2-Chloro-4,6-bis{(E)-3-methoxy-4-[(4-methoxybenzyl)oxy]styryl}pyrimidine: Synthesis, Spectroscopic and Computational Evaluation

A novel curcumin analog namely 2-chloro-4,6-bis{(E)-3-methoxy-4-[(4-methoxybenzyl)oxy]-styryl}pyrimidine (compound 7) was synthesized by three-step reaction. The condensation reaction of protected vanillin with 2-chloro-4,6-dimethylpyrimidine (6) was the most efficient step, resulting in a total yield of 72%. The characterization of compound 7 was performed by 1H and 13C nuclear magnetic resonance (NMR), as well as high-resolution mass spectrometry. The experimental spectrometric data were compared with the theoretical spectra obtained by the density functional theory (DFT) method, showing a perfect match between them. UV-visible spectroscopy and steady-state fluorescence emission studies were performed for compound 7 in solvents of different polarities and the results were correlated with DFT calculations. Compound 7 showed a solvatochromism effect presenting higher molar extinction coefficient (log ε = 4.57) and fluorescence quantum yield (ϕ = 0.38) in toluene than in acetonitrile or methanol. The simulation of both frontier molecular orbitals (FMOs) and molecular electrostatic potential (MEP) suggested that the experimental spectra profile in toluene was not interfered by a possible charge transfer. These results are an indication of a low probability of compound 7 in reacting with unsaturated phospholipids in future applications as a fluorescent dye in biological systems.

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Influence of intramolecular interactions on carbon dioxide gas adsorption capacity in Mesoporous Imine polymers

10.26434/chemrxiv.5826435 ◽

2018 ◽

Author(s):

Jaya Prakash Madda ◽

Pilli Govindaiah ◽

Sushant Kumar Jena ◽

Sabbhavat Krishna ◽

Rupak Kishor

Keyword(s):

Carbon Dioxide ◽

Adsorption Capacity ◽

Density Functional ◽

Gas Adsorption ◽

Ambient Pressure ◽

Condensation Reaction ◽

Intramolecular Interactions ◽

Carbon Dioxide Adsorption ◽

Nitrogen Gas ◽

Adsorption Characteristic

Covalent organic Imine polymers with intrinsic meso-porosity were synthesized by condensation reaction between 4,4-diamino diphenyl methane and (para/meta/ortho)-phthaladehyde. Even though these polymers were synthesized from precursors of bis-bis covalent link mode, the bulk materials were micrometer size particles with intrinsic mesoporous enables nitrogen as well as carbon dioxide adsorption in the void spaces. These polymers were showed stability up to 260o centigrade. Nitrogen gas adsorption capacity up to 250 cc/g in the ambient pressure was observed with type III adsorption characteristic nature. Carbon dioxide adsorption experiments reveal the possible terminal amine functional group to carbamate with CO2 gas molecule to the polymers. One of the imine polymers, COP-3 showed more carbon dioxide sorption capacity and isosteric heat of adsorption (Qst) than COP-1 and COP-2 at 273 K even though COP-3 had lower porosity for nitrogen gas than COP-1 and COP-2. We explained the trends in gas adsorption capacities and Qst values as a consequence of the intra molecular interactions confirmed by Density Functional Theory computational experiments on small molecular fragments.

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uMBD: A Materials-Ready Dispersion Correction that Uniformly Treats Metallic, Ionic, Covalent, and van der Waals Bonding

10.26434/chemrxiv.7938137.v2 ◽

2019 ◽

Author(s):

Minho Kim ◽

won june kim ◽

Tim Gould ◽

Eok Kyun Lee ◽

Sébastien Lebègue ◽

...

Keyword(s):

First Principles ◽

Density Functional ◽

Electrode Materials ◽

Full Range ◽

Van Der Waals ◽

Dft Method ◽

Dispersion Correction ◽

Computational Overhead ◽

System A ◽

Battery Design

Materials design increasingly relies on first-principles calculations for screening important candidates and for understanding quantum mechanisms. Density functional theory (DFT) is by far the most popular first-principles approach due to its efficiency and accuracy. However, to accurately predict structures and thermodynamics, DFT must be paired with a van der Waals (vdW) dispersion correction. Therefore, such corrections have been the subject of intense scrutiny in recent years. Despite significant successes in organic molecules, no existing model can adequately cover the full range of common materials, from metals to ionic solids, hampering the applications of DFT for modern problems such as battery design. Here, we introduce a universally optimized vdW-corrected DFT method that demonstrates an unbiased reliability for predicting molecular, layered, ionic, metallic, and hybrid materials without incurring a large computational overhead. We use our method to accurately predict the intercalation potentials of layered electrode materials of a Li-ion battery system – a problem for which the existing state-of-the-art methods fail. Thus, we envisage broad use of our method in the design of chemo-physical processes of new materials.

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First Attempts of the Use of 195Pt NMR of Phenylbenzothiazole Complexes as Spectroscopic Technique for the Cancer Diagnosis

Molecules ◽

10.3390/molecules24213970 ◽

2019 ◽

Vol 24 (21) ◽

pp. 3970 ◽

Cited By ~ 1

Author(s):

Bruna T. L. Pereira ◽

Mateus A. Gonçalves ◽

Daiana T. Mancini ◽

Kamil Kuca ◽

Teodorico C. Ramalho

Keyword(s):

Cancer Treatment ◽

Cancer Diagnosis ◽

Density Functional ◽

Chemical Shifts ◽

Chloride Ion ◽

Platinum Complexes ◽

Dft Method ◽

Ion Concentration ◽

Implicit Solvent ◽

Early Cancer Diagnosis

Platinum complexes have been studied for cancer treatment for several decades. Furthermore, another important platinum characteristic is related to its chemical shifts, in which some studies have shown that the 195Pt chemical shifts are very sensitive to the environment, coordination sphere, and oxidation state. Based on this relevant feature, Pt complexes can be proposed as potential probes for NMR spectroscopy, as the chemical shifts values will be different in different tissues (healthy and damaged) Therefore, in this paper, the main goal was to investigate the behavior of Pt chemical shifts in the different environments. Calculations were carried out in vacuum, implicit solvent, and inside the active site of P13K enzyme, which is related with breast cancer, using the density functional theory (DFT) method. Moreover, the investigation of platinum complexes with a selective moiety can contribute to early cancer diagnosis. Accordingly, the Pt complexes selected for this study presented a selective moiety, the 2-(4′aminophenyl)benzothiazole derivative. More specifically, two Pt complexes were used herein: One containing chlorine ligands and one containing water in place of chlorine. Some studies have shown that platinum complexes coordinated to chlorine atoms may suffer hydrolyses inside the cell due to the low chloride ion concentration. Thus, the same calculations were performed for both complexes. The results showed that both complexes presented different chemical shift values in the different proposed environments. Therefore, this paper shows that platinum complexes can be a potential probe in biological systems, and they should be studied not only for cancer treatment, but also for diagnosis.

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One-Pot Microwave-Assisted Synthesis of Water-Soluble Pyran-2,4,5-triol Glucose Amine Schiff Base Derivative: XRD/HSA Interactions, Crystal Structure, Spectral, Thermal and a DFT/TD-DFT

Crystals ◽

10.3390/cryst11020117 ◽

2021 ◽

Vol 11 (2) ◽

pp. 117

Author(s):

Yousef Hijji ◽

Rajeesha Rajan ◽

Hamdi Ben Yahia ◽

Said Mansour ◽

Abdelkader Zarrouk ◽

...

Keyword(s):

Schiff Base ◽

Molecular Orbital ◽

Density Functional ◽

Condensation Reaction ◽

3D Structure ◽

Water Soluble ◽

Microwave Assisted Synthesis ◽

One Pot ◽

Microwave Assisted ◽

Td Dft

The(3R,4R,6R)-3-(((E)-2-hydroxybenzylidene)amino)-6-(hydroxymethyl)tetrahydro-2H-pyran-2,4,5-triol water-soluble Glucose amine Schiff base (GASB-1) product was made available by condensation of 2-hydroxybenzaldehyde with (3R,6R)-3-amino-6-(hydroxymethyl)-tetra-hydro-2H-pyran-2,4,5-triol under mono-mode microwave heating. A one-pot 5-minute microwave-assisted reaction was required to complete the condensation reaction with 90% yield and without having byproducts. The 3D structure of GASB-1 was solved from single crystal X-ray diffraction data and computed by DFT/6-311G(d,p). The Hirshfeld surface analysis (HSA), molecular electronic potential (MEP), Mulliken atomic charge (MAC), and natural population analysis (NPA) were performed. The IR and UV-Vis spectra were matched to their density functional theory (DFT) relatives and the thermal behavior was resolved in an open-room condition via thermogravimetry/Derivative thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC). The highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO), density of state (DOS), and time-dependence TD-DFT computations were correlated to the experimental electron transfer in water and acrylonitrile solvents.

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Understanding the molecular mechanism of the stereoselective conversion of N-trialkylsilyloxy nitronates into bicyclic isoxazoline derivatives

New Journal of Chemistry ◽

10.1039/d1nj01198g ◽

2021 ◽

Author(s):

Agnieszka Kącka-Zych ◽

Radomir Jasinski

Keyword(s):

Density Functional Theory ◽

Molecular Mechanism ◽

Electron Density ◽

Density Functional ◽

Dft Method ◽

Functional Theory ◽

Molecular Electron ◽

Molecular Electron Density Theory

Conversion of N-trialkylsilyloxy nitronates into bicyclic isoxazoline derivatives has been explored using Density Functional Theory (DFT) method within the context of the Molecular Electron Density Theory (MEDT) at the B97XD(PCM)/6-311G(d,p)...

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Boron-Decorated Pillared Graphene as the Basic Element for Supercapacitors: An Ab Initio Study

Applied Sciences ◽

10.3390/app11083496 ◽

2021 ◽

Vol 11 (8) ◽

pp. 3496

Author(s):

Dmitry A. Kolosov ◽

Olga E. Glukhova

Keyword(s):

Density Functional ◽

Dft Method ◽

Heat Of Formation ◽

Basic Element ◽

Supercapacitor Electrode ◽

Functional Theory ◽

Icosahedral Clusters ◽

New Material ◽

Principle Density Functional Theory ◽

Specific Quantum

In this work, using the first-principle density functional theory (DFT) method, we study the properties of a new material based on pillared graphene and the icosahedral clusters of boron B12 as a supercapacitor electrode material. The new composite material demonstrates a high specific quantum capacitance, specific charge density, and a negative value of heat of formation, which indicates its efficiency. It is shown that the density of electronic states increases during the addition of clusters, which predictably leads to an increase in the electrode conductivity. We predict that the use of a composite based on pillared graphene and boron will increase the efficiency of existing supercapacitors.

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The Adsorption and Sensing Performances of Ir-modified MoS2 Monolayer toward SF6 Decomposition Products: A DFT Study

Nanomaterials ◽

10.3390/nano11010100 ◽

2021 ◽

Vol 11 (1) ◽

pp. 100

Author(s):

Hongcheng Liu ◽

Feipeng Wang ◽

Kelin Hu ◽

Tao Li ◽

Yuyang Yan ◽

...

Keyword(s):

Gas Sensor ◽

Density Functional ◽

Gas Adsorption ◽

Dft Method ◽

Orbital Theory ◽

Gas Sensitivity ◽

Decomposition Products ◽

Mos2 Monolayer ◽

Characteristic Decomposition ◽

Sensing Material

In this paper, the Ir-modified MoS2 monolayer is suggested as a novel gas sensor alternative for detecting the characteristic decomposition products of SF6, including H2S, SO2, and SOF2. The corresponding adsorption properties and sensing behaviors were systematically studied using the density functional theory (DFT) method. The theoretical calculation indicates that Ir modification can enhance the surface activity and improve the conductivity of the intrinsic MoS2. The physical structure formation, the density of states (DOS), deformation charge density (DCD), molecular orbital theory analysis, and work function (WF) were used to reveal the gas adsorption and sensing mechanism. These analyses demonstrated that the Ir-modified MoS2 monolayer used as sensing material displays high sensitivity to the target gases, especially for H2S gas. The gas sensitivity order and the recovery time of the sensing material to decomposition products were reasonably predicted. This contribution indicates the theoretical possibility of developing Ir-modified MoS2 as a gas sensor to detect characteristic decomposition gases of SF6.

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Geometries and properties of guanine–BH3 complex: an investigation with density functional theory (DFT) method

Journal of Molecular Structure THEOCHEM ◽

10.1016/j.theochem.2004.04.064 ◽

2004 ◽

Vol 682 (1-3) ◽

pp. 47-53 ◽

Cited By ~ 7

Author(s):

Shiguo Zhang ◽

Hong Li ◽

Pin Yang ◽

Sidian Li

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Dft Method ◽

Functional Theory

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Theoretical Insights into the Electron Capture Behavior of H2SO4···N2O Complex: A DFT and Molecular Dynamics Study

Molecules ◽

10.3390/molecules23092349 ◽

2018 ◽

Vol 23 (9) ◽

pp. 2349 ◽

Cited By ~ 2

Author(s):

Wei-Hua Wang ◽

Wen-Ling Feng ◽

Wen-Liang Wang ◽

Ping Li

Keyword(s):

Molecular Dynamics ◽

Electron Capture ◽

Atmospheric Chemistry ◽

Density Functional ◽

Molecular Complexes ◽

Dft Method ◽

Dynamics Simulation ◽

Oh Radical ◽

Before And After ◽

Reduced Density

Both sulfuric acid (H2SO4) and nitrous oxide (N2O) play a central role in the atmospheric chemistry in regulating the global environment and climate changes. In this study, the interaction behavior between H2SO4 and N2O before and after electron capture has been explored using the density functional theory (DFT) method as well as molecular dynamics simulation. The intermolecular interactions have been characterized by atoms in molecules (AIM), natural bond orbital (NBO), and reduced density gradient (RDG) analyses, respectively. It was found that H2SO4 and N2O can form two transient molecular complexes via intermolecular H-bonds within a certain timescale. However, two molecular complexes can be transformed into OH radical, N2, and HSO4− species upon electron capture, providing an alternative formation source of OH radical in the atmosphere. Expectedly, the present findings not only can provide new insights into the transformation behavior of H2SO4 and N2O, but also can enable us to better understand the potential role of the free electron in driving the proceeding of the relevant reactions in the atmosphere.

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First principles analysis of oxygen vacancy formation and migration in Sr2BMoO6 (B = Mg, Co, Ni)

RSC Advances ◽

10.1039/c6ra02297a ◽

2016 ◽

Vol 6 (38) ◽

pp. 31968-31975 ◽

Cited By ~ 9

Author(s):

Shuai Zhao ◽

Liguo Gao ◽

Chunfeng Lan ◽

Shyam S. Pandey ◽

Shuzi Hayase ◽

...

Keyword(s):

Density Functional Theory ◽

Oxygen Vacancy ◽

First Principles ◽

Density Functional ◽

Dft Method ◽

Double Perovskites ◽

Functional Theory ◽

Oxygen Vacancy Formation ◽

The Density Functional Theory ◽

And Migration

In this work, we present a detailed first-principles investigation on the stoichiometric and oxygen-deficient structures of double perovskites, Sr2BMoO6 (B = Mg, Co and Ni), using the density functional theory (DFT) method.

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