Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A Synthetic Model of Enzymatic [Fe₄S₄]-Alkyl Intermediates.

ABSTRACT: Although alkyl complexes of [Fe₄S₄] clusters have been invoked as intermediates in a number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns and electronic structures has been difficult owing to their transient nature. To address this challenge, we herein report the synthesis and characterization of a 3:1 site-differentiated [Fe₄S₄]²⁺-alkyl cluster. Whereas [Fe₄S₄]²⁺ clusters typically exhibit pairwise delocalized electronic structures in which each Fe has a formal valence of 2.5+, Mössbauer spectroscopic and computational studies suggest that the highly electron-releasing alkyl group partially localizes the charge distribution within the cubane, an effect that has not been previously observed in tetrahedrally coordinated [Fe₄S₄] clusters.

SUBMITTER: Ye M

PROVIDER: S-EPMC6748666 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A Synthetic Model of Enzymatic [Fe4S4]-Alkyl Intermediates.

Ye Mengshan M Thompson Niklas B NB Brown Alexandra C AC Suess Daniel L M DLM

Journal of the American Chemical Society 20190816 34

Although alkyl complexes of [Fe4S4] clusters have been invoked as intermediates in a number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns and electronic structures has been difficult owing to their transient nature. To address this challenge, we herein report the synthesis and characterization of a 3:1 site-differentiated [Fe4S4]2+-alkyl cluster. Whereas [Fe4S4]2+ clu ...[more]

PMID: 31373801

Similar Datasets

An [Fe4S4]3+-Alkyl Cluster Stabilized by an Expanded Scorpionate Ligand.

Project description:Alkyl-ligated iron-sulfur clusters in the [Fe4S4]3+ charge state have been proposed as short-lived intermediates in a number of enzymatic reactions. To better understand the properties of these intermediates, we have prepared and characterized the first synthetic [Fe4S4]3+-alkyl cluster. Isolation of this highly reactive species was made possible by the development of an expanded scorpionate ligand suited to the encapsulation of cuboidal clusters. Like the proposed enzymatic intermediates, this synthetic [Fe4S4]3+-alkyl cluster adopts an S = 1/2 ground state with giso > 2. Mössbauer spectroscopic studies reveal that the alkylated Fe has an unusually low isomer shift, which reflects the highly covalent Fe-C bond and the localization of Fe3+ at the alkylated site in the solid state. Paramagnetic 1H NMR studies establish that this valence localization persists in solution at physiologically relevant temperatures, an effect that has not been observed for [Fe4S4]3+ clusters outside of a protein. These findings establish the unusual electronic-structure effects imparted by the strong-field alkyl ligand and lay the foundation for understanding the electronic structures of [Fe4S4]3+-alkyl intermediates in biology.

| S-EPMC7442740 | biostudies-literature

Fe3O4-Polyaniline Nanocomposite for Non-enzymatic Electrochemical Detection of 2,4-Dichlorophenoxyacetic Acid.

Project description:This study proposes the development of an electrochemical sensor based on fabrication of a glassy carbon electrode (GCE) with Fe3O4-polyaniline (Fe3O4-PANI) nanocomposite, which was further used for enzyme-less detection of 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous medium. Spectroscopic studies, microstructural studies, and elemental analysis established the formation of Fe3O4 nanoparticles with polyaniline coating. The fabricated Fe3O4-PANI-GCE was characterized by electrochemical techniques like cyclic voltammetry and electrochemical impedance spectroscopy. The electrochemical response of 2,4-D on Fe3O4-PANI-GCE was evaluated by performing cyclic voltammetry and amperometry experiments. The synergistic effect of the composite causes the superior electrochemical behavior of Fe3O4-PANI-GCE toward the detection of 2,4-D. Amperometric measurements exhibited a linear concentration range from 1.35 to 2.7 μM. The sensitivity and detection limit were evaluated from the amperometric responses, which were found to be 4.62 × 10-7 μA μM-1 cm-2 and 0.21 μM, respectively. The electrochemical sensing response could be attributed to adsorption of 2,4-D onto the Fe3O4-PANI-modified GCE (Fe3O4-PANI-GCE) surface. Fe3O4-PANI-GCE is found to be a simple, low-cost, and biocompatible non-enzymatic sensor for detection of 2,4-D in aqueous medium at ambient temperature.

| S-EPMC8280687 | biostudies-literature

H2O2 Oxidation by FeIII-OOH Intermediates and Its Effect on Catalytic Efficiency.

Project description:The oxidation of the C-H and C=C bonds of hydrocarbons with H2O2 catalyzed by non-heme iron complexes with pentadentate ligands is widely accepted as involving a reactive FeIV=O species such as [(N4Py)FeIV=O]2+ formed by homolytic cleavage of the O-O bond of an FeIII-OOH intermediate (where N4Py is 1,1-bis(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine). We show here that at low H2O2 concentrations the FeIV=O species formed is detectable in methanol. Furthermore, we show that the decomposition of H2O2 to water and O2 is an important competing pathway that limits efficiency in the terminal oxidant and indeed dominates reactivity except where only sub-/near-stoichiometric amounts of H2O2 are present. Although independently prepared [(N4Py)FeIV=O]2+ oxidizes stoichiometric H2O2 rapidly, the rate of formation of FeIV=O from the FeIII-OOH intermediate is too low to account for the rate of H2O2 decomposition observed under catalytic conditions. Indeed, with excess H2O2, disproportionation to O2 and H2O is due to reaction with the FeIII-OOH intermediate and thereby prevents formation of the FeIV=O species. These data rationalize that the activity of these catalysts with respect to hydrocarbon/alkene oxidation is maximized by maintaining sub-/near-stoichiometric steady-state concentrations of H2O2, which ensure that the rate of the H2O2 oxidation by the FeIII-OOH intermediate is less than the rate of the O-O bond homolysis and the subsequent reaction of the FeIV=O species with a substrate.

| S-EPMC6179451 | biostudies-literature

Reversible Formation of Alkyl Radicals at [Fe4S4] Clusters and Its Implications for Selectivity in Radical SAM Enzymes.

Project description:All kingdoms of life use the transient 5'-deoxyadenosyl radical (5'-dAdo•) to initiate a wide range of difficult chemical reactions. Because of its high reactivity, the 5'-dAdo• must be generated in a controlled manner to abstract a specific H atom and avoid unproductive reactions. In radical S-adenosylmethionine (SAM) enzymes, the 5'-dAdo• is formed upon reduction of SAM by an [Fe4S4] cluster. An organometallic precursor featuring an Fe-C bond between the [Fe4S4] cluster and the 5'-dAdo group was recently characterized and shown to be competent for substrate radical generation, presumably via Fe-C bond homolysis. Such reactivity is without precedent for Fe-S clusters. Here, we show that synthetic [Fe4S4]-alkyl clusters undergo Fe-C bond homolysis when the alkylated Fe site has a suitable coordination number, thereby providing support for the intermediacy of organometallic species in radical SAM enzymes. Addition of pyridine donors to [(IMes)3Fe4S4-R]+ clusters (R = alkyl or benzyl; IMes = 1,3-dimesitylimidazol-2-ylidene) generates R•, ultimately forming R-R coupled hydrocarbons. This process is facile at room temperature and allows for the generation of highly reactive radicals including primary carbon radicals. Mechanistic studies, including use of the 5-hexenyl radical clock, demonstrate that Fe-C bond homolysis occurs reversibly. Using these experimental insights and kinetic simulations, we evaluate the circumstances in which an organometallic intermediate can direct the 5'-dAdo• toward productive H-atom abstraction. Our findings demonstrate that reversible homolysis of even weak M-C bonds is a feasible protective mechanism for the 5'-dAdo• that can allow selective X-H bond activation in both radical SAM and adenosylcobalamin enzymes.

| S-EPMC7447116 | biostudies-literature

Dielectric Properties for Nanocomposites Comparing Commercial and Synthetic Ni- and Fe3O4-Loaded Polystyrene.

Project description:Nanomaterial-loaded thermoplastics are attractive for applications in adaptive printing methods, as the physical properties of the printed materials are dependent on the nanomaterial type and degree of dispersion. This study compares the dispersion and the impact on the dielectric properties of two common nanoparticles, nickel and iron oxide, loaded into polystyrene. Comparisons between commercial and synthetically prepared samples indicate that well-passivated synthetically prepared nanomaterials are dispersed and minimize the impact on the dielectric properties of the host polymer by limiting particle-particle contacts. Commercial samples were observed to phase-segregate, leading to the loss of the low-k performance of polystyrene. The change in the real and imaginary dielectric was systematically studied in two earth abundant nanoparticles at the concentration between 0 and 13 vol % (0-50 wt %). By varying the volume percentage of fillers in the matrix, it is shown that one can increase the magnetic properties of the materials while minimizing unwanted contributions to the dielectric constant and dielectric loss. The well-dispersed nanoparticle systems were successfully modeled through the Looyenga dielectric theory, thus giving one a predictive ability for the dielectric properties. The current experimental work coupled with modeling could facilitate future material choices and guide design rules for printable polymer composite systems.

| S-EPMC6644897 | biostudies-literature

Fe-Fe bonding in the rhombic Fe4 cores of the Zintl clusters [Fe4E18]4- (E = Sn and Pb).

Project description:We report here the synthesis and characterization of two endohedral Zintl-ion clusters, [Fe4Sn18]4- and [Fe4Pb18]4-, which contain rhombic Fe4 cores. The Fe-Fe bond lengths are all below 2.5 Å, distinctly shorter than in the corresponding Cu clusters, indicating the presence of Fe-Fe bonding. Subtle differences in the structure of the Fe4 core between the two clusters suggest that the change in tetrel element causes a change in electronic ground state, with a very short Fe-Fe bond length of 2.328 Å present across the diagonal of the rhombus in the lead case.

| S-EPMC10967007 | biostudies-literature

Structural behavior of laser-irradiated γ-Fe2O3 nanocrystals dispersed in porous silica matrix : γ-Fe2O3 to α-Fe2O3 phase transition and formation of ε-Fe2O3.

Project description:The effects of laser irradiation on γ-Fe2O3 4 ± 1 nm diameter maghemite nanocrystals synthesized by co-precipitation and dispersed into an amorphous silica matrix by sol-gel methods have been investigated as function of iron oxide mass fraction. The structural properties of γ-Fe2O3 phase were carefully examined by X-ray diffraction and transmission electron microscopy. It has been shown that γ-Fe2O3 nanocrystals are isolated from each other and uniformly dispersed in silica matrix. The phase stability of maghemite nanocrystals was examined in situ under laser irradiation by Raman spectroscopy and compared with that resulting from heat treatment by X-ray diffraction. It was concluded that ε-Fe2O3 is an intermediate phase between γ-Fe2O3 and α-Fe2O3 and a series of distinct Raman vibrational bands were identified with the ε-Fe2O3 phase. The structural transformation of γ-Fe2O3 into α-Fe2O3 occurs either directly or via ε-Fe2O3, depending on the rate of nanocrystal agglomeration, the concentration of iron oxide in the nanocomposite and the properties of silica matrix. A phase diagram is established as a function of laser power density and concentration.

| S-EPMC5101921 | biostudies-literature

Local Structure and Coordination Define Adsorption in a Model Ir1 /Fe3 O4 Single-Atom Catalyst.

Project description:Single-atom catalysts (SACs) bridge homo- and heterogeneous catalysis because the active site is a metal atom coordinated to surface ligands. The local binding environment of the atom should thus strongly influence how reactants adsorb. Now, atomically resolved scanning-probe microscopy, X-ray photoelectron spectroscopy, temperature-programmed desorption, and DFT are used to study how CO binds at different Ir1 sites on a precisely defined Fe3 O4 (001) support. The two- and five-fold-coordinated Ir adatoms bind CO more strongly than metallic Ir, and adopt structures consistent with square-planar IrI and octahedral IrIII complexes, respectively. Ir incorporates into the subsurface already at 450?K, becoming inactive for adsorption. Above 900?K, the Ir adatoms agglomerate to form nanoparticles encapsulated by iron oxide. These results demonstrate the link between SAC systems and coordination complexes, and that incorporation into the support is an important deactivation mechanism.

| S-EPMC6790613 | biostudies-literature

High-capacity and high-rate Ni-Fe batteries based on mesostructured quaternary carbon/Fe/FeO/Fe3O4 hybrid material.

Project description:The Ni-Fe battery is a promising alternative to lithium ion batteries due to its long life, high reliability, and eco-friendly characteristics. However, passivation and self-discharge of the iron anode are the two main issues. Here, we demonstrate that controlling the valence state of the iron and coupling with carbon can solve these problems. We develop a mesostructured carbon/Fe/FeO/Fe3O4 hybrid by a one-step solid-state reaction. Experimental evidence reveals that the optimized system with three valence states of iron facilitates the redox kinetics, while the carbon layers can effectively enhance the charge transfer and suppress self-discharge. The hybrid anode exhibits high specific capacity of 604 mAh⋅g-1 at 1 A⋅g-1 and high cyclic stability. A Ni-Fe button battery is fabricated using the hybrid anode exhibits specific device energy of 127 Wh⋅kg-1 at a power density of 0.58 kW⋅kg-1 and maintains good capacity retention (90%) and coulombic efficiency (98.5%).

| S-EPMC8184513 | biostudies-literature

Antisymmetric magnetoresistance in van der Waals Fe3GeTe2/graphite/Fe3GeTe2 trilayer heterostructures.

Project description:With no requirements for lattice matching, van der Waals (vdW) ferromagnetic materials are rapidly establishing themselves as effective building blocks for next-generation spintronic devices. We report a hitherto rarely seen antisymmetric magnetoresistance (MR) effect in vdW heterostructured Fe3GeTe2 (FGT)/graphite/FGT devices. Unlike conventional giant MR (GMR), which is characterized by two resistance states, the MR in these vdW heterostructures features distinct high-, intermediate-, and low-resistance states. This unique characteristic is suggestive of underlying physical mechanisms that differ from those observed before. After theoretical calculations, the three-resistance behavior was attributed to a spin momentum locking induced spin-polarized current at the graphite/FGT interface. Our work reveals that ferromagnetic heterostructures assembled from vdW materials can exhibit substantially different properties to those exhibited by similar heterostructures grown in vacuum. Hence, it highlights the potential for new physics and new spintronic applications to be discovered using vdW heterostructures.

| S-EPMC6611684 | biostudies-literature