| 1. |
- Ali, Sk Imran, et al.
(författare)
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Synthesis and Magnetic Properties of the Ternary Oxofluoride Fe3Sb4O6F6
- 2020
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 2020:39, s. 3746-3752
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Tidskriftsartikel (refereegranskat)abstract
- The new compound Fe(3)Sb(4)O(6)F(6)was prepared by hydrothermal synthesis and its crystal structure was determined from single-crystal X-ray diffraction data. The synthesis was made under slightly basic conditions to prevent oxidation of Fe(2+)to Fe3+. The compound crystallizes in the cubic space groupI-43mwith separate crystallographic sites for Fe(2+)and Sb3+. Fe(3)Sb(4)O(6)F(6)is isostructural with M3Sb4O6F6(M = Co, Ni, Zn). The crystal structure is comprising distorted [FeO2F4] octahedra connected via corner sharing at F-atoms and [SbO3] trigonal pyramids that form [Sb4O6] units that connect via O-atoms to the Fe-atoms. Mossbauer spectroscopy measurements on the hydrothermal synthesis products prove the majority phase contains Fe in the oxidation state +2. Powder X-ray diffraction suggests that an additional phase of the Mossbauer sample containing Fe(3+)can be attributed to FeSbO(2)F(2)as secondary phase. Fe(3)Sb(4)O(6)F(6)exhibits antiferromagnetic order below ca. 72 K succeeded by a second magnetic phase transition at ca. 30 K. Strong antiferromagnetic spin-exchange interaction is attributed to 180 degrees Fe-F-Fe superexchange pathways identified in the crystal structure.
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| 2. |
- El Jamal, Ghada, et al.
(författare)
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H2O2-Induced Oxidative Dissolution of UO2 in Saline Solutions
- 2021
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 2021:40, s. 4175-4182
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Tidskriftsartikel (refereegranskat)abstract
- H2O2 is one of the oxidants responsible for driving the process of radiation-induced dissolution of spent nuclear fuel in geological repositories for spent nuclear fuel. As the groundwater composition will vary depending on geographical location as well as on the age of the repository (in relation to glacial cycles, etc.), it is important to elucidate the impact of different groundwater constituents. While several studies have addressed the impact of HCO3− and halide ions on the radiation chemistry of water in general and radiation-induced oxidative dissolution of spent nuclear fuel in particular, very few studies have addressed the impact of halide ions on the mechanism of the reaction between H2O2 and UO2. In this work, the impact of Cl−, Br− and ClO4− on the mechanism and kinetics of H2O2-induced oxidative dissolution of UO2-powder in aqueous suspensions with and without added HCO3− has been studied experimentally. The experiments reveal both ionic strength effects and specific ion effects on the kinetics of the reactions involved. These are discussed in connection to the results.
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| 3. |
- Khandarkhaeva, Saiana, et al.
(författare)
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Novel Rhenium Carbides at 200 GPa
- 2020
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Ingår i: European Journal of Inorganic Chemistry. - : WILEY-V C H VERLAG GMBH. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 2020:22, s. 2186-2190
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Tidskriftsartikel (refereegranskat)abstract
- Laser heating of rhenium in a diamond anvil cell to 3000 +/- 300 K at about 200 GPa results in formation of two previously unknown rhenium carbides, hexagonal WC-type structured ReC and orthorhombic TiSi2-type structured ReC2. The shortest C-C distances [1.758(3) angstrom at 219(5) GPa and 1.850(4) angstrom at 180(7) GPa] found in honeycomb-like carbon nets in the structure of ReC2 are quite unusual. The Re-C solid solution formed at multimegabar pressure has the carbon content of approximate to 20 at%.
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| 4. |
- Kumar, P. Anil, et al.
(författare)
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All-alkoxide based deposition and properties of a multilayer La0.67Sr0.33MnO3/CoFe2O4/La0.67Sr0.33MnO3 film
- 2021
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Ingår i: European Journal of Inorganic Chemistry. - : John Wiley & Sons. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 2021:18, s. 1736-1744
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Tidskriftsartikel (refereegranskat)abstract
- Single and multilayer films of La0.67Sr0.33MnO3 and CoFe2O4 were deposited by spin-coating. The all-alkoxide precursors allowed inorganic gel films of extreme homogeneity to be formed and converted to phase pure complex oxides at low temperatures. La0.67Sr0.33MnO3 films were made with La- and Ca-methoxy-ethoxides and Mn19O12(moe)(14)(moeH)(10) as precursors at 800 degrees C. The CoFe2O4 films were obtained at extremely low 275 degrees C, using a new CoFe2-methoxyethoxide precursor. The decomposition and microstructural development on heating was described by TG, TEM, XRD and IR spectroscopy. XRD showed no spurious phases and the unit-cell dimensions coincided quite well with literature values of the targeted phases. The structural, magnetic and electronic properties of these films established their phase purity and high quality with physical properties comparable to films deposited by physical deposition methods. The magnetic and magneto transport results are presented for single, bi- and tri- layer structures. The magnetically soft La0.67Sr0.33MnO3 layer was exchange coupled to the magnetically hard CoFe2O4 layer, giving rise to interesting switching behaviour in magnetism and magneto-transport properties.
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| 5. |
- Maier, Annika Carolin, et al.
(författare)
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Impact of H2 and Consecutive H2O2 Exposures on the Oxidative Dissolution of (U1–xGdx)O2 Pellets Under Deep Repository Conditions for Spent Nuclear Fuel
- 2020
-
Ingår i: European Journal of Inorganic Chemistry. - : Wiley-VCH Verlag. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 2020:20, s. 1946-1950
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Tidskriftsartikel (refereegranskat)abstract
- The reactivity of H2O2 towards (U1–xGdx)O2 (x = 0.03, 0.045, 0.08) in the presence of H2 was studied experimentally to assess the effect of H2 on oxidative dissolution of Gd-doped UO2 under deep repository conditions for spent nuclear fuel. Gd-doped UO2 was chosen as a model substance for spent nuclear fuel due to its chemical similarity but low radiotoxicity. While H2O2 is a radiolysis product capable of driving fuel matrix dissolution, H2, which is expected to evolve mainly through the corrosion of cast iron canisters encapsulating the fuel, might limit or even suppress fuel dissolution. Commercial (U1–xGdx)O2 pellets were immersed in 10 mm HCO3 – solutions and consecutively exposed to 2 mm H2O2 in an autoclave under either 40 bar H2 or 5 bar N2 atmosphere. The results indicate that H2 does not influence the oxidative dissolution of (U1–xGdx)O2. Instead, the reactivity of the pellets decreases with increasing H2O2 exposure due to an irreversible alteration of the pellet surfaces resulting in decreased redox reactivity.
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| 6. |
- Queyriaux, Nicolas, et al.
(författare)
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Electrochemical, Spectroscopic, and Computational Investigation of a Series of Polypyridyl Ruthenium(II) Complexes : Characterization of Reduced States
- 2021
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Ingår i: European Journal of Inorganic Chemistry. - : John Wiley & Sons. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 2021:13, s. 1263-1270
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Tidskriftsartikel (refereegranskat)abstract
- A series of polypyridyl ruthenium(II) complexes has been synthesized and characterized by H-1-NMR, electronic absorption and voltammetric techniques. Among this series, hexafluorophosphate salts of eight ruthenium(II) complexes were newly prepared. Due to the well-known ability of this class of compounds to assist electro- and photocatalytic reductive processes (such as the reduction of CO2, H+ and NAD(P)(+) models), particular attention has been paid to investigate the nature of their one- and two-electron reduced species through computational and spectroscopic techniques.
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| 7. |
- Rönfeldt, Pia, et al.
(författare)
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New Scandium-containing Coordination Polymers with Linear Linker Molecules : Crystal Structures and Luminescence Properties
- 2020
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 2020:28, s. 2737-2743
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Tidskriftsartikel (refereegranskat)abstract
- Two new scandium-containing coordination polymers, with the formulae {(CH3)2NH2}[Sc(BPDC)2] (1) and [Sc(OH) (BPyDC)] (2) were solvothermally synthesized by using the linear linker molecules biphenyl-4,4′-dicarboxylic acid (H2BPDC) and 2,2′-bipyridine-5,5′-dicarboxylic acid (H2BPyDC). Crystal structures were determined from single-crystal and powder Xray diffraction data, respectively. The crystal structures of 1 and 2 contain isolated ScO6 or chains of trans corner-sharing ScO6 octahedra as the inorganic building unit (IBU), which are connected by the linker molecules to a 3D framework or a layered structure, respectively. The compounds were characterized by IR-spectroscopy, elemental analysis, thermogravimetric analysis and photoluminescence spectroscopy. 1 shows blue emission at 400 nm, while 2 exhibits intense green emission at 550 nm with a high quantum yield (QY) of 69 %.
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| 8. |
- Samii, Rouzbeh, 1986-, et al.
(författare)
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Synthesis, Structure and Thermal Properties of Volatile Indium and Gallium Triazenides
- 2022
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley-V C H Verlag GMBH. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :24
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Tidskriftsartikel (refereegranskat)abstract
- Indium and gallium nitride are important semi-conductor materials with desirable properties for high-frequency and power electronics. We have previously demonstrated high-quality ALD grown InN and GaN using the hexacoordinated 1,3-diisopropyltriazenide In(III) and Ga(III) precursors. Herein we report the structural and thermal properties their analogues employing combinations of isopropyl, sec-butyl and tert-butyltriazenide alkyl groups on the exocyclic nitrogen of the triazenide ligand. The new triazenide compounds were all found to be volatile (80-120 degrees C, 0.5 mbar) and showed very good thermal stability (200 and 300 degrees C). These new triazenide analogues provide a set of precursors whose thermal properties are determined and can be accordingly tailored by strategic choice of exocyclic nitrogen alkyl substituents.
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| 9. |
- Schmitz, Georg J., et al.
(författare)
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Thermodynamics of an Empty Box
- 2023
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Ingår i: Entropy. - : MDPI AG. - 1099-4300. ; 25:2
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Tidskriftsartikel (refereegranskat)abstract
- A gas in a box is perhaps the most important model system studied in thermodynamics and statistical mechanics. Usually, studies focus on the gas, whereas the box merely serves as an idealized confinement. The present article focuses on the box as the central object and develops a thermodynamic theory by treating the geometric degrees of freedom of the box as the degrees of freedom of a thermodynamic system. Applying standard mathematical methods to the thermody- namics of an empty box allows equations with the same structure as those of cosmology and classical and quantum mechanics to be derived. The simple model system of an empty box is shown to have interesting connections to classical mechanics, special relativity, and quantum field theory.
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| 10. |
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| 11. |
- Gschwind, Wanja, et al.
(författare)
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The Influence of Water in the Vapor-Assisted Conversion Synthesis of UiO-67 MOF Thin Films
- 2023
-
Ingår i: European Journal of Inorganic Chemistry. - : Wiley-Blackwell. - 1434-1948 .- 1099-1948. ; 26:27
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Tidskriftsartikel (refereegranskat)abstract
- Abstract Water is known to play an important role for the crystallization and stability of Zr-based metal-organic frameworks (MOFs). This work investigates its effect on the vapor-assisted conversion (VAC) synthesis of UiO-67 MOF thin films on Au-coated Si substrates. We demonstrate the equilibration processes taking place during the VAC procedure, confirming the gradual equilibration of all solutions upon heating. The presence of water affects the vapor phase composition but does not significantly impact the acetic acid equilibration rate. However, the preparation of UiO-67 thin films by VAC is highly sensitive to the water content in the reaction. Some water is required for the formation of the zirconium clusters, but excessive water in the reaction vial yields poorly crystalline materials. Atmospheric water that is taken up by the vapor source can be sufficient to reduce crystallinity dramatically. This complication can be partially overcome by increasing the amount of acetic acid in the vapor source.
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| 12. |
- Wineinger, Hannah, et al.
(författare)
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Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4-Amino-1,2,4-triazole
- 2023
-
Ingår i: European Journal of Inorganic Chemistry. - : WILEY-V C H VERLAG GMBH. - 1434-1948 .- 1099-1948. ; 26:31
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Tidskriftsartikel (refereegranskat)abstract
- Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N-donor f-element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4-amino-1,2,4-triazole (4-NH2-1,2,4-Triaz), 5-amino-tetrazole (5-NH2-HTetaz), and 1,2,3-triazole (1,2,3-HTriaz) in 1:1 and 1:3 ratios with CeCl3 center dot 7H(2)O, [C(2)mim](3)[CeCl6] ([C(2)mim](+) = 1-ethyl-2-methylimidazolium), and Ce(NO3)(3)center dot 6H(2)O. Although unsuccessful in our goal, structural analysis revealed that neutral 4-NH2-1,2,4-Triaz is structure directing via eta(2)mu(2)kappa(2) bridging, with the formation of the dinuclear complexes [Ce2Cl2(mu(2)-4-NH2-1,2,4-Triaz)(4)(H2O)(8)]Cl-4 center dot 4H(2)O, [Ce-2(mu(2)-4-NH2-1,2,4-Triaz)(4)(4-NH2-1,2,4-Triaz)(2)(Cl)(6)], and [4-NH2-1,2,4-HTriaz][Ce-2(mu(2)-4-NH2-1,2,4-Triaz)(2)(mu(2)-NO3)(NO3)(6)(H2O)(2)]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce-6(mu(3)-O)(4)(mu(3)-OH)(2)(mu(3)-Cl)(2)(Cl)(6)(mu(2)-4-NH2-1,2,4-Triaz)(12)]center dot 7H(2)O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N-donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non-oxo coordinating anions in the M6X8 core, and the first reported Ce(III) hexanuclear complex of this type.
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| 13. |
- Greijer, Björn, et al.
(författare)
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Complexes of Keggin POMs [PM12O40](3-) (M=Mo, W) with GlyGlyGly and GlyGlyGlyGly Oligopeptides
- 2021
-
Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-0682. ; , s. 54-61
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Tidskriftsartikel (refereegranskat)abstract
- Complexes of Keggin phosphomolybdate and phosphotungstate anions with tri- and tetra-peptides, GlyGlyGly and GlyGlyGlyGly respectively, were isolated and investigated by single crystal X-ray diffraction, FTIR and SEM-EDS in the solid state and by H-1- and P-31 NMR and ESI-MS in solution. The trends imposed by longer chain length and increased hydrophobicity of the peptide molecules were traced both in binding in the solid state and in effects on solution stability of POMs. Hydrolysis of peptides was observed in strongly acidic solutions at enhanced temperatures in the presence of tungsten POMs.
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| 14. |
- Mousa, Abdelrazek H., et al.
(författare)
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Enhancing the Stability of Aromatic PCN Pincer Nickel Complexes by Incorporation of Pyridine as the Nitrogen Side Arm
- 2020
-
Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-0682. ; 2020:45, s. 4270-4277
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Tidskriftsartikel (refereegranskat)abstract
- New PCNPy pincer nickel complexes have been synthesized through a short synthetic route. Incorporating pyridine as the nitrogen side arm facilitated the C–H activation in the PCN ligand and allowed the cyclometallation with nickel to take place at room temperature. Pyridine also enhanced the stability of β-hydrogen-containing alkyl complexes. Also, the symmetric NCN nickel complex with pyridine side arms was successfully obtained giving a rare example of such type of complexes to be prepared through direct C–H activation. Furthermore, preliminary results showed that the (PCNPy)Ni–Br is active in Kumada coupling reactions particularly the coupling of aryl halides with aryl Grignard reagents.
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| 15. |
- Ramírez, Erick, et al.
(författare)
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Oxygen Transfer from Trimethylamine N-Oxide to CuI Complexes Supported by Pentanitrogen Ligands
- 2020
-
Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-0682. ; 2020:29, s. 2798-2808
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Tidskriftsartikel (refereegranskat)abstract
- [N,N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L1) and [N,N-bis(2-quinolylmethyl)-N-bis(2-pyridyl)methylamine] (L2) were employed to prepare CuII and CuI complexes for spectroscopic and structural characterization. [L1CuII(H2O)](NO3)2 and [L2CuII(NO3)]NO3 have Jahn–Teller distorted octahedral geometries and give rise to isotropic EPR spectra in frozen solution. [L1CuI(CH3CN)]OTf and [L2CuI(CH3CN)]OTf have distorted trigonal bipyramidal and tetrahedral solid-state structures, respectively. The N-donors display labile behavior in solution, based on variable-temperature 1H NMR studies. Addition of trimethylamine N-oxide (Me3NO) to solutions of [L1CuI(CH3CN)]OTf and [L2CuI(CH3CN)]OTf resulted in diamagnetic species tentatively assigned as the corresponding adducts upon replacement of coordinated acetonitrile, based on 1H NMR spectroscopy. Heating [L1CuI(CH3CN)]OTf to 50–60 °C in the presence of Me3NO resulted in its cupric analogue [L1CuII(CH3CN)]2+, as well as a small amount of 2-dipyridylketone, along with other oxidation by-products. In the case of [L2CuI(CH3CN)]OTf, the reaction with Me3NO resulted in the cupric complex bis(2-quinolinecarboxamidato)copper(II), along with 2-dipyridylketone as oxidation products.
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| 16. |
- Arkhypchuk, Anna I., et al.
(författare)
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Investigation of the demetallation of 10-aryl substituted synthetic chlorins under acidic conditions
- 2020
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Ingår i: Journal of Inorganic Biochemistry. - : ELSEVIER SCIENCE INC. - 0162-0134 .- 1873-3344. ; 205
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Tidskriftsartikel (refereegranskat)abstract
- The acidic demetallation of a series of sparsely substituted Zn(II) chlorins is reported. The chlorins were functionalized in the 10-position with substituents ranging from strongly electron donating mesityl and p-methoxyphenyl to electron-withdrawingp-nitrophenyl and pentafluorophenyl groups. The demetallation kinetics were investigated using UV-Visible absorption spectroscopy. Demetallation was carried out by exposing the metallochlorins dissolved in CH2Cl2 to an excess of trifiuoroacetic acid. Reasonable correlation was found between the Hammett constant of the 10-substituent and the rate constant of the loss of the metal ion. The largest differences were observed between the p-methoxyphenyl and p-nitrophenyl-substituted Zn(II) chlorins, undergoing loss of Zn(II) with pseudo first order rate constants of 0.0789 x 10(-3) and 3.70 x 10(-3) min(-1), respectively. Taken together, these data establish the dramatic influence even subtle changes can have in altering the electronic properties of chlorins, which in turn impacts metallochlorin function.
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| 17. |
- Bergmann, Justin, et al.
(författare)
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Quantum-refinement studies of the bidentate ligand of V‑nitrogenase and the protonation state of CO-inhibited Mo‑nitrogenase
- 2021
-
Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134. ; 219
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Tidskriftsartikel (refereegranskat)abstract
- Nitrogenase is the only enzyme that can cleave the triple bond in N2, making nitrogen available to plants (although the enzyme itself is strictly microbial). It has been studied extensively with both experimental and computational methods, but many details of the reaction mechanism are still unclear. X-ray crystallography is the main source of structural information for biomacromolecules, but it has problems to discern hydrogen atoms or to distinguish between elements with the same number of electrons. These problems can sometimes be alleviated by introducing quantum chemical calculations in the refinement, providing information about the ideal structure (in the same way as the empirical restraints used in standard crystallographic refinement) and comparing different interpretations of the structure with normal crystallographic and quantum mechanical quality measures. We have performed such quantum-refinement calculations to address two important issues for nitrogenase. First, we show that the bidentate ligand of the active-site FeV cluster in V‑nitrogenase is carbonate, rather than bicarbonate or nitrate. Second, we study the CO-inhibited structure of Mo‑nitrogenase. CO binds to a reduced and protonated state of the enzyme by replacing one of the sulfide ions (S2B) in the active-site FeMo cluster. We examined if it is possible to deduce from the crystal structure the location of the protons. Our results indicates that the crystal structure is best modelled as fully deprotonated.
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| 18. |
- Blomberg, Margareta R. A., 1946-, et al.
(författare)
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Reduction of molecular oxygen in flavodiiron proteins - Catalytic mechanism and comparison to heme-copper oxidases
- 2024
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Ingår i: Journal of Inorganic Biochemistry. - 0162-0134 .- 1873-3344. ; 255
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Tidskriftsartikel (refereegranskat)abstract
- The family of flavodiiron proteins (FDPs) plays an important role in the scavenging and detoxification of both molecular oxygen and nitric oxide. Using electrons from a flavin mononucleotide cofactor molecular oxygen is reduced to water and nitric oxide is reduced to nitrous oxide and water. While the mechanism for NO reduction in FDPs has been studied extensively, there is very little information available about O2 reduction. Here we use hybrid density functional theory (DFT) to study the mechanism for O2 reduction in FDPs. An important finding is that a proton coupled reduction is needed after the O2 molecule has bound to the diferrous diiron active site and before the O–O bond can be cleaved. This is in contrast to the mechanism for NO reduction, where both N–N bond formation and N–O bond cleavage occurs from the same starting structure without any further reduction, according to both experimental and computational results. This computational result for the O2 reduction mechanism should be possible to evaluate experimentally. Another difference between the two substrates is that the actual O–O bond cleavage barrier is low, and not involved in rate-limiting the reduction process, while the barrier connected with bond cleavage/formation in the NO reduction process is of similar height as the rate-limiting steps. We suggest that these results may be part of the explanation for the generally higher activity for O2 reduction as compared to NO reduction in most FDPs. Comparisons are also made to the O2 reduction reaction in the family of heme‑copper oxidases.
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| 19. |
- Blomberg, Margareta R. A.
(författare)
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The mechanism for oxygen reduction in the C family cbb(3) cytochrome c oxidases - Implications for the proton pumping stoichiometry
- 2020
-
Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134 .- 1873-3344. ; 203
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Tidskriftsartikel (refereegranskat)abstract
- Cytochrome c oxidases (CcOs) couple the exergonic reduction of molecular oxygen to proton pumping across the membrane in which they are embedded, thereby conserving a significant part of the free energy. The A family CcOs are known to pump four protons per oxygen molecule, while there is no consensus regarding the proton pumping stoichiometry for the C family cbb(3) oxidases. Hybrid density functional theory is used here to investigate the catalytic mechanism for oxygen reduction in cbb(3) oxidases. A surprising result is that the barrier for O-O bond cleavage at the mixed valence reduction level seems to be too high compared to the overall reaction rate of the enzyme. It is therefore suggested that the O-O bond is cleaved only after the first proton coupled reduction step, and that this reduction step most likely is not coupled to proton pumping. Furthermore, since the cbb3 oxidases have only one proton channel leading to the active site, it is proposed that the activated E-H intermediate, suggested to be responsible for proton pumping in one of the reduction steps in the A family, cannot be involved in the catalytic cycle for cbb(3), which results in the lack of proton pumping also in the E to R reduction step. In summary, the calculations indicate that only two protons are pumped per oxygen molecule in cbb(3) oxidases. However, more experimental information on this divergent enzyme is needed, e.g. whether the flow of electrons resembles that in the other more well-studied CcO families.
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| 20. |
- Blomberg, Margareta R. A.
(författare)
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The structure of the oxidized state of cytochrome c oxidase - experiments and theory compared
- 2020
-
Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134 .- 1873-3344. ; 206
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Tidskriftsartikel (refereegranskat)abstract
- Cytochrome c oxidase (CcO), the terminal enzyme in the respiratory chain, reduces molecular oxygen to water. Experimental data on the midpoint potentials of the heme iron/copper active site cofactors do not match the overall reaction energetics, and are also in conflict with the observed efficiency of energy conservation in CcO. Therefore it has been postulated that the ferric/cupric intermediate (the oxidized state) exists in two forms. One form, labelled O-H, is presumably involved during catalytic turnover, and should have a high Cu-B midpoint potential due to a metastable high energy structure. When no more electrons are supplied, the O-H state supposedly relaxes to the resting form, labelled O, with a lower energy and a lower midpoint potential. It has been suggested that there is a pure geometrical difference between the O-H and O states, obtained by moving a water molecule inside the active site. It is shown here that the difference between the two forms of the oxidized state must be of a more chemical nature. The reason is that all types of geometrically relaxed structures of the oxidized intermediate have similar energies, all with a high proton coupled reduction potential in accordance with the postulated O-H state. One hypothesized chemical modification of the O-H state is the transfer of an extra proton, possibly internal, into the active site. Such a protonated state has several properties that agree with experimental data on the relaxed oxidized state, including a decreased midpoint potential.
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| 21. |
- Brânzanic, Adrian M.V., et al.
(författare)
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Importance of the iron–sulfur component and of the siroheme modification in the resting state of sulfite reductase
- 2020
-
Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134. ; 203
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Tidskriftsartikel (refereegranskat)abstract
- The active site of sulfite reductase (SiR) consists of an unusual siroheme–Fe4S4 assembly coupled via a cysteinate sulfur, and serves for multi-electron reduction reactions. Clear explanations have not been demonstrated for the reasons behind the choice of siroheme (vs. other types of heme) or for the single-atom coupling to an Fe4S4 center (as opposed to simple adjacency or to coupling via chains consisting of more than one atom). Possible explanations for these choices have previously been invoked, relating to the control of the spin state of the substrate-binding (siro)heme iron, modulation of the trans effect of the (Fe4S4–bound) cysteinate, or modulation of the redox potential. Reported here is a density functional theory (DFT) investigation of the structural interplay (in terms of geometry, molecular orbitals and magnetic interactions) between the siroheme and the Fe4S4 center as well as the importance of the covalent modifications within siroheme compared to the more common heme b, aiming to verify the role of the siroheme modification and of the Fe4S4 cluster at the SiR active site, with focus on previously-formulated hypotheses (geometrical/sterics, spin state, redox and electron-transfer control). A calibration of various DFT methods/variants for the correct description of ground state spin multiplicity is performed using a set of problematic cases of bioinorganic Fe centers; out of 11 functionals tested, M06-L and B3LYP offer the best results – though none of them correctly predict the spin state for all test cases. Upon examination of the relative energies of spin states, reduction potentials, energy decomposition (electrostatic, exchange-repulsion, orbital relaxation, correlation and dispersion interactions) and Mayer bond indices in SiR models, the following main roles of the siroheme and cubane are identified: (1) the cubane cofactor decreases the reduction potential of the siroheme and stabilizes the siroheme–cysteine bond interaction, and (2) the siroheme removes the quasi-degeneracy between the intermediate and high-spin states found in ferrous systems by preserving the latter as ground state; the higher-spin preference and the increased accessibility of multiple spin states are likely to be important in selective binding of the substrate and of the subsequent reaction intermediates, and in efficient changes in redox states throughout the catalytic cycle.
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| 22. |
- Das, Biswanath, et al.
(författare)
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A di‑iron(III) μ-oxido complex as catalyst precursor in the oxidation of alkanes and alkenes
- 2022
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Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134. ; 231
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Tidskriftsartikel (refereegranskat)abstract
- The oxido-bridged diiron(III) complex [Fe2(μ-O)(μ-OAc)(DPEAMP)2](OCH3) (1), based on a new unsymmetrical ligand with an N4O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H2O2 as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in excellent retention of configuration. Monitoring of the reaction of 1 with H2O2 and acetic acid in the absence of substrate, using low-temperature UV–Vis spectroscopy, suggests the in situ formation of a transient Fe(III)2-peroxido species. While the selectivity and nature of oxidation products implicate a high-valent iron-oxido complex as a key intermediate, the low alcohol/ketone ratios suggest a simultaneous radical-based process.
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| 23. |
- Durigon, Daniele C., et al.
(författare)
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The influence of thioether-substituted ligands in dicopper(II) complexes : Enhancing oxidation and biological activities
- 2024
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Ingår i: Journal of Inorganic Biochemistry. - 0162-0134. ; 256
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Tidskriftsartikel (refereegranskat)abstract
- This paper describes the synthesis, structural analysis, as well as the magnetic and spectroscopic characterizations of three new dicopper(II) complexes with dinucleating phenol-based ligands containing different thioether donor substituents: aromatic (1), aliphatic (2) or thiophene (3). Temperature-dependent magnetometry reveals the presence of antiferromagnetic coupling for 1 and 3 (J = −2.27 cm−1 and -5.01 cm−1, respectively, H = -2JS1S2) and ferromagnetic coupling for 2 (J = 5.72 cm−1). Broken symmetry DFT calculations attribute this behavior to a major contribution from the dz2 orbitals for 1 and 3, and from the dx2-y2 orbitals for 2, along with the p orbitals of the oxygens. The bioinspired catalytic activities of these complexes related to catechol oxidase were studied using 3,5-di-tert-butylcatechol as substrate. The order of catalytic rates for the substrate oxidation follows the trend 1 > 2 > 3 with kcat of (90.79 ± 2.90) × 10−3 for 1, (64.21 ± 0.99) × 10−3 for 2 and (14.20 ± 0.32) × 10−3 s−1 for 3. The complexes also cleave DNA through an oxidative mechanism with minor-groove preference, as indicated by experimental and molecular docking assays. Antimicrobial potential of these highly active complexes has shown that 3 inhibits both Staphylococcus aureus bacterium and Epidermophyton floccosum fungus. Notably, the complexes were found to be nontoxic to normal cells but exhibited cytotoxicity against epidermoid carcinoma cells, surpassing the activity of the metallodrug cisplatin. This research shows the multifaceted properties of these complexes, making them promising candidates for various applications in catalysis, nucleic acids research, and antimicrobial activities.
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| 24. |
- Gabriel, Philipe, et al.
(författare)
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A heterotrinuclear bioinspired coordination complex capable of binding to DNA and emulation of nuclease activity
- 2022
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Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134. ; 226
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Tidskriftsartikel (refereegranskat)abstract
- The investigation of compounds capable of strongly and selectively interacting with DNA comprises a field of research in constant development. In this work, we demonstrate that a trinuclear coordination complex based on a dinuclear Fe(III)Zn(II) core designed for biomimicry of the hydrolytic enzyme kidney bean purple acid phosphatase, containing an additional pendant arm coordinating a Pd(II) ion, has the ability to interact with DNA and to promote its hydrolytic cleavage. These results were found through analysis of plasmid DNA interaction and cleavage by the trinuclear complex 1 and its derivatives 2 and 3, in addition to the analysis of alteration in the DNA structure in the presence of the complexes through circular dichroism and DNA footprinting techniques. The suggested covalent interaction of the palladium-containing complex with DNA was analysed using an electrophoretic mobility assay, circular dichroism, high resolution gel separation techniques and kinetic analysis. This is a new and promising metal complex targeted to nucleic acids and acting in two separate ways: strong DNA interaction and hydrolytic cleavage.
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| 25. |
- González-Mendoza, Victor M., et al.
(författare)
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Biochemical characterization of phospholipases C from Coffea arabica in response to aluminium stress
- 2020
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Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134 .- 1873-3344. ; 204
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Tidskriftsartikel (refereegranskat)abstract
- Signal transduction in plants determines their successful adaptation to diverse stress factors. Our group employed suspension cells to study the phosphoinositide pathway, which is triggered by aluminium stress. We investigated about members of the PI-specific phospholipase C (PLC) family and evaluated their transcription profiles in Coffea arabica (Ca) suspension cells after 14 days of culture when treated or not with 100 μM AlCl3. The four CaPLC1-4 members showed changes in their transcript abundance upon AlCl3 treatment. The expression profiles of CaPLC1/2 exhibited a rapid and transitory increase in abundance. In contrast, CaPLC3 and CaPLC4 showed that transcript levels were up-regulated in short times (at 30 s), while only CaPLC4 kept high levels and CaPLC3 was reduced to basal after 3 h of treatment. CaPLC proteins were heterologously expressed, and CaPLC2 and CaPLC4 were tested for in vitro activity in the presence or absence of AlCl3 and compared to Arabidopsis PLC2 (AtPLC2). A crude extract was isolated from coffee cells. CaPLC2 showed a similar inhibition (30%) as in AtPLC2 and in the crude extract, while in CaPLC4, the activity was enhanced by AlCl3. Additionally, we visualized the yellow fluorescent protein PH domain of human PLCδ1 (YFP-PHPLCδ1) subcellular localization in cells that were treated or not with AlCl3. In non-treated cells, we observed a polar fluorescence signal towards the fused membrane. However, when cells were treated with AlCl3, these signals were disrupted. Finally, this is the first time that PLC activity has been shown to be stimulated in vitro by AlCl3.
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| 26. |
- Hizbullah, Lintang, et al.
(författare)
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Synthesis of phosphine derivatives of [Fe2(CO)6(μ-sdt)] (sdt = SCH2SCH2S) and investigation of their proton reduction capabilities
- 2023
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Ingår i: Journal of Inorganic Biochemistry. - 0162-0134. ; 246
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Tidskriftsartikel (refereegranskat)abstract
- The reactions of [Fe2(CO)6(μ-sdt)] (1) (sdt = SCH2SCH2S) with phosphine ligands have been investigated. Treatment of 1 with dppm (bis(diphenylphosphino)methane) or dcpm (bis(dicyclohexylphosphino)methane) affords the diphosphine-bridged products [Fe2(CO)4(μ-sdt)(μ-dppm)] (2) and [Fe2(CO)4(μ-sdt)(μ-dcpm)] (3), respectively. The complex [Fe2(CO)4(μ-sdt)(κ2-dppv)] (4) with a chelating diphosphine was obtained by reacting 1 with dppv (cis-1,2-bis(diphenylphosphino)ethene). Reaction of 1 with dppe (1,2-bis(diphenylphosphino)ethane) produces [{Fe2(CO)4(μ-sdt)}2(μ-κ1-dppe)] (5) in which the diphosphine forms an intermolecular bridge between two diiron cluster fragments. Three products were obtained when dppf (1,1′-bis(diphenylphosphino)ferrocene) was introduced to complex 1; they were [Fe2(CO)5(μ-sdt)(κ1-dppfO)] (6), the previously known [{Fe2(CO)5(μ-sdt)}2(μ-κ1-κ1-dppf)] (7), and [Fe2(CO)4(μ-sdt)(μ-dppf)] (8), with complex 8 being produced in highest yield. Single crystal X-ray diffraction analysis was performed on compounds 2, 3 and 8. All structures reveal the adoption of an anti-arrangement of the dithiolate bridges, while the diphosphines occupy dibasal positions. Infra-red spectroscopy indicates that the mono-substituted complexes 5, 6, and 7 are inert to protonation by HBF4.Et2O, but complexes 2, 3, 4 and [Fe2(CO)5(μ-sdt)(κ1-PPh3)] (9) show shifts of their ν(C-O) resonances that indicate that protons bind to the metal cores of the clusters. Addition of the one-electron oxidant [Cp2Fe]PF6 does not lead to any discernable shift in the IR resonances. The redox chemistry of the complexes was investigated by cyclic voltammetry, and the abilities of complexes to catalyze electrochemical proton reduction were examined.
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| 27. |
- Marzo, T., et al.
(författare)
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Oxaliplatin inhibits angiogenin proliferative and cell migration effects in prostate cancer cells
- 2022
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Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134. ; 226
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Tidskriftsartikel (refereegranskat)abstract
- Angiogenin (Ang) is a potent angiogenic protein that is overexpressed in many types of cancer at concentration values correlated to the tumor aggressiveness. Here, by means of an integrated multi-technique approach based on crystallographic, spectrometric and spectroscopic analyses, we demonstrate that the anti-cancer drug oxaliplatin efficiently binds angiogenin. Microscopy cellular studies, carried out on the prostate cancer cell (PC-3) line , show that oxaliplatin inhibits the angiogenin prompting effect on cell proliferation and migration, which are typical features of angiogenesis process. Overall, our findings point to angiogenin as a possible target of oxaliplatin, thus suggesting a potential novel mechanism for the antineoplastic activity of this platinum drug and opening the avenue to novel approaches in the combined anti-cancer anti-angiogenic therapy.
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| 28. |
- Ohmer, Christopher J., et al.
(författare)
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XFEL serial crystallography reveals the room temperature structure of methyl-coenzyme M reductase
- 2022
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Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134 .- 1873-3344. ; 230, s. 111768-
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Tidskriftsartikel (refereegranskat)abstract
- Methyl-Coenzyme M Reductase (MCR) catalyzes the biosynthesis of methane in methanogenic archaea, using a catalytic Ni-centered Cofactor F430 in its active site. It also catalyzes the reverse reaction, that is, the anaerobic activation and oxidation, including the cleavage of the C-H bond in methane. Because methanogenesis is the major source of methane on earth, understanding the reaction mechanism of this enzyme can have massive implications in global energy balances. While recent publications have proposed a radical-based catalytic mechanism as well as novel sulfonate-based binding modes of MCR for its native substrates, the structure of the active state of MCR, as well as a complete characterization of the reaction, remain elusive. Previous attempts to structurally characterize the active MCR-Ni(I) state have been unsuccessful due to oxidation of the redox- sensitive catalytic Ni center. Further, while many cryo structures of the inactive Ni(II)-enzyme in various substrates bound forms have been published, no room temperature structures have been reported, and the structure and mechanism of MCR under physiologically relevant conditions is not known. In this study, we report the first room temperature structure of the MCRred1-silent Ni(II) form using an X-ray Free-Electron Laser (XFEL), with simultaneous X-ray Emission Spectroscopy (XES) and X-ray Diffraction (XRD) data collection. In celebration of the seminal contributions of inorganic chemist Dick Holm to our understanding of nickel-based catalysis, we are honored to announce our findings in this special issue dedicated to this remarkable pioneer of bioinorganic chemistry.
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| 29. |
- Polukeev, Alexey V.
(författare)
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Synthesis, Structure, and Catalytic Activity of Cyclometalated Iridium Complexes with a Bidentate POC Ligand
- 2023
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Ingår i: European Journal of Inorganic Chemistry. - 1434-1948. ; 26:31
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Tidskriftsartikel (refereegranskat)abstract
- Synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand is presented. Metalation of POC-H (di-tert-butyl(phenoxy)phosphane) with [Ir(COD)Cl]2 proceeded rapidly at room temperature and afforded mixture of (POC)(POC-H)IrHCl (1 a) and (POC)(COD)IrHCl (1 b), from which complexes (POC)(L)IrHCl where L=PPh3 (1 c), bipyridine (1 d) and [2,2′-bipyridine]-6,6′-diol (1 e) were prepared through ligand exchange. The compounds were tested in acceptorless dehydrogenation of 1-phenylethanol and transfer dehydrogenation of ethanol in a context of comparison with pincer counterparts (POCOP)IrHCl and (PCN)IrHCl. An attempt to prepare a dihydride complex from 1 e led to dimeric complex [(POC)(bipy-diol−)IrH]2 (3) that could explain the low activity of 1 e. DFT studies provided insight into POC-H vs POCOP-H metalation mechanism.
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| 30. |
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| 31. |
- Zhang, Xiaolu, 1983, et al.
(författare)
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Memo1 reduces copper-mediated reactive oxygen species in breast cancer cells
- 2023
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Ingår i: Journal of Inorganic Biochemistry. - 1873-3344 .- 0162-0134. ; 247
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Tidskriftsartikel (refereegranskat)abstract
- The mediator of ERBB2-driven cell motility protein 1, Memo1, plays important roles in cancer signaling pathways. We recently reported Memo1 to coordinate reduced copper ions and protect them from reactive oxygen species (ROS) generation in vitro. We here assess if this Memo1 activity is at play in breast cancer cells. Copper additions to MDA-MB-231 cells promoted cell death, and this toxicity was exaggerated when Memo1 expression was reduced by silencing RNA. Using three different commercial ROS probes, we revealed that copper additions increased intracellular ROS levels, and these were further elevated when Memo1 expression was silenced. We propose that, in addition to other functions, Memo1 protects cancer cells from unwanted copper-mediated redox reactions. This may be a required safety mechanism in cancer cells as they have a high demand for copper.
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