A photometric study of the complexation reaction between Alizarin complexan and zinc(II), nickel(II), lead(II), cobalt(II) and copper(II)

The complexation reaction between Alizarin complexan ([3-N,N-di(carboxymethyl)aminomethyl]-1,2-dihydroxyanthraquinone; H(4)L) and zinc(II), nickel(II), lead(II), cobalt(II) and copper(II) has been studied by a spectrophotometric method. All these metal ions form 1:1 complexes with HL; 2:1 metal:ligand complex were found only for Pb(II) and Cu(II). The stability constants are (ionic strength I = 0.1, 20 degrees C): Zn(2+) + HL(3-) right harpoon over left harpoon ZnHL(-) log K +/- 3sigma(log K) = 12.19 +/- 0.09 (I = 0.5) Ni(2+) + HL(3-) right harpoon over left harpoon NiHL(-) log K +/- 3sigma(log K) = 12.23 +/- 0.21 Pb(2+) + HL(3-) right harpoon over left harpoon PbHL(-) log K +/- 3sigma(log K) = 11.69 +/- 0.06 PbHL(-) + Pb(2+) right harpoon over left harpoon Pb(2)L + H(+) log K approximately -0.8 Co(2+) + HL(3-) right harpoon over left harpoon CoHL(-) log K 3sigma(log K) = 12.25 + 0.13 Cu(2+) + HL(3-) right harpoon over left harpoon CuHL(-) log K 3sigma(log K) = 14.75 +/- 0.07 Cu(2+) + CuHL(-) right harpoon over left harpoon Cu(2)L + H(+) log K approximately 3.5 The solubility and stability of both the reagent and the complexes and the closenes of the values of the stability constants make this reagent suitable for the photometric detection of several metal ions in the eluate from an ion-exchange column.     

Irving-Williams order in the framework of connectivity index ³χv enables simultaneous prediction of stability constants of bivalent transition metal complexes

Logarithms of stability constants, log K? and log β?, of the first transition series metal mono- and bis-complexes with any of four aliphatic amino acids (glycine, alanine, valine and leucine) decrease monotonously with third order valence connectivity index, 3χv, from Cu2+ to Mn2+. While stability of the complexes with the same metal is linearly dependent on 3χv, stability constants of Mn2+, Fe2+, Co2+, and Ni2+complexes with the same ligand show a quadratic dependence on 3χv. As Cu2+ complexes deviate significantly from quadratic functions, models for the simultaneous estimation of the stability constants, yielding r = 0.999 (S.E. = 0.05) and r = 0.998 (S.E. = 0.11), for log K? and log β?, respectively, were developed only for Mn2+, Fe2+, Co2+, and Ni2+ complexes with amino acids.     

Mass spectrometric investigations of the kinetic stability of chromium and copper complexes with humic substances by isotope-labelling experiments

Isotope-labelling exchange experiments were carried out to investigate the kinetic stability of Cr(III) complexes with humic substances (HS). To compare the results with those of an ion, not expected to form kinetically stable HS complexes with respect to its electron configuration, Cu(II) was investigated under the same conditions. HS solutions of different origin were therefore spiked with ⁵³Cr(III) or ⁶⁵Cu(II) after saturation of HS with chromium and copper of natural isotopic composition. In fractions of metal/HS complexes with different molecular weight, obtained by ultrafiltration and HPLC/ICP-MS using size exclusion chromatography (SEC), respectively, the isotope ratios of chromium and copper were determined by ICP and thermal ionisation mass spectrometry. Distinct differences in the isotopic composition of chromium were found in the permeate of the ultrafiltration compared with the corresponding unseparated solution, which indicates kinetically stable Cr(III)/HS complexes. On the other hand, the copper isotopic composition was identical in the permeate and the unseparated solution, which shows that a total exchange of Cu²⁺ ions took place between free and HS complexed copper ions. The SEC/ ICP-MS experiments also resulted in a different isotopic distribution of chromium in the chromatographically separated complexes whereas the copper complexes, separated by SEC, showed identical isotopic composition. The kinetic stability of Cr(III)/HS complexes could be explained by the d³ electron configuration of Cr³⁺ ions, a fact which is well known from classical Cr(III) complexes, and influences substantially the mobility of this heavy metal in the environment.     

Investigations on the conditional kinetic and thermodynamic stability of aquatic humic substance-metal complexes by means of EDTA exchange, ultrafiltration and atomic spectrometry

The conditional metal availability and the kinetic stability of humic substance-metal species in humic-rich waters (e.g. bog water) was characterized by means of EDTA exchange. For this purpose a combined procedure consisting of time-controlled ligand exchange by EDTA, species differentiation by a fast single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods (e.g. AAS, ICP-OES, TXRF) was developed. The kinetics and the yield of the EDTA exchange served as operational parameters for assessing the kinetic stability and EDTA availability of HS-metal species, respectively. Considerable fractions of natural HS-metal species studied were shown to be EDTA-inert (e.g. 31% of the total Fe, 44% of the total Al) even after long reaction times (48 h), in contrast to artificial ones formed in solutions of isolated HS. Moreover, the conditional thermodynamic stability of HS-metal complexes formed by successive loading of an aquatic reference HS (HO14) with a number of heavy metal ions (e.g. Cr(III), Cu(II), Fe(III), Mn(II), Zn(II)) was also evaluated discriminating the free metal concentrations by means of TF-UF. In addition, from the loading isotherms obtained conditional complexation capacities could be derived for the studied HS exhibiting the order Fe(III)>Cu(II)>Cr(III)>Co(II)>Mn(II).     

Mass spectrometric investigations of the kinetic stability of chromium and copper complexes with humic substances by isotope-labelling experiments

Isotope-labelling exchange experiments were carried out to investigate the kinetic stability of Cr(III) complexes with humic substances (HS). To compare the results with those of an ion, not expected to form kinetically stable HS complexes with respect to its electron configuration, Cu(II) was investigated under the same conditions. HS solutions of different origin were therefore spiked with ⁵³Cr(III) or ⁶⁵Cu(II) after saturation of HS with chromium and copper of natural isotopic composition. In fractions of metal/HS complexes with different molecular weight, obtained by ultrafiltration and HPLC/ICP-MS using size exclusion chromatography (SEC), respectively, the isotope ratios of chromium and copper were determined by ICP and thermal ionisation mass spectrometry. Distinct differences in the isotopic composition of chromium were found in the permeate of the ultrafiltration compared with the corresponding unseparated solution, which indicates kinetically stable Cr(III)/HS complexes. On the other hand, the copper isotopic composition was identical in the permeate and the unseparated solution, which shows that a total exchange of Cu²⁺ ions took place between free and HS complexed copper ions. The SEC/ ICP-MS experiments also resulted in a different isotopic distribution of chromium in the chromatographically separated complexes whereas the copper complexes, separated by SEC, showed identical isotopic composition. The kinetic stability of Cr(III)/HS complexes could be explained by the d³ electron configuration of Cr³⁺ ions, a fact which is well known from classical Cr(III) complexes, and influences substantially the mobility of this heavy metal in the environment. Received: 7 December 1998 / Revised: 25 March 1999 / Accepted: 27 March 1999     

Labile/inert metal species in aquatic humic substances: an ion-exchange study

Summary An ion-exchange procedure has been developed for the analytical fractionation of metals (e.g. Al, Co, Cu, Fe, Mn, Ni, Pb, Zn) forming labile/inert complexes with aquatic humic substances (HS) isolated (XAD 2, XAD 8, ultrafiltration) from bog, forest, ground and lake water. Using 1-(2-hydroxyphenylazo)-2-naphthol groups immobilized on cellulose (Cellulose HYPHAN) as chelating collector (batch and column procedure, resp.) for reactive metal fractions in dissolved HS, the kinetics and the degree of separation (referred to the total metal content) serve for the operational characterization of the metal lability. According to the separation kinetics (96 h), mostly the reactivity order Mn>Zn>Co>Pb>Ni>CuAl>Fe is observed for the above metals in HS, resulting in recoveries of >98% for Mn and Zn, but strongly varying for the other metals (e.g., 44–95% Cu, 18–84% Fe). By means of cellulose HYPHAN four metal fractions (e.g. Cu) can be distinguished kinetically: (a) about 50% of Cu freshly complexed with HS are directly exchanged (2nd order kinetics, k=0.275 1 · mol^–1 · s^–1) followed by (b) a less labile fraction (20–30%) of 1st to 2nd order exchange; (c) a hardly reactive fraction (5–10%) revealing uniform half times t_1/2 of 25 h closes the Cu exchange from HS. Moreover the Cu fraction (d), being exchange-inert in HS, amounts to 5–10% and increases by slow transformation processes of the formed HS/Cu species.     

On-site characterization of humic-rich hydrocolloids and their metal loading by means of mobile size-fractionation and exchange techniques

Humic-rich hydrocolloids and their metal loading in selected German bog-waters have been characterized by a novel on-site approach. By use of an on-line multistage ultrafiltration (MST-UF) unit equipped with conventional polyethersulfone (PES)-based flat membranes (nominal cut-off 0.45, 0.22, and 0.1 microm, or 100, 50, 10, 5, 3 kDa) the hydrocolloids could be fractionated on-site in both sub-particulate and macromolecular size ranges. Characterization (dissolved organic carbon (DOC), metals) of the colloid fractions obtained this way was performed off-site by use of conventional instrumental methods (carbon analyzer, AAS, ICP-OES, and TXRF (total reflection X-ray fluorescence)). Major DOC fractions of the hydrocolloids studied were found to be in the size range <5 kDa. The assessed metals (Al, Cu, Fe, Mn, Pb, and Zn) were, however, predominantly enriched in the macromolecular and sub-particulate range, depending on the metal and the sample, respectively. In addition, metal species bound to these hydrocolloids were kinetically characterized on-site by use of competitive ligand (EDTA (ethylenediaminetetraacetate)) and metal (Cu(II)) exchange; the EDTA complexes formed and the metal ions exchanged were separated by means of a small time-controlled tangential-flow UF unit (cut-off 1 kDa). Bound metal fractions, in particular Al and Fe, reacted only slowly (500 to 1000 min) with EDTA; the conditional availability was 60-99%, depending on the hydrocolloid. In contrast, the Cu(II) exchange of colloid-bound metal species approached equilibrium within 5-10 min, with characteristic exchange constants, Kex, of the order of 0.01 to 90 for the metals (Fe相似文献   

Equilibrium and formation/dissociation kinetics of some Ln(III)PCTA complexes

The protonation constants () of 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9-triacetic acid (PCTA) and stability constants of complexes formed between this pyridine-containing macrocycle and several different metal ions have been determined in 1.0 M KCl at 25 degrees C and compared to previous literature values. The first protonation constant was found to be 0.5-0.6 log units higher than the value reported previously, and a total of five protonation steps were detected (log = 11.36, 7.35, 3.83, 2.12, and 1.29). The stability constants of complexes formed between PCTA and Mg2+, Ca2+, Cu2+, and Zn2+ were also somewhat higher than those previously reported, but this difference could be largely attributed to the higher first protonation constant of the ligand. Stability constants of complexes formed between PCTA and the Ln3+ series of ions and Y3+ were determined by using an "out-of-cell" potentiometric method. These values ranged from log K = 18.15 for Ce(PCTA) to log K = 20.63 for Yb(PCTA), increasing along the Ln series in proportion to decreasing Ln3+ cation size. The rates of complex formation for Ce(PCTA), Eu(PCTA), Y(PCTA), and Yb(PCTA) were followed by conventional UV-vis spectroscopy in the pH range 3.5-4.4. First-order rate constants (saturation kinetics) obtained for different ligand-to-metal ion ratios were consistent with the rapid formation of a diprotonated intermediate, Ln(H(2)PCTA)(2+). The stabilities of the intermediates as determined from the kinetic data were 2.81, 3.12, 2.97, and 2.69 log K units for Ce(H(2)PCTA), Eu(H(2)PCTA), Y(H(2)PCTA), and Yb(H(2)PCTA), respectively. Rearrangement of these intermediates to the fully chelated complexes was the rate-determining step, and the rate constant (k(r)) for this process was found to be inversely proportional to the proton concentration. The formation rates (k(OH)) increased with a decrease in the lanthanide ion size [9.68 x 10(7), 1.74 x 10(8), 1.13 x 10(8), and 1.11 x 10(9) M(-1) s(-1) for Ce(PCTA), Eu(PCTA), Y(PCTA), and Yb(PCTA), respectively]. These data indicate that the Ln(PCTA) complexes exhibit the fastest formation rates among all lanthanide macrocyclic ligand complexes studied to date. The acid-catalyzed dissociation rates (k1) varied with the cation from 9.61 x 10(-4), 5.08 x 10(-4), 1.07 x 10(-3), and 2.80 x 10(-4) M(-1) s(-1) for Ce(PCTA), Eu(PCTA), Y(PCTA), and Yb(PCTA), respectively.     

Potentiometric studies of ternary complex formation Cu(II), Ni, Zn or Cd iminodiacetic acid/amino-acid complexes

The formation constants, log K(mab), for the reactions MA + B right harpoon over left harpoon MAB [where M = Cu(II), Ni, Zn or Cd, A = terdentate ligand and B = bidentate or terdentate ligand] have been determined. Potentiometric evidence is presented for the stepwise addition of the secondary ligand B to the 1:1 metal iminodiacetate (MA). The formation constants and the free energies of formation (DeltaG) have been calculated at 25 +/- 1 degrees and mu = 0.10. The order in terms of secondary ligands has been found to be ASPA > Gly > Aln and Gly > Aln > ASPA with iminodiacetic and nitrilotriacetic acid as primary ligands respectively (ASPA = aspartic acid, Gly = glycine, Aln = dl-alanine). The plot of log K(mab) against log k(mb)(2) shows a linear relationship between the formation constants of the ternary and 1:2 M(II)secondary ligand complexes.     

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.     

Metal ion complexing properties of dipyridoacridine, a highly preorganized tridentate homologue of 1,10-phenanthroline

DPA (dipyrido[4,3-b;5,6-b]acridine) may be considered as a tridentate homologue of phen (1,10-phenanthroline). In this paper some of the metal ion complexing properties of DPA in aqueous solution are reported. Using UV-visible spectroscopy to follow the intense π-π* transitions of DPA as a function of pH gave protonation constants at ionic strength (μ) = 0 and 25 °C of pK(1) = 4.57(3) and pK(2) = 2.90(3). Titration of 10(-5) M solutions of DPA with a variety of metal ions gave log K(1) values as follows: Zn(II), 7.9(1); Cd(II), 8.1(1); Pb(II), 8.3(1); La(III), 5.23(7); Gd(III), 5.7(1); Ca(II), 3.68; all at 25 °C and μ = 0. Log K(1) values at μ = 0.1 were obtained for Mg(II), 0.7(1); Sr(II), 2.20(1); Ba(II), 1.5(1). The log K(1) values show that the high level of preorganization of DPA leads to complexes 3 log units more stable than the corresponding terpyridyl complexes for large metal ions such as La(III) or Ca(II), but that for small metal ions such as Mg(II) and Zn(II) such stabilization is minimal. Molecular mechanics calculations (MM) are used to show that the best-fit M-N length for coordination with DPA is 2.60 ?, accounting for the high stability of Ca(II) or La(III) complexes of DPA, which are found to have close to this M-N bond length in their phen complexes.     

Stability constants of some metal complexes of triethylenetetraminehexa-acetic acid and complexometric titration of rare earths and other metals

The stability constants of some non-protonated 1:1 metal complexes of triethylenetetraminehexa-acetic acid are reported; log K values are Cd 19.8, Co(II) 20.4, Ni 19.9, Pb 19.5, Sm(III) 24.3, Zn 20.1.     

Metal ion-binding properties of (1H-benzimidazol-2-yl-methyl)phosphonate (Bimp2-) in aqueous solution. Isomeric equilibria, extent of chelation, and a new quantification method for the chelate effect

The acidity constants of the 2-fold protonated (1H-benzimidazol-2-yl-methyl)phosphonate, H2(Bimp)(+/-), are given, and the stability constants of the M(H;Bimp)+ and M(Bimp) complexes with the metal ions M2+ = Mg2+, Ca2+, Ba2+, Mn2+, Co2+, Cu2+, Zn2+, or Cd2+ have been determined by potentiometric pH titrations in aqueous solution at I = 0.1 M (NaNO3) and 25 degrees C. Application of previously determined straight-line plots of log KM(M(Bi-R)) versus pKH(H(Bi-R)) for benzimidazole-type ligands, Bi-R, where R represents a residue which does not affect metal ion binding, proves that the primary binding site in the M(H;Bimp)+ complexes is (mostly) N3 and that the proton is located at the phosphonate group; outersphere interactions seem to be important, and the degree of chelate formation is above 60% for all metal ion complexes studied, except for Zn(H;Bimp)+. A similar evaluation based on log KM(M(R-PO3)) versus pKH(H(R-PO3)) straight-line plots for simple phosph(on)ate ligands, R-, where R represents a residue which cannot participate in the coordination process, reveals that the primary binding site in the M(Bimp) complexes is (mostly) the phosphonate group with all metal ions studied. In this case, the formation degree of the chelates varies more widely in dependence on the kind of metal ion involved, i.e., from 17 +/- 11% to nearly 100% for Ba(Bimp) and Cu(Bimp), respectively. For all the M(H;Bimp)+ and M(Bimp) systems, the intramolecular equilibria between the isomeric complexes are evaluated in a quantitative manner. The fact that for Bimp2- the metal ion affinity of the two binding sites, N3 and PO3(2-), can be calculated independently, i.e., the corresponding micro stability constants become known, allows us to present for the first time a method for the quantification of the chelate effect solely based on comparisons of stability constants which carry the same dimensions. This effect is often ill defined in textbooks because equilibrium constants of different dimensions are compared, which is avoided in the present case. For the M(Bimp) complexes, it is shown that the chelate effect is close to zero for Ba(Bimp) whereas for Cu(Bimp) it amounts to about four log units. This method is also applicable to other chelating systems. Finally, considering that benzimidazole as well as phosphonate derivatives are employed as therapeutic agents, the potential biological properties of Bimp, especially regarding nucleic acid polymerases, are briefly discussed.     

Determination of stability constants of some bivalent metal complexes with thiovioluric and diphenylthiovioluric acids

Stability constants of complexes of some bivalent metal ions, viz, Cu(II), Ni(II), Zn(II), Pb(II) and Mg(II) with thiovioluric and diphenylthiovioluric acid have been determined potentiometrically in 50 and 75% dioxan media, respectively. The order of stability constants for the complexes investigated has been found to be: Mn < Ni < Cu > Zn. The stability of lead complexes has been found to be intermediate between Mn(II) and Ni(II) while magnesium forms the least stable complexes.     

Membrane filtration studies of aquatic humic substances and their metal species: a concise overview. Part 2. Evaluation of conditional stability constants by using ultrafiltration

The assessment of conditional stability constants of aquatic humic substance (HS) metal complexes is overviewed with special emphasis on the application of ultrafiltration methods. Fundamentals and limitations of stability functions in the case of macromolecular and polydisperse metal-HS species in aquatic environments are critically discussed. The review summarizes the advantages and application of ultrafiltration for metal-HS complexation studies, discusses the comparibility and reliability of stability constants. The potential of ultrafiltration procedures for characterizing the lability of metal-HS species is also stressed.     

Binary and ternary complexes of inosine

Formation of binary and ternary complexes of Cu(II) and Ni(II) metal ions with inosine as a primary ligand and some biologically important aliphatic and aromatic carboxylic acids (succinic, oxalic, malic, maleic, malonic, tartaric, 5-sulfosalicylic, salicylic and phthalic acids) as secondary ligands was studied by the potentiometric technique at 25 degrees C and 0.10 M (NaNO(3)) ionic strength. The ternary complex formation was found to take place in a stepwise manner. The stability constants of these binary and ternary systems were calculated. The lower stability of 1:2 complexes of inosine compared to the corresponding 1:1 systems is in accord with statistical considerations. The values of Delta log K for the ternary complexes studied have been evaluated and discussed. The mode of chelation of ternary complexes was ascertained by conductivity measurements.     

Analytical fractionation of aquatic humic substances and their metal species by means of multistage ultrafiltration

The molecular-size fractionation of aquatic humic substances (HS) and their metal species by means of a novel sequential-stage ultrafiltration (UF) device equipped with five appropriate ultramembranes (1, 5, 10, 50 and 100 kD) is described. First of all, the concentration dynamics of macromolecules, particulary HS, during five-stage UF and its subsequent washing step has been modelled. Based on these results, the fractionation of aquatic HS (from ground and bog water) by means of multistage UF has been optimized for an analytical scale (10 ml sample, 1 mg/ml HS, 10 ml washing solution, pH 6.0). The molecular size-distribution of selected aquatic HS (BOC 1/2 from the "DFG-Versuchsfeld Bocholt", VM 5 from "Venner Moor", Germany) studied by five-stage UF exhibited strong systematic influences of the procedure used for their isolation. The molecular-size distribution of HS obtained by on-line UF and gel permeation chromatography (GPC) showed a satisfactory agreement in the range 1-50 kD. Moreover, when interrupting multistage UF for > 48 h a slow transformation in the HS samples has been found as gradually additional HS fractions of < 1 kD have been formed. Besides unloaded HS molecules, the molecular-size distribution of freshly formed metal species of HS (1.0 mg metal/g HS of Al(III), Cd(II), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), Zn(II), each) has been characterized by multistage UF as a function of pH-value, degree of loading and complexation time. Metal determinations as carried out by flame AAS, showed that considerable metal fractions in HS especially are present in molecules > 50 kD, which seemed to be rather acid-inert. With complexation times of < 2 days a transient shift of the molecular size distribution of both HS and their metal species (e.g., Al(III), Fe(III) to higher values (> 10 kD) has been found.     

Protonation Equilibria of Carminic Acid and Stability Constants of Its Complexes with Some Divalent Metal Ions in Aqueous Solution

The dissociation constants of carminic acid (7-D-glucopyronosyl-3,5,6,8-tetra- hydroxy-1-methyl-9,10-dioxo-anthracene-2-carboxylic acid) (CA), together with the stability constants of its Cu(II), Zn(II), Ni(II), Co(II) and Hg(II) complexes, were studied potentiometrically in aqueous medium at 25.0?(1)?°C, and at the ionic background of 0.1?mol?dm^?3 of NaCl, and determined with the SUPERQUAD computer program. It has been observed that carminic acid has five dissociation constants, and for H₅L their values are 3.39?(7), 5.78?(7), 8.35?(7), 10.27?(7), and 11.51?(7). This ligand behaves as a bi-dentate ligand, and the carboxyl and the ortho hydroxy groups of the ligand coordinate to the metal ions. Various metal complexes were produced in solution under the experimental conditions, for each metal ion used, including hydrolyzed species. The species distribution curves of the complexes formed in the solution were calculated and reviewed. The stability of the complexes was found to follow the order: Cu(II) > Zn(II) > Ni(II) > Co(II) > Hg(II).     

Effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water coordination on the structure of glycine and zwitterionic glycine

Interactions between metal ions and amino acids are common both in solution and in the gas phase. Here, the effect of metal ions and water on the structure of glycine is examined. The effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water on structures of Gly.Mn+(H2O)m and GlyZwitt.Mn+(H2O)m (m = 0, 2, 5) complexes have been determined theoretically by employing the hybrid B3LYP exchange-correlation functional and using extended basis sets. Selected calculations were carried out also by means of CBS-QB3 model chemistry. The interaction enthalpies, entropies, and Gibbs energies of eight complexes Gly.Mn+ (Mn+ = Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) were determined at the B3LYP density functional level of theory. The computed Gibbs energies DeltaG degrees are negative and span a rather broad energy interval (from -90 to -1100 kJ mol(-1)), meaning that the ions studied form strong complexes. The largest interaction Gibbs energy (-1076 kJ mol(-1)) was computed for the NiGly2+ complex. Calculations of the molecular structure and relative stability of the Gly.Mn+(H2O)m and GlyZwitt.Mn+(H2O)m (Mn+ = Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+; m = 0, 2, and 5) systems indicate that in the complexes with monovalent metal cations the most stable species are the NO coordinated metal cations in non-zwitterionic glycine. Divalent cations Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+ prefer coordination via the OO bifurcated bonds of the zwitterionic glycine. Stepwise addition of two and five water molecules leads to considerable changes in the relative stability of the hydrated species. Addition of two water molecules at the metal ion in both Gly.Mn+ and GlyZwitt.Mn+ complexes reduces the relative stability of metallic complexes of glycine. For Mn+ = Li+ or Na+, the addition of five water molecules does not change the relative order of stability. In the Gly.K+ complex, the solvation shell of water molecules around K+ ion has, because of the larger size of the potassium cation, a different structure with a reduced number of hydrogen-bonded contacts. This results in a net preference (by 10.3 kJ mol(-1)) of the GlyZwitt.K+H2O5 system. Addition of five water molecules to the glycine complexes containing divalent cations Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+ results in a net preference for non-zwitterionic glycine species. The computed relative Gibbs energies are quite high (-10 to -38 kJ mol(-1)), and the NO coordination is preferred in the Gly.Mn+(H2O)5 (Mn+ = Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) complexes over the OO coordination.     

Dioxadiaza- and trioxadiaza-macrocycles containing one dibenzofuran unit selective for cadmium

The binding properties of dioxadiaza- ([17](DBF)N2O2) and trioxadiaza- ([22](DBF)N2O3), macrocyclic ligands containing a rigid dibenzofuran group (DBF), to metal cations and structural studies of their metal complexes have been carried out. The protonation constants of these two ligands and the stability constants of their complexes with Ca2+, Ba2+, and Mn2+, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+, were determined at 298.2 K in methanol-water (1:1, v/v), and at ionic strength 0.10 mol dm-3 in KNO3. The values of the protonation constants of both ligands are similar, indicating that no cavity size effect is observed. Only mononuclear complexes of these ligands with the divalent metal ions studied were found, and their stability constants are lower than expected, especially for the complexes of the macrocycle with smaller cavity size. However, the Cd2+ complex with [17](DBF)N2O2 exhibits the highest value of stability constant for the whole series of metal ions studied, indicating that this ligand reveals a remarkable selectivity for cadmium(II) in the presence of all the metal ions studied, except copper(II), indicating that this ligand reveals a remarkable selectivity for cadmium(II) in the presence of the mentioned metal ions. The crystal structures of H2[17](DBF)N2O3(2+) (diprotonated form of the ligand) and of its cadmium complex were determined by X-ray diffraction. The Cd2+ ion fits exactly inside the macrocyclic cavity exhibiting coordination number eight by coordination to all the donor atoms of the ligand, and additionally to two oxygen atoms from one nitrate anion and one oxygen atom from a water molecule. The nickel(II) and copper(II) complexes with the two ligands were further studied by UV-vis-NIR and the copper(II) complexes also by EPR spectroscopic techniques in solution indicating square-pyramidal structures and suggesting that only one nitrogen and oxygen donors of the ligands are bound to the metal. However an additional weak interaction of the second nitrogen cannot be ruled out.