Theoretical study of the inclusion processes of octopamine with β-cyclodextrin: PM6, ONIOM, and NBO analysis

Lachi, Nadia; Khatmi, Djameleddine; Djemil, Rayenne

doi:10.1016/j.crci.2014.03.010

Cited by 10 publications

(4 citation statements)

References 34 publications

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“…The model in question revealed a crucial electronic charge density between the orbitals of the lone pairs of oxygen (O83) and the antibonding orbitals σ* of the atom (O7-H 14). This interaction resulted in a substantial stabilization energy of 27.73 kcal/mol, corresponding to the shortest interatomic distance of 1.7 Å [59].…”

Section: Natural Bond Orbital (Nbo) Analysismentioning

confidence: 99%

A proposed process for trichlorfon and β-cyclodextrinInclusion complexation by DFT investigation

Chekkal,

Naili,

Benaissa

et al. 2024

Struct Chem

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The current investigation uses the Density Functional Theory (DFT) with the M06-2X functional and 6-31G (d, p) basis set to examine the interaction between trichlorfon (TCF) and the cavity of βcyclodextrin (β-CD). The primary objective of our study is to gain an insight into the molecular characteristics of this interaction by analyzing quantum parameters such as the HOMO-LUMO gap, the HOMO and the LUMO. Two potential encapsulation modes, designated as A and B models, were identified for TCF. The thermodynamic assessments including complexation energies and alterations in enthalpy, entropy, and Gibbs free energy indicate a stable and advantageous encapsulation procedure. The Independent Gradient Model (IGMH) provides insights into the noncovalent interactions in developing the TCF@β-CD complex. The observed stability can be mainly attributed to a significant intermolecular hydrogen bond emphasized by the NBO and EDA and weak van der Waals forces. The results of our study indicate that β-CD as macrocycle has the potential to be a suitable trap for trichlorfon.

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Section: Natural Bond Orbital (Nbo) Analysismentioning

confidence: 99%

A proposed process for trichlorfon and β-cyclodextrinInclusion complexation by DFT investigation

Chekkal,

Naili,

Benaissa

et al. 2024

Struct Chem

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“…To identify TDI and TDTS, the energetic span model offers a quantification of the influence of each Int and TS on the TOF, namely, the “degree of TOF control” ( X TOF ). X TOF (energies) was developed based on the degree of rate control and measures the effect of each TS or Int for TOF. X TOF (energies) can determine the rate‐ “determining states” for the reaction using:

\begin{matrix} X_{TOF, T_{normali}} = \frac{\sum_{j} \exp (T_{i} - I_{j} - Δ G_{i j}) / R T}{\sum_{i} \sum_{j} \exp (T_{i} - I_{j} - Δ G_{i j}) / R T} \\ X_{TOF, I_{j}} = \frac{\sum_{i} \exp (T_{i} - I_{j} - Δ G_{i j}) / R T}{\sum_{j} \sum_{i} \exp (T_{i} - I_{j} - Δ G_{i j}) / R T} \end{matrix}

…”

Section: Computational Detailsmentioning

confidence: 99%

“…In addition, computational and experimental chemistry can be linked through the energetic span model, and the physical factors that govern the potential activation barriers have been explored using the activation strain model (ASM) …”

Section: Computational Detailsmentioning

confidence: 99%

Reaction mechanism and Z‐selectivity for chelated Ru‐catalyzed AROCM of endic anhydride and propene: A DFT study

Zhu

Pang

Wang

2015

Int J of Quantum Chemistry

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Density functional theory calculations were performed to investigate the complete mechanism and selectivity for asymmetric ring opening cross‐metathesis of endic anhydride and propene through a chelated Ru catalyst with nitrato ligand. The preferred mechanism begins with the endic anhydride attacking the catalyst from the “side” position and forming a Ru four‐membered ring complex. Subsequently, the endic anhydride isomerizes with another four‐membered ring complex via the substituent groups rotating their locations. The ring then ruptures and leads to a Ru‐alkylidene complex. Afterward, propene reacts with the Ru‐alkylidene complex through a similar pathway, resulting in rapid a cycloaddition reaction, isomerization to undergo cycloreversion, and the release of (Z)‐ or (E)‐olefin homodimers. The overall preferred mechanism is in accordance with the mechanism of a previously reported chelated Ru catalyst containing a carboxylate ligand. The energy barrier of the transition state for cycloreversion differs by 2.72 kcal/mol from (Z)‐olefin to (E)‐olefin, indicating that the reaction has high Z‐selectivity, in accordance with experimental results. Moreover, cycloreversion is the rate‐determining step. The turnover frequency for selectivity is analyzed to determine the relationship between the theoretically computed catalytic cycle and its experimental counterpart. The activation strain was also analyzed to illustrate the mechanism from the point of quantum chemistry. All of the methods in this article were performed to explain the preference for Z‐olefin, which is attributed to a combination of the steric and electronic effects of the chelated catalyst. Finally, the catalyst is compared with the previously reported chelated Ru catalyst with a carboxylate ligand; results reveal that smaller nitrato sizes lead to higher selectivity efficiency of the catalyst. © 2015 Wiley Periodicals, Inc.

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“…A variety of physicochemical techniques and computational modeling tools are used to obtain physical insights into the formation of CD-ICs and elucidating their stoichiometries; − for soluble CD-ICs, isothermal titration calorimetry and 2D nuclear magnetic resonance are commonly used. Mass spectrometry (MS) has been an increasingly popular approach for soluble ICs because of its high sensitivity and high mass accuracy, in addition to how fast binding can be determined relative to other approaches. − Specifically, quadrupole-time-of-flight (Q-TOF) tandem mass spectrometers are very useful in chemical analyses and structural elucidation of a wide variety of molecular systems; hybrid instruments combine the performance characteristics from various analyzers into one mass spectrometer, thus providing unique applications and expanded fields of research. − Electrospray ionization (ESI) is the most widely used ionization technique nowadays and is commonly coupled with Q-TOF mass spectrometers; ESI is generally accepted as a soft ionization method because little or no fragmentation occurs during ionization.…”

Section: Introductionmentioning

confidence: 99%

Physical Characterization of Inclusion Complexes of Triphenyl Phosphate and Cyclodextrins in Solution

et al. 2019

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The goal of this work is to provide physical insights into the formation and stability of inclusion complexes (ICs) in aqueous solution between cyclodextrins (CDs) and a common flame retardant, triphenyl phosphate (TPP). Quantum chemistry calculations reveal the possible energetically favorable geometries of TPP in their 1:1 IC form with α-, β-, and γ-CDs as well as their associated complexation, conformational, and interaction energies. High-resolution mass spectrometry (MS) and tandem MS were used with electrospray ionization to study the soluble ICs formed between TPP and CDs. Successful formation of TPP ICs with both βand γ-CD in solution was detected in the ratio of 1:1 using high-resolution MS in the positive ion mode. Collision-induced dissociation confirmed the formation of TPP ICs with βand γ-CDs by generating two product ions, TPP and βor γ-CD, in both cases. Although quantum chemistry calculations suggest that IC formation with α-CD is energetically possible, an IC with α-CD is not observed in aqueous solution using MS, which aligns with what we also previously observed in the solid state. Since TPP forms stable ICs with βand γ-CDs both in the solid state and in solution suggests that complexation could be a safer alternative than applying TPP directly to a substrate. In addition, complexation with CDs in solution also opens up new processing methods to create flame-retardant fabrics and foams with TPP.

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Theoretical study of the inclusion processes of octopamine with β-cyclodextrin: PM6, ONIOM, and NBO analysis

Cited by 10 publications

References 34 publications

A proposed process for trichlorfon and β-cyclodextrinInclusion complexation by DFT investigation

A proposed process for trichlorfon and β-cyclodextrinInclusion complexation by DFT investigation

Reaction mechanism and Z‐selectivity for chelated Ru‐catalyzed AROCM of endic anhydride and propene: A DFT study

Physical Characterization of Inclusion Complexes of Triphenyl Phosphate and Cyclodextrins in Solution

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