Mantle Redox Evolution and the Oxidation State of the Archean Atmosphere

1993 ◽  
Vol 101 (2) ◽  
pp. 245-257 ◽  
Author(s):  
James F. Kasting ◽  
David H. Eggler ◽  
Stuart P. Raeburn
Keyword(s):  
Oxidation State ◽  
Redox Evolution

Deep magma ocean formation set the oxidation state of Earth’s mantle

Science ◽  
2019 ◽  
Vol 365 (6456) ◽  
pp. 903-906 ◽  
Author(s):  
Katherine Armstrong ◽  
Daniel J. Frost ◽  
Catherine A. McCammon ◽  
David C. Rubie ◽  
Tiziana Boffa Ballaran
Keyword(s):  
Oxidation State ◽  
Upper Mantle ◽  
Metallic Iron ◽  
Redox State ◽  
High Pressures ◽  
Important Variable ◽  
Magma Ocean ◽  
The Core ◽  
Earth’S Mantle ◽  
Redox Evolution

The composition of Earth’s atmosphere depends on the redox state of the mantle, which became more oxidizing at some stage after Earth’s core started to form. Through high-pressure experiments, we found that Fe2+ in a deep magma ocean would disproportionate to Fe3+ plus metallic iron at high pressures. The separation of this metallic iron to the core raised the oxidation state of the upper mantle, changing the chemistry of degassing volatiles that formed the atmosphere to more oxidized species. Additionally, the resulting gradient in redox state of the magma ocean allowed dissolved CO2 from the atmosphere to precipitate as diamond at depth. This explains Earth’s carbon-rich interior and suggests that redox evolution during accretion was an important variable in determining the composition of the terrestrial atmosphere.

Chromium oxidation state mapping in human cells

2003 ◽  
Vol 104 ◽  
pp. 289-292 ◽  
Author(s):  
R. Ortega ◽  
B. Fayard ◽  
M. Salomé ◽  
G. Devès ◽  
J. Susini
Keyword(s):  
Oxidation State ◽  
Human Cells ◽  
Chromium Oxidation

A Short Synthesis of (+)-Brefeldin C via Enantioselective Radical Hydroalkynylation

2019 ◽  
Author(s):  
Lars Gnägi ◽  
Severin Vital Martz ◽  
Daniel Meyer ◽  
Robin Marc Schärer ◽  
Philippe Renaud
Keyword(s):  
Total Synthesis ◽  
Natural Product ◽  
Oxidation State ◽  
Single Step ◽  
Radical Process ◽  
Target Molecule ◽  
Short Synthesis ◽  
The One

<div><div><div><div><p>A very concise total synthesis of (+)-brefeldin C starting from 2-furanylcyclopentene is described. This approach is based on an unprecedented enantioselective radical hydroalkynylation process to introduce the two cyclopentane stereocenters in a single step. The use of a furan substituent allows to achieve a high trans diastereoselectivity during the radical process and it contains the four carbon atoms C1–C4 of the natural product in an oxidation state closely related to the one of the target molecule. The eight-step synthesis require six product purifications and it provides (+)-brefeldin C in 18% overall yield.</p></div></div></div></div>

Piperazine as an Inexpensive and Efficient Ligand for Pd-Catalyzed Homocoupling Reactions to Synthesize Bipyridines and Their Analogues

2019 ◽  
Vol 16 (1) ◽  
pp. 173-180
Author(s):  
Mingwei Chen ◽  
Jinyu Hu ◽  
Xiaoli Tang ◽  
Qiming Zhu
Keyword(s):  
Transition Metal ◽  
Oxidation State ◽  
Coupling Reaction ◽  
Aryl Halides ◽  
Metal Species ◽  
Good Substrate ◽  
Active Metal ◽  
Homocoupling Reaction ◽  
Catalytic Cycles ◽  
Reductive Homocoupling

Aim and Objective: The synthesis of bipyridines, especially 2, 2’-bipyridines, remains challenging because the catalytic cycle can be inhibited due to coordination of bipyridine to transition metal. Thus, the development of efficient methods for the synthesis of bipyridines is highly desirable. In the present work, we presented a promising approach for preparation of bipyridines via a Pd-catalyzed reductive homocoupling reaction with simple piperazine as a ligand. Materials and Methods: Simple and inexpensive piperazine was used as a ligand for Pd-catalyzed homocoupling reaction. The combination of Pd(OAc)2 and piperazine in dimethylformamide (DMF) was observed to form an excellent catalyst and efficiently catalyzed the homocoupling of azaarenyl halides, in which DMF was used as the solvent without excess reductants although stoichiometric reductant was generally required to generate the low-oxidation-state active metal species in the catalytic cycles. </P><P> Results: In this case, good to excellent yields of bipyridines and their (hetero) aromatic analogues were obtained in the presence of 2.5 mol% of Pd(OAc)2 and 5 mol% of piperazine, using K3PO4 as a base in DMF at 140°C. Conclusion: According to the results, piperazine as an inexpensive and efficient ligand was used in the Pd(OAc)2-catalyzed homocoupling reaction of heteroaryl and aryl halides. The coupling reaction was operationally simple and displayed good substrate compatibility.

Voltammetric Studies of Some Novel Fe(III) Complexes with Quadridentate Ligands. The Axial Ligand-Exchange Reactions in DMF and DMSO

1995 ◽  
Vol 60 (7) ◽  
pp. 1140-1157 ◽  
Author(s):  
Ljiljana S. Jovanovic ◽  
Luka J. Bjelica
Keyword(s):  
Oxidation State ◽  
Chemical Reactions ◽  
Ligand Exchange ◽  
Kinetic Data ◽  
Central Atom ◽  
Axial Ligand ◽  
Exchange Reactions ◽  
Ligand Effect ◽  
Condensation Products ◽  
Voltammetric Studies

The electrochemistry of four novel Fe(III) complexes of the type [Fe(L)Cl], involving quadridentate ligands based on the condensation products of benzoylacetone-S-methylisothiosemicarbazone with salicylaldehyde, 5-chlorosalicylaldehyde, 3,5-dichlorosalicylaldehyde or 5-nitrosalicylaldehyde, was studied in DMF and DMSO at a GC electrode. All complexes undergo a two-step one-electron reductions, usually complicated by chemical reactions. In solutions containing Cl-, the ligand-exchange reactions Cl--DMF and Cl--DMSO take place. Stability of the chloride-containing complexes was discussed in terms of the coordinated ligand effect, oxidation state of the central atom and, in particular, of the donor effect of the solvent. Some relevant kinetic data were calculated.

Studies of the Synthesis of Large VAPO-5 Crystals and Incorporation of Vanadium Ions

1992 ◽  
Vol 57 (4) ◽  
pp. 767-773 ◽  
Author(s):  
Jan Kornatowski ◽  
Mikhail Sychev ◽  
Werner H. Baur ◽  
Gerd Finger
Keyword(s):  
Oxidation State ◽  
Molecular Sieve ◽  
Model Substance ◽  
Vanadium Ions

The molecular sieve VAPO-5 has been synthesized hydrothermally in form of large crystals up to 660 μm in length. They have been used as a model substance for the study of vanadium incorporation into the framework. Our results show that vanadium was incorporated into the framework though in relatively small amounts. The results are in agreement with earlier findings for powder preparations of VAPO-5, except for the oxidation state of the vanadium ions and its stability. These conclusions agree with those arrived at previously for vanadium silicate KVS-5.

scholarly journals Biogeochemical Controls on the Redox Evolution of Earth’s Oceans and Atmosphere

Elements ◽  
2020 ◽  
Vol 16 (3) ◽  
pp. 191-196 ◽  
Author(s):  
Christopher T. Reinhard ◽  
Noah J. Planavsky
Keyword(s):  
Redox State ◽  
Modeling Tools ◽  
Evolutionary Trajectory ◽  
Geochemical Tracers ◽  
Atmosphere System ◽  
Ocean Atmosphere ◽  
Dramatic Shift ◽  
Redox Evolution

The redox state of Earth’s atmosphere has undergone a dramatic shift over geologic time from reducing to strongly oxidizing, and this shift has been coupled with changes in ocean redox structure and the size and activity of Earth’s biosphere. Delineating this evolutionary trajectory remains a major problem in Earth system science. Significant insights have emerged through the application of redox-sensitive geochemical systems. Existing and emerging biogeochemical modeling tools are pushing the limits of the quantitative constraints on ocean–atmosphere redox that can be extracted from geochemical tracers. This work is honing our understanding of the central role of Earth’s biosphere in shaping the long-term redox evolution of the ocean–atmosphere system.

Gd/Sm dopant-modified oxidation state and defect generation in nano-ceria

2014 ◽  
Vol 260 ◽  
pp. 21-29 ◽  
Author(s):  
S.A. Acharya ◽  
V.M. Gaikwad ◽  
S.W. D'Souza ◽  
S.R. Barman
Keyword(s):  
Oxidation State ◽  
Defect Generation ◽  
Nano Ceria
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