#Concordancia Electronica Online Free Radical Forms

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Para caracterizar las especies derivadas de la apomorfina que se pueden generar ya sea por vГa metabГіlicas o quГmicas y en especial las formas radicalarias producidas en estos procesos se realizГі un estudio electroquГmico y de Resonancia de EspГn ElectrГіnico para los metabolitos o y p-quinona en ausencia y presencia de iones Calcio. Esta o-quinona se obtiene tambiГ©n por oxidaciГіn de la apomorfina en medio ГЎcido, formГЎndose una hidroxi-p-quinona por oxidaciГіn en condiciones bГЎsicas. Esta funciГіn se manifiesta con un proceso de autoxidaciГіn, produciГ©ndose la correspondiente o-quinona.

Finalmente, estos resultados estarГan avalando la posible existencia de especies radicalarias en el mecanismo reductivo de las o y p-quinonas, asГ como tambiГ©n en la oxidaciГіn de la apomorfina las cuales podrГan estar involucradas en la actividad contrГЎctil.Palabras Claves: ESR, apomorfina, quinonas, voltametrГa cГclica Spin Trapping.Apomorphine acts as contractile muscular agent through an extra cellular calcium mechanism dependent. AdemГЎs, se detectГі la existencia de especies radicalarias en el oxidaciГіn de la apomorfina a travГ©s de las tГ©cnicas de Spin Trapping. Los cГЎlculos teГіricos de las constantes de acoplamiento estuvieron en concordancia con los obtenidos experimentales. Los radicales generados fueron caracterizados mediante la espectroscopia de resonancia de espГn electrГіnica. No se observГі ningГєn efecto de los iones calcio en las culplas de reducciГіn de estos compuestos.

Concordancia Electronica Online Free Radical Forms

Electronic Spin Resonance spectroscopy was used to characterize the radical species generated. Calcium ions not modified the reduction couples of these compounds. The electrochemical study of these compounds using cyclic voltametric indicated that the reduction mechanism consists of two steps, the formation of semiquinonic radical and finally the production of hydroquinone derivatives. In order to characterize the apomorphine derivates species generated via metabolism or chemical mechanism, specially free radical forms, electrochemical and Electronic Spin Resonance studies were done to o and p-quinones metabolites in presence or absence of Calcium ions. O-Quinone is also obtained by apomorphine oxidation in acid medium in basic conditions a hydroxi-p-quinone is formed.

This response implies calcium entry from the extracelular space because it can not be elicited in Ca 2+-free medium and could be due to the contractile activity of autoxidation products or radical intermediates in the oxidation process ( 1- 2). Finally, these results would be indicating the possible existence of radicals species in the reduction mechanism of o and p-quinone as well oxidation process of apomorphine which could be involved in the contractile activity mechanism.KEYWORK : ESR, apomorphine, quinones, Cyclic Voltammetry,Spin Trapping.In isolated rat aorta, apomorphine induces a contractile response depending on its autoxidation. Beside, the radical species generated through apomorphine oxidation were detected using Spin Trapping technique.

The compound 1 and 2 were synthesized and supplied as described in references ( 3- 5).Cyclic voltammetry. The geometry of each quinone in both spin-paired and free radical forms was fully optimized by AM1 methodologySamples. 1 Apomorphine and o-quinone 1 and p-quinones derivated.To estimate the theoretical hyperfine constants, INDO-SCF calculations were carried out. Also, the radical species generated through apomorhine oxidation were detected using DMPO.Fig. The anion radicals produced in the electrochemical process were characterised by EPR.

ESR spectra were recorded in X band (9.85 GHz) using a Bruker ECS 106 spectrometer with a rectangular cavity and 50 KHz field modulation. The radicals of compounds 1 and 2 were generated by electrolytic reduction in situ at room temperature.ESR Spectroscopy. A mercury-dropping electrode was used as the working electrode, a platinum wire as the auxiliary electrode, and saturated calomel as the reference electrode. Cyclic voltammetry was carried out using a Weenking POS 88 instrument with a Kipp Zenen BD93 recorder, in DMSO or DMF ( ca 1.0 x 10 -2 mol dm -3), under a nitrogen atmosphere, with TBAP ( ca 0.1 mol dm -3), using three-electrode cells. The tetrabutylammonium perchlorate (TBAP) used as supporting electrolyte was purchased from Fluka.

The second cathodic peak is cuasirreversible in the whole range of sweep rates used (50-2000 mV/s). This is attributable to the reduction of a quinone to a semiquinone stable anion radical at room temperature. According to the standard reversibility criteria this couple corresponds to a reversible diffusion-controlled one-electron transfer ( 7- 8).

Table 2 shows both the experimental and calculated hyperfine constants. 5 ESR spectra of apomorphine radical generated by electrochemical oxidation in presence of 100 mM of DMPO.For the AM1 calculations of both electron-paired and anion radical forms, all internal coordinates were completely optimised.In order to obtain the theoretical hyperfine constants, INDO calculations were performed using the geometries obtained using AM1 calculations. Figure 2 show the Voltamogram of p-quinone in ACN solvent.Fig. We can attribute this wave to the production of the corresponding hydroquinones.

Also, o-semiquinone radical was detected when apomorphine was oxidated by Spin Trapping technique.The hyperfine constants obtained by INDO calculations show very good agreement with the experimental ones.Finally, these results would be indicating the possible existence of radicals species in the reduction mechanism of o and p-quinone as well oxidation process of apomorphine which could be involved in the contractile activity mechanism.The authors are grateful for partial funding by FONDECYT, Grant 1000834 and INTERCAMPUS scholarship1.- K. The second peak was attributed to the production of the hydroquinonic derivatives. The hyperfine pattern obtained indicated that the spin distribution is not homogeneous. The ESR spectra of the anion radicals for molecules 1 and 2 were well resolved. The p-quinone showed lower reduction potential than o-quinone. The first wave corresponded to a reversible one-electron transfer in which the anion radicals were formed.

Chem Soc., (1985), 107: 3902. Ges., (1969), 302:487 6.- M.J.S. Linde y M.S.Ragab, Helvetica Chimica Acta, (1968),51: 683 5.- K.