M.J. Aguirre

University of Santiago, Chile, CiudadSantiago, Santiago, Chile

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Publications (37)67.32 Total impact

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    ABSTRACT: Electrochemical and photoelectrochemical reduction of carbon dioxide was studied in aqueous solution, using an ITO/multilayer modified electrode. The multilayer formation was carried out by the Layer-by-Layer method (LBL), using a μ-(meso-5,10,15,20-tetra(pirydil)porphyrin)tetrakis {bis(bipyridine)chloride ruthenium(II)} coordinated with Mn(III), Zn(II) and Ni(II) in its central cavity and an anionic polyoxotungstate [SiW12O40]4−. The multilayer formation was corroborated by electrochemical methods and UV–visible spectroscopy. For this study, 3 multilayers were formed on the ITO surface. Carbon dioxide reduction was studied by linear sweep voltammetry at pseudo stationary state (5 mV s−1) in a 0.1 M NaClO4, CO2 saturated solution. Photoelectrochemical reduction of carbon dioxide was studied in the same conditions described above under light irradiation at 440 nm. In dark conditions, an enhancement in current is detected at −0.75 V indicating carbon dioxide reduction. Under light irradiation the reduction process shifts to −0.60 V. Chemical analysis after controlled potential electrolysis shows that in dark conditions, formic acid, carbon monoxide and methanol are the reduction products. Under light irradiation there is a change in the product distribution and for some metals; formaldehyde can be detected, evidencing a change in the reduction mechanism. These results support the fact that [MTRP]n+/[SiW12O40]4− multilayer modified electrodes act as electrocatalysts for carbon dioxide reduction and that this activity is enhanced by a combination of light and potential where light produces excited states sites on the multilayer, that are more reactive toward carbon dioxide reduction.
    Electrochimica Acta. 01/2014; 115:146–154.
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    ABSTRACT: a b s t r a c t This work describes the influence of n-octyl pyridinium cations based ionic liquids–carbon paste modified electrodes on the oxidation mechanism of dopamine. Ionic liquids formed by hexafluorophosphate anion and n-octyl pyridinium [R-OPy] + ; R = CH 3 , H, CF 3 , where ionic liquids containing CH 3 and CF 3 are new products, were synthesized and characterized. Modified carbon paste electrodes with these salts were characterized by electrochemical impedance spectroscopy and cyclic voltammetry. Electrochemical oxi-dation of dopamine was studied in PBS buffer solution at pH = 7.4. The influence of the ionic liquids in the oxidation of dopamine was studied by cyclic voltammetry and rotating disk electrode. The results show that typical carbon paste electrode presents an electrochemical/chemical mechanism; whereas [OPy]PF 6 and [CF 3 -OPy]PF 6 modified electrodes present an electrochemical/chemical/electrochemical mechanism. The experimental study is complemented with a theoretical analysis of substituent effects in terms of the molecular electrostatic potential, Mulliken population analysis and second order perturbation theory probed at the cation moiety of the IL. These indices consistently show an electron density accumulation at the ipso position of the pyridinium moiety of the IL that is in agreement with the electrochemical characterization.
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    ABSTRACT: The anthocyanin content of grape pomace from different Chilean grape varieties (Vitis vinifera var. Cabernet Sauvignon, Carménère and Syrah) from two vineyards (Misiones de Rengo and Miguel Torres) was determined by the differential pH method and the anthocyanin perfile was characterized by HPLC. In all chromatograms, a major peak corresponding to malvidin-3-O-glucoside was observed. Also, the in vitro antifungal activity of these extracts against mycelia growth of the phytopathogenic fungus Botrytis cinerea was evaluated. The anthocyanin containing extract from Cabernet Sauvignon grape pomace of Misiones de Rengo vineyard was the most active. The extract from the same variety form Miguel Torres vineyard did not inhibit mycelia growth of B. cinerea. In general, the other extracts were less active against the fungus.
    Journal of the Chilean Chemical Society 12/2012; 58(2):1725-1727. · 0.38 Impact Factor
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    ABSTRACT: Glassy carbon electrodes modified with conducting polymers of Ni(II), Zn(II) and metal free tetraruthenated porphyrin were evaluated for reduction and oxidation processes of S(IV) oxoanions in Na2SO3/water-ethanol at pH 1.0 and 3.5, showing electrocatalytic activity. A Ni(II) film was able to reduce the S(IV) oxoanions selectively in presence of high concentration of gallic acid. The Ni(II) film was also used as an amperometric sensor toward S(IV) oxoanions reduction in white wine samples showing a detection and quantification limit of 1.40 mg L−1 and 4.68 mg L−1, respectively. These results are promising for the electrochemical determination of S(IV) using conducting polymers from these macrocycles.
    Electroanalysis 08/2012; 24(8). · 2.82 Impact Factor
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    ABSTRACT: This work describes the formation of modified electrodes layer-by-layer assembly of a μ-{meso-5,10,15,20-tetra(pyridyl)porphyrin}tetrakis{bis(bipyridine)chloride ruthenium(II)} coordinated with Zn(II) and Mn(III) in its central cavity and an anionic polyoxotungstate [SiW12O40]4−. The bilayer formation was monitored using electrochemical and UV–vis techniques, following the oxidation process of the RuIII/II couple and the absorbance of the Soret band of porphyrin complexes respectively. It was possible to form 10 stable bilayers onto ITO surface. SEM studies were carried out finding that the morphology of the film depends on the metal center in the porphyrin. The thickness of these films was estimated as 0.603 μm for [Zn(II)TRP]4+/[SiW12O40]4− and 2.18 μm for [Mn(III)TRP]5+/[SiW12O40]4− modified electrodes respectively. Raman spectroscopy showed that new bands appeared for [Mn(III)TRP]5+/[SiW12O40]4− assembly confirming stronger interactions than only electrostatic forces. Kinetics parameters such as charge transfer coefficient, α, and heterogeneous electron transfer rate constant, ks were obtained for both electrodes. Using electrochemical and UV–vis data it was possible to estimate the energy levels involved in the charge transfer process through the films formed. Sensor properties of [Zn(II)TRP]4+/[SiW12O40]4− modified electrode toward chlorite oxidation was tested. The results show electrocatalytic activity, amperometric determination demonstrate a detection limit of 13.8 μM.
    Electrochimica Acta 01/2012; · 4.09 Impact Factor
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    ABSTRACT: In the present work, known concentration of sulfite aqueous solutions in the presence and absence of gallic acid was measured to corroborate the validity of modified Monier-Williams method. Free and bound-sulfite was estimated by differential pulse voltammetry. To our surprise, the modified Monier-Williams method (also known as aspiration method) showed to be very inaccurate for free-sulfite, although suitable for bound-sulfite determination. The differential pulse approach, using the standard addition method and a correction coefficient, proved to be swift, cheap, and very precise and accurate.
    The Scientific World Journal 01/2012; 2012:168148. · 1.73 Impact Factor
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    ABSTRACT: This work describes the preparation of modified electrodes with Poly-tetraruthenated porphyrin. Also, a detailed Raman and electrochemical characterization of these surfaces is shown. Glassy carbon electrodes were modified with Ni (II), Zn (II) and metal free polymeric film of tetrapyridylporphyrin coordinated to four [Ru(5-NO2-phen)2Cl]+ moieties.These modified electrodes are very stable in aqueous solutions, and were evaluated for the electrochemical reduction of nitrite ion at pH=5.9 in 0.1M NaClO4. When the solution contains 0.01M nitrite, linear sweep voltammetry results, show an enhancement in the current from −0,3V with the conducting polymers, compared to the bare electrode behavior. Analyses after controlled potential electrolysis experiments verify the production of hydrazine, hydroxylamine and ammonia. Hydroxylamine was the product of higher production among the three studied catalysts.The behavior of the modified electrodes allows predicting that the reduction process of nitrite takes place through reduced macrocycle ring. The electrocatalytic activity of the modified electrodes, measured as turn over frequency is dependent on the potential and the central ion in the cavity of the macrocycle. Finally, the modified electrode containing Ni2+ in the cavity of the macrocycle was used as an amperometric sensor toward nitrite detection. The results show a limit of detection of 9.37×10−6 M and a linear rage of concentration of 1.49×10−5 to 1.24×10−4 M.
    Electrochimica Acta 05/2011; 56(14):5230-5237. · 4.09 Impact Factor
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    ABSTRACT: The electro-oxidation of 2-mercaptoethanol by poly-Co-tetraaminophthalocyanine (p-Co-TAPc) and poly-metal-free-tetraaminophthalocyanine (p-H2TAPc), absorbed on electrode surfaces has been investigated by UV-visible spectroelectrochemistry and electrochemical techniques. In the case of p-CoTAPc, an irreversible oxidation wave is obtained by cyclic voitammetry, whereas p-H2PcTA practically does not show activity. The foot of the oxidation, as the open circuit potential measurements indicate that the responsible redox couple is Co(II)/Co(I). The p-CoTAPc modified-electrode loses its activity after a first potential cycle. UV-visible spectroelectrochemical measurements show a charge transfer band (metal to ligand) for the p-CoTAPc between Q and Soret bands when negative potentials are applied and Co(I) is obtained. The presence of 2-mercaptoethanol promotes the appearance of the charge transfer band at open circuit potential and retain this band even at potentials as positive as +0.2V where normally the Co center is in +2 oxidation state. The permanence of a stable charge transfer band indicates the formation of a stable charge-transfer adduct between Co(I) and the thiol. This adduct would be responsible for the loss of catalytic activity for p-CoTAPc after the first oxidation cycle.
    Journal of Coordination Chemistry. 03/2011; 54(3):183-191.
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    ABSTRACT: In contrast to the UV-photoinduced ligand photoionization of the flavonoid complexes of FeIII, redox reactions initiated in ligand-to-metal charge-transfer excited states were observed on irradiation of the quercetin (1) and rutin (2) complexes of CuII. Solutions of complexes with stoichiometries [CuIIL2] (L=quercetin, rutin) and [CuII2Ln] (n=1, L=quercetin; n=3, L=rutin) were flash-irradiated at 351 nm. Transient spectra observed in these experiments showed the formation of radical ligands corresponding to the one-electron oxidation of L and the reduction of CuII to CuI. The radical ligands remained coordinated to the CuI centers, and the substitution reactions replacing them by solvent occurred with lifetimes τ1 ms) of the quercetin and rutin radical's decay.
    Helvetica Chimica Acta 02/2011; 94(2):293 - 300. · 1.38 Impact Factor
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    ABSTRACT: The antifungal effect of three furyl compounds closely related to resveratrol, (E)-3,4,5-trimethoxy-β-(2-furyl)-styrene (1), (E)-4-methoxy-β-(2-furyl)-styrene (2) and (E)-3,5-dimethoxy-β-(2-furyl)-styrene (3) against Botrytis cinerea was analyzed. The inhibitory effect, at 100 µg ml(-1) of compounds 1, 2, 3 and resveratrol on conidia germination, was determined to be about 70%, while at the same concentration pterostilbene (a dimethoxyl derivative of resveratrol) produced complete inhibition. The title compounds were more fungitoxic towards in vitro mycelial growth than resveratrol and pterostilbene. Compound 3 was the most active and a potential explanation of this feature is given using density functional theory (DFT) calculations on the demethoxylation/demethylation process. Compound 3 was further evaluated for its effects on laccase production, oxygen consumption and membrane integrity of B. cinerea. An increase of the laccase activity was observed in the presence of compound 3 and, using Sytox Green nucleic acid stain, it was demonstrated that this compound altered B. cinerea membrane. Finally, compound 3 partially affected conidia respiration.
    PLoS ONE 01/2011; 6(10):e25421. · 3.53 Impact Factor
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    ABSTRACT: The fungotoxicity against Botrytis cinerea of a flavonoid isolated from Pseudognaphalium robustum was analyzed. Two absorption column chromatographies and one semipreparative thin layer chromatography were used to purify the active flavonoid. It was determined, by 1 H-NMR spectroscopy and co-elution with standards in HPLC, that this compound was 5,7-dihydroxy-3,8-dimethoxyflavone (gnaphaliin A). To determine the fungitoxicity of the purified compound, the effect on in vitro mycelial growth and conidial germination was studied. The compound concentration that reduced mycelial growth by 50% was 45.5 μg/mL. This compound also partially affected conidial germination of B. cinerea, reduced oxygen consumption by germinating conidia and affected the integrity of plasma membrane. Finally, using cyclic voltammetry, it was shown that the purified flavone had a pro-oxidant effect.
    Molecules. 01/2011; 16:3885-3895.
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    ABSTRACT: This paper describes the electrochemical reduction of nitrite ion in neutral aqueous solution mediated by tetraruthenated metalloporphyrins (Co(II), Ni(II) and Zn(II)) electrostatically assembled onto a Nafion film previously adsorbed on glassy carbon or ITO electrodes. Scanning electron microscope (SEM-EDX) and transmission electron microscopy (TEM) results have shown that on ITO electrodes the macrocycles forms multiple layers with a disordered stacking orientation over the Nafion film occupying hydrophobic and hydrophilic sites in the polyelectrolyte. Atomic force microscopy (AFM) results demonstrated that the Nafion film is 35nm thick and tetraruthenated metalloporphyrins layers 190nm thick presenting a thin but compacted morphology. Scanning electrochemical microscopy (SECM) images shows that the Co(II) tetraruthenated porphyrins/Nf/GC modified electrode is more electrochemically active than their Ni and Zn analogues.These modified electrodes are able to reduce nitrite at −660mV showing enhanced reduction current and a decrease in the required overpotential compared to bare glassy carbon electrode. Controlled potential electrolysis experiments verify the production of ammonia, hydrazine and hydroxylamine at potentials where reduction of solvent is plausible demonstrating some selectivity toward the nitrite ion. Rotating disc electrode voltammetry shows that the factor that governs the kinetics of nitrite reduction is the charge propagation in the film.
    Electrochimica Acta 01/2011; 56:8484. · 4.09 Impact Factor
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    ABSTRACT: This work describes electrocatalytic detection of S(IV) compounds in water-ethanol solutions under acidic conditions, on a glassy carbon electrode modified with Co(II) tetraruthenated porphyrin electrostatically assembled onto a Nafion film. The Ipc current shows a linear relationship with the concentration of S(IV) oxo-anions. Controlled potential electrolysis shows that thiosulfate was detected as reaction product. Rotating disk electrode and UV-visible spectroelectrochemistry experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film and the formation of an intermediary between Co center and S(IV) species. The reproducibility of the modification methodology presents a RSD of 4.1%. This work was supported by the program “Anillo Bicentenario de Ciencia y Tecnolog a CONICYT”ACTN824. K. C. and M. G. are grateful to CONICYT doctoral scholarships.
    Electroanalysis 01/2010; · 2.82 Impact Factor
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    ABSTRACT: The anthocyanin fractions were extracted from Cabernet Sauvignon red wine, skins of Vitis vinifera grapes and raspberry fruits (Rubus idaeus). In red wine extract, 16 anthocyanins were identified, malvidin-3-Oglucoside being the main anthocyanin, which comprised 53.6% of the total anthocyanin in grape extract. Raspberry extract contained mainly delphinidin-3-O-glucoside and cyanidin-3-O-glucoside. The antioxidant capacity of the extracts was assayed by electrochemical methods. Best resolution of the oxidation peaks for the extracts and diluted wine was obtained by pulse differential voltammetry. The wine diluted 20 presented values of P1 (443 mV) and P2 (676 mV) similar to those corresponding to wine extract, and to the anthocyanin malvidin-3-O-glucoside. The antioxidant capacity of anthocyanins in extracts of wine, grape skin and raspberry fruit was also determined by the Trolox equivalent antioxidant capacity (TEAC) method. The financial support of Programa Bicentenario en Ciencia y Tecnología, CONICYT-Banco Mundial, Proyecto Anillo ACT-24 is gratefully acknowledged.
    01/2010;
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    ABSTRACT: In this work, the modification of a glassy carbon electrode with tetraruthenated porphyrins electrostatically assembled onto a Nafion film, previously adsorbed on the electrode surface, is reported. This modified electrode was characterized by scanning electron microscopy–energydispersive X-ray, Raman spectroscopy, UV-Vis spectroelectrochemistry, and cyclic voltammetry. The Nafion film onto the glassy carbon electrode shows a smooth disposition; when the tetraruthenated porphyrin is incorporated on the Nafion film, the complex is adsorbed in a homogeneous way. The modified electrode catalyzes HSO3 − oxidation in water– ethanol solutions and shows an enhanced stability compared with the electrode modified with the dip coating method. Rotating disk electrode experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film. I/E curves show a Tafel slope of 120 mV/decade corresponding to a first electron-transfer reaction, depending on the potential, as the determining step. Spectroelectrochemical experiments demonstrated that Ru(II) is the active site for the electrocatalysis. This work was supported by the program “Anillo Bicentenario de Ciencia y Tecnología CONICYT” ACT No. 24. AECID and A/012666707 PCI projects. KC is grateful to CONICYT for the doctoral scholarship.
    Journal of Solid State Electrochemistry 01/2010; · 2.28 Impact Factor
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    ABSTRACT: The aim of this work is to study four types of modification of a glassy carbon electrode by Fe(III)-tetrakis(p-tetraaminophenyl)porphyrin and determine the influence of the method of immobilization of the complex on glassy carbon in electrocatalytic properties for the sulfite and hydrogensulfite oxidation in ethanol–water. The first modification was deposition of a drop of solution containing the porphyrin on a glassy carbon electrode and evaporation of the solvent (dry-drop method). The second method was immersion of the electrode at 54°C in a solution of dimethylformamide containing the porphyrin for 2 h. The third method consisted of the same heating treatment but after formation of a chemical bond of 4-aminopyridine on the glassy carbon surface, which acts as an axial ligand for the first layer of porphyrin. The fourth method involves electropolymerization of the porphyrin on the electrode surface. Important differences in stability, the potential where the oxidation wave begins and selectivity of the electrode to sulfite or hydrogensulfite were observed. The behavior of the polymer-modified electrode is different in water compared to ethanol–water.
    Journal of Coordination Chemistry 09/2009; 62(17):2782-2791. · 1.80 Impact Factor
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    ABSTRACT: A neutral fraction (PS-SI) (0.3g/L) with MW of 74kDa, which contained galactose, arabinose, mannose, and glucose in the molar ratio of 1.0:0.6:0.4:0.2 was obtained by treatment of the whole polysaccharide extracted from red wine with cetrimide, followed by gel permeation chromatography. Spectroscopic and methylation analyses indicated that PS-SI is a mixture of neutral polysaccharides, consisting mainly of beta (1-->3)-linked galactopyranosyl residues, with side chains of galactopyranosyl residues at positions O-6. Arabinofuranosyl residues linked alpha (1-->5), alpha-mannopyranosyl and glucosyl residues appear to be components of different polysaccharides. The in vitro antioxidant capacity of fractions of wine polysaccharide was studied by hydroxyl radical scavenging and ORAC assays. Fraction PS-SI presented the strongest effect on hydroxyl radicals (IC(50)=0.21).
    Carbohydrate research 04/2009; 344(9):1095-101. · 2.03 Impact Factor
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    ABSTRACT: A modified synthetic route for the complexes [Cu(II)5,7,12,14-tetramethyldinaphtho [b,i][1,4,8,11]tetraaza[14]annulene], [Cu(II)tmdnTAA], and [Cu(II) 5,7,12,14-tetramethyl-6,13-dichloro-dinaphtho[b,i][1,4,8,11]tetraaza[14]annulene], [Cu(II)dCltmdnTAA], is presented in this work. The electrochemical characterization of both complexes and their precursors, [bis(2,4-pentanedionato)copper(II)], [Cu(II)(acac)2] and [bis(3-chloro-2,4-pentanedionato)copper(II)], [Cu(II)(3-Cl-acac)2], respectively, under nitrogen and carbon dioxide is also presented. The voltammetric response of [Cu(II)(acac)2] and [Cu(II)(3-Cl-acac)2] are different compared to [Cu(II)tmdnTAA] and [Cu(II)dCltmdnTAA] under nitrogen. Precursors show the reduction of Cu(I) to Cu(0) and the tetraazadinaphtho[14]annulene complexes do not. The chlorine substituted complex has a lower reduction potential than the unsubstituted homologue under nitrogen atmosphere. However, the contrary response is obtained in the presence of carbon dioxide: the unsubstituted complex is more catalytic in terms of potential because the current discharge appears 270 mV shifted to the anodic region. These facts can be explained in terms of electronic and steric effects. The modified electrode obtained by oxidative electropolymerization of [Cu(II)tmdnTAA] over glassy carbon electrode presented a suitable amperometric response for the sulfite reduction in acidic medium (pH = 2.7). A linear correlation was observed for the catalytic current and sulfite concentration between 0.6–6.0 mM range.
    Journal of Coordination Chemistry 02/2008; 61(4):479-489. · 1.80 Impact Factor
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    ABSTRACT: 5,15-Bis(veratryl)porphyrin (1), 5,10,15-tris(veratryl)porphyrin (2), and 5,10,15,20-tetrakis(veratryl)porphyrin (3), C36H30N4O4, C44H38N4O6, and C52H46N4O8 were synthesized by an acid-catalyzed, one-pot reaction of meso-dipyrromethane, 3,4- di-OCH3-benzaldehyde (veratraldehyde), and trifluoroacetic acid (TFA). These three different products were obtained as a result of scrambling reactions. The molecular structures have been characterized by elemental analysis, ESI mass spectra, 1D and 2D NMR techniques (1H and 13C), and UV-visible spectroscopy.
    Synthetic Communications 01/2007; 37(12):2001-2009. · 1.06 Impact Factor
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    ABSTRACT: Reactions of photochemically or radiolytically generated radicals with tetrakis(x-aminophenyl)porphyrin, tapp2−, initiate the polymerization of the porphyrin complexes Mtapp, where M=Ni or Zn. In the photochemical process, the porphyrin-centered excited state of Mtapp reacts with the ground state to generate oxidized and reduced radical species. The cationic radical, M(tapp+), appears to be the initiator of the porphyrin polymerization. An electron transfer reaction between the excited state of Mtapp and a Co(III) complex generates also the cation radical and initiates the polymerization process. Pulse radiolytically generated Cl2- and OH radicals were also able to initiate the polymerization of the porphyrin complexes.
    Inorganica Chimica Acta - INORG CHIM ACTA. 01/2006; 359(7):2281-2284.

Publication Stats

84 Citations
67.32 Total Impact Points

Institutions

  • 1998–2014
    • University of Santiago, Chile
      • • Departamento de Ingeniería Química
      • • Departamento de Química de los Materiales
      • • Facultad de Química y Biología
      CiudadSantiago, Santiago, Chile
  • 1992
    • Universidade Federal de São Carlos
      • Departamento de Química (DQ)
      São Carlos, Estado de Sao Paulo, Brazil