Publicaciones 2011-2020 – Departamento de Química

A DFT analysis of the relationships between electronic structure and affinity for dopamine D2, D3 and D4 receptor subtypesin a group of 77-LH-28-1 derivatives Artículo de revista

Chemistry Research Journal,, 4 , pp. 30-42, 2019, ISSN: 2455-8990.

Resumen | BibTeX | Etiquetas: 77-LH-28-1, D2 receptor, D3 receptor, D4 receptor, dft, dopamine, electronic structure, KPG method, qsar, receptor affinity

Gomez-Jeria, J S; Gatica-Diaz, N

A preliminary quantum chemical analysis of the relationships between electronic structure and 5-HT1A and 5-HT2A receptor affinity in a series of 8-acetyl-7-hydroxy-4-methylcoumarin derivatives Artículo de revista

Chemistry Research Journal, 4 , pp. 85-100, 2019, ISSN: 2455-8990.

Resumen | BibTeX | Etiquetas: 5-HT1A receptor, 5-HT2A receptor, density functional theory, dft, KPG method, methylcoumarin, qsar, serotonin

2017

Santander-Nelli, M; Silva, C P; Espinoza-Vergara, J; Silva, J F; Olguin, C F; Cortes-Arriagada, D; Zagal, J H; Mendizabal, F; Diez-Perez, I; Pavez, J

Tailoring Electroactive Surfaces by Non-Template Molecular Assembly. Towards Electrooxidation of L-Cysteine Artículo de revista

Electrochimica Acta, 254 , pp. 201-213, 2017, ISSN: 0013-4686.

Resumen | Enlaces | BibTeX | Etiquetas: arrays, assembly, bottom-up carbon chemistry, construction, dft, electrocatalytic electrode, graphite hardness, intermolecular iron metal metallophthalocyanines, model modified molecular nanoelectrode nanotube, nanotubes, phthalocyanines phthalocyanines, sams, set single substituted tetra-aminophthalocyanine, walled

@article{RN356,
title = {Tailoring Electroactive Surfaces by Non-Template Molecular Assembly. Towards Electrooxidation of L-Cysteine},
author = { M. Santander-Nelli and C.P. Silva and J. Espinoza-Vergara and J.F. Silva and C.F. Olguin and D. Cortes-Arriagada and J.H. Zagal and F. Mendizabal and I. Diez-Perez and J. Pavez},
url = {/brokenurl#<Go to ISI>://WOS:000413239600022},
doi = {10.1016/j.electacta.2017.09.082},
issn = {0013-4686},
year = {2017},
date = {2017-01-01},
journal = {Electrochimica Acta},
volume = {254},
pages = {201-213},
publisher = {2017 Elsevier Ltd.},
abstract = {We have prepared a nanoelectrode ensemble containing vertically aligned single walled carbon nanotubes (SWCNTs) using a non-template molecular self-assembling strategy. We used a bottom-up construction approach to assemble amino functionalized SWCNTs (af-SWCNTs) in a well-defined architecture. These af-SWCNTs were linked and vertically aligned to pre-formed self-assembled monolayers of 4-MBA. A Cobalt(II) tetracarboxyphthalocyanine (Co(COOH)(4)Pc) complex was covalently bonded to external portion of af-SWCNTs to complete the final nanoelectrode ensemble. X-ray photoelectron spectroscopy (XPS) and Atomic Force Microcopy (AFM) confirmed the effectiveness of the assembling steps on the gold surface starting from the Au/MBA SAMs. The system Au/4-MBA/af-SWCNTs shows an interface with large ordered array, which exhibits a high activity for the electrooxidation of L-cysteine (L-cys). Theoretical calculations suggest that the incorporation of the af-SWCNTs increased the activity of the assembly to electronic transfer and it was observed that the electrooxidation reaction is energetically favorable.},
keywords = {arrays, assembly, bottom-up carbon chemistry, construction, dft, electrocatalytic electrode, graphite hardness, intermolecular iron metal metallophthalocyanines, model modified molecular nanoelectrode nanotube, nanotubes, phthalocyanines phthalocyanines, sams, set single substituted tetra-aminophthalocyanine, walled},
pubstate = {published},
tppubtype = {article}
}

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2016

Martinez-Cifuentes, M; Clavijo-Allancan, G; Zuniga-Hormazabal, P; Aranda, B; Barriga, A; Weiss-Lopez, B; Araya-Maturana, R

Protonation Sites, Tandem Mass Spectrometry and Computational Calculations of O-Carbonyl Carbazolequinone Derivatives Artículo de revista

International Journal of Molecular Sciences, 17 (7), 2016, ISSN: 1422-0067.

Resumen | Enlaces | BibTeX | Etiquetas: antitumor assignment, basicities, c-13 carbazole, chemistry complete derivatives, dft, gas-phase hydroquinone ionization, mass molecules, nmr-spectra, qcisd, quinones, respiration, spectrometry, tumor-cell

Mera-Adasme, R; Xu, W H; Sundholm, D; Mendizabal, F

Calculations of the Light Absorption Spectra of Porphyrinoid Chromophores for Dye-Sensitized Solar Cells Artículo de revista

Physical Chemistry Chemical Physics, 18 (40), pp. 27877-27884, 2016, ISSN: 1463-9076.

Resumen | Enlaces | BibTeX | Etiquetas: adsorption, approximation, basis-sets, correlation-energy, dft, efficiency hartree-fock, model, organic-dyes, performance, screening

@article{RN305,
title = {Calculations of the Light Absorption Spectra of Porphyrinoid Chromophores for Dye-Sensitized Solar Cells},
author = { R. Mera-Adasme and W.H. Xu and D. Sundholm and F. Mendizabal},
url = {/brokenurl#<Go to ISI>://WOS:000385180600020},
doi = {10.1039/c6cp04627d},
issn = {1463-9076},
year = {2016},
date = {2016-01-01},
journal = {Physical Chemistry Chemical Physics},
volume = {18},
number = {40},
pages = {27877-27884},
abstract = {Solar power is a strong alternative to the currently used fossil fuels in order to satisfy the world's energy needs. Among them, dye-sensitized solar cells (DSSC) represent a low-cost option. Efficient and cheap dyes are currently needed to make DSSCs competitive. Computational chemistry can be used to guide the design of new light-absorbing chromophores. Here, we have computationally studied the lowest excited states of ZnPBAT, which is a recently synthesized porphyrinoid chromophore with high light-absorption efficiency. The calculations have been performed at ab initio correlated levels of theory employing second-order coupled clusters (CC2) and algebraic diagrammatic construction using second order (ADC(2)) methods and by performing density functional theory (DFT) calculations using the time-dependent DFT (TDDFT) approach for excitation energies. The ultraviolet-visible (UV-vis) spectrum calculated at the ADC(2) and CC2 levels agrees well with the experimental one. The calculations show that ZnPBAT has six electronic transitions in the visible range of the absorption spectrum. The ab initio correlated calculations and previously reported experimental data have been used to assess the performance of several well-known density functionals that have been employed in the present TDDFT study. Solvent effects have been estimated by using the conductor-like screening model (COSMO). The influence of the addition of a TiO2 cluster to the chromophore systems has also been investigated. The results indicate that both CAM-B3LYP and Becke's "half-and-half'' (BHLYP) density functionals are appropriate for the studies of excitation energies in the blue range of the visible spectrum for these kinds of porphyrinoid chromophores, whereas the excitation energies of the Q band calculated at the ab initio correlated level are more accurate than those obtained in the present TDDFT calculations. The inclusion of solvent effects has a modest influence on the spectrum of the protonated form of the studied chromophores, whereas solvent models are crucial when studying the absorption spectrum of the anionic chromophore. The calculated UV-vis spectrum for the chromophore anion is not significantly affected by attaching a TiO2 cluster to it.},
keywords = {adsorption, approximation, basis-sets, correlation-energy, dft, efficiency hartree-fock, model, organic-dyes, performance, screening},
pubstate = {published},
tppubtype = {article}
}

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Solar power is a strong alternative to the currently used fossil fuels in order to satisfy the world's energy needs. Among them, dye-sensitized solar cells (DSSC) represent a low-cost option. Efficient and cheap dyes are currently needed to make DSSCs competitive. Computational chemistry can be used to guide the design of new light-absorbing chromophores. Here, we have computationally studied the lowest excited states of ZnPBAT, which is a recently synthesized porphyrinoid chromophore with high light-absorption efficiency. The calculations have been performed at ab initio correlated levels of theory employing second-order coupled clusters (CC2) and algebraic diagrammatic construction using second order (ADC(2)) methods and by performing density functional theory (DFT) calculations using the time-dependent DFT (TDDFT) approach for excitation energies. The ultraviolet-visible (UV-vis) spectrum calculated at the ADC(2) and CC2 levels agrees well with the experimental one. The calculations show that ZnPBAT has six electronic transitions in the visible range of the absorption spectrum. The ab initio correlated calculations and previously reported experimental data have been used to assess the performance of several well-known density functionals that have been employed in the present TDDFT study. Solvent effects have been estimated by using the conductor-like screening model (COSMO). The influence of the addition of a TiO2 cluster to the chromophore systems has also been investigated. The results indicate that both CAM-B3LYP and Becke's "half-and-half'' (BHLYP) density functionals are appropriate for the studies of excitation energies in the blue range of the visible spectrum for these kinds of porphyrinoid chromophores, whereas the excitation energies of the Q band calculated at the ab initio correlated level are more accurate than those obtained in the present TDDFT calculations. The inclusion of solvent effects has a modest influence on the spectrum of the protonated form of the studied chromophores, whereas solvent models are crucial when studying the absorption spectrum of the anionic chromophore. The calculated UV-vis spectrum for the chromophore anion is not significantly affected by attaching a TiO2 cluster to it.

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2014

Martinez-Cifuentes, M; Weiss-Lopez, B; Santos, L S; Araya-Maturana, R

Intramolecular Hydrogen Bond in Biologically Active O-Carbonyl Hydroquinones Artículo de revista

Molecules, 19 (7), pp. 9354-9368, 2014, ISSN: 1420-3049.

Resumen | Enlaces | BibTeX | Etiquetas: ab-initio, bond bond, chemistry, derivatives, dft, diels-alder electrostatic hydrogen hydroquinone, inhibitors, molecular molecules, natural orbital, potential, quinones, radicals reaction, resonance, respiration, tumor-cell

@article{RN215,
title = {Intramolecular Hydrogen Bond in Biologically Active O-Carbonyl Hydroquinones},
author = { M. Martinez-Cifuentes and B. Weiss-Lopez and L.S. Santos and R. Araya-Maturana},
url = {/brokenurl#<Go to ISI>://WOS:000340036200041},
doi = {10.3390/molecules19079354},
issn = {1420-3049},
year = {2014},
date = {2014-01-01},
journal = {Molecules},
volume = {19},
number = {7},
pages = {9354-9368},
abstract = {Intramolecular hydrogen bonds (IHBs) play a central role in the molecular structure, chemical reactivity and interactions of biologically active molecules. Here, we study the IHBs of seven related o-carbonyl hydroquinones and one structurally-related aromatic lactone, some of which have shown anticancer and antioxidant activity. Experimental NMR data were correlated with theoretical calculations at the DFT and ab initio levels. Natural bond orbital (NBO) and molecular electrostatic potential (MEP) calculations were used to study the electronic characteristics of these IHB. As expected, our results show that NBO calculations are better than MEP to describe the strength of the IHBs. NBO energies (Delta E-ij((2))) show that the main contributions to energy stabilization correspond to LP ->sigma* interactions for IHBs, (O1O2)-O-center dot center dot center dot-H-2 and the delocalization LP ->pi* for O-2-C-2 = C-alpha(beta). For the (O1O2)-O-center dot center dot center dot-H-2 interaction, the values of Delta E-ij((2)) can be attributed to the difference in the overlap ability between orbitals i and j (F-ij), instead of the energy difference between them. The large energy for the LP O-2 ->pi* C-2 = C-alpha(beta) interaction in the compounds 9-Hydroxy-5-oxo-4,8, 8-trimethyl-1, 9(8H)-anthracenecarbolactone (VIII) and 9,10-dihydroxy-4,4-dimethylanthracen-1(4H)-one (VII) (55.49 and 60.70 kcal/mol, respectively) when compared with the remaining molecules (all less than 50 kcal/mol), suggests that the IHBs in VIII and VII are strongly resonance assisted.},
keywords = {ab-initio, bond bond, chemistry, derivatives, dft, diels-alder electrostatic hydrogen hydroquinone, inhibitors, molecular molecules, natural orbital, potential, quinones, radicals reaction, resonance, respiration, tumor-cell},
pubstate = {published},
tppubtype = {article}
}

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2011

Dobado, J A; Gomez-Tamayo, J C; Calvo-Flores, F G; Martinez-Garcia, H; Cardona, W; Weiss-Lopez, B; Ramirez-Rodriguez, O; Pessoa-Mahana, H; Araya-Maturana, R

Nmr Assignment in Regioisomeric Hydroquinones Artículo de revista

Magnetic Resonance in Chemistry, 49 (6), pp. 358-365, 2011, ISSN: 0749-1581.

Resumen | Enlaces | BibTeX | Etiquetas: basis-sets, c-13 calculations, chemical-shifts, coupling-constants, derivatives, dft, diels-alder giao, h, h-1 hmbc, hmqc, hydroquinone, nmr, o3lyp, organic-molecules, reaction, respiration, sensitivity, spin theoretical tumor-cell