96/03697 Role of aromatic structure in pathways of hydrogen tranfer and bond cleavage in coal liquefaction. Theoretical studies

1996 ◽  
Vol 37 (4) ◽  
pp. 261
Keyword(s):  
Bond Cleavage ◽  
Coal Liquefaction ◽  
Theoretical Studies ◽  
Aromatic Structure

scholarly journals σ-Bond Hydroboration of Cyclopropanes

2020 ◽  
Author(s):  
Hiroki Kondo ◽  
Shin Miyamura ◽  
Chisa Kobayashi ◽  
Arifin ◽  
Stephan Irle ◽  
...  
Keyword(s):  
Double Bond ◽  
Natural Product ◽  
Organic Synthesis ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
High Reactivity ◽  
Natural Product Synthesis ◽  
Theoretical Studies ◽  
Single Bond

Hydroboration of alkenes is a classical reaction in organic synthesis, in which alkenes react with boranes to give alkylboranes, with subsequent oxidation resulting in alcohols. The double bond (π-bond) of alkenes can be readily reacted with boranes owing to its high reactivity. However, the single bond (σ-bond) of alkanes has never been reacted. To pursue the development of σ-bond cleavage, we selected cyclopropanes as model substrates since they present a relatively weak σ-bond. Herein, we describe an iridium-catalyzed hydroboration of cyclopropanes, resulting in β-methyl alkylboronates. These unusually branched boronates can be derivatized by oxidation or cross-coupling chemistry, accessing “designer” products that are desired by practitioners of natural product synthesis and medicinal chemistry. Furthermore, mechanistic investigations and theoretical studies revealed the enabling role of the catalyst.

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

Mechanisms of ATP to cAMP Conversion Catalyzed by the Mammalian Adenylyl Cyclase: A Role of Magnesium Coordination Shells and Proton Wires

2019 ◽  
Author(s):  
Bella Grigorenko ◽  
Igor Polyakov ◽  
Alexander Nemukhin
Keyword(s):  
Adenylyl Cyclase ◽  
Bond Cleavage ◽  
Cyclic Adenosine Monophosphate ◽  
Adenosine Monophosphate ◽  
Md Simulations ◽  
Coordination Shell ◽  
Energy Profile ◽  
One Step ◽  
Type V

<p>We report a mechanism of adenosine triphosphate (ATP) to cyclic adenosine monophosphate (cAMP) conversion by the mammalian type V adenylyl cyclase revealed in molecular dynamics (MD) and quantum mechanics/molecular mechanics (QM/MM) simulations. We characterize a set of computationally derived enzyme-substrate (ES) structures showing an important role of coordination shells of magnesium ions in the solvent accessible active site. Several stable six-fold coordination shells of Mg<sub>A</sub><sup>2+ </sup>are observed in MD simulations of ES complexes. In the lowest energy ES conformation, the coordination shell of Mg<sub>A</sub><sup>2+ </sup>does not include the O<sub>δ1</sub> atom of the conserved Asp440 residue. Starting from this conformation, a one-step reaction mechanism is characterized which includes proton transfer from the ribose O<sup>3'</sup>H<sup>3' </sup>group in ATP to Asp440 via a shuttling water molecule and P<sup>A</sup>-O<sup>3A</sup> bond cleavage and O<sup>3'</sup>-P<sup>A</sup> bond formation. The energy profile of this route is consistent with the observed reaction kinetics. In a higher energy ES conformation, Mg<sub>A</sub><sup>2+</sup> is bound to the O<sub>δ1</sub>(Asp440) atom as suggested in the relevant crystal structure of the protein with a substrate analog. The computed energy profile initiated by this ES is characterized by higher energy expenses to complete the reaction. Consistently with experimental data, we show that the Asp440Ala mutant of the enzyme should exhibit a reduced but retained activity. All considered reaction pathways include proton wires from the O<sup>3'</sup>H<sup>3' </sup>group via shuttling water molecules. </p>

scholarly journals Anomalous transport due to Weyl fermions in the chiral antiferromagnets Mn3X, X = Sn, Ge

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Taishi Chen ◽  
Takahiro Tomita ◽  
Susumu Minami ◽  
Mingxuan Fu ◽  
Takashi Koretsune ◽  
...  
Keyword(s):  
Technological Innovation ◽  
Essential Role ◽  
Condensed Matter ◽  
Zero Field ◽  
Theoretical Studies ◽  
Planar Hall Effect ◽  
Topological States ◽  
Experimental And Theoretical Studies ◽  
Weyl Fermions

AbstractThe recent discoveries of strikingly large zero-field Hall and Nernst effects in antiferromagnets Mn3X (X = Sn, Ge) have brought the study of magnetic topological states to the forefront of condensed matter research and technological innovation. These effects are considered fingerprints of Weyl nodes residing near the Fermi energy, promoting Mn3X (X = Sn, Ge) as a fascinating platform to explore the elusive magnetic Weyl fermions. In this review, we provide recent updates on the insights drawn from experimental and theoretical studies of Mn3X (X = Sn, Ge) by combining previous reports with our new, comprehensive set of transport measurements of high-quality Mn3Sn and Mn3Ge single crystals. In particular, we report magnetotransport signatures specific to chiral anomalies in Mn3Ge and planar Hall effect in Mn3Sn, which have not yet been found in earlier studies. The results summarized here indicate the essential role of magnetic Weyl fermions in producing the large transverse responses in the absence of magnetization.

scholarly journals Media Massa dalam Situasi Konflik: dari Bandwagon Effect Sampai Peace Narrative

2017 ◽  
Vol 1 (6) ◽  
pp. 503
Author(s):  
Aloysius Ranggabumi Nuswantoro
Keyword(s):  
Public Opinion ◽  
Public Space ◽  
Theoretical Studies ◽  
Bandwagon Effect ◽  
Conflict Situations ◽  
The Media ◽  
The Relationship

Conflict occurs between two or more parties with different interests. Media related to conflict. The ability of the media to influence public opinion is the biggest element in the relationship between media with conflict. The media in this context can be a party that sparked the conflict but could also act as resolutor conflict. Media as a provocateur when play became an arm of one of the conflicting parties, while a conciliator conflict when showing neutrality and information that tends to peace (peace narrative). And theoretical studies should be conducted searches empirical facts on this subject, to clarify the position, the position and role of media in conflict situations. The results can also be used to see the extent to which the media contribute to creating conditions of public space and democratic deliberative. Against this, the choice to stick with journalism be the most appropriate choice for the media in an effort to maintain its position as an agent of democracy in society.

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