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Redalyc.Ternary Complex Formation Between Vanadium(III), 8 Avances en Química ISSN: 1856-5301 [email protected] Universidad de los Andes Venezuela Roque, Erika; Araujo, Mary Lorena; Martínez, José Daniel; Brito, Felipe; Hernández, Lino; Del Carpio, Edgar; Lubes, Vito Ternary Complex Formation between Vanadium(III), 8-Hydroxiquinoline and Small Blood Serum Bioligands Avances en Química, vol. 10, núm. 3, 2015, pp. 143-148 Universidad de los Andes Mérida, Venezuela Available in: http://www.redalyc.org/articulo.oa?id=93343694004 How to cite Complete issue Scientific Information System More information about this article Network of Scientific Journals from Latin America, the Caribbean, Spain and Portugal Journal's homepage in redalyc.org Non-profit academic project, developed under the open access initiative www.saber.ula.v e/avancesenquimica 143 Avances en Química, 10(3 ), 1 4 3 - 14 8 (2015) Nota técnica Ternary Complex Formation between Vanadium(III), 8 - Hydroxiquinoline and Small Blood Serum Bioligands Erika Roque 1 , Mary Lorena Araujo 1* , José Daniel Martínez 1 , Felipe Brito 1 , Lino Hernández 2 , Edgar Del Carpio 2 and Vito Lubes 2 1) Centro de Equilibrios en Solución. Escuela de Química. Facultad de Ciencias. Universidad Central de Venezuela (UCV). Caracas – Venezuela. 2 2) Departamento de Química. Universidad Simón Bolívar (USB). Apartado 89000. Caracas 1080 A. Venezuela. (*) [email protected] Recibido : 14 / 0 9 /20 1 5 Revisado : 16 / 1 2 /20 1 5 Aceptado : 3 0 /1 2 /20 1 5 -- -------- ------------------ - ----------------------------------------------------------------------------------- -- - Resumen A fin de evaluar el papel d e los bioligandos de bajo peso molecular en el suero sanguíneo con el vanadio, se realizó un estudio de las interacciones de los complejos formados en el sistema de Vanadio(III)/8 - Hidroxiquinolina (H8HQ) con diversos componentes del suero de la sangu í neo, como el ácido láctico (HLac), ácido oxálico (H 2 Ox), ácido cítrico (H 3 Cit) y ácido fosfórico (H 3 PO 4 ). La especiación de los sistemas ternarios fue estudiada por potenciometría - pH a 25 °C empleando una fuerza iónica I = 3,0 mol.dm - 3 KCl. Palabras claves : com plejos de Vanadi o (III); 8 - H idroxi quinolina (H8HQ); estudios potenciométricos ; e specia ción ; c omplejos ternarios . Abstract In order to assess the role of the low molecular mass bioligands of blood serum in vanadium binding, a study was made of the interactio ns of the complexes formed in the Vanadium (III) /8 - Hydroxyquinoline (H8HQ) system with various low molecular mass constituents of blood serum, such as lactic acid (HLac), oxalic acid (H 2 Ox), citric acid (H 3 Cit) and phosphoric acid (H 3 PO 4 ). The speciation o f the ternary systems was studied by pH - potentiometry at 25 °C using an ionic strength I = 3.0 mol.dm - 3 KCl. Keywords : Vanadium(III) complexes; 8 - Hydroxyquinoline; potentiometric studies; speciation; ternary complexes. Introduc tio n binding molecules present in extracellular or intracellular Vanadium is a trace bi oelement that plays an important role biological fluids. These latter ligands may partially or com - in several metabolic and mitogenic processes. For deeper pletely displace the origin al vanadium carrier molecules from understanding of the biological role of vanadium it is the coordination sphere of the metal. Accordingly, ternary necessary to do studies of model compounds. The coordina - complex formation should be taken into account in a tion chemistry of the vanadium(III) compounds has been speciation description of these complexes in biological fluids. investigated far less than the corresponding chemistry of Such ternary complexes might be of great impor tance in the absorption and transport process of the v anadium complexes vanadium(IV) and vanadium(V). Complex compounds of 3 vanadium(III), however, can play important role in bio - and even in their physiological activity . chemical redox processes. In addition, there are organisms The study of the vanadium(III) speciation has been limited, such as ascidians in which the principal oxidation state of because the easy oxidation of the vanadium(III) and the high 1 vanadium is +3 . tendency to the hydr olysis of this metal ion 4 .Until know, there The trismaltolato - vanadium(III) complex has been studied are no reports on the spec iation of ternary v anadium(III)/ 8 - and its insulin - mimetic activity demonstrated 2 , being this the h ydroxyquinoline complexes with Lactic acid (HLac) , o xalic first report on the insulin - mimetic activity of some acid (H 2 Ox), phosphoric acid (H 3 PO 4 ) and c itric acid 5,6 vanadium(III) complex. (H 3 Cit) . The idea is that after oral administration of these complexes, In this work we report the results on mixed ligand complex they may encounter many other potential vanadium(III) formation in the V ( III ) – 8 - Hydroxyquinoline – ligands B 144 E Roque, ML Araujo, JD Martínez, F Brito, L Hernández, E Del Carpio, V Lubes / Avances en Química 1 0( 3 ), 1 4 3 - 14 8 (2015 ) systems, where ligands B were the most important low which takes into account the liquid junction potential 10 . The molecular mass ( l.m.m. ) V (II I ) binders presents in blood experiments were carried out as follows: a fixed volume of − 3 serum: HLac, H 2 Ox, H 3 PO 4 and H 3 Cit . The pH - potentiometry 0.100 mol.dm HCl was titrated with successive additions of tech nique was used to determine the stoichiometr ies and 0.100 mol.dm − 3 KOH until near neutrality in order to get the stability constants of the complexes formed in aqueous parameters E 0 and j . Then, aliquots of H8HQ, and the ligand solution. B and an aliquot of the vanadium(III) stock solution were added sequentially. Finally, the titration was continued with E xperimental 0.100 mol.dm − 3 KOH. The measurements were done using a − 3 Reagents and Methods total metal concentration, M T = 2 – 3 mmol.dm and vanadium(III):H8HQ:ligand Bmolar ratios R = 1:1:1, 1:2:1 The VCl 3 (Merck p.a) and the 8 - h ydroxyquinoline (H8HQ) and 1:1:2. (Merck p.a.), and the HLac, Na 2 Ox, Na 3 PO 4 and Na 3 Cit (Merck p.a.), were used without purification. The HCl and The V(III) - H8HQ - ligand B systems were studied acc ording KOH solutions were prepared using 100.0 mmol.dm − 3 to the reaction scheme: Titrisol Merck ampoules. The KOH solution was stan - 3+ pH 2 O + qV + rH8HQ + sH j B dardized against potassium hydrogen phthalate. The solutions + [V (OH) (H8HQ) (H B) ]+ pH where ligand B were prepared using triple glass - distilled water, boiled before q p r j s the preparation of the solutions in order to remove dissolved represents the ligands: HLac, H 2 Ox, H 3 PO 4 and H 3 Cit, and [V q (OH) p (H8HQ) r (H j B) s ] is the ternary (p, q, r, s) CO 2 . To prevent the hydrolysis of the VCl 3 stock solution, it − 3 contained 200 mmol.dm HCl and was maintained under a complex and β p,q,r,s is the respective stabilit y constant. H 2 atmosphere in the presence of a Pt platinized net in order 7 The potentiometric data were analysed using the program to avoid oxidation of the V(III) solution to V(IV) . In this 11,12 LETAGROP , in order to minimize the function Z B = ( h − case, the H 2 can not induce redu ction to V(II), because the + 0 8 H ) /M T , where H is the total (analytical)concentration of H , h V(III)/V(II) standard potential is negative (E = − 0 . 26 V) . + represents the equilibrium concentration of H , and M T Moreover, if there is any oxidation to V(IV), the solution is represents t he total (analytical) concentration of V 3 + . immediately reduced to V(III) because of the standard Equilibria corresponding to the formation of the hydroxo potential of the reaction: complexes of V(III) were considered in the calculation of the 2+ + 3+ VO + H + ½ H 2 (g) V + H 2 O(l) stability constants of the ternary complexes. The following 2 + 9 species were assumed: [V(OH)] , log β 1 , - 1 = − 3 . 07(3); is 366.3(3) mV . Under these conditions, the V(III) solution 4 + 3 + [V 2 O] , log β 2 , - 2 = − 3 . 94(2); and [V 2 O(OH)] , log β 2 , - 3 = can be maintained. The stability of the V(III) solution was − 7 . 87(9) 9 . In the case of the V(III) - H8HQ system 13 the checked periodically by spectrophotometric measurements + complexes [V(8HQ)(OH)] , log β 1,1, - 2 = 8.7 (1); V(8HQ)(OH) 2 , and it was shown to be stable for several weeks. The emf(H) + log β = 5.85 (8); [V(8HQ) ] , log β = 17.9 (3); V(8HQ) , m easurements were carried out in aqueous solution at an 1,1, - 3 2 1,2, - 2 3 − 3 log β 1 ,3, - 3 = 25.8 max 26.1 were considered . In the binary ionic strength of 3.0 mol.dm in KCl. Nitrogen free O 2 and 14 2+ V(III)/HLac system t he complexes: [V(Lac)] , log β 1,1, - 1 = CO 2 was used to maintain an inert atmosphere. + 0.11 (4); [V(Lac)(OH)] , log β 1,1, - 2 = - 2.29 (2); [V(Lac)(OH) 2 ], The emf (H) measurements were done using the following log β 1,1, - 3 = - 7.74 (3) were taken into account. In the V(III)/H 2 Ox 15 2+ instruments: Thermo Orion model 520ApH meter, Metrohm system t he comple xes: [V(HOx)] , log β 1,1, - 1 = 6.83 (3); 2+ EA 876 – 20 titration vessel, Lauda Brikmann RM6 thermostat [V(Ox)] , log β 1,1, - 2 = 5.16 (3); [V(Ox)(OH)], log β 1,1, - 3 = - - bath, Shimad zu UV - 1601 PC spectrophotometer, and a quartz 0.97 (5); [V(Ox)(OH) 2 ] , log β 1,1, - 4 = - 4.76 (7); [V(Ox) 2 ] , 2 - cell with a 10.0 mm path length.
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