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PubMed2003

Self-assembly of achiral and chiral macrocyclic ligands: synthesis, protonation constants, conformation and asymmetric catalysis.

New 30-membered achiral and chiral polyaza macrocyclic ligands, L1 and L2 were synthesized directly from [3 + 3] condensation of phthalic dicarboxaldehyde with cis- and (1R,2R)-diaminocyclohexane, respectively. The trimeric macrocyclic structures were confirmed by electrospray ionization mass spectrometry (ESI-MS), 1H NMR, 13C NMR spectroscopy and elemental analysis. Potentiometry was used to determine the protonation constants of the ligands. UV-vis spectrophotometric titration was employed to investigate the coordination and conformational properties of the chiral ligand (L2). Direct enantioselective aldol reaction has been successfully performed using 4-nitrobenzaldehyde and acetone in the presence of the chiral macrocycle and its zinc(II) complexes as catalysts.

Journal Article↗
PubMed2003

Novel chiral N4S2- and N6S3-donor macrocyclic ligands: synthesis, protonation constants, metal-ion binding and asymmetric catalysis in the Henry reaction.

New hydrophobic chiral macrocyclic ligands L1-L3 with chiral diamino and thiophene moieties have been synthesized by the Schiff base condensation approach. Protonation constants of L1 and L2 were determined by potentiometry titration. Metal-ion binding experiments exhibited that L1 and L3 are pronounced in selective recognition, Ag+, Cu2+ and Ca2+ ions among the surveyed metal ions (Cu2+, Co2+, Ni2+, Zn2+, Cd2+, Pb2+, Ag+, Li+, Na+, K+, and Ca2+). L1 was found to spectroscopically detect the presence of Cu2+ and Ca2+ to function as a multiple readout sensor. The detection limit for Ca2+ ions was found to be 9.8 x 10(-5) M in CH2Cl2-MeOH solution. The trimeric chiral ligand L3 has been shown to be an efficient auxiliary in a Zn(II)-mediated enantioselective Henry reaction.

Journal Article↗
PubMed2004

Complexation of thorium(IV) with acetate at variable temperatures.

The complexation between Th(IV) and acetate in 1.05 mol kg(-1) NaClO4 was studied at variable temperatures (10, 25, 40, 55 and 70 degrees C). The formation constants of five successive complexes, Th(Ac)j(4-j)+ where Ac = CH3COO- and j = 1-5, and the molar enthalpies of complexation were determined by potentiometry and calorimetry. Extended X-ray absorption fine structure spectroscopy (EXAFS) provided additional information on the complexes in solution. The effect of temperature on the stability of the complexes is discussed in terms of the electrostatic model.

Journal Article↗
PubMed2005

Synthesis and complexation properties of DTPA-N,N''-bis[bis(n-butyl)]-N'-methyl-tris(amide). Kinetic stability and water exchange of its Gd3+ complex.

A novel DTPA-tris(amide) derivative ligand, DTPA-N,N''-bis[bis(n-butyl)]-N'-methyl-tris(amide)(H2L3) was synthesized. With Gd3+, it forms a positively charged [Gd(L3)]+ complex, whereas with Cu2+ and Zn2+ [ML3], [MHL3]+ and [M2L3]2+ species are formed. The protonation constants of H2L3 and the stability constants of the complexes were determined by pH potentiometry. The stability constants are lower than those for DTPA-N,N''-bis[bis(n-butyl)amide)](H3L2), due to the lower negative charge and reduced basicity of the amine nitrogens in (L3)2-. The kinetic stability of [Gd(L3)]+ was characterised by the rates of metal exchange reactions with Eu3+, Cu2+ and Zn2+. The exchange reactions, which occur via proton and metal ion assisted dissociation of [Gd(L3)]+, are significantly slower than for [Gd(DTPA)]2-, since the amide groups cannot be protonated and interact only weakly with the attacking metal ions. The relaxivities of [Gd(L2)] and [Gd(L3)]+ are constant between 10-20 degrees C, indicating a relatively slow water exchange. Above 25 degrees C, the relaxivities decrease, similarly to other Gd3+ DTPA-bis(amide) complexes. The pH dependence of the relaxivities for [Gd(L3)]+ shows a minimum at pH approximately 9, thus differs from the behaviour of Gd3+-DTPA-bis(amides) which have constant relaxivities at pH 3-8 and an increase below and above. The water exchange rates for [Gd(L2)(H2O)] and [Gd(L3)(H2O)]+, determined from a variable temperature (17)O NMR study, are lower than that for [Gd(DTPA)(H2O)]2-. This is a consequence of the lower negative charge and decreased steric crowding at the water binding site in amides as compared to carboxylate analogues. Substitution of the third acetate of DTPA5- with an amide, however, results in a less pronounced decrease in kex than substitution of the first two acetates. The activation volumes derived from a variable pressure (17)O NMR study prove a dissociative interchange and a limiting dissociative mechanism for [Gd(L2)(H2O)] and [Gd(L3)(H2O)]+, respectively.

Chelating Agents↗
PubMed2005

A systematic investigation of aluminium ion speciation at high temperature. Part 1. Solution studies.

Speciation diagrams of aluminium ions in aqueous solution (0.2 M) at high temperature (90 degrees C) have been obtained from 48 h time-resolved multi-batch titration experiments monitored by 27Al NMR spectroscopy, potentiometry and dynamic light scattering. The quantitative speciation patterns and kinetic data obtained offer a dynamic picture of the distribution of soluble and insoluble Al species as a function of hydrolysis ratio h(h=[OH-]/[Al3+]) over a very broad range of conditions (-1.0 < or =h < or = 4.0). Monomeric, small oligomeric, tridecameric (the 'Al13-mer') and the recently characterised 30-meric aluminium species (the 'Al30-mer') as well as aluminium hydroxide have been identified and quantified. The Al13-mer species dominates over a relatively broad range of hydrolysis ratios (1.5 < or =h< or = 2.7) during the first 6 h of experiment, but are gradually replaced by Al30-mers at longer reaction times. Kinetic profiles indicate that the formation of the Al30-mer is limited by the disappearance of the Al13 species at mildly acidic conditions. The estimated rate constants of both hydrolytic processes show good internal correlation at h> or = 1.5. The effect of local perturbations leading to the formation of aluminium hydroxide below the electroneutrality point (h= 3.0) has been estimated quantitatively.

Journal Article↗
PubMed2005

Coordination properties of 3-functionalized beta-cyclodextrins. Thermodynamic stereoselectivity of copper(II) complexes of the A,B-diamino derivative and its exploitation in LECE.

The bis-amino AB derivative of beta-cyclodextrin on the secondary rim was synthesised and spectroscopically characterised by different techniques. Its binary systems both with protons and copper(II) were thermodynamically characterised by pH-metric potentiometry. In addition the ternary systems with each of the enantiomers of tryptophan and alanine were investigated. A thermodynamic stereoselectivity was observed for the tryptophan enantiomers and this was exploited to separate them by capillary electrophoresis through a ligand exchange mechanism (LECE). LECE separation of racemates of phenylalanine and tyrosine was also obtained.

Binding Sites↗
PubMed2005

Oxovanadium(IV) complexes of salicyl-L-aspartic acid and salicylglycyl-L-aspartic acid.

The dipeptide and tripeptide analogues salicyl-L-aspartic acid (Sal-L-Asp) and salicylglycyl-L-aspartic acid (SalGly-L-Asp) were synthesized and their protonation and complex formation with V(IV)O2+ were studied in aqueous solution through the use of pH-potentiometry and spectroscopic (UV-Vis, CD and EPR) techniques. The phenolate terminus proved to be a good anchoring site to promote (i) the metal ion-induced deprotonation and subsequent coordination of the peptide amide group(s) in the pH range 4-5 for the dipeptide analogue, (ii) and in the pH range 5-6 in a very cooperative way for the tripeptide analogue. The results suggest that the presence of good anchoring donors on both sides of the amide groups is responsible for the cooperative deprotonation of the two amide-NH groups.

Aspartic Acid↗
PubMed2005

Solution chemical properties and catecholase-like activity of the copper(II)-Ac-His-His-Gly-His-OH system, a relevant functional model for copper containing oxidases.

The solution chemical properties, superoxide dismutase and catecholase activity of the copper(ii)-Ac-His-His-Gly-His-OH (hhgh) complexes were studied to identify functional and structural models of copper-containing oxidases. The solution speciation was determined in the pH range 3-11 by two independent methods (potentiometry and pH-dependent EPR measurements). The results obtained by the two methods agree very well with each other and show the formation of differently protonated CuH(x)L complexes (where x= 2 ,1, 0, -1, -2, -3) in aqueous solution. The spectroscopic (UV-Vis, CD, EPR) data indicate that the coordination of the imidazole rings is a determinant factor in all these complexes. Amide coordinated complexes are dominant only above pH 8. This offers excellent possibilities for structural/functional modelling of copper(ii) containing metalloenzymes. Indeed, the {3N(im)} coordinated CuL species (pH = 6-7) has efficient superoxide dismutase-like activity. The {3N(im),OH(-)} coordinated CuH(-1)L possesses outstanding activity to catalyze the oxidation of 3,5-di-tert-butylcatechol (H(2)dtbc) by dioxygen in 86 wt% methanol-water, providing the first example that copper(ii)-peptide complexes are able to mimic copper containing oxidases.

Biomimetic Materials↗
PubMed2006

Silver complexes of peptidomimetic polyazapyridinophanes. The influence of the bonding cavity size and the nature of side chains.

Several peptidomimetic macrocycles containing a pyridine spacer and ring sizes ranging from 15 to 17 have been efficiently synthesized starting from valine and phenylalanine. The complexes formed have been investigated by potentiometry and NMR. Log K values show that phenylalanine derivatives are consistently more stable than valine derivatives , whilst macrocycles with ring sizes of 16 members are the most appropriate for the complexation. The NMR data, in combination with molecular modeling, allow rationalization of the structure of the complexes formed and the participation of the aromatic rings from the side chain of phenylalanine in pi-Ag+ interactions to be discarded.

Journal Article↗
PubMed2006

Chemical speciation in concentrated alkaline aluminate solutions in sodium, potassium and caesium media. Interpretation of the unusual variations of the observed hydroxide activity.

A detailed electrochemical investigation using H2/Pt electrode potentiometry as well as Raman and NMR spectroscopy was carried out to develop a comprehensive chemical explanation for the unusual patterns of hydroxide concentrations observed in strongly alkaline, highly concentrated aluminate solutions (Bayer-liquors). For this, aluminate solutions with various alkaline metal background cations were investigated. The effect of the temperature on the observed patterns was also studied, and for comparison with solutions of similar concentrations, the chemical speciation of borate solutions was also studied. The formation of the NaOH 0 ion-pair has been proven with the formation constant (defined in terms of activities) beta 0 = 0.78 +/- 0.08. The formation of analogous KOH 0 or CsOH 0 ion-pairs under the experimental conditions applied is negligible. Assuming the formation of the NaAl(OH)4 (0) ion-pair is not necessary for modeling the experimental findings, as its formation causes only secondary effects on the potentiometric patterns. It has also been shown that all experimental data can be interpreted quantitatively if the formation of the doubly charged dimeric aluminate species is included in the calculation of the changes in the mean activity coefficients. The formation constant of the aluminate dimer could not be estimated purely from the H2/Pt potentiometric data but a lower limit for its formation constant (defined in terms of activities) has been derived. These conclusions are in full congruency with those derived from the Raman spectra of solutions with similar concentrations, so the two independent experimental methods lead to the same set of chemical species in highly concentrated alkaline aluminate solutions.

Journal Article↗
PubMed2005

Equilibrium and NMR studies on GdIII, YIII, CuII and ZnII complexes of various DTPA-N,N''-bis(amide) ligands. Kinetic stabilities of the gadolinium(III) complexes.

Three DTPA-derivative ligands, the non-substituted DTPA-bis(amide) (L(0)), the mono-substituted DTPA-bis(n-butylamide) (L(1)) and the di-substituted DTPA-bis[bis(n-butylamide)] (L(2)) were synthesized. The stability constants of their Gd3+ complexes (GdL) have been determined by pH-potentiometry with the use of EDTA or DTPA as competing ligands. The endogenous Cu2+ and Zn2+ ions form ML, MHL and M(2)L species. For the complexes CuL(0) and CuL(1) the dissociation of the amide hydrogens (CuLH(-1)) has also been detected. The stability constants of complexes formed with Gd3+, Cu2+ and Zn2+ increase with an increase in the number of butyl substituents in the order ML(0) < ML(1) < ML(2). NMR studies of the diamagnetic YL(0) show the presence of four diastereomers formed by changing the chirality of the terminal nitrogens of their enantiomers. At 323 K, the enantiomerization process, involving the racemization of central nitrogen, falls into the fast exchange range. By the assignment and interpretation of 1H and 13C NMR spectra, the fractions of the diastereomers were found to be equal at pH = 5.8 for YL(0). The kinetic stabilities of GdL(0), GdL(1) and GdL(2) have been characterized by the rates of the exchange reactions occurring between the complexes and Eu3+, Cu2+ or Zn2+. The rates of reaction with Eu3+ are independent of the [Eu3+] and increase with increasing [H+], indicating the rate determining role of the proton assisted dissociation of complexes. The rates of reaction with Cu2+ and Zn2+ increase with rising metal ion concentration, which shows that the exchange can take place with direct attack of Cu2+ or Zn2+ on the complex, via the formation of a dinuclear intermediate. The rates of the proton, Cu2+ and Zn2+ assisted dissociation of Gd3+ complexes decrease with increasing number of the n-butyl substituents, which is presumably the result of steric hindrance hampering the formation or dissociation of the intermediates. The kinetic stabilities of GdL(0) and GdL(1) at pH = 7.4, [Cu2+] = 1 x 10(-6) M and [Zn(2+)] = 1 x 10(-5) M are similar to that of Gd(DTPA)2-, while the complex GdL2 possesses a much higher kinetic stability.

Amides↗
PubMed2006

Bis- and tris-(3-aminopropyl) derivatives of 14-membered tetraazamacrocycles containing pyridine: synthesis, protonation and complexation studies.

New N-(3-aminopropyl) (L1, L2) and (2-cyanoethyl) (L3, L4) derivatives of a 14-membered tetraazamacrocycle containing pyridine have been synthesized. The protonation constants of L1 and L2 and the stability constants of their complexes with Ni2+, Cu2+, Zn2+ and Cd2+ metal ions were determined in aqueous solutions by potentiometry, at 298.2 K and ionic strength 0.10 mol dm(-3) in KNO3. Both compounds have high overall basicity due to the presence of the aminopropyl arms. Their copper(II) complexes exhibit very high stability constants, which sharply decrease for the complexes of the other studied metal ions, as usually happens with polyamine ligands. Mono- and dinuclear complexes are formed with L2 as well as with L1, but the latter exhibits mononuclear complexes with slightly higher K(ML) values while the dinuclear complexes of L2 are thermodynamically more stable. The presence of these species in solution was supported by UV-VIS-NIR and EPR spectroscopic data. The single crystal structures of [Cu(H2L2)(ClO4)]3+ and [CoL3Cl]+ revealed that the metal centres are surrounded by the four nitrogen atoms of the macrocycle and one monodentate ligand, adopting distorted square pyramidal geometries. In the [CoL3Cl]+ complex, the macrocycle adopts a folded arrangement with the nitrogen atom opposite to the pyridine at the axial position while in the [Cu(H2L2)(ClO4)]3+ complex, the macrocycle adopts a planar conformation with the three aminopropyl arms located at the same side of the macrocyclic plane.

Journal Article↗
PubMed2006

Nitro-functionalization and luminescence quantum yield of Eu(III) and Tb(III) benzoic acid complexes.

In our pursuit of luminescent lanthanide ion-based coordination polymers, we have isolated several complexes with nitrobenzoic acid ligands and characterized these by X-ray crystallography and luminescence spectroscopy. 2-Nitrobenzoic acid reacts with Eu(III) to form 1, which crystallizes in the P-1 space group, with a = 12.385(3), b = 12.912(3), c = 17.889(4) A, alpha = 97.49(3), beta = 109.64(3) and gamma = 101.99(3) degrees . 3-Nitrobenzoic acid forms a one-dimensional coordination polymer with Eu(III), 2, which crystallizes in the triclinic space group P-1 with a = 9.7100(19), b = 10.579(2), c = 13.361(3) A, alpha = 77.41(3), beta = 88.78(3) and gamma = 88.16(3) degrees. Structures 3 and 4 correspond to the isostructural one-dimensional coordination polymers of Eu(III) and Tb(III), respectively, with the 4-nitrobenzoato anion. These crystallize in the triclinic space group P-1 with a = 9.2242(18), b = 15.102(3), c = 18.587(4) A, alpha = 75.93(3), beta = 82.88(3) and gamma = 79.00(3) degrees for 3 and a = 9.2692(19), b = 15.369(3), c = 18.353(4) A, alpha = 75.37(3), beta = 81.32(3) and gamma = 78.15(3) degrees for 4. Potentiometry, absorption and NMR spectroscopy indicate that in solution only 1 : 1 species are present. All compounds are weakly luminescent as solids and the photophysics of solutions of ligands with Ln(III) in 1 : 1 stoichiometry were studied. Quantum yields around 1 and 3% for Eu(III)-and Tb(III)-containing methanolic solutions were measured.

Journal Article↗
PubMed1978

Synthesis of the native copper(II)-transport site of human serum albumin and its copper(II)-binding properties.

A derivative of the native-sequence tripeptide of the specific Cu(II)-transport site of human serum albumin, L-aspartyl-L-alanyl-L-histidine N-methylamide, was synthesized, and its binding to Cu(II) was examined to determine the influence of the side-chain groups on the Cu(II) binding. The equilibria involved in the Cu(II)-L-aspartyl-L-alanyl-L-histidine N-methylamide system were investigated by analytical potentiometry. Three complex species were found in the pH range 4-10. The same species were identified in both the visible and circular-dichroism spectra. The main species present in the physiological pH range is shown to have the same ligands around the square-planar Cu(II) ion as those reported for albumin and tripeptides diglycyl-L-histidine and its N-methylamide derivative. The results obtained from competition experiments showed that this tripeptide has a higher affinity towards Cu(II) than has albumin itself. The overall findings are compared with those from albumin. At neutral pH the side chains do not play any important role in the Cu(II) binding, but at low pH the beta-carboxyl group of the N-terminal aspartic residue becomes important. A possible competition site on albumin for Cu(II) at low pH is discussed.

Binding Sites↗
PubMed1982

Nickel(II) transport in human blood serum. Studies of nickel(II) binding to human albumin and to native-sequence peptide, and ternary-complex formation with L-histidine.

Detailed studies are reported on the Ni(II)-binding site of human serum albumin (HSA) and the results are compared with those obtained from the N-terminal native-sequence peptide, l-aspartyl-l-alanyl-l-histidine N-methylamide (Asp-Ala-His-NHMe). Equilibrium dialysis of HSA and Ni(II) in 0.1m-N-ethylmorpholine/HCl buffer, pH 7.53, demonstrates a specific Ni(II)-binding site on the protein. l-Histidine, the low-molecular-weight Ni(II)-binding constituent of human serum, is shown to have a greater affinity for Ni(II) than does HSA. A small but significant amount of ternary complex HSA-Ni(II)-l-histidine is also present in the equilibrium mixture containing the three components. The log (association constant) values for the binary and ternary Ni(II) complexes are 9.57 and 16.23 respectively. The complex equilibria between Asp-Ala-His-NHMe and Ni(II) have been investigated by analytical potentiometry in aqueous solution (0.15m-NaCl, 25 degrees C). Several species, including MA, MA(2), MH(-2)A, and MH(-1)A(2) [where M and A represent Ni(II) ion and anionic peptide respectively], were detected in the system, MH(-2)A being the major complex species. Equilibrium studies involving Asp-Ala-His-NHMe, Ni(II) and l-histidine reveal the presence of a ternary complex MH(-1)AB (where B represents anionic l-histidine) at physiological pH. Detailed studies of visible-absorption spectra of HSA in the presence of Cu(II) and Ni(II) reveal that the two metal ions bind HSA at the same site. The visible-absorption spectrum of Ni(II)-HSA complex shows a highly absorbing peak at 420nm (epsilon(max.) = 137; with shoulder at 450-480nm) characteristic of a square planar or square pyramidal co-ordination arrangement about the metal ion. Similar visible-absorption characteristics were observed for the major species MH(-2)A in the Asp-Ala-His-NHMe-Ni(II) system (lambda(max.) = 420nm; epsilon(max.) = 135; with shoulder at 450-480nm). The combination of experimental results from the protein studies and the peptide analyses provides strong evidence for the structure of the Ni(II)-binding site of HSA as one that involves the alpha-amino nitrogen atom, two deprotonated peptide nitrogen atoms, the imidazole nitrogen atom and the side-chain carboxy group of the aspartic acid residue. On the basis of the results obtained from the individual ternary systems involving protein and peptide, a mechanism for the transportation of Ni(II) in the serum is proposed.

Binding Sites↗
PubMed1982

The non-specificity of dog serum albumin and the N-terminal model peptide glycylglycyl-L-tyrosine N-methylamide for nickel is due to the lack of histidine in the third position.

Equilibrium dialysis of dog serum albumin (DSA) against Ni(II) in 0.1 M-N-ethylmorpholine/HCl, pH 7.53, demonstrates the absence of a specific Ni(II)-binding site in DSA. To evaluate at the molecular level the influence of the genetic substitution of L-tyrosine for L-histidine at the N-terminal of DSA, a simple model tripeptide of the N-terminal residues, glycylglycyl-L-tyrosine N-methylamide, was synthesized and its Ni(II)-binding properties studied. A comparison of the visible absorption characteristics of Ni(II)-DSA with those of Ni(II)-glycylglycyl-L-tyrosine N-methylamide reveals a similar change from octahedral to planar co-ordination as the pH is increased. Both systems exhibit a low Ni(II)-binding affinity at physiological pH, with DSA binding a greater percentage of Ni(II) owing to the availability of at least two binding sites of similar affinities. The complex equilibria between Ni(II) and glycylglycyl-L-tyrosine N-methylamide were studied by analytical potentiometry (0.15 M-NaCl, 25 degrees C). Four major complex species, MHA, MH-1A2, MH-2A2 and MH-3A [where M and A represent Ni(II) ion and anionic peptide respectively], were detected, MHA being the single species at physiological pH. There is no evidence for the involvement of the phenolic hydroxy group in the octahedral MHA complex, or within the plane of co-ordination in the high-pH species. The results provide direct evidence that the low Ni(II)-binding affinity of DSA is due to the genetic substitution of tyrosine for histidine at the N-terminal region of the protein.

Animals↗
PubMed2003

Electron transfer in human cytochrome P450 reductase.

Cytochrome P450 reductase (CPR) is a diflavin enzyme responsible for electron donation to mammalian cytochrome P450 enzymes in the endoplasmic reticulum. Dissection of the enzyme into functional domains and studies by site-directed mutagenesis have enabled detailed characterization of the mechanism of electron transfer using stopped-flow and equilibrium-perturbation methods, and redox potentiometry. These studies and the mechanism of electron transfer in CPR are reported herein.

Amino Acid Sequence↗
PubMed2002

Short peptides are not reliable models of thermodynamic and kinetic properties of the N-terminal metal binding site in serum albumin.

A comparative study of thermodynamic and kinetic aspects of Cu(II) and Ni(II) binding at the N-terminal binding site of human and bovine serum albumins (HSA and BSA, respectively) and short peptide analogues was performed using potentiometry and spectroscopic techniques. It was found that while qualitative aspects of interaction (spectra and structures of complexes, order of reactions) could be reproduced, the quantitative parameters (stability and rate constants) could not. The N-terminal site in HSA is much more similar to BSA than to short peptides reproducing the HSA sequence. A very strong influence of phosphate ions on the kinetics of Ni(II) interaction was found. This study demonstrates the limitations of short peptide modelling of Cu(II) and Ni(II) transport by albumins.

Animals↗