Chemical reactivity prediction: current methods and different application areas

2021 ◽  
Author(s):  
Peter Ertl ◽  
Gregori Gerebtzoff ◽  
Richard A. Lewis ◽  
Hagen Muenkler ◽  
Nadine Schneider ◽  
...  
Keyword(s):  
Chemical Reactivity

Spatially Resolved Photoelectron Spectroscopy: Recent Progress and Future Plans

1990 ◽  
Vol 48 (2) ◽  
pp. 388-389
Author(s):  
A. M. Bradshaw
Keyword(s):  
Photoelectron Spectroscopy ◽  
Chemical Reactivity ◽  
Target Material ◽  
Orbital Energy ◽  
Light Sources ◽  
Analytical Technique ◽  
Hartree Fock ◽  
Spatially Resolved ◽  
Koopmans Theorem ◽  
Surface Analytical Technique

X-ray photoelectron spectroscopy (XPS or ESCA) was not developed by Siegbahn and co-workers as a surface analytical technique, but rather as a general probe of electronic structure and chemical reactivity. The method is based on the phenomenon of photoionisation: The absorption of monochromatic radiation in the target material (free atoms, molecules, solids or liquids) causes electrons to be injected into the vacuum continuum. Pseudo-monochromatic laboratory light sources (e.g. AlKα) have mostly been used hitherto for this excitation; in recent years synchrotron radiation has become increasingly important. A kinetic energy analysis of the so-called photoelectrons gives rise to a spectrum which consists of a series of lines corresponding to each discrete core and valence level of the system. The measured binding energy, EB, given by EB = hv−EK, where EK is the kineticenergy relative to the vacuum level, may be equated with the orbital energy derived from a Hartree-Fock SCF calculation of the system under consideration (Koopmans theorem).

Cluster analysis for large data sets: applications to individual aerosol particles from the mid-pacific

1992 ◽  
Vol 50 (2) ◽  
pp. 1488-1489
Author(s):  
Thomas W. Shattuck ◽  
James R. Anderson ◽  
Neil W. Tindale ◽  
Peter R. Buseck
Keyword(s):  
Cluster Analysis ◽  
Chemical Reactivity ◽  
Large Data ◽  
Large Data Sets ◽  
Particle Analysis ◽  
Data Sets ◽  
Halogen Chemistry ◽  
Complete Study ◽  
Components Analysis ◽  
Automated Scanning

Individual particle analysis involves the study of tens of thousands of particles using automated scanning electron microscopy and elemental analysis by energy-dispersive, x-ray emission spectroscopy (EDS). EDS produces large data sets that must be analyzed using multi-variate statistical techniques. A complete study uses cluster analysis, discriminant analysis, and factor or principal components analysis (PCA). The three techniques are used in the study of particles sampled during the FeLine cruise to the mid-Pacific ocean in the summer of 1990. The mid-Pacific aerosol provides information on long range particle transport, iron deposition, sea salt ageing, and halogen chemistry.Aerosol particle data sets suffer from a number of difficulties for pattern recognition using cluster analysis. There is a great disparity in the number of observations per cluster and the range of the variables in each cluster. The variables are not normally distributed, they are subject to considerable experimental error, and many values are zero, because of finite detection limits. Many of the clusters show considerable overlap, because of natural variability, agglomeration, and chemical reactivity.

Chemical reactivity of organized monolayers at the air-water interface

1988 ◽  
Vol 85 ◽  
pp. 1041-1045 ◽  
Author(s):  
Rolf Loschek ◽  
Dietmar Mobius
Keyword(s):  
Chemical Reactivity ◽  
Water Interface ◽  
Air Water Interface

Structure Revision of Protoaculeine B, a Posttranslationally Modified N-Terminal Residue in the Peptide Toxin Aculeine B

2020 ◽  
Author(s):  
Raku Irie ◽  
Kei Miyako ◽  
Satoko Matsunaga ◽  
Ryuichi Sakai ◽  
Masato Oikawa
Keyword(s):  
Mass Spectra ◽  
Chemical Reactivity ◽  
Model Compounds ◽  
Structural Revision ◽  
Structure Revision ◽  
Peptide Toxin ◽  
One Step ◽  
Marine Peptide ◽  
Synthetic Models ◽  
Long Chain

<div>Here, we newly propose the structure of protoaculeine B, an N-terminal moiety of the marine peptide toxin aculeine B, as possessing the cis-disubstituted tetrahydro-beta-carboline framework. We prepared two truncated model compounds that lack long-chain polyamine by one-step Pictet-Spengler reaction of tryptophan, and compared the NMR and mass spectra and chemical reactivity with those of natural protoaculeine B. The synthetic models reproduced the profiles of the natural product well, which was conclusive for the structural revision.</div>

Atom Condensed Fukui Function for Condensed Phases and Biological Systems and Its Application to Enzymatic Fixation of Carbon Dioxide

2019 ◽  
Author(s):  
Javier Oller ◽  
David A. Sáez ◽  
Esteban Vöhringer-Martinez
Keyword(s):  
Carbon Dioxide ◽  
Aqueous Solution ◽  
Molecular System ◽  
Chemical Reactivity ◽  
Nucleophilic Attack ◽  
Stable Conformation ◽  
Fukui Functions ◽  
Reactivity Descriptors ◽  
Dynamics Simulations ◽  
Fixation Of Carbon Dioxide

<div><div><div><p>Local reactivity descriptors such as atom condensed Fukui functions are promising computational tools to study chemical reactivity at specific sites within a molecule. Their applications have been mainly focused on isolated molecules in their most stable conformation without considering the effects of the surroundings. Here, we propose to combine QM/MM Born-Oppenheimer molecular dynamics simulations to obtain the microstates (configurations) of a molecular system using different representations of the molecular environment and calculate Boltzmann weighted atom condensed local reac- tivity descriptors based on conceptual DFT. Our approach takes the conformational fluctuations of the molecular system and the polarization of its electron density by the environment into account allowing us to analyze the effect of changes in the molecular environment on reactivity. In this contribution, we apply the method mentioned above to the catalytic fixation of carbon dioxide by crotonyl-CoA carboxylase/reductase and study if the enzyme alters the reactivity of its substrate compared to an aqueous solution. Our main result is that the protein en- vironment activates the substrate by the elimination of solute-solvent hydrogen bonds from aqueous solution in the two elementary steps of the reaction mechanism: the nucleophilic attack of a hydride anion from NADPH on the α, β unsaturated thioester and the electrophilic attack of carbon dioxide on the formed enolate species.</p></div></div></div>

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