Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 25
Filtrar
Más filtros










Intervalo de año de publicación
1.
Talanta ; 223(Pt 2): 121702, 2021 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-33298256

RESUMEN

A electrochemical biosensor for As(III) determination has been developed by immobilization of the Alcaligenis faecalis bacteria on gold nanoparticle-modified screen-printed carbon electrode (AuNPs-SPCE). The detection of As(III) is due to the catalytic activity of arsenite oxidase enzyme which oxidizes As(III) to As(V) producing an analytical signal. To enhance the performance of the biosensor, was optimized the amount of bacteria, amount of glutaraldehyde and incubation time applied in the preparation of the electrode, in addition to the effect of pH and applied potential. The analytical application was carried out applying 300 mV (pH = 7) obtaining a LOD of 6.61 µmol L-1 (R = 0.9975) and 700 mV (pH = 12) obtaining a LOD of 1.84 µmol L-1 (R = 0.9983). AF/AuNPs-SPCE was applied to the determination of total arsenic in Loa river water samples after reduction, with satisfactory results.


Asunto(s)
Alcaligenes faecalis , Técnicas Biosensibles , Nanopartículas del Metal , Carbono , Técnicas Electroquímicas , Electrodos , Oro
2.
J Pharm Anal ; 9(1): 62-69, 2019 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-30740259

RESUMEN

This study presents for the first time a new composite of carbon paste (CP), single-walled carbon nanotubes (SWCNTs) and Nd2O3 (NdOX). This versatile composite (NdOX-SWCNT/CPE) was applied to the oxidation of paracetamol (PCM). The newly formed surface was characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The results showed greater conductivity and a higher surface area for the composite than those of the carbon paste alone. Moreover, the anodic peak currents for PCM increased from 1.6 to 3.6 µA with CPE and NdOX-SWCNT/CPE, indicating an increase of nearly 51.0% for the anodic peak current. On the other hand, the anodic peak potentials shifted from 0.67 to 0.57 V. The detection limits were 0.05 µmol/L with NdOX-SWCNT/CPE and 0.50 µmol/L with SWCNT/CPE. The relative standard deviations (RSDs) were 1.5% (n = 7). The accuracy and interference of the methods were evaluated with a urine chemistry control spiked with known quantities of PCM, uric acid, dopamine, ascorbic acid, caffeine, acetylsalicylic acid, tartrazine, sunset yellow, allure red, rutin, morin and metal ions. Finally, the novelty and usefulness of the composite were evaluated to quantify PCM in pharmaceutical dosage forms such as tablets, powders and syrups for children.

3.
Anal Chim Acta ; 1048: 22-30, 2019 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-30598153

RESUMEN

The development of a methodology for the determination of Se(IV) concentration via cathodic stripping voltammetry is described in this work. The methodology is based on the formation of copper selenide (Cu2Se), whose reduction signal at -0.60 V has been used as an analytical response to quantify the Se(IV) concentration in solution. The novelty of our methodology is the study of this system in the presence of a ligand such as ammonium diethyl dithiophosphate (ADTTP), which forms complexes with Cu(II) and Se(IV). The results showed that the presence of ADTTP plays an important role, increasing the sensitivity of the determination by almost a factor of two compared with the methodology in the absence of the ligand. The optimized conditions were pH 1.6 (phosphoric acid, 2.0 × 10-2 mol L-1), CCu(II) = 1.5 mg L-1, CADTTP = 2.0 µmol L-1, Eacc = -0.40 V and tacc = 45 s. The detection and the quantification limits obtained were 0.065 and 0.21 µg L-1, respectively, and linearity was maintained up to 4.0 µg L-1 of Se(IV). The sensitivity was 10.26 nA L µg-1. On the other hand, the relative standard deviation for 15 replicate measurements at 1.0 µg L-1 of Se(IV) was 1.6%. The usefulness of the method was evaluated by determining Se(IV) in two certified reference materials (TMDW and TM-28.4) with relative errors of less than 2.0%. The proposed method was successfully applied to the determination of Se(IV) in spiked tap water and in a liquid pharmaceutical formulation with satisfactory results. The developed methodology presents a low detection limit, good repeatability, selectivity and linear range. Furthermore, the sensibility of the method was achieved by applying a short accumulation time (45 s).


Asunto(s)
Cobre/química , Técnicas Electroquímicas/métodos , Organotiofosfatos/química , Selenio/análisis , Complejos de Coordinación/síntesis química , Complejos de Coordinación/química , Concentración de Iones de Hidrógeno , Ligandos , Límite de Detección , Selenio/química
4.
Artículo en Chino | WPRIM (Pacífico Occidental) | ID: wpr-744109

RESUMEN

This study presents for the first time a new composite of carbon paste (CP), single-walled carbon na-notubes (SWCNTs) and Nd2O3 (NdOX). This versatile composite (NdOX-SWCNT/CPE) was applied to the oxidation of paracetamol (PCM). The newly formed surface was characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The re-sults showed greater conductivity and a higher surface area for the composite than those of the carbon paste alone. Moreover, the anodic peak currents for PCM increased from 1.6 to 3.6 mA with CPE and NdOX-SWCNT/CPE, indicating an increase of nearly 51.0% for the anodic peak current. On the other hand, the anodic peak potentials shifted from 0.67 to 0.57 V. The detection limits were 0.05 mmol/L with NdOX-SWCNT/CPE and 0.50 mmol/L with SWCNT/CPE. The relative standard deviations (RSDs) were 1.5%(n =7). The accuracy and interference of the methods were evaluated with a urine chemistry control spiked with known quantities of PCM, uric acid, dopamine, ascorbic acid, caffeine, acetylsalicylic acid, tartrazine, sunset yellow, allure red, rutin, morin and metal ions. Finally, the novelty and usefulness of the composite were evaluated to quantify PCM in pharmaceutical dosage forms such as tablets, powders and syrups for children.

5.
Sensors (Basel) ; 18(9)2018 Sep 04.
Artículo en Inglés | MEDLINE | ID: mdl-30181437

RESUMEN

This work reports the development of a composite of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BP4) and chitosan (CS) described in previous reports through a new method using cyclic voltammetry with 10 cycles at a scan rate of 50.0 mV s-1. This method is different from usual methods such as casting, deposition, and constant potential, and it allows the development of an electroactive surface toward the oxidation of rutin by stripping voltammetry applied to the detection in tropical fruits such as orange, lemon, and agraz (Vaccinium meridionale Swartz), with results similar to those reported in previous studies. In addition, the surface was characterized by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and Raman spectroscopy. The limit of detection was 0.07 µmol L-1 and the relative standard deviation (RSD) of 10 measurements using the same modified electrode was 0.86%. Moreover, the stability of the sensor was studied for six days using the same modified electrode, where the variation of the signal using a known concentration of rutin (RT) was found to be less than 5.0%. The method was validated using a urine chemistry control spiked with known amounts of RT and possible interference was studied using ten substances including organic and biological compounds, metal ions, and dyes. The results obtained in this study demonstrated that this electrodeveloped composite was sensitive, selective, and stable.


Asunto(s)
Carbono , Quitosano/química , Técnicas Electroquímicas , Frutas/química , Líquidos Iónicos/química , Rutina/análisis , Electrodos , Clima Tropical
6.
Talanta ; 187: 259-264, 2018 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-29853044

RESUMEN

An adsorptive stripping voltammetric method for the determination of As(III) and Astotal in water samples using a carrageenan modified carbon paste electrode is presented for the first time (CAR-CPE). The modified electrode was prepared in different ways: by adding CAR in solid form or as a hydrogel together with graphite and paraffin, as well as adsorbing CAR by applying a potential on an unmodified carbon paste electrode. The best results were obtained when CAR was incorporated as hydrogel (HCAR-CPE). The selection of the ratio amounts for electrode preparation was carried out applying a multivariate experimental design. Variables like amount of graphite (U1), HCAR (U2) and paraffin (U3) were optimized using a (2K+2K+C) model. The results showed that the amount of HCAR was the most significant factor, and the adequate U1:U2:U3 ratio to prepare the electrode was: 493 mg of graphite, 214 µL of paraffin and 134 µL of carrageenan as gel. The optimum parameters for the determination of As(III) were pH = 3.25 (0.01 mol L-1 H3PO4/H2PO4- solution); Eacc = -0.50 V and tacc = 30 s. The electrode presents good linear behavior concentration range from 0.50 to 6.70 µg L-1, with a limit of detection of 0.22 µg L-1. The relative standard deviation was 5.0% at the 1.5 µg L-1 As(III) level (n = 16). The method was validated by quantifying As(III) in spiked tap water from laboratory (RE: 3.0%), and it was applied for the determination of Astotal in water samples from the Loa River (North of Chile) prior reduction of As(V) with Na2S2O3 solution, obtaining 814.00 ±â€¯0.03 µg L-1. The results of the proposed method were compared with those obtained by adsorptive stripping voltammetry with HMDE and by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) techniques.

7.
RSC Adv ; 8(55): 31261-31266, 2018 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-35548216

RESUMEN

A new probe (E)-7-(diethylamino)-3-(3-(thiophen-2-yl)acryloyl)-2H-chromen-2-one (ChC16) was synthesized and studied as a turn-on fluorescent probe, based on a Michael addition mechanism for sensing SO2 derivatives, which is favored in the presence of cationic micellar media such as cetylpyridinium bromide (CPB). The probe showed high selectivity and sensitivity toward bisulfite over other anions and biothiols, including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), with a detection limit of 240 nM. Moreover, the probe showed great potential for its practical application in the detection of bisulfite in real samples, such as dry white wine, and in bioimaging.

8.
Sensors (Basel) ; 17(11)2017 Nov 18.
Artículo en Inglés | MEDLINE | ID: mdl-29156561

RESUMEN

A fast, sensitive, and selective method for the simultaneous determination of one pair of synthetic colorants commonly found mixed in food products, Amaranth (AM) and Tartrazine (TZ), based on their adsorption and oxidation on a screen-printed electrode (SPE) is presented. The variation of peak current with pH, supporting electrolyte, adsorption time, and adsorption potential were optimized using square wave adsorptive voltammetry. The optimal conditions were found to be: pH 3.2 (PBS), Eads 0.00 V, and tads 30 s. Under these conditions, the AM and TZ signals were observed at 0.56 and 0.74 V, respectively. A linear response were found over the 0.15 to 1.20 µmol L-1 and 0.15 to 0.80 µmol L-1 concentrations, with detection limits (3σ/slope) of 26 and 70 nmol L-1 for AM and TZ, respectively. Reproducibility for 17.7 µmol L-1 AM and TZ solutions were 2.5 and 3.0% (n = 7), respectively, using three different electrodes. The method was validated by determining AM and TZ in spiked tap water and unflavored gelatin spiked with AM and TZ. Because a beverage containing both AM and TZ was not found, the method was applied to the determination of AM in a kola soft drink and TZ in an orange jelly and a soft drink powder.

9.
Food Chem ; 212: 807-13, 2016 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-27374598

RESUMEN

An efficient, fast and sensitive method for the determination of Sudan I (SI) in drinks containing Sunset yellow (Sy) is developed and validated using an adsorptive stripping voltammetric procedure. Sy is currently added to a large number of foods; however during their synthesis SI may be produced. The determination is based on adsorption of Sy and SI onto HMDE and later reduction of the azo group at -0.71 and -0.82V, respectively. Using the best set of the experimental conditions (pH 12.3; Eads: -0.40V) for the determination of SI in Sy, a linear response for SI in the concentration range 0.5-27.2µgL(-1) was found, with a detection limit of 1.5µgL(-1) in a tads of only 30s. The method was applied to the determination of SI in commercial drinks with satisfactory results. The presence of SI was confirmed by mass spectrometry.


Asunto(s)
Compuestos Azo/metabolismo , Bebidas/análisis , Colorantes/análisis , Electroquímica/instrumentación , Naftoles/análisis , Adsorción , Límite de Detección
10.
Talanta ; 155: 21-7, 2016 08 01.
Artículo en Inglés | MEDLINE | ID: mdl-27216652

RESUMEN

The determination of Sb(III) on an ex-situ bismuth screen-printed carbon electrode (ex-situ BiSPCE) by means of adsorptive stripping voltammetry (AdSV) using quercetin-5'-sulfonic acid as chelating agent was optimized. The effect of different experimental parameters such pH, ligand concentration (CQSA), accumulation potential (Eacc) and accumulation time (tacc) were studied to obtain a wide linear range, the highest sensitivity and the lowest detection limit. Ex-situ BiSPCE was analytically compared with a sputtered bismuth screen-printed electrode (BispSPE) under optimal conditions. The obtained analytical parameters suggest that ex-situ BiSPCE behaves much better than BispSPE and the first was selected for this study. Optimal parameters were pH=4.6; CQSA=10.0 to 20.0×10(-6)molL(-1); Eacc=-0.5V and tacc=60s. Peak area is proportional to Sb(III) concentration up to 100.0µgL(-1) (tacc 60s) and 45.0µgL(-1) (tacc 120s) range, with detection limits of 1.2µgL(-)(1) (tacc 60s) and 0.8µgL(-1) (tacc 120s). The relative standard deviation for a Sb(III) solution (20.0µgL(-1)) was 3.9% for ten successive assays. Thus, the effect of various interfering metal ions was studied and the methodology was validated using a spiked groundwater reference material with very satisfactory results.

11.
Molecules ; 19(1): 726-39, 2014 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-24406784

RESUMEN

The synthesis of a variety of 1-aryl-7-phenylaminoisoquinolinequinones from 1,4-benzoquinone and arylaldehydes via the respective 1-arylisoquinolinequinones is reported. The cyclic voltammograms of the new compounds exhibit two one-electron reduction waves to the corresponding radical-anion and dianion and two quasi-reversible oxidation peaks. The half-wave potential values (EI½) of the members of the series have proven sensitive to the electron-donor effect of the aryl group (phenyl, 2-thienyl, 2-furyl) at the 1-position as well as to the phenylamino groups (anilino, p-anisidino) at the 7-position. The antiproliferative activity of the new compounds was evaluated in vitro using the MTT colorimetric method against one normal cell line (MRC-5 lung fibroblasts) and two human cancer cell lines: AGS human gastric adenocarcinoma and HL-60 human promyelocytic leukemia cells in 72-h drug exposure assays. Among the series, compounds 5a, 5b, 5g, 5h, 6a and 6d exhibited interesting antiproliferative activities against human gastric adenocarcinoma. The 1-arylisoquinolinequinone 6a was found to be the most promising active compound against the tested cancer cell lines in terms of IC50 values (1.19; 1.24 µM) and selectivity index (IS: 3.08; 2.96), respect to the anti-cancer agent etoposide used as reference (IS: 0.57; 0.14).


Asunto(s)
Antineoplásicos/síntesis química , Antineoplásicos/farmacología , Isoquinolinas/química , Quinonas/síntesis química , Quinonas/farmacología , Línea Celular Tumoral , Proliferación Celular/efectos de los fármacos , Humanos , Concentración 50 Inhibidora , Relación Estructura-Actividad
12.
Molecules ; 18(1): 721-34, 2013 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-23299551

RESUMEN

A variety of phenylaminoisoquinolinequinones were synthesized and tested for their antiproliferative activity against three human-tumor derived cancer cell lines. The new aminoquinones were prepared from 4-methoxycarbonyl-3-methylisoquinoline-5,8-quinone (1) via acid-induced amination and bromination reactions. Remarkable differences in antiproliferative activity were observed depending upon the location and donor capacity of the substituted phenylamino group at the quinone nucleus. The effect of the substituents on the biological activity is discussed in terms of the donor-acceptor interactions which were evaluated through the redox properties of the aminoquinones.


Asunto(s)
Compuestos de Anilina/farmacología , Antineoplásicos/farmacología , Quinolonas/farmacología , Aminación , Compuestos de Anilina/síntesis química , Antineoplásicos/síntesis química , Benzaldehídos/química , Línea Celular Tumoral , Proliferación Celular/efectos de los fármacos , Crotonatos/química , Ensayos de Selección de Medicamentos Antitumorales , Halogenación , Humanos , Concentración 50 Inhibidora , Isoquinolinas/química , Oxidación-Reducción , Quinolonas/síntesis química , Relación Estructura-Actividad
13.
Talanta ; 99: 119-24, 2012 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-22967530

RESUMEN

An adsorptive stripping voltammetric (AdSV) method is presented for the simultaneous determination of Pb(II) and Cd(II) at trace levels in natural waters, based on metal complexation with pyrogallol red (PR) and subsequent adsorptive deposition on a Nafion-mercury coated glassy carbon electrode (NHgFE). Pyrogallol red forms complexes with a metal:ligand stoichiometry of 1:1 with Pb(II) and of 1:2 with Cd(II). Optimal analytical conditions were pH 4.0 (acetate buffer); C(PR)=2.8 µmol L(-1); E(ads)=-0.40 V vs. Ag/AgCl; t(ads)=100 s. The linear calibration curves ranged from 1.0 µg L(-1) to 16.0 µg L(-1) for Pb(II) and from 1.0 µg L(-1) to 13.0 µg L(-1) for Cd(II). The detection limits (S/N=3) were 0.05 µg L(-1) for Pb(II) and 0.01 µg L(-1) for Cd(II). The relative standard deviation was 1.0% and 2.0% (n=7), respectively, for a solution containing 5.0 µg L(-1) Pb(II) and Cd(II). The method was validated by determining Pb(II) and Cd(II) in certified reference waste water (SPS-WW1). Finally, the method was applied to the determination of Pb(II) and Cd(II) in commercial mineral water samples after UV digestion.


Asunto(s)
Cadmio/análisis , Electroquímica/métodos , Polímeros de Fluorocarbono/química , Plomo/análisis , Mercurio/química , Pirogalol/análogos & derivados , Contaminantes Químicos del Agua/análisis , Adsorción , Cadmio/química , Carbono/química , Electroquímica/instrumentación , Electrodos , Vidrio/química , Concentración de Iones de Hidrógeno , Plomo/química , Pirogalol/química , Reproducibilidad de los Resultados , Contaminantes Químicos del Agua/química
14.
Talanta ; 85(5): 2316-9, 2011 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-21962648

RESUMEN

A sensitive procedure is presented for the voltammetric determination of nickel. The procedure involves an adsorptive accumulation of nickel 1-nitroso-2-napthol (NN) complex on a bismuth film electrode prepared ex situ by electrodeposition. The most suitable operating conditions and parameters such as pH, ligand concentration (C(NN)), adsorptive potential (E(ads)), adsorptive time (t(ads)), scan rate and others were selected and the determination of nickel in aqueous solutions using the standard addition method was possible. The adsorbed Ni-NN complex gives a well defined cathodic stripping peak current at -0.70 V, which was used for the determination of nickel in the concentration range of 10.0-70.0 µg L(-1) (pH 7.5; C(NN) 6.5 µmol L(-1); E(ads) -0.30 V; t(ads) 60s) with a detection limit of 0.1 µg L(-1). The relative standard deviation for a solution containing 10.0 µg L(-1) of Ni(II) was 3.5% (n=4). The proposed method was validated determining Ni(II) in certified reference waste water (SPS-WW1) and Certified Reference Water for Trace Elements (TMDA 51.3) with satisfactory results. Then lake water samples were analyzed.

15.
Talanta ; 80(1): 184-8, 2009 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-19782211

RESUMEN

A simple and sensitive electroanalytical method is developed for the determination of lead by adsorptive stripping voltammetry (AdSV) in the presence of morin-5'-sulfonic acid (MSA) and sodium dodecyl sulfate (SDS). The Pb-MSA complex accumulates on the surface of a hanging mercury drop electrode (HMDE) and peak current is measured by square wave voltammetry (SWV). The complex is reduced at -0.48 V and peak current increases when low concentrations of SDS are added to the sample solution. The experimental variables pH, MSA concentration (C(MSA)); accumulation time (t(acc)); accumulation potential (E(acc)), and SDS concentration (C(SDS)), as well as potential interferences, are investigated. Under the optimized conditions (pH 3.2; C(MSA): 0.5 micromol L(-1); t(acc): 60s; E(acc): -0.35 V, and C(SDS): 20 micromol L(-1)), peak current is proportional to the concentration of Pb(II) over the 0.1-32.0 microg L(-1) range, with a detection limit of 0.04 microg L(-1). The relative standard deviation for a solution containing 5.0 microg L(-1) of Pb(II) solution was 1.5% for seven successive assays. The method was validated by determining Pb(II) in synthetic sea water (ASTM D665) spiked with ICP multi-element standard solution and in certified reference water (GBW08607). Finally, the method was successfully applied to the determination of Pb(II) in tap water and sea water after UV digestion.


Asunto(s)
Electroquímica/métodos , Plomo/análisis , Dodecil Sulfato de Sodio/química , Ácidos Sulfónicos/química , Adsorción , Electroquímica/instrumentación , Flavonoides/química , Concentración de Iones de Hidrógeno , Plomo/química , Reproducibilidad de los Resultados , Agua de Mar/análisis , Agua de Mar/química , Abastecimiento de Agua/análisis
16.
Bioorg Med Chem ; 17(7): 2894-901, 2009 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-19269832

RESUMEN

A variety of 7-aminoisoquinoline-5,8-quinone derivatives were prepared from 2,5-dihydroxyacetophenone, methyl aminocrotonate, and the corresponding amines, through a highly efficient three-step sequence. The members of this series were tested on normal human fibroblasts and on a panel of three human cancer cell lines and their redox properties were determined by cyclic voltammetry in acetonitrile. Both the cytotoxicity and antitumor activity of 7-phenylaminoisoquinoline-5,8-quinone derivatives showed correlation with their half wave potentials and lipophilicities.


Asunto(s)
Antineoplásicos/toxicidad , Quinonas/toxicidad , Antineoplásicos/síntesis química , Antineoplásicos/química , Línea Celular Tumoral , Ensayos de Selección de Medicamentos Antitumorales , Fibroblastos/efectos de los fármacos , Humanos , Quinonas/síntesis química , Quinonas/química
17.
Talanta ; 75(4): 973-7, 2008 May 30.
Artículo en Inglés | MEDLINE | ID: mdl-18585171

RESUMEN

An adsorptive stripping voltammetry method for the determination of iron has been developed. The procedure is based on the adsorptive collection of a complex of iron with 1-(2-piridylazo)-2-naphthol (PAN) on a bismuth-coated glassy carbon electrode (BiFE). Factors affecting the stripping performance, such as pH, PAN concentration (C(PAN)), potential, accumulation time (E(ads), t(ads)), and interference by other ions were also studied. The optimum conditions were obtained in a 0.1 mol L(-1) acetate buffer at pH 4.0, C(PAN) 5.0 micromol L(-1), t(ads) 60 s, E(ads) -400 mV, pulse height 4.0 mV, pulse amplitude 25 mV, and frequency 15 Hz. The detection limit was found to be 0.1 microg L(-1) when a t(ads) of 60 s was used, and the linear range was from 0.4 to 60.0 microg L(-1). The proposed procedure was validated by determining of Fe(III) in CRM-MFD, QCS-19 and CRM-SW certified reference materials and applied in seawater samples with satisfactory results.

18.
Neurotoxicology ; 28(3): 445-9, 2007 May.
Artículo en Inglés | MEDLINE | ID: mdl-17382398

RESUMEN

Successful trials with 5-chloro-7-iodo-8-hydroxyquinoline (clioquinol, CQ) for Alzheimer's disease treatment prompted renewed interest in assessing whether its therapeutic action is related to the coordination of neurotoxic trace metals, such as Cu(II) and Zn(II). We now report conditional stability constants (K(C')) for CQ Cu(II) and Zn(II) complexes measured in a biological buffer containing Ca(II) and Mg(II) ions. UV-vis spectroscopy and polarography evidenced a 1:2 stoichiometry of Cu(II) and Zn(II) CQ complexes; the K(C')s calculated were: Cu(CQ)(2) 1.2x10(10), and Zn(CQ)(2) 7.0x10(8)M(-2); the CQ affinity for Cu(II) is at least an order of magnitude higher than for Zn(II). To test the possible functional relevance of the Cu(II) CQ complexes in the brain, we bioassayed free Cu(II) concentration by the metal-induced inhibition of ATP-gated currents of the P2X(4) receptor, a predominant brain P2X receptor. CQ reduced concentration-dependently the Cu(II) inhibition of the ATP-gated currents. In view that the stability constant of CQ for Zn(II) is similar to that of Abeta-amyloid for Zn(II), and the fact that CQ may form complexes with Cu(II), even in the presence of competing ions, the present results highlight that the formation of Cu(II) CQ complexes in the brain may act by diminishing free Cu(II) concentrations modifying thereby brain excitability, or favoring the degradation of beta-amyloid plaques or huntingtin, rather than through a specific effect of CQ itself.


Asunto(s)
Enfermedad de Alzheimer/tratamiento farmacológico , Clioquinol/química , Clioquinol/uso terapéutico , Cobre/química , Enfermedad de Huntington/tratamiento farmacológico , Zinc/química , Adenosina Trifosfato/fisiología , Algoritmos , Animales , Fenómenos Químicos , Química Física , Cobre/metabolismo , Electrofisiología , Humanos , Activación del Canal Iónico/efectos de los fármacos , Microinyecciones , Oocitos/fisiología , Polarografía , Receptores Purinérgicos P2/genética , Receptores Purinérgicos P2X4 , Soluciones , Espectrofotometría Ultravioleta , Xenopus laevis
19.
Talanta ; 73(3): 546-52, 2007 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-19073069

RESUMEN

A fast, sensitive and selective method for the determination of aluminium based on the reaction of the metal with pyrogallol red (PR) in the presence of tetrabutylammonium tetrafluoroborate (TBATFB) to form an Al(PR)(3)x9TBATFB complex which is adsorbed on the mercury electrode is presented. Under these conditions complexation of aluminium is rapid and no waiting period or heating of the sample is required. The reduction current of the accumulated complex is measured by scanning the potential in the cathodic direction. The variation of peak current with pH, adsorption time, adsorption potential, ligand and quaternary ammonium salt concentration, and some instrumental parameters, such as stirring rate in the accumulation stage, and step amplitude, pulse amplitude and step duration while obtaining the square wave voltamperograms were optimized. The best experimental parameters were pH 8.5, (NH(4)Ac-NH(3) buffer), C(PR)=25mumolL(-1), C(TBATFB) over 75mumolL(-1), t(ads)=60s, and E(ads)=-0.60V versus Ag/AgCl. A linear response is observed over the 0.0-30.0mugL(-1) concentration range, with a detection limit of 1.0mugL(-1). Reproducibility for 9.0mugL(-1) aluminium solution was 2.3% (n=6). Synthetic sea water and sea water reference material CRM-SW were used for validation measurements. Aluminium in urine samples of a volunteer who ingested 800mg of Al(OH)(3) was analyzed.

20.
Anal Sci ; 22(9): 1197-200, 2006 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-16966809

RESUMEN

The objective of this study was to determine the complexing capacity of four types of powdered commercial milks with copper(II) using square wave adsorptive stripping voltammetry. Two were types of cow milk adapted for babies under one year (A and B), one was soymilk (C) and the other was normal milk (D). Milk solutions were prepared following the instructions shown on the milk container, and they were mixed with a pepsin solution simulating a baby's stomach conditions (pepsin and salts concentration, pH and temperature). Complexing capacity was determined by titrating milk samples with aliquots of a standard copper solution until the peak current due to solvated or free copper ions was increasing. Assuming a 1:1 copper-milk complex, the apparent stability constant was found using the pseudopolarogram method. The log K'(Cu-milk) values were 4.9, 5.0, 3.0 and 5.1 for A, B, C and D types of milk, respectively. Voltammograms of the milk solution as a function of copper added show that the binding properties of the four types of powdered milk studied were different and that saturation of the four types, occurs at different copper concentrations. Concentrations obtained were: 4.9, 5.8, 1.1 and 10.1 mM for A, B, C and D types, respectively. The best complexing agent was the solution prepared with powdered milk D and the worst was that of C. This is important for the bioavailability of this element as a micronutrient.


Asunto(s)
Quelantes/farmacología , Cobre/metabolismo , Fórmulas Infantiles , Estómago/fisiología , Animales , Alimentación con Biberón , Quelantes/análisis , Cobre/análisis , Relación Dosis-Respuesta a Droga , Electroquímica/métodos , Humanos , Concentración de Iones de Hidrógeno , Recién Nacido , Leche , Modelos Biológicos , Ciencias de la Nutrición , Leche de Soja , Estómago/efectos de los fármacos , Temperatura
SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA
...