2019 |
Gomez-Jeria, J S; Kpotin, G A A Density Functional Theory Analysis of the relationships between electronic structure and KCNQ2 potassium channels inhibition by a series of retigabine derivatives Artículo de revista Chemistry Research Journal, 4 , pp. 68-79, 2019, ISSN: 2455-8990. Resumen | Enlaces | BibTeX | Etiquetas: dft, KCNQ2 potassium channels, KPG method, local atomic reactivity indices, local molecular orbitals., molecular electrostatic potential, qsar, Retigabine @article{RN1006, title = {A Density Functional Theory Analysis of the relationships between electronic structure and KCNQ2 potassium channels inhibition by a series of retigabine derivatives}, author = {J.S. Gomez-Jeria and G.A. Kpotin}, url = {https://www.researchgate.net/publication/328582641_A_density_Functional_Analysis_of_the_relationships_between_electronic_structure_and_KCNQ2_potassium_channels_inhibition_by_a_series_of_retigabine_derivatives}, issn = {2455-8990}, year = {2019}, date = {2019-01-12}, journal = {Chemistry Research Journal}, volume = {4}, pages = {68-79}, publisher = {Leon Publications}, abstract = {A quantum-chemical analysis of the relationships between electronic structure and KCNQ2 potassium channels inhibition was carried out for a group of retigabine derivatives. For the quantitative structure-activity relationship (QSAR) investigation, we have employed the Klopman-Peradejordi-Gomez formal method. A statistically significant equation, relating the variation of the inhibitory capacity to the variation of the numerical value of several local atomic reactivity indices was found. The mechanism of action is orbital-controlled. The obtained results allowed building the partial 2D pharmacophore that should be useful to design new derivatives with enhanced inhibitory capacity.}, keywords = {dft, KCNQ2 potassium channels, KPG method, local atomic reactivity indices, local molecular orbitals., molecular electrostatic potential, qsar, Retigabine}, pubstate = {published}, tppubtype = {article} } A quantum-chemical analysis of the relationships between electronic structure and KCNQ2 potassium channels inhibition was carried out for a group of retigabine derivatives. For the quantitative structure-activity relationship (QSAR) investigation, we have employed the Klopman-Peradejordi-Gomez formal method. A statistically significant equation, relating the variation of the inhibitory capacity to the variation of the numerical value of several local atomic reactivity indices was found. The mechanism of action is orbital-controlled. The obtained results allowed building the partial 2D pharmacophore that should be useful to design new derivatives with enhanced inhibitory capacity. |
Gomez-Jeria, J S; Contreras-Lira, V Chemistry Research Journal, 4 , pp. 34-45, 2019, ISSN: 2455-8990. Resumen | Enlaces | BibTeX | Etiquetas: Aurora kinase A, common skeleton, dft, electronic structure, epidermal growth factor receptor kinase, Klopman-Peradejordi-Gomez method., KPG model, pharmacophore, qsar @article{RN1005, title = {A DFT analysis of the relationships between electronic structure and inhibition of aurora kinase A and epidermal growth factor receptor kinase by a set of N4-phenyl substituted-7H-pyrrolo[2,3-d]pyrimidin-4-amines}, author = {J.S. Gomez-Jeria and V. Contreras-Lira}, url = {https://www.researchgate.net/publication/336684277_A_DFT_analysis_of_the_relationships_between_electronic_structure_and_inhibition_of_aurora_kinase_A_and_epidermal_growth_factor_receptor_kinase_by_a_set_of_N_4_-phenyl_substituted-7H-pyrrolo23-dpyrimid}, issn = {2455-8990}, year = {2019}, date = {2019-01-10}, journal = {Chemistry Research Journal}, volume = {4}, pages = {34-45}, publisher = {Leon Publications}, abstract = {A quantum-chemical structure-activity study is carried out for the inhibition of aurora kinase A and epidermal growth factor receptor kinase by a group of N4-phenylsubstituted-7H-pyrrolo[2,3-d]pyrimidin-4-amines. The Klopman-Peradejordi-Gomez method was employed. Statistically significant relationships between the variation of the inhibitory capacity of a group of N4-phenylsubstituted-7H-pyrrolo[2,3-d]pyrimidin-4-amines against aurora kinase A and epidermal growth factor receptor kinase and the variation of the values of several local atomic reactivity indices were obtained. The results are presented in the form of a partial pharmacophore that could be useful in the synthesis of new and more powerful molecules.}, keywords = {Aurora kinase A, common skeleton, dft, electronic structure, epidermal growth factor receptor kinase, Klopman-Peradejordi-Gomez method., KPG model, pharmacophore, qsar}, pubstate = {published}, tppubtype = {article} } A quantum-chemical structure-activity study is carried out for the inhibition of aurora kinase A and epidermal growth factor receptor kinase by a group of N4-phenylsubstituted-7H-pyrrolo[2,3-d]pyrimidin-4-amines. The Klopman-Peradejordi-Gomez method was employed. Statistically significant relationships between the variation of the inhibitory capacity of a group of N4-phenylsubstituted-7H-pyrrolo[2,3-d]pyrimidin-4-amines against aurora kinase A and epidermal growth factor receptor kinase and the variation of the values of several local atomic reactivity indices were obtained. The results are presented in the form of a partial pharmacophore that could be useful in the synthesis of new and more powerful molecules. |
Gomez-Jeria, J S; Sanchez-Jara, B Chemistry Research Journal, 4 , pp. 46-59, 2019, ISSN: 2455-8990. Resumen | Enlaces | BibTeX | Etiquetas: adenosine receptors, common skeleton, dft, electronic structure, KPG method, pharmacophore, purine, purine derivatives, qsar, receptor affinity @article{RN1001, title = {An introductory theoretical investigation of the relationships between electronic structure and A1, A2A and A3 adenosine receptor affinities of a series of N6-8,9-trisubstituted purine derivatives}, author = {J.S. Gomez-Jeria and B. Sanchez-Jara}, url = {https://www.researchgate.net/publication/330521580_An_introductory_theoretical_analysis_of_the_relationships_between_electronic_structure_and_A1_A2A_and_A3_adenosine_receptor_affinities_of_a_series_of_N6-89-trisubstituted_purine_derivatives}, issn = {2455-8990}, year = {2019}, date = {2019-01-01}, journal = {Chemistry Research Journal}, volume = {4}, pages = {46-59}, publisher = {Leon Publications}, abstract = {A study of the relationships between receptor affinity and electronic structure was performed in a group of N6-8,9-trisubstituted purine derivatives interacting with A1, A2A and A3 adenosine receptors. Statistically significant equations were obtained for all cases.}, keywords = {adenosine receptors, common skeleton, dft, electronic structure, KPG method, pharmacophore, purine, purine derivatives, qsar, receptor affinity}, pubstate = {published}, tppubtype = {article} } A study of the relationships between receptor affinity and electronic structure was performed in a group of N6-8,9-trisubstituted purine derivatives interacting with A1, A2A and A3 adenosine receptors. Statistically significant equations were obtained for all cases. |
Gautier, K S; Kpotin, G A; Mensah, J -B; Gomez-Jeria, J S Quantum-Chemical Study of the Relationships between Electronic Structure and the Affinity of Benzisothiazolylpiperazine Derivatives for the Dopamine Hd2l and Hd3 Receptors Artículo de revista The Pharmaceutical and Chemical Journal, 6 , pp. 73-90, 2019, ISSN: 2349-7092. Resumen | Enlaces | BibTeX | Etiquetas: dft, hD2L receptor, hD3 receptor, KPG method, qsar, Schizophrenia @article{RN1011, title = {Quantum-Chemical Study of the Relationships between Electronic Structure and the Affinity of Benzisothiazolylpiperazine Derivatives for the Dopamine Hd2l and Hd3 Receptors}, author = {K.S. Gautier and G.A. Kpotin and J.-B. Mensah and J.S. Gomez-Jeria}, url = {http://tpcj.org/download/vol-6-iss-5-2019/TPCJ2019-06-05-73-90.pdf}, issn = {2349-7092}, year = {2019}, date = {2019-01-01}, journal = {The Pharmaceutical and Chemical Journal}, volume = {6}, pages = {73-90}, abstract = {Schizophrenia is a mental illness that induces a cognitive deficit, affects a large part of the world's population, and in particular Africa where it is ignored. To treat this disease, the antipsychotic derivatives of benzisothiazolylpiperazine (N-(trans-4-(2-(4-(benzo [d] isothiazol-3-yl) piperazin-1-yl) ethyl)cyclohexyl) amides) are employed because of their inhibitory powerfor the dopamine HD2L and HD3 receptors. The present study aims to establishrelationships between the electronic structure and the antipsychotic activity of benzisothiazolylpiperazine derivatives andto generate a 2D pharmacophore for predicting the antipsychotic activity of these derivatives. The KPG technique was employed. The electronic structure of all the molecules was calculatedat the DFT/B3LYP/6-31G (d,p) level of theory. We obtained two statistically significant equationsfor predicting the inhibition constant.The process seems to be charge and orbital controlled for receptor HD2L and orbital controlled for HD3. The two prediction equations obtained can be useful for proposing new derivatives with antipsychotic activity having an affinity with the dopamineHD2L and HD3 receptors.The two pharmacophores derived from these prediction models would be very useful for proposing newmolecules with potent antipsychotic activity.}, keywords = {dft, hD2L receptor, hD3 receptor, KPG method, qsar, Schizophrenia}, pubstate = {published}, tppubtype = {article} } Schizophrenia is a mental illness that induces a cognitive deficit, affects a large part of the world's population, and in particular Africa where it is ignored. To treat this disease, the antipsychotic derivatives of benzisothiazolylpiperazine (N-(trans-4-(2-(4-(benzo [d] isothiazol-3-yl) piperazin-1-yl) ethyl)cyclohexyl) amides) are employed because of their inhibitory powerfor the dopamine HD2L and HD3 receptors. The present study aims to establishrelationships between the electronic structure and the antipsychotic activity of benzisothiazolylpiperazine derivatives andto generate a 2D pharmacophore for predicting the antipsychotic activity of these derivatives. The KPG technique was employed. The electronic structure of all the molecules was calculatedat the DFT/B3LYP/6-31G (d,p) level of theory. We obtained two statistically significant equationsfor predicting the inhibition constant.The process seems to be charge and orbital controlled for receptor HD2L and orbital controlled for HD3. The two prediction equations obtained can be useful for proposing new derivatives with antipsychotic activity having an affinity with the dopamineHD2L and HD3 receptors.The two pharmacophores derived from these prediction models would be very useful for proposing newmolecules with potent antipsychotic activity. |
Gomez-Jeria, J S; Garrido-Saez, N 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 @article{RN10012, title = {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}, author = {J.S. Gomez-Jeria and N. Garrido-Saez}, issn = {2455-8990}, year = {2019}, date = {2019-01-01}, journal = {Chemistry Research Journal,}, volume = {4}, pages = {30-42}, publisher = {Leon Publications}, abstract = {We have studied the relationships between electronic structure and affinity for D2, D3 and D4 dopamine receptor subtypesin a group of 1-[3-(4-butylpiperidin-1-yl)propyl]-1,2,3,4-tetrahydroquinolin-2-one (77-LH-28-1) derivatives. The Klopman-Peradejordi-Gomez method was employed. Statistically significant results were obtained for all the cases. The analysis of the resulting equations provided data that can be used to design new derivatives with enhanced affinity through appropriate substitutions at selected atoms.}, keywords = {77-LH-28-1, D2 receptor, D3 receptor, D4 receptor, dft, dopamine, electronic structure, KPG method, qsar, receptor affinity}, pubstate = {published}, tppubtype = {article} } We have studied the relationships between electronic structure and affinity for D2, D3 and D4 dopamine receptor subtypesin a group of 1-[3-(4-butylpiperidin-1-yl)propyl]-1,2,3,4-tetrahydroquinolin-2-one (77-LH-28-1) derivatives. The Klopman-Peradejordi-Gomez method was employed. Statistically significant results were obtained for all the cases. The analysis of the resulting equations provided data that can be used to design new derivatives with enhanced affinity through appropriate substitutions at selected atoms. |
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 @article{RN1013, title = {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}, author = {J.S. Gomez-Jeria and N. Gatica-Diaz}, issn = {2455-8990}, year = {2019}, date = {2019-01-01}, journal = {Chemistry Research Journal}, volume = {4}, pages = {85-100}, publisher = {Leon Publications}, abstract = {We present the results of a quantum-chemical analysis of the relationships between electronic structure and 5-HT1A and 5-HT2A receptor binding affinity for a series of 8-acetyl-7-hydroxy-4-methylcoumarin derivatives. The KPG model coupled with DFT calculations at the 6-31G(d,p) level were employed. Two statistically significant results were obtained. The results are synthesized in the corresponding partial pharmacophores. The most important result suggests that an unsaturated ring is an almost sure target for the development of new compounds with affinity for both receptors.}, keywords = {5-HT1A receptor, 5-HT2A receptor, density functional theory, dft, KPG method, methylcoumarin, qsar, serotonin}, pubstate = {published}, tppubtype = {article} } We present the results of a quantum-chemical analysis of the relationships between electronic structure and 5-HT1A and 5-HT2A receptor binding affinity for a series of 8-acetyl-7-hydroxy-4-methylcoumarin derivatives. The KPG model coupled with DFT calculations at the 6-31G(d,p) level were employed. Two statistically significant results were obtained. The results are synthesized in the corresponding partial pharmacophores. The most important result suggests that an unsaturated ring is an almost sure target for the development of new compounds with affinity for both receptors. |
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} } 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. |
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 @article{RN321, title = {Protonation Sites, Tandem Mass Spectrometry and Computational Calculations of O-Carbonyl Carbazolequinone Derivatives}, author = { M. Martinez-Cifuentes and G. Clavijo-Allancan and P. Zuniga-Hormazabal and B. Aranda and A. Barriga and B. Weiss-Lopez and R. Araya-Maturana}, url = {/brokenurl#<Go to ISI>://WOS:000381500900086}, doi = {UNSP 1071, 10.3390/ijms17071071}, issn = {1422-0067}, year = {2016}, date = {2016-01-01}, journal = {International Journal of Molecular Sciences}, volume = {17}, number = {7}, abstract = {A series of a new type of tetracyclic carbazolequinones incorporating a carbonyl group at the ortho position relative to the quinone moiety was synthesized and analyzed by tandem electrospray ionization mass spectrometry (ESI/MS-MS), using Collision-Induced Dissociation (CID) to dissociate the protonated species. Theoretical parameters such as molecular electrostatic potential (MEP), local Fukui functions and local Parr function for electrophilic attack as well as proton affinity (PA) and gas phase basicity (GB), were used to explain the preferred protonation sites. Transition states of some main fragmentation routes were obtained and the energies calculated at density functional theory (DFT) B3LYP level were compared with the obtained by ab initio quadratic configuration interaction with single and double excitation (QCISD). The results are in accordance with the observed distribution of ions. The nature of the substituents in the aromatic ring has a notable impact on the fragmentation routes of the molecules.}, keywords = {antitumor assignment, basicities, c-13 carbazole, chemistry complete derivatives, dft, gas-phase hydroquinone ionization, mass molecules, nmr-spectra, qcisd, quinones, respiration, spectrometry, tumor-cell}, pubstate = {published}, tppubtype = {article} } A series of a new type of tetracyclic carbazolequinones incorporating a carbonyl group at the ortho position relative to the quinone moiety was synthesized and analyzed by tandem electrospray ionization mass spectrometry (ESI/MS-MS), using Collision-Induced Dissociation (CID) to dissociate the protonated species. Theoretical parameters such as molecular electrostatic potential (MEP), local Fukui functions and local Parr function for electrophilic attack as well as proton affinity (PA) and gas phase basicity (GB), were used to explain the preferred protonation sites. Transition states of some main fragmentation routes were obtained and the energies calculated at density functional theory (DFT) B3LYP level were compared with the obtained by ab initio quadratic configuration interaction with single and double excitation (QCISD). The results are in accordance with the observed distribution of ions. The nature of the substituents in the aromatic ring has a notable impact on the fragmentation routes of the molecules. |
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} } 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. |
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} } 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. |
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 @article{RN34e, title = {Nmr Assignment in Regioisomeric Hydroquinones}, author = { J.A. Dobado and J.C. Gomez-Tamayo and F.G. Calvo-Flores and H. Martinez-Garcia and W. Cardona and B. Weiss-Lopez and O. Ramirez-Rodriguez and H. Pessoa-Mahana and R. Araya-Maturana}, url = {/brokenurl#<Go to ISI>://WOS:000291114500009}, doi = {10.1002/mrc.2745}, issn = {0749-1581}, year = {2011}, date = {2011-01-01}, journal = {Magnetic Resonance in Chemistry}, volume = {49}, number = {6}, pages = {358-365}, publisher = {2011 John Wiley & Sons, Ltd.}, abstract = {A set of regioisomeric pairs of tricyclic hydroquinones, analogues of antitumor 9,10-dihydroxy-4,4-dimethyl-5,8dihydroanthracen- 1(4H)-one (1) and other derivatives, were synthesized and their regiochemistry and NMR spectra assigned by using 1H-detected one-bond(C-H) HMQC and long-range C-HHMBC, in good agreement with theoretical O3LYP/Alhrichs-pVTZ calculations. The 5-hydroxymethyl derivatives (11, 15, 19) showed a 3 integral H,H coupling constant of methylene protons evidencing the presence of a seven-membered intramolecular hydrogen bonded ring, not observed for the 8-hydroxymethyl isomers.}, keywords = {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}, pubstate = {published}, tppubtype = {article} } A set of regioisomeric pairs of tricyclic hydroquinones, analogues of antitumor 9,10-dihydroxy-4,4-dimethyl-5,8dihydroanthracen- 1(4H)-one (1) and other derivatives, were synthesized and their regiochemistry and NMR spectra assigned by using 1H-detected one-bond(C-H) HMQC and long-range C-HHMBC, in good agreement with theoretical O3LYP/Alhrichs-pVTZ calculations. The 5-hydroxymethyl derivatives (11, 15, 19) showed a 3 integral H,H coupling constant of methylene protons evidencing the presence of a seven-membered intramolecular hydrogen bonded ring, not observed for the 8-hydroxymethyl isomers. |
2019 |
A Density Functional Theory Analysis of the relationships between electronic structure and KCNQ2 potassium channels inhibition by a series of retigabine derivatives Artículo de revista Chemistry Research Journal, 4 , pp. 68-79, 2019, ISSN: 2455-8990. |
Chemistry Research Journal, 4 , pp. 34-45, 2019, ISSN: 2455-8990. |
Chemistry Research Journal, 4 , pp. 46-59, 2019, ISSN: 2455-8990. |
Quantum-Chemical Study of the Relationships between Electronic Structure and the Affinity of Benzisothiazolylpiperazine Derivatives for the Dopamine Hd2l and Hd3 Receptors Artículo de revista The Pharmaceutical and Chemical Journal, 6 , pp. 73-90, 2019, ISSN: 2349-7092. |
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. |
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. |
2017 |
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. |
2016 |
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. |
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. |
2014 |
Intramolecular Hydrogen Bond in Biologically Active O-Carbonyl Hydroquinones Artículo de revista Molecules, 19 (7), pp. 9354-9368, 2014, ISSN: 1420-3049. |
2011 |
Nmr Assignment in Regioisomeric Hydroquinones Artículo de revista Magnetic Resonance in Chemistry, 49 (6), pp. 358-365, 2011, ISSN: 0749-1581. |