A proposal for a new local hardness as selectivity index

Meneses, Lorena; Tiznado, William; Contreras, Renato; Fuentealba, Patricio

doi:10.1016/j.cplett.2003.11.019

Cited by 79 publications

(56 citation statements)

References 24 publications

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“…(11)] and the replacement of the Fukui function by other functions, which integrate to unity, have cast some doubts about the correct definition of these reactivity indexes. 19,30,34,47,50,51 For instance, Harbola et al 50 proposed that ðrÞ is constant and equal to the global hardness in all the positions of the space. According to our opinion, the local hardness and its relation with the hardness kernel is still one of the most vexing yet fascinating problems in the field of conceptual DFT.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

On the quality of the hardness kernel and the Fukui function to evaluate the global hardness

et al. 2006

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An approximated hardness kernel, which includes the second derivative with respect to the density of the kinetic energy, the electron-electron coulomb repulsion, and the exchange density functionals, has been tested for the calculation of the global hardness. The results obtained for a series of 40 cations and neutral systems and 16 anions represent in most cases an improvement of the results obtained using the HOMO-LUMO gap approach and indicate the viability of this approach to evaluate global hardness. In addition, the relevance of the Fukui function approximation and the role of the three components of the hardness kernel in the evaluation of the global hardness have been analyzed.

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Section: Theoretical Backgroundmentioning

confidence: 99%

On the quality of the hardness kernel and the Fukui function to evaluate the global hardness

et al. 2006

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“…Varios trabajos de investigación han reportado la utilidad de este esquema de análisis de población, para la determinación de descriptores locales. 20,65 La función de Fukui, filicidad y suavidad local para el ataque nucleofílico, se calcularon a partir de las Ecuaciones 10a, 11 y 12 respectivamente. Los descriptores atómicos (sf ) k α y (ωf ) k α se calcularon mediante las Ecuaciones 13 y 14 respectivamente, mientras que los nuevos descriptores definidos mediante la aproximación de grupo, y que de ahora en adelante designaremos como DG, se calcularon empleando las Ecuaciones 16a y 16b respectivamente.…”

Section: Metodologíaunclassified

Descriptores globales y locales de la reactividad para el diseño de nuevos fármacos anticancerosos basados en cis-platino(II)

López¹,

Robles²

2013

Quím. Nova

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Recebido em 6/2/13; aceito em 21/6/13; publicado na web em 2/8/13 GLOBAL AND LOCAL REACTIVITY DESCRIPTORS FOR THE DESIGN OF NEW ANTICANCER DRUGS BASED ON CIS-PLATINUM(II). Density functional theory was used to investigate the global and local reactivity of some cis-platinum(II) complexes including anticancer drugs, such as cisplatin and carboplatin. Calculated equilibrium geometries at mPW1PW/LANL2DZ* are in close agreement with their available X-ray data. We develop three new local reactivity descriptors: atomic descriptor of philicity, atomic descriptor group and atomic descriptor of philicity group for determining chemical reactivity and selectivity of the studied complexes. This contribution on chemical reactivity allow us to establish qualitative trends, which enable our descriptors for use in rational platinum based anticancer drug design.Keyword: DFT calculations; cisplatin; electrophilicity index. INTRODUCCIÓNLas novedosas técnicas de modelización y las aproximaciones desarrolladas en el campo de la teoría de estructura electrónica molecular, están asumiendo un papel importante en las investigaciones de química cuántica medicinal y en el diseño de nuevos agentes terapéuticos para el tratamiento de numerosas patologías.1-5 Dentro de los temas de investigación en el área de la química cuántica medicinal, un campo interesante de estudio comprende la química del fármaco anticanceroso cisplatino (cis-diaminodicloroplatino(II)), el cual desde su descubrimiento hace más de cuatro décadas por el biofísico Rosenberg, 6 se ha convertido en un paradigma para el tratamiento de tumores testiculares y ováricos.7 Este notable interés por investigar la estructura electrónica del fármaco anticanceroso cisplatino, se debe al hecho que, aun cuando existe información experimental suficiente sobre los principales aspectos farmacodinámicos que gobiernan la acción antitumoral de este agente, se requiere el desarrollo de modelos teóricos que permitan dar soporte a la evidencia experimental generada, pues aun existen muchos interrogantes con respecto al modo de acción de este fármaco que todavía no han sido totalmente comprendidos, 5 pues si bien es cierto, que el mecanismo de acción tradicionalmente establecido para cisplatino indica que éste, se une al ADN formando aductos inter e intrahebra de los cuales los más abundantes son aquellos donde se forma un enlace 1,2-intrahebra entre los átomos de N(7), de dos bases guanina adyacentes, 8 aun permanecen aspectos sin desentrañar (material Suplementario, Figura 1S).9 De modo que en su aspecto más simple, la unión Pt-N(7), corresponde a una interacción electrófilo/nucleófilo.Por otro lado, aunque cisplatino es un fármaco anticanceroso exitoso, (con tasa de curación que supera el 90%), presenta una serie de reacciones colaterales indeseables que limitan su aplicación terapéutica.10 Además, se han encontrado casos de resistencia de algunos tumores frente a la acción del fármaco.11 En razón a lo anterior, se han sintetizado números compuestos análogos a cisplatino con el fin de superar...

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“…As it has been stated before [13], the proposed local hardness is an empirical one which cannot be derived from the hardness kernel, because of the known ambiguities in the grand canonical ensemble definitions. Note also that usually the hardness is associated with charged-controlled reactions.…”

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confidence: 97%

“…The recently defined local hardness index has been very useful as an intramolecular selectivity descriptor in the orientation of electrophilic aromatic substitution reactions and alkylation and acylation of lithium enolates [13]. In this article, it is shown that the Markovnikov's rule may be also interpreted applying the local hardness index to substituted ethylenes taking in account the electronic effects of the substituent groups [14].…”

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confidence: 98%

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Theoretical studies of reactivity and selectivity in some organic reactions

Meneses

Araya

Pilaquinga

et al. 2010

Int J of Quantum Chemistry

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Some organic reactions with biological or commercial interest have been studied by using reactivity and selectivity indices proposed in the density functional theory. The reactions studied include the electrophilic additions, the BaeyerVilliger oxidations, and the nucleophilic substitutions. For the study, the concepts of electrophilicity and nucleophilicity have been applied as reactivity descriptors. The local hardness has been applied as well as a selectivity descriptor. In this way, the reactivity and selectivity patterns have been studied for the reactants involved in these organic reactions. They have been ranked in theoretical scales which are comparable with experimental scales obtained from kinetic data.

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A proposal for a new local hardness as selectivity index

Cited by 79 publications

References 24 publications

On the quality of the hardness kernel and the Fukui function to evaluate the global hardness

On the quality of the hardness kernel and the Fukui function to evaluate the global hardness

Descriptores globales y locales de la reactividad para el diseño de nuevos fármacos anticancerosos basados en cis-platino(II)

Theoretical studies of reactivity and selectivity in some organic reactions

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