Biomedical subjects

E Chamorro

Publications and source records attributed to E Chamorro.

7 recordsLinked to original sources

PubMed2007

Spin-polarized conceptual density functional theory study of the regioselectivity in ring closures of radicals.

The regioselectivity of ring-forming radical reactions is investigated within the framework of the so-called spin-polarized conceptual density functional theory. Two different types of cyclizations were studied. First, a series of model reactions of alkyl- and acyl-substituted radicals were investigated. Next, attention was focused on the radical cascade cyclizations of N-alkenyl-2-aziridinylmethyl radicals (a three-step mechanism). In both of these reactions, the approaching radical (carbon or nitrogen centered) adds to a carbon-carbon double bond within the same molecule to form a radical ring compound. In this process, the number of electrons is changing from a local point of view (a charge transfer occurs from one part of the molecule to another one) at constant global spin number Ns (both the reactant and the product ring compound are in the doublet state). It is shown that the experimentally observed regioselectivities for these ring-closure steps can be predicted using the spin-polarized Fukui functions for radical attack, f0NN(r).

Cyclization↗

PubMed2006

Philicity indices within the spin-polarized density-functional theory framework.

The electrophilicity index is analyzed within the framework of spin-polarized density-functional theory. In this context, constrained philicities, omega(N) identical with (mu(N))(2)(2eta(NN)), are introduced in order to define the capability of a system to acquire or donate electrons in a process at constant spin number. The spin-philicity/spin-donicity indices, omega(S)(+/-) identical with (mu(S) (+/-))(2)(2eta(SS)), are examined and rationalized here as the philicity of a given system to change its spin-polarization state, as being defined through the spin potential mu(S) and spin hardness eta(SS) for a process at constant number of electrons. The local extension of these indices has been also outlined and numerical results have been discussed on the analysis of the electrophilic nature of some simple carbene systems both in the singlet and triplet states.

Journal Article↗

PubMed2005

Empirical energy-density relationships applied to the analysis of the basicity of strong organic superbases.

Site selectivity and reactivity in some strong organic super bases RN=C(NR(2))R, containing several possible sites for protonation, have been analyzed qualitatively in terms of global and local chemical reactivity descriptors defined in the context of conceptual density functional theory. On the basis of the condensed-to-site Fukui function values, the protonation site is predicted to be located at the imino nitrogen. Linear relationships between global energy-dependent quantities and the variation of the Fukui function (or the local softness) at the protonation site have been also found. These linear relationships can be interpreted within a local HSAB rule framework, as observed for instance for the gas-phase basicity of alkylamines and gas-phase acidity of alcohols and thioalcohols. This work extends the range of applicability of reactivity models developed for the treatment of substituent effects based on empirical energy-density Hammett-like relationships.

Models, Chemical↗

PubMed2005

Generalized nuclear Fukui functions in the framework of spin-polarized density-functional theory.

An extension of Cohen's nuclear Fukui function is presented in the spin-polarized framework of density-functional theory (SP-DFT). The resulting new nuclear Fukui function indices PhiNalpha and PhiSalpha are intended to be the natural descriptors for the responses of the nuclei to changes involving charge transfer at constant multiplicity and also the spin polarization at constant number of electrons. These generalized quantities allow us to gain new insights within a perturbative scheme based on DFT. Calculations of the electronic and nuclear SP-DFT quantities are presented within a Kohn-Sham framework of chemical reactivity for a sample of molecules, including H2O, H2CO, and some simple nitrenes (NX) and phosphinidenes (PX), with X=H, Li, F, Cl, OH, SH, NH2, and PH2. Results have been interpreted in terms of chemical bonding in the context of Berlin's theorem, which provides a separation of the molecular space into binding and antibinding regions.

Journal Article↗

PubMed2005

Nature of bonding in the cyclization reactions of (2-Ethynylphenyl)triazene and 2-Ethynylstyrene.

The topological analysis of the electron localization function (ELF) has been applied to explore the nature of bonding in thermal cyclizations of (2-ethynylphenyl)triazene and 2-ethynylstyrene. These processes have been proposed to occur through both five- (i.e., coarctate) and six-membered (i.e., pericyclic) transition states. The analysis of electron delocalization, as measured from an irreducible ELF f-localization domain reduction diagram, allows us to characterize these cyclizations of 2-ethynylstyrene in terms of a more pronounced pericyclic or coarctate character than those associated with (2-ethynylphenyl)triazene. The latter evolve through pseudopericyclic and pseudocoarctate pathways. It is found that ELF results are also in good agreement with recent magnetic evidence data obtained from the anisotropy of induced current density (ACID) calculations.

Journal Article↗

PubMed2005

Comparison among four different ways to condense the Fukui function.

Four different ways to condense the Fukui function are compared. Three of them perform a numerical integration over different basins to define the condensed Fukui function, and the other one is the most traditional Fukui function using Mulliken population analysis. The basins are chosen to be the basins of the electron density (AIM), the basins of the electron localization function (ELF), and the basins of the Fukui function itself. The use of the last two basins is new and presented for the first time here. It is found that the last three methods yield results which are stable against a change in the basis set. The condensed Fukui function using the basins of the ELF is not able to give information on the reactivity of an acceptor molecule. In general, the condensed Fukui function using the basins of the density or the basins of the Fukui function describe the reactivity trends well. The latter is preferred, because it only contains information about the Fukui function itself and it gives the right information for donor as well as acceptor centers.

Journal Article↗

PubMed2003

Electron probability distribution in AIM and ELF basins.

The probabilities of finding a certain number of electrons enclosed in a given volume is calculated and discussed for a series of molecules. Two different methodologies to do the partition of the molecular space in separate volumes are investigated: the Atoms in the Molecules, AIM, topologic analysis of the density, and the topologic analysis of the Electron Localization Function (ELF). The formulas to calculate the probability distribution are reviewed and the way to implement them shortly explained. For a series of molecules, we present how the probability distribution complement the chemical information about the localization of the electrons in certain regions of the space. The calculations show that the probability of finding Z electrons in the AIM atomic basin associated to an atom of atomic number Z is, in general, low, even when the average number of electrons is close to Z. The probability distribution on the ELF basins associated to bonds yields new insight about the nature of the respective bond.

Journal Article↗