Role of defects in radiation chemistry of crystalline organic materials. 2. Effective and selective formation of solute radicals and its dependence on the carbon-chain difference in the radiolysis products of CmH2m+2/C10D22 normal hydrocarbon mixed crystals as studies by ESR spectroscopy

1990 ◽  
Vol 94 (1) ◽  
pp. 418-423 ◽  
Author(s):  
Hachizo. Muto ◽  
Keichi. Nunome ◽  
Mitsuharu. Fukaya
Keyword(s):  
Esr Spectroscopy ◽  
Organic Materials ◽  
Carbon Chain ◽  
Radiation Chemistry ◽  
Mixed Crystals ◽  
Radiolysis Products ◽  
Selective Formation

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.

scholarly journals Catalytic Systems Based on Cp2ZrX2 (X = Cl, H), Organoaluminum Compounds and Perfluorophenylboranes: Role of Zr,Zr- and Zr,Al-Hydride Intermediates in Alkene Dimerization and Oligomerization

Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 39
Author(s):  
Lyudmila V. Parfenova ◽  
Pavel V. Kovyazin ◽  
Almira Kh. Bikmeeva ◽  
Eldar R. Palatov
Keyword(s):  
Diffusion Coefficients ◽  
Organoaluminum Compounds ◽  
Zirconium Hydride ◽  
Nmr Studies ◽  
Catalytic Systems ◽  
Selective Formation

The activity and chemoselectivity of the Cp2ZrCl2-XAlBui2 (X = H, Bui) and [Cp2ZrH2]2-ClAlEt2 catalytic systems activated by (Ph3C)[B(C6F5)4] or B(C6F5)3 were studied in reactions with 1-hexene. The activation of the systems by B(C6F5)3 resulted in the selective formation of head-to-tail alkene dimers in up to 93% yields. NMR studies of the reactions of Zr complexes with organoaluminum compounds (OACs) and boron activators showed the formation of Zr,Zr- and Zr,Al-hydride intermediates, for which diffusion coefficients, hydrodynamic radii, and volumes were estimated using the diffusion ordered spectroscopy DOSY. Bis-zirconium hydride clusters of type x[Cp2ZrH2∙Cp2ZrHCl∙ClAlR2]∙yRnAl(C6F5)3−n were found to be the key intermediates of alkene dimerization, whereas cationic Zr,Al-hydrides led to the formation of oligomers.

A study of the radiation chemistry of poly(chlorotrifluoroethylene) by ESR spectroscopy

2003 ◽  
Vol 68 (5) ◽  
pp. 857-864 ◽  
Author(s):  
David J.T. Hill ◽  
Kristofer J. Thurecht ◽  
Andrew K. Whittaker
Keyword(s):  
Esr Spectroscopy ◽  
Radiation Chemistry

3D simulations of warm and hot Jupiter atmospheres: the role of 3D mixing in shaping CH4-to-CO conversion pathways

2021 ◽  
Author(s):  
Maria Zamyatina ◽  
Eric Hebrard ◽  
Nathan Mayne ◽  
Benjamin Drummond
Keyword(s):  
Chemical Structure ◽  
Three Dimensional ◽  
Chemical Species ◽  
Radiation Chemistry ◽  
3D Simulations ◽  
Horizontal Advection ◽  
Co Conversion ◽  
Area Of Influence ◽  
Different Parts

<p>We present results from a set of cloud-free simulations of exoplanet atmospheres using a coupled three-dimensional (3D) hydrodynamics-radiation-chemistry model. We report in particular our investigation of the thermodynamic and chemical structure of the atmospheres of HAT-P-11b and WASP-17b and their comparison with the results for the atmospheres of HD 189733b and HD 209458b presented in Drummond et al. (2020). We found that the abundances of chemical species from simulations with interactive chemistry depart from their respective abundances computed at local chemical equilibrium, especially at higher latitudes. To understand this departure, we analysed the CH<sub>4</sub>-to-CO conversion pathways within the Venot et al. (2019) reduced chemical network used in our model using a chemical network analysis. We found that at steady state nine CH<sub>4</sub>-to-CO conversion pathways manifest in our 3D simulations with interactive chemistry, with different pathways dominating different parts of the atmosphere and their area of influence being determined by the vertical and horizontal advection and shifting between planets.</p>

Role of the FAD-dependent polyamine oxidase in the selective formation of N1,N8-bis(γ- glutamyl)spermidine protein cross-links1

2007 ◽  
Vol 35 (2) ◽  
pp. 396-400 ◽  
Author(s):  
A. Lentini ◽  
P. Mattioli ◽  
B. Provenzano ◽  
A. Abbruzzese ◽  
M. Caraglia ◽  
...  
Keyword(s):  
Stratum Corneum ◽  
Polyamine Oxidase ◽  
Polyamine Metabolism ◽  
Suitable Model ◽  
Cross Link ◽  
Cellular Mechanisms ◽  
Preferential Formation ◽  
Cross Links ◽  
Selective Formation

Protein-bound γ-glutamylpolyamines have highlighted a new pathway in polyamine metabolism. Human foreskin keratinocytes offer a suitable model for this study. Indeed, they develop polymerized envelopes, as they differentiate, rich in ϵ-(γ-glutamyl)lysine and N1,N8-bis(γ-glutamyl)spermidine cross-links. We have found that the selective oxidation of N1-(γ-glutamyl)spermidine and N-(γ-glutamyl)spermine by FAD-dependent polyamine oxidase (PAO) may be one of the cellular mechanisms regulating the preferential formation of a sterically defined bis(γ-glutamyl)spermidine cross-link. The significance of this finding is unknown, but it suggests that the target of this PAO-modulation is to achieve the biochemical prerequisite for production of a normal epidermal stratum corneum.

Sign in / Sign up

Export Citation Format

Share Document