scholarly journals Theoretical Investigation of Oxidative Cleavage of Cholesterol by Dual O2 Activation and Sulfide Reduction

2016 ◽  
Vol 69 (9) ◽  
pp. 933 ◽  
Author(s):  
Richmond Lee ◽  
Michelle L. Coote
Keyword(s):  
Singlet State ◽  
Theoretical Calculations ◽  
Methionine Sulfoxide ◽  
Oxidative Cleavage ◽  
Amyloid Peptide ◽  
Intersystem Crossing ◽  
Aβ Amyloid ◽  
Plausible Mechanism ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Theoretical calculations are used to explore a plausible mechanism for oxidative cleavage of cholesterol mediated by two ground-state O2 molecules. It is shown that cholesterol can form a stable pre-complex with the two triplet dioxygen molecules, which could be further stabilized in an enzyme environment by methionine (modelled here as Me2S). Triplet O2 can then react to form a metastable biradical species that is then further stabilized by reaction with a second triplet O2, resulting in an intermediate that undergoes an intersystem crossing to form a diperoxy intermediate. This in turn is reduced to the final cholesterol secosterol aldehyde product by the same methionine, which may provide an explanation for the presence of methionine sulfoxide fractions in Aβ amyloid peptide. The mechanistic theozyme model predicts an energetically viable pathway that is unusual in that triplet oxygen is normally considered to be unreactive in this context unless first excited to the singlet state. Although we show that the same reaction can also proceed via photosensitization of the complex if an appropriate cofactor is available, the energetics for the triplet oxygen reaction are competitive. Reactivity studies revealed that the reaction can also occur with other unsaturated substrates, with the lowest barriers occurring with more nucleophilic alkenes, or by rendering the 3O2 more electrophilic via non-covalent interactions with Me2S.

scholarly journals On the Proton-Bound Noble Gas Dimers (Ng-H-Ng)+ and (Ng-H-Ng')+ (Ng, Ng'= He-Xe): Relationships betweenStructure, Stability, and Bonding Character

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1305
Author(s):  
Stefano Borocci ◽  
Felice Grandinetti ◽  
Nico Sanna
Keyword(s):  
Theoretical Calculations ◽  
Noble Gas ◽  
Structure Stability ◽  
Covalent Bonds ◽  
Dissociation Energies ◽  
Non Covalent Interactions ◽  
The Difference ◽  
Noble Gas Dimers ◽  
Covalent Interactions ◽  
Cluster Level

The structure, stability, and bonding character of fifteen (Ng-H-Ng)+ and (Ng-H-Ng')+ (Ng, Ng' = He-Xe) compounds were explored by theoretical calculations performed at the coupled cluster level of theory. The nature of the stabilizing interactions was, in particular, assayed using a method recently proposed by the authors to classify the chemical bonds involving the noble-gas atoms. The bond distances and dissociation energies of the investigated ions fall in rather large intervals, and follow regular periodic trends, clearly referable to the difference between the proton affinity (PA) of the various Ng and Ng'. These variations are nicely correlated with the bonding situation of the (Ng-H-Ng)+ and (Ng-H-Ng')+. The Ng-H and Ng'-H contacts range, in fact, between strong covalent bonds to weak, non-covalent interactions, and their regular variability clearly illustrates the peculiar capability of the noble gases to undergo interactions covering the entire spectrum of the chemical bond.

scholarly journals Deciphering the H-Bonding Preference on Nucleoside Molecular Recognition through Model Copper(II) Compounds

2021 ◽  
Vol 14 (3) ◽  
pp. 244
Author(s):  
Inmaculada Velo-Gala ◽  
Miquel Barceló-Oliver ◽  
Diego M. Gil ◽  
Josefa M. González-Pérez ◽  
Alfonso Castiñeiras ◽  
...  
Keyword(s):  
Molecular Recognition ◽  
Magnetic Measurements ◽  
Theoretical Calculations ◽  
X Ray Diffraction ◽  
Paramagnetic Resonance ◽  
Vis Spectroscopy ◽  
Non Covalent Interactions ◽  
Electron Paramagnetic ◽  
Covalent Interactions ◽  
Coordination Plane

The synthetic nucleoside acyclovir is considered an outstanding model of the natural nucleoside guanosine. With the purpose of deepening on the influence and nature of non-covalent interactions regarding molecular recognition patterns, three novel Cu(II) complexes, involving acyclovir (acv) and the ligand receptor N-(2-hydroxyethyl)ethylenediamine (hen), have been synthesized and thoroughly characterized. The three novel compounds introduce none, one or two acyclovir molecules, respectively. Molecular recognition has been evaluated using single crystal X-ray diffraction. Furthermore, theoretical calculations and other physical methods such as thermogravimetric analysis, infrared and UV-Vis spectroscopy, electron paramagnetic resonance and magnetic measurements have been used. Theoretical calculations are in line with experimental results, supporting the relevance of the [metal-N7(acv) + H-bond] molecular recognition pattern. It was also shown that (hen)O-H group is used as preferred H-donor when it is found within the basal coordination plane, since the higher polarity of the terminal (hen)O-H versus the N-H group favours its implication. Otherwise, when (hen)O-H occupies the distal coordination site, (hen)N-H groups can take over.

Exploring catecholase activity in dinuclear Mn(ii) and Cu(ii) complexes: an experimental and theoretical approach

2020 ◽  
Vol 44 (19) ◽  
pp. 7998-8009 ◽  
Author(s):  
M. Shahwaz Ahmad ◽  
Mohd Khalid ◽  
M. Shahnawaz Khan ◽  
M. Shahid ◽  
Musheer Ahmad ◽  
...  
Keyword(s):  
Theoretical Approach ◽  
Theoretical Calculations ◽  
Catecholase Activity ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Two dinuclear Mn(ii) and Cu(ii) complexes were prepared, characterised and assessed for non-covalent interactions and catecholase oxidase properties. The catecholase activity of 2 is further corroborated by theoretical calculations using DFT.

NON COVALENT INTERACTIONS IN LARGE DIAMONDOID DIMERS IN THE GAS PHASE - A MICROWAVE STUDY

2017 ◽  
Author(s):  
Cristobal Perez ◽  
Melanie Schnell ◽  
Peter Schreiner ◽  
Norbert Mitzel ◽  
Yury Vishnevskiy ◽  
...  
Keyword(s):  
Gas Phase ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Vapour Pressure Isotope Effect on Evaporation from Pure Organic Phases - a PIMD Approach

2020 ◽  
Author(s):  
Luis Vasquez ◽  
Agnieszka Dybala-Defratyka
Keyword(s):  
Path Integral ◽  
Vapour Pressure ◽  
Density Functional ◽  
Isotope Effects ◽  
Tight Binding ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Special Importance ◽  
Non Covalent Interactions ◽  
Covalent Interactions

<p></p><p>Very often in order to understand physical and chemical processes taking place among several phases fractionation of naturally abundant isotopes is monitored. Its measurement can be accompanied by theoretical determination to provide a more insightful interpretation of observed phenomena. Predictions are challenging due to the complexity of the effects involved in fractionation such as solvent effects and non-covalent interactions governing the behavior of the system which results in the necessity of using large models of those systems. This is sometimes a bottleneck and limits the theoretical description to only a few methods.<br> In this work vapour pressure isotope effects on evaporation from various organic solvents (ethanol, bromobenzene, dibromomethane, and trichloromethane) in the pure phase are estimated by combining force field or self-consistent charge density-functional tight-binding (SCC-DFTB) atomistic simulations with path integral principle. Furthermore, the recently developed Suzuki-Chin path integral is tested. In general, isotope effects are predicted qualitatively for most of the cases, however, the distinction between position-specific isotope effects observed for ethanol was only reproduced by SCC-DFTB, which indicates the importance of using non-harmonic bond approximations.<br> Energy decomposition analysis performed using the symmetry-adapted perturbation theory (SAPT) revealed sometimes quite substantial differences in interaction energy depending on whether the studied system was treated classically or quantum mechanically. Those observed differences might be the source of different magnitudes of isotope effects predicted using these two different levels of theory which is of special importance for the systems governed by non-covalent interactions.</p><br><p></p>

scholarly journals Heterogenisation of polyoxometalates and other metal-based complexes in metal–organic frameworks: from synthesis to characterisation and applications in catalysis

2021 ◽  
Author(s):  
P. Mialane ◽  
C. Mellot-Draznieks ◽  
P. Gairola ◽  
M. Duguet ◽  
Y. Benseghir ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Coordination Complexes ◽  
Metal Organic ◽  
Non Covalent Interactions ◽  
Molecular Catalysts ◽  
Covalent Interactions

This review provides a thorough overview of composites with molecular catalysts (polyoxometalates, or organometallic or coordination complexes) immobilised into MOFs via non-covalent interactions.

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