scholarly journals QTAIM-Based Local Potential Energy Model: Applications and Limitations to Quantify the Binding Energy of Intra/intermolecular Interactions

2020 ◽  
Author(s):  
CAIO FIRME
Keyword(s):  
Binding Energy ◽  
Potential Energy ◽  
Electrostatic Force ◽  
Decomposition Analysis ◽  
Energy Model ◽  
Local Potential ◽  
Intramolecular Interactions ◽  
Energy Decomposition Analysis ◽  
Polarization Component ◽  
Classical Hydrogen Bond

<p>In previous work, we developed the local potential energy model, LPE, based on the electrostatic force and QTAIM topological data to quantify classical hydrogen bond energies. In this work, we extended the investigation to other inter/intramolecular interactions (non-conventional hydrogen bonds and others). The LPE presented high precision and linearity with supramolecular binding energy, when excluding interactions of an ion with π-bonded groups or polar molecule. The energy decomposition analysis from SAPT-DFT and LMOEDA showed that dispersion and electrostatic components are important to LPE, while polarization component impairs it. The LPE cannot be used for complexes with predominant polarization component. </p>

scholarly journals QTAIM-Based Local Potential Energy Model: Applications and Limitations to Quantify the Binding Energy of Intra/intermolecular Interactions

2020 ◽  
Author(s):  
CAIO FIRME
Keyword(s):  
Binding Energy ◽  
Potential Energy ◽  
Electrostatic Force ◽  
Decomposition Analysis ◽  
Energy Model ◽  
Local Potential ◽  
Intramolecular Interactions ◽  
Energy Decomposition Analysis ◽  
Polarization Component ◽  
Classical Hydrogen Bond

<p>In previous work, we developed the local potential energy model, LPE, based on the electrostatic force and QTAIM topological data to quantify classical hydrogen bond energies. In this work, we extended the investigation to other inter/intramolecular interactions (non-conventional hydrogen bonds and others). The LPE presented high precision and linearity with supramolecular binding energy, when excluding interactions of an ion with π-bonded groups or polar molecule. The energy decomposition analysis from SAPT-DFT and LMOEDA showed that dispersion and electrostatic components are important to LPE, while polarization component impairs it. The LPE cannot be used for complexes with predominant polarization component. </p>

scholarly journals Interaction and Reactivity of Cisplatin Physisorbed on Graphene Oxide Nano-Prototypes

Nanomaterials ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 1074
Author(s):  
Ma del Refugio Cuevas-Flores ◽  
Massimiliano Bartolomei ◽  
Marco Antonio García-Revilla ◽  
Cecilia Coletti
Keyword(s):  
Graphene Oxide ◽  
Binding Energy ◽  
Physical Adsorption ◽  
Drug Loading ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Pristine Graphene ◽  
Nano Structures ◽  
Carboxylic Groups ◽  
Oxygen Groups

The physical adsorption of cisplatin (CP) on graphene oxide (GO) and reduced graphene oxide (rGO) is investigated at the DFT level of theory by exploiting suitable molecular prototypes representing the most probable adsorbing regions of GO and rGO nano-structures. The results show that the CP binding energy is enhanced with respect to that for the interaction with pristine graphene. This is due to the preferential adsorption of the drug in correspondence of the epoxy and hydroxy groups located on GO basal plane: an energy decomposition analysis of the corresponding binding energy reveals that the most attractive contribution comes from the electrostatic attraction between the -NH 3 ends of CP and the oxygen groups on (r)GO, which can be associated with hydrogen bonding effects. Moreover, it is found that the reactivity of the physically adsorbed CP is practically unaltered being the free energy variation of the first hydrolysis reaction almost matching that of its free (unadsorbed drug) counterpart. The reported results suggest that the CP physical adsorption on GO and rGO carriers is overall feasible being an exergonic process in aqueous solution. The CP adsorption could facilitate its solubility and transport in water solutions, exploiting the high hydrophilicity of the peripheral carboxylic groups located on the edge of the GO and rGO nano-structures. Moreover, the the higher affinity of CP with respect to the oxidized sites suggests a possible dependence of drug loading and release on pH conditions, which would highly facilitate its specific delivery.

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>

On the Nature of Halide-Water Interactions: Insights from Many-Body Representations and Density Functional Theory

2019 ◽  
Author(s):  
Brandon B. Bizzarro ◽  
Colin K. Egan ◽  
Francesco Paesani
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Molecular Orbital ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Orbital Energy ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Many Body ◽  
Functional Theory

<div> <div> <div> <p>Interaction energies of halide-water dimers, X<sup>-</sup>(H<sub>2</sub>O), and trimers, X<sup>-</sup>(H<sub>2</sub>O)<sub>2</sub>, with X = F, Cl, Br, and I, are investigated using various many-body models and exchange-correlation functionals selected across the hierarchy of density functional theory (DFT) approximations. Analysis of the results obtained with the many-body models demonstrates the need to capture important short-range interactions in the regime of large inter-molecular orbital overlap, such as charge transfer and charge penetration. Failure to reproduce these effects can lead to large deviations relative to reference data calculated at the coupled cluster level of theory. Decompositions of interaction energies carried out with the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA) method demonstrate that permanent and inductive electrostatic energies are accurately reproduced by all classes of XC functionals (from generalized gradient corrected (GGA) to hybrid and range-separated functionals), while significant variance is found for charge transfer energies predicted by different XC functionals. Since GGA and hybrid XC functionals predict the most and least attractive charge transfer energies, respectively, the large variance is likely due to the delocalization error. In this scenario, the hybrid XC functionals are then expected to provide the most accurate charge transfer energies. The sum of Pauli repulsion and dispersion energies are the most varied among the XC functionals, but it is found that a correspondence between the interaction energy and the ALMO EDA total frozen energy may be used to determine accurate estimates for these contributions. </p> </div> </div> </div>

scholarly journals Nanotechnology-based approaches for targeting and delivery of drugs via Hexakis (m-PE) macrocycles

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Samaneh Pasban ◽  
Heidar Raissi
Keyword(s):  
Drug Delivery ◽  
Density Functional ◽  
Water Solution ◽  
Decomposition Analysis ◽  
Binding Energies ◽  
Energy Decomposition Analysis ◽  
Partial Density ◽  
High Propensity ◽  
The Stability ◽  
Novel Applications

AbstractHexakis (m-phenylene ethynylene) (m-PE) macrocycles, with aromatic backbones and multiple hydrogen-bonding side chains, had a very high propensity to self-assemble via H-bond and π–π stacking interactions to form nanotubular structures with defined inner pores. Such stacking of rigid macrocycles is leading to novel applications that enable the researchers to explored mass transport in the sub-nanometer scale. Herein, we performed density functional theory (DFT) calculations to examine the drug delivery performance of the hexakis dimer as a novel carrier for doxorubicin (DOX) agent in the chloroform and water solvents. Based on the DFT results, it is found that the adsorption of DOX on the carrier surface is typically physisorption with the adsorption strength values of − 115.14 and − 83.37 kJ/mol in outside and inside complexes, respectively, and so that the essence of the drug remains intact. The negative values of the binding energies for all complexes indicate the stability of the drug molecule inside and outside the carrier's cavities. The energy decomposition analysis (EDA) has also been performed and shown that the dispersion interaction has an essential role in stabilizing the drug-hexakis dimer complexes. To further explore the electronic properties of dox, the partial density of states (PDOS and TDOS) are calculated. The atom in molecules (AIM) and Becke surface (BS) methods are also analyzed to provide an inside view of the nature and strength of the H-bonding interactions in complexes. The obtained results indicate that in all studied complexes, H-bond formation is the driving force in the stabilization of these structures, and also chloroform solvent is more favorable than the water solution. Overall, our findings offer insightful information on the efficient utilization of hexakis dimer as drug delivery systems to deliver anti-cancer drugs.

scholarly journals A Generalized Dynamic Potential Energy Model for Multiagent Path Planning

2020 ◽  
Vol 2020 ◽  
pp. 1-14
Author(s):  
Liu He ◽  
Haoning Xi ◽  
Tangyi Guo ◽  
Kun Tang
Keyword(s):  
Path Planning ◽  
Potential Energy ◽  
Multiagent System ◽  
Small Time ◽  
Energy Model ◽  
Dijkstra Algorithm ◽  
Energy Field ◽  
Space Potential ◽  
Dynamic Potential ◽  
Planning Decision

Path planning for the multiagent, which is generally based on the artificial potential energy field, reflects the decision-making process of pedestrian walking and has great importance on the field multiagent system. In this paper, after setting the spatial-temporal simulation environment with large cells and small time segments based on the disaggregation decision theory of the multiagent, we establish a generalized dynamic potential energy model (DPEM) for the multiagent through four steps: (1) construct the space energy field with the improved Dijkstra algorithm, and obtain the fitting functions to reflect the relationship between speed decline rate and space occupancy of the agent through empirical cross experiments. (2) Construct the delay potential energy field based on the judgement and psychological changes of the multiagent in the situations where the other pedestrians have occupied the bottleneck cell. (3) Construct the waiting potential energy field based on the characteristics of the multiagent, such as dissipation and enhancement. (4) Obtain the generalized dynamic potential energy field by superposing the space potential energy field, delay potential energy field, and waiting potential energy field all together. Moreover, a case study is conducted to verify the feasibility and effectiveness of the dynamic potential energy model. The results also indicate that each agent’s path planning decision such as forward, waiting, and detour in the multiagent system is related to their individual characters and environmental factors. Overall, this study could help improve the efficiency of pedestrian traffic, optimize the walking space, and improve the performance of pedestrians in the multiagent system.

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