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Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol·L−1 KNO3 for the interaction of Eu–Glycylhistidine (Glyhis) with five biologically important zwitterionic buffers (Z) (HEPES, EPPS, PIPES, POPSO and HEPPSO). The formation constants for the binary Eu(III) + Glyhis or Eu(III) + Z systems and ternary Eu(III) + Glyhis + Z systems have been evaluated, and the lowest value for formation constant is assigned to the system Eu(III) + Glyhis + PIPES. The electrochemical behavior of the Eu–Glyhis complex with selected zwitterionic buffers was studied on the surface of a glassy carbon electrode using cyclic, differential pulse and square wave voltammetric techniques. The values of the standard heterogeneous rate constant (K s), diffusion coefficients of the reduction (D red) and oxidation (D ox) processes were calculated for all the studied systems. The data reveal that PIPES is the most suitable of these zwitterionic buffers for study of the biological behavior of Glycylhistidine in its europium complexes.

The luminescence arising from lanthanide cations offers several advantages over organic fluorescent molecules: sharp, distinctive emission bands allow for easy resolution between multiple lanthanide signals; long emission lifetimes (μs -ms) make them excellent candidates for time-resolved measurements; and high resistance to photo bleaching allow for long or repeated experiments. A method is presented for determination of nucleosides using the effect of enhancement of fluorescence of the easily accessible europium(III)-TNB in presence of different nucleosides. The latter coordinates to Eu(III) -TNB and enhances its luminescence intensity as a result of the displacement of water from the inner coordination sphere of the central metal. A similar method for the determination of DNA based on the quenching of Eu(III)-TNB has been established. The interaction of Eu(III)-4,4,4 trifluoro-1-(2-naphthyl)1,3-butanedione (TNB) complex with nucleosides (NS) (guanosine, adenosine, cytidine, inosine) and DNA has been studied using normal and time-resolved luminescence techniques. Binding constants were determined at 293 K, 298 K, 303 K, 308 K and 313 K by using Benesi-Hildebrand equation. A thermodynamic analysis showed that the reaction is spontaneous with ΔG being negative. The enthalpy ΔH and the entropy ΔS of reactions were all determined. The formation of binary and ternary complexes of Eu(III) with nucleosides and TNB has been studied potentiometrically at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol.dm(-3) (KNO3) . The formation of the 1:1 binary and 1:1:1 ternary complexes are inferred from the corresponding titration curves. Initial estimates of the formation constants of the resulting species and the protonation constants of the different ligands used have been refined with the HYPERQUAD computer program. Electrochemical investigations for the systems under investigations have been carried out using cyclic voltammetry (CV), differential pulse polarography (DPP), and square wave voltammetry (SWV) on a glassy carbon electrode in I = 0.1 mol/L p-toluenesulfonate as supporting electrolyte.

Eu(III)-9-acridinecarboxylate (9-ACA) complex was synthesized and characterized by elemental analysis, conductivity measurement, IR spectroscopy, thermal analysis, mass spectroscopy, (1)H-NMR, fluorescence and ultraviolet spectra. The results indicated that the composition of this complex is [Eu(III)-(9-ACA)(2)(NCS)(C(2)H(5)OH)(2)] 2.5 H(2)O and the oxygen of the carbonyl group coordinated to Eu(III). The interaction between the complex with nucleotides guanosine 5'- monophosphate (5'-GMP), adenosine 5'-diphosphates (5'-ADP), inosine (5'-IMP) and CT-DNA was studied by fluorescence spectroscopy. The fluorescence intensity of Eu(III)-9-acridinecarboxylate complex was enhanced with the addition of CT-DNA. The effect of pH values on the fluorescence intensity of Eu(III) complex was investigated. Under experimental conditions, the linear range was 9-50 ng mL(-1) for calf thymus DNA (CT- DNA) and the corresponding detection limit was 5 ng mL(-1). The results showed that Eu(III)-(9-ACA)(2) complex binds to CT-DNA with stability constant of 2.41 × 10(4) M.

The formation of binary and ternary model complexes of Eu(III) with the nucleobases 5-aminouracil (5-amino 2,4-dioxy pyrimidine), dihydrouracil (5,6-dihydro-2,4-dioxy pyrimidine), thymine (2,4-dihydroxy 5-methyl pyrimidine), adenine (6-aminopurine), uracil (2,4-dioxy pyrimidine), and PIPES (piperazine 1,4-bis(2-ethane sulfonic acid) dissodium salt) has been studied potentiometrically at (25.0 ± 0.1) °C and at an ionic strength of I = 0.1 mol·dm−3 (KNO3). The formation of the 1:1, 2:1 binary, and 1:1:1 and 2:1:1 ternary complexes is inferred from the corresponding titration curves. Initial estimates of the formation constants of the resulting species and the protonation constants of the different ligands used have been refined with the SUPERQUAD computer program. The experimental conditions were selected such that self-association of the nucleobases and their complexes was negligibly small; that is, the monomeric and protonated complexes were studied. Recognition of nucleobases and CT-DNA by the luminescen...

The interaction of Eu(9-ANCA)3 (9-ANCA = anthracene-9-carboxylic acid) with DNA has been investigated by a fluorescence method. Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol·dm−3 KNO3 for the interaction of Eu(III) and 9-ANCA with adenosine 5′-diphosphate (ADP), adenosine 5′-triphosphate (ATP), N-acetyl glutamic acid (Nc-Glu), N-acetyl leucine (Nc-Leu), and N-acetyl lysine (Nc-Lys) in a 1:1:1 ratio. The formation of various mixed ligand complexes was inferred from the potentiometric titration curves. The formation constants of the binary and ternary complexes have been refined with the SUPERQUAD computer program. The interaction of Eu(III)-(9-ANCA) with Nc-Glu, Nc-Leu, and Nc-Lys has been investigated by electroanalytical methods including cyclic voltammetry (CV), differential pulse polarography (DPP), and square wave voltammetry (SWV) on a glassy carbon (GC) electrode.

Equilibrium constant measurements have been performed potentiometrically at (25±0.1) °C and an ionic strength I=0.1 mol⋅dm−3 KNO3 for the interaction of La(III), Ce(III), Pr(III) and Er(III) with the purine nucleotides adenosine 5′-mono, 5′-di, and 5′-triphosphate and with the biologically relevant secondary ligand zwitterionic buffers 3-(cyclohexyl amino)-1-propanesulfonic acid (CAPS), 3-(cyclohexylamino)-2-hydroxy-1-propane sulfonic acid (CAPSO), N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid (TAPS), 3-[N-bis(hydroxyethyl)amino]-2-hydroxypropanesulfonic acid (DIPSO), N,N-bis(2-hydroxyethyl)glycine (BICINE), and N-(2-acetamido)-2-iminodiacetic acid (ADA) in a 1:1:1 ratio. The formation of various 1:1:1 normal and protonated mixed-ligand complex species was inferred from the potentiometric pH titration curves. The experimental conditions were selected such that self-association of the purine nucleotides and their complexes was negligibly small; that is, the monomeric normal and protonated ternary complexes were studied. Initial estimates of the formation constants of the resulting species and the acid dissociation constants of adenosine 5′-mono-, 5′-di-, and 5′-triphosphate and the zwitterionic buffer secondary ligands were refined with the Superquade computer program. In some Ln(III) mixed-ligand systems, interligand interactions between the coordinating ligands, possibly involving H-bond formation, have been found to be the most important factors in deciding the stability of the mixed-ligand complexes in solutions. The thermodynamic ΔG° values of the monomeric normal and protonated ternary complexes were calculated and discussed.

Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol·dm−3 KNO3 for the interaction of the biologically important ligands N-acetylhistidine, N-acetyl l-leucine, N-acetylglutamic acid, N-acetylhistamine, N-acetylaspartic acid, and La(III), Gd(III), Sm(III), Tb(III), Eu(III), and Dy(III) with the nucleotides guanosine 5′-monophosphate (5′-GMP), cytedine 5′-monophosphate (5′-CMP), inosine 5′-monophosphate (5′-IMP), adenosine 5′-monophosphate (5′-AMP), adenosine 5′-diphosphate (5′-ADP), adenosine 5′-triphosphate (5′-ATP), and cytedine 5′-triphosphate (5′-CTP) in 1:1:1 and 1:2:1 ratios. The formation constants of various mixed ligand complexes were inferred from the potentiometric titration curves. Initial estimates of the formation constants of the resulting species and the formation constants of the different N-acetyl amino acid (NAA) and nucleotide (NU) complexes in metal ligand ratios 1:1 and 2:1 have been refined with the SUPERQUAD computer program. ...

The formation of binary and ternary complexes of Eu(III) with nucleobases (NB), guanine (2-amino-6-oxypurine), thymine (2,4-dihydroxy 5-methyl pyrimidine), adenine (6-aminopurine), uracil (2,4-dioxypyrimidine), and anthracene-9-carboxylic acid (ANCA) has been studied potentiometrically at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol·dm−3 (KNO3) in 10 % ethanol−water mixture solvent. The acid−base properties of the ligands were investigated and discussed. The formation of the 1:1, 2:1 binary, and 1:1:1 and 2:1:1 ternary complexes is inferred from the corresponding titration curves. The ternary complexes formed are monoprotonated complexes. The stability constants of the binary and ternary systems were evaluated. Initial estimates of the formation constants of the resulting species and the protonation constants of the different ligands used have been refined with the SUPERQUAD computer program. The experimental conditions were selected such that self-association of the nucleobase and their complexes was n...

Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol·dm-3 KNO3 for the interaction of glycylglycine, glycylhistidine, glycylglycylglycine, glycylhistidylglycine, and Al(III), Ga(III), In(III), and Tl(I) with the biologically important secondary ligands bicine [N,N-bis(2-hydroxyethyl)glycine], tricine [N,N,N-tris(hydroxymethyl)methylglycine], PIPES [piperazine-1,4-bis(2-ethanesulfonic acid)], HEPES (N-[2-hydroxyethyl]piperazine-N-[2-ethanesulfonic acid]), and EPPS 4-(2-hydroxyethyl)piperazine 1-propanesulfonic acid in a 1:1:1 ratio. Ternary complexes of the type Al(III)−glycylglycine−guanosine, Al(III)−glycylglycine−guanosine 5‘-monophosphate (GMP), Al(III)−glycylglycylglycine−guanosine, Al(III)−glycylglycylglycine−GMP, Al(III)−glycylhistidine−guanosine, Al(III)−glycylhistidine−GMP, Al(III)−glycylhistidylglycine−guanosine, Al(III)−glycylhistidylglycine−GMP in a 1:1:1 ratio have been investigated. The experimental conditions were selected such that se...

Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol·dm-3 (KNO3) for the interaction of guanine (2-amino-6-oxypurine), thymine (2,4-dihydroxy-5-methylpyrimidine), adenine (6-aminopurine), uracil (2,4-dioxypyrimidine), hypoxanthine (6-oxypurine), and Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Ca(II), and Mg(II) with the biologically important secondary ligands glycine (aminoethanoic acid), bicine [N,N-bis(2-hydroxyethyl)glycine], tricine [N,N,N-tris(hydroxymethyl)methylglycine], and ADA [N-(2-acetamido)-3-iminodiacetic acid] in a 1:1:1 ratio. The experimental conditions were selected such that self-association of the nucleobases and their complexes was negligibly small; that is, the monomeric normal and protonated complexes were studied. The formation of various 1:1:1 mixed ligand complexes was inferred from the potentiometric titration curves. Initial estimates of the formation constants of the resulting species and the acid dissociation constants of g...

Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol dm-3 KNO3 for the interaction of adenosine 5‘-monophosphate, guanosine 5‘-monophosphate, cytidine 5‘-monophosphate, and La(III), Ce(III), Pr(III), and Eu(III) with the biologically important secondary ligand zwitterionic buffers (3-[N-morpholinol])-2-hydroxypropanesulfonic acid, 2-(N-morpholino)ethanesulfonic acid, N-2-acetamido-2-aminoethanesulfonic acid, and N-2-hydroxyethylpiperazine-N-2-ethanesulfonic acid. Measurements were made in a 1:1:1 ratio. Formation constants for the monohydroxy, dihydroxy, and dimeric ligand complexes for the binary systems Ln(III) + adenosine 5‘-monophosphate, Ln(III) + guanosine 5‘-monophosphate, Ln(III) + cytidine 5‘-monophosphate, and Ln(III) + zwitterionic buffers have been evaluated. The formation of various 1:1:1 normal and protonated mixed ligand complex species was inferred from the potentiometric pH-titration curves. The experimental conditions were selected...

Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol dm-3 KNO3 for the interaction of the purine nucleotides adenosine 5‘-mono, 5‘-di, and 5‘-triphosphate and Cu(II), Co(II), Ni(II), Mn(II), Zn(II), Ca(II), and Mg(II) with the biologically important secondary ligand zwitterionic buffers 3-(N-morpholino)propanesulfonic acid, 3-[(1,1-dimethyl-2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid, N-(2-hydroxyethyl)piperazine-N‘-2-hydroxypropanesulfonic acid, piperazine-N,N‘-bis(2-ethanesulfonic acid), and piperazine-N,N‘-bis(2-hydroxypropanesulfonic acid) in a 1:1:1 ratio and the formation of various 1:1:1 normal and protonated mixed-ligand complex species was inferred from the potentiometric pH titration curves. The experimental conditions were selected such that self-association of the purine nucleotides and their complexes was negligibly small; i.e., the monomeric normal and protonated ternary complexes were studied. Initial estimates of the formatio...

Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol dm-3 (KNO3) for the interaction of guanosine 5‘-monophosphate, inosine 5‘-monophosphate...

Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol dm-3 KNO3 for the interaction of adenosine 5‘-mono-, 5‘-di-, and 5‘-triphosphate and Cu(II), Co(II), Ni(II), Mn(II), Zn(II), Ca(II), and Mg(II) with the biologically important secondary ligand zwitterionic buffers 3-[N-bis(hydroxyethyl)amino]-2-hydroxypropanesulfonic acid, 3-[N-tris(hydroxymethyl)methylamino]-2-hydroxypropanesulfonic acid, (3-[N-morpholinol)-2-hydroxy propanesulfonic acid, N-(2-acetamido)-2-aminoethanesulfonic acid, and 2-(cyclohexylamino)ethanesulfonic acid in a 1:1:1 ratio, and the formation of various 1:1:1 normal and protonated mixed ligand complex species was inferred from the potentiometric pH titration curves. The experimental conditions were selected such that self-association of the nucleotides and their complexes was negligibly small; i.e., the monomeric normal and protonated ternary complexes were studied. Initial estimates of the formation constants of the resulting sp...

Potentiometric equilibrium measurements have been performed at (25.0 ± 0.1) °C and ionic strength I = 0.1 mol dm-3 (KNO3) for the interaction of glycine (aminoethanoic acid), serine (2-amino-3-hydroxypropanoic acid), methionine (2-amino-4-(methylthio)butanoic acid), aspartic acid (aminobutanedioic acid), glutamic acid (2-aminopropanedioic acid), and histidine (α-amino-1H-imidazole-4-propanoic acid) and Cu(II), Co(II), Ni(II), Mn(II), and Zn(II) with the biologically important secondary ligand zwitterionic buffers β-hydroxy-4-morpholinepropanesulfonic acid (MOPSO), 4-morpholinepropanesulfonic acid (MOPS), 3-[bis(2-hydroxyethyl)amino]-2-hydroxy-1-propanesulfonic acid (DIPSO), and 3-[N-tris(hydroxymethyl)methyl)amino]-2-hydroxypropanesulfonic acid (TAPSO) in 1:1:1 and 1:1:2 ratios, and the formation of various 1:1:1 ternary complexes and 1:1:2 quaternary complex species was inferred from the potentiometric pH titration curves. Initial estimates of the formation constants of the resulting species and the acid...

The complexes formed by the Na/sup +/, K/sup +/, Rb/sup +/, Ca/sup 2 +/, UO/sub 2//sup 2 +/, and Ag/sup +/ cations with the macrocyclic polyethers 18-crown-6, benzo-15-crown-5, and dicyclohexyl-18-crown-6 are investigated. The stability constants of these complexes have been determined potentiometrically in (90% vol.) ethanol-water solutions at 25/sup 0/C and an ionic strength ..mu.. = 0.1 (achieved with tetrabutylammonium perchlorate). The stability of the investigated complexes was interpreted in terms of caging the metal cation into the cavity of the macrocyclic ligand, an effect which depends on the ratio of the diameter of the complexed cation over the diameter of the cavity of the complexing ligand.