scholarly journals Polarity effects in 4-fluoro- and 4-(trifluoromethyl)prolines

2020 ◽  
Vol 16 ◽  
pp. 1837-1852
Author(s):  
Vladimir Kubyshkin
Keyword(s):  
Main Chain ◽  
Spectroscopic Studies ◽  
Amide Bond ◽  
Molecular Models ◽  
Acid Base ◽  
Bond Rotation ◽  
Base Transition ◽  
Fundamental Understanding ◽  
Polarity Effects ◽  
Kinetics Of

Fluorine-containing analogues of proline are valuable tools in engineering and NMR spectroscopic studies of peptides and proteins. Their use relies on the fundamental understanding of the interplay between the substituents and the main chain groups of the amino acid residue. This study aims to showcase the polarity-related effects that arise from the interaction between the functional groups in molecular models. Properties such as conformation, acid–base transition, and amide-bond isomerism were examined for diastereomeric 4-fluoroprolines, 4-(trifluoromethyl)prolines, and 1,1-difluoro-5-azaspiro[2.4]heptane-6-carboxylates. The preferred conformation on the proline ring originated from a preferential axial positioning for a single fluorine atom, and an equatorial positioning for a trifluoromethyl- or a difluoromethylene group. This orientation of the substituents explains the observed trends in the pK a values, lipophilicity, and the kinetics of the amide bond rotation. The study also provides a set of evidences that the transition state of the amide-bond rotation in peptidyl-prolyl favors C4-exo conformation of the pyrrolidine ring.

scholarly journals Unexpected Resistance to Base-Catalyzed Hydrolysis of Nitrogen Pyramidal Amides Based on the 7-Azabicyclic[2.2.1]heptane Scaffold

Molecules ◽  
2018 ◽  
Vol 23 (9) ◽  
pp. 2363 ◽  
Author(s):  
Diego Ocampo Gutiérrez de Velasco ◽  
Aoze Su ◽  
Luhan Zhai ◽  
Satowa Kinoshita ◽  
Yuko Otani ◽  
...  
Keyword(s):  
Nitrogen Atom ◽  
Amide Bond ◽  
Free Energies ◽  
Amide Nitrogen ◽  
Bond Rotation ◽  
Entropy Term ◽  
And Inversion ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Amide Nitrogen Atom

Non-planar amides are usually transitional structures, that are involved in amide bond rotation and inversion of the nitrogen atom, but some ground-minimum non-planar amides have been reported. Non-planar amides are generally sensitive to water or other nucleophiles, so that the amide bond is readily cleaved. In this article, we examine the reactivity profile of the base-catalyzed hydrolysis of 7-azabicyclo[2.2.1]heptane amides, which show pyramidalization of the amide nitrogen atom, and we compare the kinetics of the base-catalyzed hydrolysis of the benzamides of 7-azabicyclo[2.2.1]heptane and related monocyclic compounds. Unexpectedly, non-planar amides based on the 7-azabicyclo[2.2.1]heptane scaffold were found to be resistant to base-catalyzed hydrolysis. The calculated Gibbs free energies were consistent with this experimental finding. The contribution of thermal corrections (entropy term, –TΔS‡) was large; the entropy term (ΔS‡) took a large negative value, indicating significant order in the transition structure, which includes solvating water molecules.

scholarly journals Ice Coverage Induced by Depositing a Water Drop onto the Supercooled Substrate at Extreme Low Vapor Pressure

Crystals ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 691
Author(s):  
Yugang Zhao ◽  
Zichao Zuo ◽  
Haibo Tang ◽  
Xin Zhang
Keyword(s):  
Vapor Pressure ◽  
Substrate Temperature ◽  
Water Drop ◽  
Industrial Processes ◽  
Aircraft Icing ◽  
Ice Coverage ◽  
Fundamental Understanding ◽  
Order Of Magnitude ◽  
The Impact ◽  
Kinetics Of

Icing/snowing/frosting is ubiquitous in nature and industrial processes, and the accretion of ice mostly leads to catastrophic consequences. The existing understanding of icing is still limited, particularly for aircraft icing, where direct observation of the freezing dynamics is inaccessible. In this work, we investigate experimentally the impact and freezing of a water drop onto the supercooled substrate at extremely low vapor pressure, to mimic an aircraft passing through clouds at a relatively high altitude, engendering icing upon collisions with pendant drops. Special attention is focused on the ice coverage induced by an impinging drop, from the perimeter pointing outward along the radial direction. We observed two freezing regimes: (I) spread-recoil-freeze at the substrate temperature of Ts = −15.4 ± 0.2 °C and (II) spread (incomplete)-freeze at the substrate temperature of Ts = −22.1 ± 0.2 °C. The ice coverage is approximately one order of magnitude larger than the frozen drop itself, and counterintuitively, larger supercooling yields smaller ice coverage in the range of interest. We attribute the variation of ice coverage to the kinetics of vapor diffusion in the two regimes. This fundamental understanding benefits the design of new anti-icing technologies for aircraft.

The thermodynamics and kinetics of the synthesis of poly(acid) amides with alicyclic structures in the main chain

1977 ◽  
Vol 19 (11) ◽  
pp. 2878-2884 ◽  
Author(s):  
B.A Zhubanov ◽  
V.A Solomin ◽  
P.Ye Messerle ◽  
N.G Avetisyan ◽  
V.D Moiseyev
Keyword(s):  
Main Chain ◽  
Thermodynamics And Kinetics ◽  
Kinetics Of

Kinetics of the reaction OH + NOCl as a possible source of ClOH for spectroscopic studies

1981 ◽  
Vol 17 (1) ◽  
pp. 142-143
Author(s):  
G. Poulet ◽  
J.L. Jourdain ◽  
G. Laverdet ◽  
G. Le Bras
Keyword(s):  
Spectroscopic Studies ◽  
Kinetics Of

scholarly journals Toward a mechanistic understanding of electrocatalytic nanocarbon

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Erik J. Askins ◽  
Marija R. Zoric ◽  
Matthew Li ◽  
Zhengtang Luo ◽  
Khalil Amine ◽  
...  
Keyword(s):  
Spectroscopic Studies ◽  
Synthetic Methods ◽  
Computational Studies ◽  
Molecular Models ◽  
Chemical Production ◽  
True Nature ◽  
Catalytic Mechanisms ◽  
Mechanistic Understanding ◽  
Further Development

AbstractElectrocatalytic nanocarbon (EN) is a class of material receiving intense interest as a potential replacement for expensive, metal-based electrocatalysts for energy conversion and chemical production applications. The further development of EN will require an intricate knowledge of its catalytic behaviors, however, the true nature of their electrocatalytic activity remains elusive. This review highlights work that contributed valuable knowledge in the elucidation of EN catalytic mechanisms. Experimental evidence from spectroscopic studies and well-defined molecular models, along with the survey of computational studies, is summarized to document our current mechanistic understanding of EN-catalyzed oxygen, carbon dioxide and nitrogen electrochemistry. We hope this review will inspire future development of synthetic methods and in situ spectroscopic tools to make and study well-defined EN structures.

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