role of the central N atom (N_c) of the anthyridine moiety on the pyan backbone ligand as a neighboring proton acceptor site for concerted intramolecular electron/proton transfers.     

Synthesis,Crystal Structure and Luminescent Property of Mg(II) Complex with N-Benzenesulphonyl-L-Leucine and 1,10-Phenanthroline

A new complex [Mg(L)₂(phen)(H₂O)₂](phen)(H₂O)₂ [L= N-benzenesulphonyl-L-leucine] was synthesized by the reaction of magnesium chloride hexahydrate with N-benzenesulphonyl-L-leucine and 1,10-phenanthroline in the CH₃CH₂OH/H₂O (v:v = 5:1). It was characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The crystal of the title complex [Mg(L)₂(phen)(H₂O)₂](phen)(H₂O)₂ belongs to triclinic, space group P-1 with a = 0.72772(15) nm, b = 1.4279(3) nm, c = 1.4418(3) nm, α = 63.53(3)°, β = 79.75(3)°, γ = 81.83(3)°, V = 1.3163(5) nm³, Z =1, D_c= 1.258 μg·m⁻³, μ = 0.177 mm⁻¹, F(000) = 526, and final R₁ = 0.0506, ωR₂ = 0.1328. The complex comprises a six-coordinated magnesium(II) center, with a N₂O₄ distorted octahedron coordination environment. The molecules are connected by hydrogen bonds and π-π stacking to form one dimensional chain structure. The luminescent property of the Mg(II) complex has been investigated in solid.     

Transformation of Tri-Titanium(IV)-Substituted α-Keggin Polyoxometalate (POM) into Tetra-Titanium(IV)-Substituted POMs : Reaction Products of Titanium(IV) Sulfate with the Dimeric Keggin POM Precursor under Acidic Conditions

Reaction products of titanium(IV) sulfate in HCl-acidic aqueous solution with the dimeric species linked through three intermolecular Ti-O-Ti bonds of the two tri-titanium(IV)-substituted α-Keggin polyoxometalate (POM) subunits are described. Two novel titanium(IV)-containing α-Keggin POMs were obtained under different conditions. One product was a dimeric species through two intermolecular Ti-O-Ti bonds of the two tetra-titanium(IV)-substituted α-Keggin POM subunits, i.e., [[{Ti(H₂O)₃}₂(μ-O)](α-PW₉Ti₂O₃₈)]₂^6- (1). The other product was a monomeric α-Keggin species containing the tetra-titanium(IV) oxide cluster and two coordinated sulfate ions, i.e., [{Ti₄(μ-O)₃(SO₄)₂(H₂O)₈}(α-PW₉O₃₄)]^3- (2). Molecular structures of 1 and 2 were also discussed based on host (lacunary site)-guest (titanium atom) chemistry.     

Insight into the mechanism of an iron dioxygenase by resolution of steps following the FeIV═O species

Iron oxygenases generate elusive transient oxygen species to catalyze substrate oxygenation in a wide range of metabolic processes. Here we resolve the reaction sequence and structures of such intermediates for the archetypal non-heme Fe^II and α-ketoglutarate-dependent dioxygenase TauD. Time-resolved Raman spectra of the initial species with ¹⁶O¹⁸O oxygen unequivocally establish the Fe^IV═O structure. ¹H/²H substitution reveals direct interaction between the oxo group and the C1 proton of substrate taurine. Two new transient species were resolved following Fe^IV═O; one is assigned to the ν_FeO mode of an Fe^III─O(H) species, and a second is likely to arise from the vibration of a metal-coordinated oxygenated product, such as Fe^II─O─C₁ or Fe^II─OOCR. These results provide direct insight into the mechanism of substrate oxygenation and suggest an alternative to the hydroxyl radical rebinding paradigm.     

Crystal Structure,Spectroscopic Characterization,Antioxidant and Cytotoxic Activity of New Mg(II) and Mn(II)/Na(I) Complexes of Isoferulic Acid

The Mg(II) and heterometallic Mn(II)/Na(I) complexes of isoferulic acid (3-hydroxy-4-methoxycinnamic acid, IFA) were synthesized and characterized by infrared spectroscopy FT-IR, FT-Raman, electronic absorption spectroscopy UV/VIS, and single-crystal X-ray diffraction. The reaction of MgCl₂ with isoferulic acid in the aqueous solutions of NaOH resulted in synthesis of the complex salt of the general formula of [Mg(H₂O)₆]⋅(C₁₀H₉O₄)₂⋅6H₂O. The crystal structure of this compound consists of discrete octahedral [Mg(H₂O)₆]²⁺ cations, isoferulic acid anions and solvent water molecules. The hydrated metal cations are arranged among the organic layers. The multiple hydrogen-bonding interactions established between the coordinated and lattice water molecules and the functional groups of the ligand stabilize the 3D architecture of the crystal. The use of MnCl₂ instead of MgCl₂ led to the formation of the Mn(II)/Na(I) complex of the general formula [Mn₃Na₂(C₁₀H₇O₄)₈(H₂O)₈]. The compound is a 3D coordination polymer composed of centrosymmetric pentanuclear subunits. The antioxidant activity of these compounds was evaluated by assays based on different antioxidant mechanisms of action, i.e., with ^•OH, DPPH^• and ABTS^•+ radicals as well as CUPRAC (cupric ions reducing power) and lipid peroxidation inhibition assays. The pro-oxidant property of compounds was measured as the rate of oxidation of Trolox. The Mg(II) and Mn(II)/Na(I) complexes with isoferulic acid showed higher antioxidant activity than ligand alone in DPPH (IFA, IC₅₀ = 365.27 μM, Mg(II) IFA IC₅₀ = 153.50 μM, Mn(II)/Na(I) IFA IC₅₀ = 149.00 μM) and CUPRAC assays (IFA 40.92 μM of Trolox, Mg(II) IFA 87.93 μM and Mn(II)/Na(I) IFA 105.85 μM of Trolox; for compounds’ concentration 10 μM). Mg(II) IFA is a better scavenger of ^•OH than IFA and Mn(II)/Na(I) IFA complex. There was no distinct difference in ABTS^•+ and lipid peroxidation assays between isoferulic acid and its Mg(II) complex, while Mn(II)/Na(I) complex showed lower activity than these compounds. The tested complexes displayed only slight antiproliferative activity tested in HaCaT human immortalized keratinocyte cell line within the solubility range. The Mn(II)/Na(I) IFA (16 μM in medium) caused an 87% (±5%) decrease in cell viability, the Mg salt caused a comparable, i.e., 87% (±4%) viability decrease in a concentration of 45 μM, while IFA caused this level of cell activity attenuation (87% ± 5%) at the concentration of 1582 μM (significant at α = 0.05).     

The ferritin Fe2 site at the diiron catalytic center controls the reaction with O2 in the rapid mineralization pathway

Oxidoreduction in ferritin protein nanocages occurs at sites that bind two Fe(II) substrate ions and O₂, releasing Fe(III)₂–O products, the biomineral precursors. Diferric peroxo intermediates form in ferritins and in the related diiron cofactor oxygenases. Cofactor iron is retained at diiron sites throughout catalysis, contrasting with ferritin. Four of the 6 active site residues are the same in ferritins and diiron oxygenases; ferritin-specific Gln¹³⁷ and variable Asp/Ser/Ala¹⁴⁰ substitute for Glu and His, respectively, in diiron cofactor active sites. To understand the selective functions of diiron substrate and diiron cofactor active site residues, we compared oxidoreductase activity in ferritin with diiron cofactor residues, Gln¹³⁷ → Glu and Asp¹⁴⁰ → His, to ferritin with natural diiron substrate site variations, Asp¹⁴⁰, Ser¹⁴⁰, or Ala¹⁴⁰. In Gln¹³⁷ → Glu ferritin, diferric peroxo intermediates were undetectable; an altered Fe(III)–O product formed, ΔA₃₅₀ = 50% of wild type. In Asp¹⁴⁰ → His ferritin, diferric peroxo intermediates were also undetectable, and Fe(II) oxidation rates decreased 40-fold. Ferritin with Asp¹⁴⁰, Ser¹⁴⁰, or Ala¹⁴⁰ formed diferric peroxo intermediates with variable kinetic stabilities and rates: t_1/2 varied 1- to 10-fold; k_cat varied approximately 2- to 3-fold. Thus, relatively small differences in diiron protein catalytic sites determine whether, and for how long, diferric peroxo intermediates form, and whether the Fe–active site bonds persist throughout the reaction cycle (diiron cofactors) or break to release Fe(III)₂–O products (diiron substrates). The results and the coding similarities for cofactor and substrate site residues—e.g., Glu/Gln and His/Asp pairs share 2 of 3 nucleotides—illustrate the potential simplicity of evolving active sites for diiron cofactors or diiron substrates.     

Detailed Inspection of γ-ray,Fast and Thermal Neutrons Shielding Competence of Calcium Oxide or Strontium Oxide Comprising Bismuth Borate Glasses

For both the B₂O₃-Bi₂O₃-CaO and B₂O₃-Bi₂O₃-SrO glass systems, γ-ray and neutron attenuation qualities were evaluated. Utilizing the Phy-X/PSD program, within the 0.015–15 MeV energy range, linear attenuation coefficients (µ) and mass attenuation coefficients (μ/ρ) were calculated, and the attained μ/ρ quantities match well with respective simulation results computed by MCNPX, Geant4, and Penelope codes. Instead of B₂O₃/CaO or B₂O₃/SrO, the Bi₂O₃ addition causes improved γ-ray shielding competence, i.e., rise in effective atomic number (Z_eff) and a fall in half-value layer (HVL), tenth-value layer (TVL), and mean free path (MFP). Exposure buildup factors (EBFs) and energy absorption buildup factors (EABFs) were derived using a geometric progression (G–P) fitting approach at 1–40 mfp penetration depths (PDs), within the 0.015–15 MeV range. Computed radiation protection efficiency (RPE) values confirm their excellent capacity for lower energy photons shielding. Comparably greater density (7.59 g/cm³), larger μ, μ/ρ, Z_eff, equivalent atomic number (Z_eq), and RPE, with the lowest HVL, TVL, MFP, EBFs, and EABFs derived for 30B₂O₃-60Bi₂O₃-10SrO (mol%) glass suggest it as an excellent γ-ray attenuator. Additionally, 30B₂O₃-60Bi₂O₃-10SrO (mol%) glass holds a commensurably bigger macroscopic removal cross-section for fast neutrons (Σ_R) (=0.1199 cm⁻¹), obtained by applying Phy-X/PSD for fast neutrons shielding, owing to the presence of larger wt% of ‘Bi’ (80.6813 wt%) and moderate ‘B’ (2.0869 wt%) elements in it. 70B₂O₃-5Bi₂O₃-25CaO (mol%) sample (B: 17.5887 wt%, Bi: 24.2855 wt%, Ca: 11.6436 wt%, and O: 46.4821 wt%) shows high potentiality for thermal or slow neutrons and intermediate energy neutrons capture or absorption due to comprised high wt% of ‘B’ element in it.     

Preparation of Fe3O4-Embedded Poly(styrene)/Poly(thiophene) Core/Shell Nanoparticles and Their Hydrogel Patterns for Sensor Applications

This research describes the preparation and sensor applications of multifunctional monodisperse, Fe₃O₄ nanoparticles-embedded poly(styrene)/poly(thiophene) (Fe₃O₄-PSt/PTh), core/shell nanoparticles. Monodisperse Fe₃O₄-PSt/PTh nanoparticles were prepared by free-radical combination (mini-emulsion/emulsion) polymerization for Fe₃O₄-PSt core and oxidative seeded emulsion polymerization for PTh shell in the presence of FeCl₃/H₂O₂ as a redox catalyst, respectively. For applicability of Fe₃O₄-PSt/PTh as sensors, Fe₃O₄-PSt/PTh-immobilized poly(ethylene glycol) (PEG)-based hydrogels were fabricated by photolithography. The hydrogel patterns showed a good sensing performance under different H₂O₂ concentrations. They also showed a quenching sensitivity of 1 μg/mL for the Pd²⁺ metal ion within 1 min. The hydrogel micropatterns not only provide a fast water uptake property but also suggest the feasibility of both H₂O₂ and Pd²⁺ detection.     

Crystal structure of the channel-forming polypeptide antiamoebin in a membrane-mimetic environment

Crystals of an ion-channel-forming peptaibol peptide in a partial membrane environment have been obtained by cocrystallizing antiamoebin with n-octanol. The antiamoebin molecule has a bent helical conformation very similar to that established for Leu-zervamicin, despite a significantly different sequence for residues 1–8. The bent helices assemble to form a polar channel in the shape of an hour glass that is quite comparable to that of Leu-zervamicin. The molecules of cocrystallized octanol are found in two different areas with respect to the assembly of peptide molecules. One octanol molecule mimics a membrane segment along the hydrophobic exterior of the channel assembly. The other octanol molecules fill the channel in such a way that their OH termini satisfy the C=O moieties directed into the interior of the channel. Structure parameters for C₈₂H₂₇N₁₇O₂₀3C₈H₁₈O are space group P2₁2₁2₁, a = 9.143(2) Å, b = 28.590(8) Å, c = 44.289(8) Å, Z = 4, agreement factor R₁ = 11.95% for 4,113 observed reflections [>4σ(F)], resolution ~1.0 Å.     

Fenton chemistry at aqueous interfaces

In a fundamental process throughout nature, reduced iron unleashes the oxidative power of hydrogen peroxide into reactive intermediates. However, notwithstanding much work, the mechanism by which Fe²⁺ catalyzes H₂O₂ oxidations and the identity of the participating intermediates remain controversial. Here we report the prompt formation of O=Fe^IVCl₃⁻ and chloride-bridged di-iron O=Fe^IV·Cl·Fe^IICl₄⁻ and O=Fe^IV·Cl·Fe^IIICl₅⁻ ferryl species, in addition to Fe^IIICl₄⁻, on the surface of aqueous FeCl₂ microjets exposed to gaseous H₂O₂ or O₃ beams for <50 μs. The unambiguous identification of such species in situ via online electrospray mass spectrometry let us investigate their individual dependences on Fe²⁺, H₂O₂, O₃, and H⁺ concentrations, and their responses to tert-butanol (an ·OH scavenger) and DMSO (an O-atom acceptor) cosolutes. We found that (i) mass spectra are not affected by excess tert-butanol, i.e., the detected species are primary products whose formation does not involve ·OH radicals, and (ii) the di-iron ferryls, but not O=Fe^IVCl₃⁻, can be fully quenched by DMSO under present conditions. We infer that interfacial Fe(H₂O)_n²⁺ ions react with H₂O₂ and O₃ >10³ times faster than Fe(H₂O)₆²⁺ in bulk water via a process that favors inner-sphere two-electron O-atom over outer-sphere one-electron transfers. The higher reactivity of di-iron ferryls vs. O=Fe^IVCl₃⁻ as O-atom donors implicates the electronic coupling of mixed-valence iron centers in the weakening of the Fe^IV–O bond in poly-iron ferryl species.High-valent Fe^IV=O (ferryl) species participate in a wide range of key chemical and biological oxidations (1–4). Such species, along with ·OH radicals, have long been deemed putative intermediates in the oxidation of Fe^II by H₂O₂ (Fenton’s reaction) (5, 6), O₃, or HOCl (7, 8). The widespread availability of Fe^II and peroxides in vivo (9–12), in natural waters and soils (13), and in the atmosphere (14–18) makes Fenton chemistry and Fe^IV=O groups ubiquitous features in diverse systems (19). A lingering issue regarding Fenton’s reaction is how the relative yields of ferryls vs. ·OH radicals depend on the medium. For example, by assuming unitary ·OH radical yields, some estimates suggest that Fenton’s reaction might account for ∼30% of the ·OH radical production in fog droplets (20). Conversely, if Fenton’s reaction mostly led to Fe^IV=O species, atmospheric chemistry models predict that their steady-state concentrations would be ∼10⁴ times larger than [·OH], thereby drastically affecting the rates and course of oxidative chemistry in such media (20). Fe^IV=O centers are responsible for the versatility of the family of cytochrome P450 enzymes in catalyzing the oxidative degradation of a vast range of xenobiotics in vivo (21–28), and the selective functionalization of saturated hydrocarbons (29). The bactericidal action of antibiotics has been linked to their ability to induce Fenton chemistry in vivo (9, 30–34). Oxidative damage from exogenous Fenton chemistry likely is responsible for acute and chronic pathologies of the respiratory tract (35–38).Despite its obvious importance, the mechanism of Fenton’s reaction is not fully understood. What is at stake is how the coordination sphere of Fe²⁺ (39–46) under specific conditions affects the competition between the one-electron transfer producing ·OH radicals (the Haber–Weiss mechanism) (47), reaction R1, and the two-electron oxidation via O-atom transfer (the Bray–Gorin mechanism) into Fe^IVO²⁺, reaction R2 (6, 23, 26, 27, 45, 48–51):Ozone reacts with Fe²⁺ via analogous pathways leading to (formally) the same intermediates, reactions R3a, R3b, and R4 (8, 49, 52, 53):At present, experimental evidence about these reactions is indirect, being largely based on the analysis of reaction products in bulk water in conjunction with various assumptions. Given the complex speciation of aqueous Fe²⁺/Fe³⁺ solutions, which includes diverse poly-iron species both as reagents and products, it is not surprising that classical studies based on the identification of reaction intermediates and products via UV-absorption spectra and the use of specific scavengers have fallen short of fully unraveling the mechanism of Fenton’s reaction. Herein we address these issues, focusing particularly on the critically important interfacial Fenton chemistry that takes place at boundaries between aqueous and hydrophobic media, such as those present in atmospheric clouds (16), living tissues, biomembranes, bio-microenvironments (38, 54, 55), and nanoparticles (56, 57).We exploited the high sensitivity, surface selectivity, and unambiguous identification capabilities of a newly developed instrument based on online electrospray mass spectrometry (ES-MS) (58–62) to identify the primary products of reactions R1–R4 on aqueous FeCl₂ microjets exposed to gaseous H₂O₂ and O₃ beams under ambient conditions [in N₂(g) at 1 atm at 293 ± 2 K]. Our experiments are conducted by intersecting the continuously refreshed, uncontaminated surfaces of free-flowing aqueous microjets with reactive gas beams for τ ∼10–50 μs, immediately followed (within 100 μs; see below) by in situ detection of primary interfacial anionic products and intermediates via ES-MS (Methods, SI Text, and Figs. S1 and S2). We have previously demonstrated that online mass spectrometric sampling of liquid microjets under ambient conditions is a surface-sensitive technique (58, 62–67).     

Hydrothermal Treatment of Arsenopyrite Particles with CuSO4 Solution

The nature of the hydrothermal reaction between arsenopyrite particles (FeAsS) and copper sulfate solution (CuSO₄) was investigated in this study. The effects of temperature (443–523 K), CuSO₄ (0.08–0.96 mol/L) and H₂SO₄ (0.05–0.6 mol/L) concentrations, reaction time (1–120 min), stirring speed (40–100 rpm) and particle size (10–100 μm) on the FeAsS conversion were studied. The FeAsS conversion was significant at >503 K, and it is suggested that the reaction is characterized by the formation of a thin layer of metallic copper (Cu⁰) and elemental sulfur (S⁰) around the unreacted FeAsS core. The shrinking core model (SCM) was applied for describing the process kinetics, and the rate of the overall reaction was found to be controlled by product layer diffusion, while the overall process was divided into two stages: (Stage 1: mixed chemical reaction/product layer diffusion-controlled) interaction of FeAsS with CuSO₄ on the mineral’s surface with the formation of Cu¹⁺ and Fe²⁺ sulfates, arsenous acid, S⁰, and subsequent diffusion of the reagent (Cu²⁺) and products (As³⁺ and Fe²⁺) through the gradually forming layer of Cu⁰ and molten S⁰; (Stage 2: product layer diffusion-controlled) the subsequent interaction of CuSO₄ with FeAsS resulted in the formation of a denser and less porous Cu⁰ and S⁰ layer, which complicates the countercurrent diffusion of Cu²⁺, Cu¹⁺, and Fe²⁺ across the layer to the unreacted FeAsS core. The reaction orders with respect to CuSO₄ and H₂SO₄ were calculated as 0.41 and −0.45 for Stage 1 and 0.35 and −0.5 for Stage 2. The apparent activation energies of 91.67 and 56.69 kJ/mol were obtained for Stages 1 and 2, respectively.     

One-Pot Self-Assembly of Dinuclear,Tetranuclear, and H-Bonding-Directed Polynuclear Cobalt(II), Cobalt(III), and Mixed-Valence Co(II)/Co(III) Complexes of Schiff Base Ligands with Incomplete Double Cubane Core

The reaction of 2,6-diformyl-4-methylphenol (DFMF) with 1-amino-2-propanol (AP) and tris(hydroxymethyl)aminomethane (THMAM) was investigated in the presence of Cobalt(II) salts, (X = ClO₄⁻, CH₃CO₂⁻, Cl⁻, NO₃⁻), sodium azide (NaN₃), and triethylamine (TEA). In one pot, the variation in Cobalt(II) salt results in the self-assembly of dinuclear, tetranuclear, and H-bonding-directed polynuclear coordination complexes of Cobalt(III), Cobalt(II), and mixed-valence Co^IICo^III: [Co₂^III(H₂L⁻¹)₂(AP⁻¹)(N₃)](ClO₄)₂ (1), [Co₄(H₂L⁻¹)₂(µ₃-1,1,1-N₃)₂(µ-1,1-N₃)₂Cl₂(CH₃OH)₂]·4CH₃OH (2), [Co₂^IICo₂^III(HL⁻²)₂(µ-CH₃CO₂)₂(µ₃-OH)₂](NO₃)₂·2CH₃CH₂OH (3), and [Co₂^IICo₂^III (H₂L1²⁻)₂(THMAM⁻¹)₂](NO₃)₄ (4). In 1, two cobalt(III) ions are connected via three single atom bridges; two from deprotonated ethanolic oxygen atoms in the side arms of the ligands and one from the1-amino-2-propanol moiety forming a dinuclear unit with a very short (2.5430(11) Å) Co-Co intermetallic separation with a coordination number of 7, a rare feature for cobalt(III). In 2, two cobalt(II) ions in a dinuclear unit are bridged through phenoxide O and μ₃-1,1,1-N₃ azido bridges, and the two dinuclear units are interconnected by two μ-1,1-N₃ and two μ₃-1,1,1-N₃ azido bridges generating tetranuclear cationic [Co₄(H₂L⁻¹)₂(µ₃-1,1,1-N₃)₂(µ-1,1-N₃)₂Cl₂(CH₃OH)₂]²⁺ units with an incomplete double cubane core, which grow into polynuclear 1D-single chains along the a-axis through H-bonding. In 3, HL²⁻ holds mixed-valent Co(II)/Co(III) ions in a dinuclear unit bridged via phenoxide O, μ-1,3-CH₃CO₂⁻, and μ₃-OH⁻ bridges, and the dinuclear units are interconnected through two deprotonated ethanolic O in the side arms of the ligands and two μ₃-OH⁻ bridges generating cationic tetranuclear [Co₂^IICo₂^III(HL⁻²)₂(µ-CH₃CO₂)₂(µ_3-OH)₂]²⁺ units with an incomplete double cubane core. In 4, H₂L1⁻² holds mixed-valent Co(II)/Co(III) ions in dinuclear units which dimerize through two ethanolic O (μ-RO⁻) in the side arms of the ligands and two ethanolic O (μ₃-RO⁻) of THMAM bridges producing centrosymmetric cationic tetranuclear [Co₂^IICo₂^III (H₂L1⁻²)₂(THMAM⁻¹)₂]⁴⁺ units which grow into 2D-sheets along the bc-axis through a network of H-bonding. Bulk magnetization measurements on 2 demonstrate that the magnetic interactions are completely dominated by an overall ferromagnetic coupling occurring between Co(II) ions.     

Geometric and electronic structure differences between the type 3 copper sites of the multicopper oxidases and hemocyanin/tyrosinase

The coupled binuclear “type 3” Cu sites are found in hemocyanin (Hc), tyrosinase (Tyr), and the multicopper oxidases (MCOs), such as laccase (Lc), and play vital roles in O₂ respiration. Although all type 3 Cu sites share the same ground state features, those of Hc/Tyr have very different ligand-binding properties relative to those of the MCOs. In particular, the type 3 Cu site in the MCOs (Lc^T3) is a part of the trinuclear Cu cluster, and if the third (i.e., type 2) Cu is removed, the Lc^T3 site does not react with O₂. Density functional theory calculations indicate that O₂ binding in Hc is ≈9 kcal mol⁻¹ more favorable than for Lc^T3. The difference is mostly found in the total energy difference of the deoxy states (≈7 kcal mol⁻¹), where the stabilization of deoxy Lc^T3 derives from its long equilibrium Cu–Cu distance of ≈5.5–6.5 Å, relative to ≈4.2 Å in deoxy Hc/Tyr. The O₂ binding in Hc is driven by the electrostatic destabilization of the deoxy Hc site, in which the two Cu(I) centers are kept close together by the protein for facile 2-electron reduction of O₂. Alternatively, the lack of O₂ reactivity in Lc^T3 reflects the flexibility of the active site, capable of minimizing the electrostatic repulsion of the 2 Cu(I)s. Thus, the O₂ reactivity of the MCOs is intrinsic to the trinuclear Cu cluster, leading to different O₂ intermediates as required by its function of irreversible reduction of O₂ to H₂O.     

Non-enzymatic Hydrogen Peroxide Sensors Based on Multi-wall Carbon Nanotube/Pt Nanoparticle Nanohybrids

A novel strategy to fabricate a hydrogen peroxide (H₂O₂) sensor was developed by using platinum (Pt) electrodes modified with multi-wall carbon nanotube-platinum nanoparticle nanohybrids (MWCNTs/Pt nanohybrids). The process to synthesize MWCNTs/Pt nanohybrids was simple and effective. Pt nanoparticles (Pt NPs) were generated in situ in a potassium chloroplatinate aqueous solution in the presence of multi-wall carbon nanotubes (MWCNTs), and readily attached to the MWCNTs convex surfaces without any additional reducing reagents or irradiation treatment. The MWCNT/Pt nanohybrids were characterized by transmission electron microscope (TEM), and the redox properties of MWCNTs/Pt nanohybrids-modified Pt electrode were studied by electrochemical measurements. The MWCNTs/Pt-modified electrodes exhibited a favorable catalytic ability in the reduction of H₂O₂. The modified electrodes can be used to detect H₂O₂ in the range of 0.01–2 mM with a lower detection limit of 0.3 μM at a signal-to-noise ratio of 3. The sensitivity of the electrode to H₂O₂ was calculated to be 205.80 μA mM⁻¹ cm⁻² at working potential of 0 mV. In addition, the electrodes exhibited an excellent reusability and long-term stability as well as negligible interference from ascorbic acid, uric acid, and acetaminophen.     

Oxygen isotope anomaly observed in water vapor from Alert,Canada and the implication for the stratosphere

To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003−2005 at Alert station, Canada (82°30′N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ¹⁷O and δ¹⁸O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λ_MDF(H₂O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003−2005. An oxygen isotopic anomaly of Δ¹⁷O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ¹⁷O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930−1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ¹⁷O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l''Environnement, Gif sur Yvette, France, had ¹⁷O_excess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water.     

Preparation and Characterization of Cu and Ni on Alumina Supports and Their Use in the Synthesis of Low-Temperature Metal-Phthalocyanine Using a Parallel-Plate Reactor

Ni- and Cu/alumina powders were prepared and characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), and N₂ physisorption isotherms were also determined. The Ni/Al₂O₃ sample reveled agglomerated (1 μm) of nanoparticles of Ni (30–80 nm) however, NiO particles were also identified, probably for the low temperature during the H₂ reduction treatment (350 °C), the Cu/Al₂O₃ sample presented agglomerates (1–1.5 μm) of nanoparticles (70–150 nm), but only of pure copper. Both surface morphologies were different, but resulted in mesoporous material, with a higher specificity for the Ni sample. The surfaces were used in a new proposal for producing copper and nickel phthalocyanines using a parallel-plate reactor. Phthalonitrile was used and metallic particles were deposited on alumina in ethanol solution with CH₃ONa at low temperatures; ≤60 °C. The mass-transfer was evaluated in reaction testing with a recent three-resistance model. The kinetics were studied with a Langmuir-Hinshelwood model. The activation energy and Thiele modulus revealed a slow surface reaction. The nickel sample was the most active, influenced by the NiO morphology and phthalonitrile adsorption.     

Carbon Felt-Based Bioelectrocatalytic Flow-Through Detectors: 2,6-Dichlorophenol Indophenol and Peroxidase Coadsorbed Carbon-Felt for Flow-Amperometric Determination of Hydrogen Peroxide

2,6-dichlorophenol indophenol (DCIP) and horseradish peroxidase (HRP) were coadsorbed on a porous carbon felt (CF) from their mixed aqueous solution under ultrasound irradiation for 5 min. The resulting DCIP and HRP-coadsorbed CF (DCIP/HRP-CF) showed an excellent bioelectrocatalytic activity for the reduction of H₂O₂. The coadsorption of DCIP together with HRP was essential to obtain larger bioelectrocatalytic current to H₂O₂. The DCIP/HRP-CF was successfully used as a working electrode unit of a bioelectrocatalytic flow-through detector for highly sensitive and continuous amperometric determination of H₂O₂. Under the optimized operational conditions (i.e., applied potential, +0.2 V versus Ag/AgCl; carrier pH 5.0, and carrier flow rate, 1.9 mL/min), the cathodic peak current of H₂O₂ linearly increased over the concentration range from 0.1 to 30 μM (the sensitivity, 0.88 μA/μM (slope of linear part); the limit of detection, 0.1 μM (S/N = 3) current noise level, 30 nA) with a sample through-put of ca. 40–90 samples/h.     

Enhancement of Bentonite Materials with Cement for Gamma-Ray Shielding Capability

The gamma-ray shielding ability of various Bentonite–Cement mixed materials from northeast Egypt have been examined by determining their theoretical and experimental mass attenuation coefficients, μ_m (cm²g⁻¹), at photon energies of 59.6, 121.78, 344.28, 661.66, 964.13, 1173.23, 1332.5 and 1408.01 keV emitted from ²⁴¹Am, ¹³⁷Cs, ¹⁵²Eu and ⁶⁰Co point sources. The μ_m was theoretically calculated using the chemical compositions obtained by Energy Dispersive X-ray Analysis (EDX), while a NaI (Tl) scintillation detector was used to experimentally determine the μ_m (cm²g⁻¹) of the mixed samples. The theoretical values are in acceptable agreement with the experimental calculations of the XCom software. The linear attenuation coefficient (μ), mean free path (MFP), half-value layer (HVL) and the exposure buildup factor (EBF) were also calculated by knowing the μ_m values of the examined samples. The gamma-radiation shielding ability of the selected Bentonite–Cement mixed samples have been studied against other puplished shielding materials. Knowledge of various factors such as thermo-chemical stability, availability and water holding capacity of the bentonite–cement mixed samples can be analyzed to determine the effectiveness of the materials to shield gamma rays.