Complexation and Electronic Spectra of Neodymium(III)–Amino Acid–1,10-Phenanthroline Systems in Aqueous Solution

Complexation of neodymium(III)-glutamate(glu)-phenanthroline(phen), neodymium(III)-aspartate(asp)-phenanthroline(phen) ternary systems and the corresponding binary systems in aqueous solution are discussed at various values of pH. Based on change regularity of hypersensitive transition intensities, the neodymium(III)-aspartate-phenanthroline ternary complex has a general formula of Nd(asp)₃phen, but the composition of the complex of Nd(III) with glutamate and phenanthroline is complicated and has not been determined. The electronic spectra of these complexes were studied, Slater-Condon parametersF _k ^s and the Lande parameter ξ_4f were obtained. The rms deviation between calculated and observed energy levels is less than 43 cm⁻¹. Bonding in these complexes are also investigated and bonding parameters calculated. The results show that Nd(III) and amino acids form complexes by ionic linkage with carboxylic oxygens, but with some weak covalency. Besides, the degrees of covalency in ternary complexes are larger than those in binary complexes.     

Copper(II), iron(III), and chromium(III) complexes with 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene derivatives

Six copper(II), iron(III), and chromium(III) complexes with 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene derivatives (H₂L¹-H₂L³) have been synthesized and studied by physical methods (IR and electronic absorption spectroscopy, quantum-chemical calculations). The composition of the complexes has been determined and their stability constants in aqueous dimethylformamide solutions have been calculated. The energy characteristics, electronic structure and geometry of isolated diazapyrenes and their tautomeric forms have been calculated by the PM6 method, and their complexes have been modeled.     

Ferric Chloride Complexes in Aqueous Solution: An EXAFS Study

A series of concentrated aqueous solutions of ferric chloride with different chloride:iron(III) ratios has been studied by means of EXAFS to determine the structure around the iron(III) ion of the dominating species in such solutions. The dominating species in dilute acidic aqueous solution of ferric chloride, at less than 1 mmol·dm^?3, are the hydrated iron(III) and chloride ions, while in concentrated aqueous solution and in solutions with an excess of chloride ions, up to 1.0 mol·dm^?3, it is the trans-[FeCl₂(H₂O)₄]⁺ complex. Possible higher chloroferrate(III) or dimeric [Fe₂Cl₆] complexes at room temperature, as proposed in the literature, were not observed in any of the studied solutions in spite of an excess of chloride ions of 1 mol·dm^?3.     

Chiral Sensing of Various Amino Acids Using Induced Circularly Polarized Luminescence from Europium(III) Complexes of Phenanthroline Dicarboxylic Acid Derivatives

Circularly polarized luminescence (CPL) was observed from [Eu(dppda)₂]^? (dppda=4,7‐diphenyl‐1,10‐phenanthroline‐2,9‐dicarboxylic acid) and [Eu(pzpda)₂]^? (pzpda=pyrazino[2,3‐f][1,10]phenanthroline‐7,10‐dicarboxylic acid) in aqueous solutions containing various amino acids. The selectivity of these complexes towards amino acids enabled them to be used as chiral sensors and their behavior was compared with that of [Eu(pda)₂]^? (pda=1,10‐phenanthroline‐2,9‐dicarboxylic acid). As these Eu^III complexes have achiral D_2d structures under ordinary conditions, there were no CPL signals in the emission assigned to f–f transitions. However, when the solutions contained particular amino acids they exhibited detectable CPL signals with g_lum values of about 0.1 (g_lum=CPL/2 TL; TL=total luminescence). On examining 13 amino acids with these three Eu^III complexes, it was found that whether an amino acid induced a detectable CPL depended on the Eu^III complex ligands. For example, when ornithine was used as a chiral agent, only [Eu(dppda)₂]^? exhibited intense CPL in aqueous solutions of 10^?2 mol dm^?3. Steep amino acid concentration dependence suggested that CPL in [Eu(dppda)₂]^? and [Eu(pzpda)₂]^? was induced by the association of four or more amino acid molecules, whereas CPL in [Eu(pda)₂]^? was induced by association of two arginine molecules.     

Mössbauer, vibrational spectroscopic and solution X-ray diffraction studies of the structure of iron(III) complexes formed with indole-3-alkanoic acids in acidic aqueous solutions

The chemical reactions between iron(III) and indole-3-acetic (IAA), -propionic (IPA), and -butyric (IBA) acids were studied in acidic aqueous solutions. The motivation of this work was that IAA is one of the most powerful natural plant-growth-regulating substances (phytohormones of the auxin series). Mössbauer spectra of the frozen aqueous solutions of iron(III) with indole-3-alkanoic acids as ligands (L), showed parallel reactions between Fe³⁺ and the ligands. Partly, it resulted in a complex formation which precipitated in aqueous solution and partly, in a redox process with iron(II) and the oxidised indole-3-alkanoic acids as products. The Mössbauer parameters of the Fe²⁺ species suggested a hexaaquo coordination environment. The chemical composition and coordination structure of the precipitated complexes were investigated using elemental analysis, Mössbauer spectroscopy, Fourier transform infrared (FTIR) and Raman spectroscopic techniques. The complexes were soluble in some organic solvents. So, Mössbauer, FTIR and solution X-ray diffraction measurements were carried out on the solution of complexes in acetone, hexadeutero acetone and methanol, respectively. The data obtained supported the existence of the μ-dihydroxo-bridging structure of the dimer: [L₂Fe<(OH)₂>FeL₂] (where L is indole-3-propionate, -acetate or -butyrate).     

Direct 1H, 13C, and 15N NMR Study of Lanthanum(III), Thulium(III), and Ytterbium(III) Complex Formation with Nitrate and Isothiocyanate

An ¹H, ¹³C, and ¹⁵N NMR study has been completed for the complexes of La(III), Tm(III), and Yb(III) with nitrate and isothiocyanate in aqueous solvent mixtures. Signals for four complexes are observed for both the Tm³⁺–NO₃ ^– and Yb³⁺–NO₃ ^– solutions, with the species identified as the mono-, di-, tetra-, and either the penta - or hexanitrato. These results are consistent with those determined for the nitrate complexes of the Ce(III)–Eu(III) metal ions. The chemical shifts for the Tm(III) and Yb(III) nitrate complexes indicate a pseudocontact binding mechanism prevails. The complexes of diamagnetic La(III) with NO₃ ^– produce three signals in the ¹⁵NO₃ ^– spectra, with assignments paralleling those observed with the paramagnetic lanthanides. Three complexes are formed in the La³⁺–NCS^– solutions, with signals assigned to the mono-, di-, and triisothiocyanato species.     

Interactions of some amino acids and glycine peptides with aqueous sodium dodecyl sulfate and cetyltrimethylammonium bromide at T=298.15 K: a volumetric approach

The apparent molar volumes V_φ of glycine, alanine, valine, leucine, and lysine have been determined in aqueous solutions of 0.05, 0.5, 1.0 mol · kg⁻¹ sodium dodecyl sulfate (SDS) and 1.0 mol · kg⁻¹ cetyltrimethylammonium bromide (CTAB) by density measurements at T=298.15 K. The apparent molar volumes have also been determined for diglycine and triglycine in 1 mol · kg⁻¹ SDS and CTAB solutions. These data have been used to calculate the infinite dilution apparent molar volumes V₂⁰ for the amino acids and peptides in aqueous SDS and CTAB and the standard partial molar volumes of transfer (Δ_trV_2,m⁰) of the amino acids and peptides to these aqueous surfactant solutions. The linear correlation of V₂⁰ for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH₃⁺, COO⁻), CH₂ group and other alkyl chains of the amino acids to V₂⁰. The results on the partial molar volumes of transfer from water to aqueous SDS and CTAB have been interpreted in terms of ion–ion, ion–polar and hydrophobic–hydrophobic group interactions. The volume of transfer data suggests that ion–ion or ion–hydrophilic group interactions of the amino acids and peptides are stronger with SDS compared to those with CTAB. Comparison of the hydration numbers of amino acids calculated in the present studies with those in other solvents from literature shows that these numbers are almost the same at 1 mol · kg⁻¹ level of the cosolvent/cosolute. Increasing molality of the cosolvent/cosolute beyond 1 mol · kg⁻¹ lowers the hydration number of the amino acids due to increased interactions with the solvent and reduced electrostriction.     

Cobalt(III)-Gemischtligandenkomplexe mit Phenanthrolin und Picolinsäure. Darstellung,Charakterisierung und einige photochemische Eigenschaften

Mixed-Ligand Complexes of Cobalt(III) with Phenanthroline and Picolinate. Preparation, Characterization, and Some Photochemical Properties Three new cobalt(III) complexes, Co(phen)₂pic²⁺, trans(N)? Co(pic)₂phen⁺, and trans(O)? Co(pic)₂phen⁺ (phen-1, 10-phenanthroline, pic-picolinate), have been isolated and characterized by ¹H-NMR and UV-VIS spectra. Some preliminary data concerning biacetyl-sensitized photochemical decomposition of these complexes in aqueous solutions are reported.     

Partial Molar Volumes of Amino Acids and Peptides in Aqueous Salt Solutions at 25°C and a Correlation with Stability of Proteins in the Presence of Salts

Partial molar volumes for a homologous series of amino acids and peptides have been measured in aqueous 1M sodium acetate, sodium thiocyanate, and sodium sulfate at 25^°C. These data have been utilized in conjunction with the data in water to deduce partial molar volumes of transfer V _2,m ⁰(tr) from water to these aqueous salt solutions. The volumes of transfer for the amino acids and peptides are found to be positive. The interpretation is that this result arises from the dominant interaction of the sodium salts with the charged centers of amino acids and peptides. Thermal denaturation of the structurally homologous proteins lysozyme and -lactalbumin has been studied in the presence of these salts. Significant thermal stabilization of hen egg-white lysozyme has been observed in the presence of sodium acetate and sodium sulfate. However, the thermal stabilization observed for -lactalbumin is very small in the presence of these salts and sodium thiocyanate leads to a lowering of its thermal denaturation temperature. The rise in the surface tension of aqueous salt solutions with salt concentration has been correlated with the calorimetric and volumetric measurements. The results show that V _2,m ⁰(tr) depends less on the type of electrolyte than on the ionic strength of the solution. The V _2,m ⁰(tr) values correlate very well with the increase in the surface tension of aqueous salt solutions, indicating significant role of surface tension in interactions of amino acids, peptides, or protein with the salts.     

Preparation, spectroscopic and high field NMR relaxometry studies of gadolinium(III) complexes with the asymmetric tetraamine 1,4,7,11-tetraazaundecane

The reaction of Gd(III) with asymmetric tetramine 1,4,7,11-tetraazaundecane (2,2,3-tet, L¹) ligand has been studied via NMR spectroscopy. The ligand proton longitudinal relaxation rates (R₁) have been used to estimate the distances of these protons from the Gd(III) center, in Gd(III)–L¹ reaction solutions, in H₂O/D₂O 5/1 mixtures.Two Gd(III) complexes [Gd(III)(L¹)(NH₃)(H₂O)₄](CH₃COO)₃·2H₂O (1) and [Gd(III)(L¹)(NH₃)(H₂O)₂]Cl₃·EtOH (2) have been isolated and characterized by elemental analyses, TGA, IR, NMR and relaxometry measurements. The NMR relaxation measurements of 2 in aqueous solutions have been performed, under various temperature or concentration conditions, and compared with those of the commercial contrast agents Gd(III)–DTPA and Gd(III)–DTPA-BMA. It has also been studied the influence of (i) the Gd(III) inner-sphere water molecule number (q) alteration and (ii) the steric constraint enhancement on the metal site, over the relaxation rate values of the parent aqueous solution of Gd(III)–2,2,3-tet, and of the aqueous solutions of 2.     

Mixed-ligand fluorocuprates(II). Synthesis and characterisation of [CuF3L(H2O)2]− containing amino acids as coligands

Complex species of the type NH₄[CuF₃L(H₂O)₂] · nH₂O (L = glycine, n = 1; 1-alanine, n = 0) have been prepared by reacting hydrated copper(II) oxide, CuO · nH₂O, with the amino acids in the presence of bifluoride, HF₂ ^–, in aqueous solution. The order of addition of the ligands, fluoride and amino acids is crucial to the synthesis. A reaction solution pH lower than the isoelectric point of the respective amino acids seems to favour the formation of mixed-ligand fluoro complexes. Occurring as zwitterions, the amino acids in the complexes have been shown to be bonded to the copper(II) centre via the carboxyl (—COO^–) moiety representing an unexpected non-chelated form of the coligands. Magnetic moments and e.s.r. data are consistent with six-coordinate copper(II) complexes.     

Solution Properties of Azidokojatoiron(III) Complexes

The formation of iron(III) complexes with chelating azidokojate anions L⁻ was investigated in aqueous solutions as a function of the pH and the c(Fe³⁺):c(HL) molar ratio. Based on the stability constants, the distribution among the above complexes, [Fe(H₂O)₆]³⁺, and [Fe(H₂O)₅(OH)]²⁺ were calculated in solutions of various compositions. The complexes are redox stable in aqueous solutions both in the dark and in visible laboratory light. Properties of the investigated azidokojic acid and its iron(III) complexes are compared with those required for therapeutic applications as alternative iron chelators.     

Volumetric Properties of Amino Acids and Hen-Egg White Lysozyme in Aqueous Triton X-100 at 298.15 K

The apparent molar volumes, V_,2, of glycine, alanine, -amino-n-butyric acid, valine, leucine, and lysine monohydrochloride have been determined in aqueous solutions of 0.05, 0.1, and 0.4 mol-kg^–1 Triton X-100 (TX-100), and the partial specific volume, v⁰, of hen-egg-white lysozyme in 0.4 mol-kg^–1 TX-100 by density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volumes, V_2,m⁰, for the amino acids in aqueous TX-100 solutions and the standard partial molar volumes of transfer, _tr V_2,m⁰, of the amino acids from water to the aqueous surfactant solutions. The linear correlation of V_2,m⁰ for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH₃⁺, COO^–), CH₂ group and other alkyl chains of the amino acids to V_2,m⁰. The results on _tr V_2,m⁰, of amino acids from water to aqueous TX-100 solutions have been interpreted in terms of ion–ion, ion–polar, hydrophilic–hydrophilic and hydrophobic–hydrophobic group interactions. For all the six amino acids studied, the values of _tr V_2,m⁰ from water to all the studied concentrations of aqueous TX-100 are small in spite of their different hydrophobic content, indicating an overall balance in interactions of zwitterionic/hydrophilic groups of amino acids with the hydrophilic groups of TX-100, and of hydrophobic and ionic/hydrophilic groups of the amino acids with hydrophobic groups of TX-100. Comparison of the interactions of the amino acids with nonionic, anionic and cationic surfactants has also been made and discussed. The partial specific volume of transfer of lysozyme from water to aqueous TX-100 solutions also indicates a balance of the hydrophobic and hydrophilic interactions in the protein–nonionic surfactant system.     

Partial Molar Volumes of Some of α-Amino Acids in Binary Aqueous Solutions of MgSO4·7H2O at 298.15 K

The apparent molar volume, V ^o _{φ, 2}, of glycine, alanine, α-amino-n-butyric acid, valine and leucine have been determined in aqueous solutions of 0.25, 0.5 and 1.0 mol⋅dm⁻³ magnesium sulfate, and the partial specific volume from density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volume, V ^o _2,m , group contribution of amino acids and partial molar volume of transfer, Δ_tr V _2,m ^o, from water to aqueous magnesium sulfate solutions. The linear correlation of V _2,m ^o for a homologous series of amino acids has been utilized to calculate the contributions of charged end groups (NH₃ ⁺, COO⁻), CH₂ - groups and other alkyl chains of amino acids to V _2,m ^o. The results for Δ_tr V _2,m ^o of amino acids from water to aqueous magnesium sulfate solutions have been interpreted in terms of ion-ion, ion-polar, hydrophilic-hydrophilic and hydrophobic-hydrophobic group interactions. The values of the standard partial molar volume of transfer for the amino acids with different hydrophobic contents, from water to aqueous MgSO₄ are in general positive, indicating the predominance of the interactions of zwitterionic/hydrophilic groups of amino acids with ions of the salt. The hydration number decreases with increasing concentration of salt. The number of water molecules hydrated to amino acids decreases, further strengthening the predominance of ionic/hydrophilic interactions in this system.     

Use of Different Salt Solutions in Salting-Out TLC of Co(III) Complexes on Silica Gel

Saturated aqueous solutions of 28 different salts have been studied as a potential mobile phases for salting-out thin-layer chromatography, on silica gel, of a series of four mixed bis-aminocarboxylato cobalt(III) complexes. In addition, by linear regression analysis of chromatographic data obtained for fifteen mixed aminocarboxylato Co(III) complexes (four series) with solutions of ammonium chloride, three alkali metal chlorides, and four alkaline earth metal chlorides, four linear dependences previously established on different adsorbents with (NH₄)₂SO₄ solutions were confirmed. The qualities of the separations achieved with the salts were compared and Li⁺, Mg²⁺, and Ca²⁺ chlorides are proposed as the most suitable.     

Extraction and sorption preconcentration of rhenium with the use of 2-phosphorylphenoxyacetamides

Interfacial distribution of micro amount of ReO₄ ^- between aqueous solutions of mineral acids and solutions of 2-phosphorylphenoxyacetamides in dichloroethane has been studied. Stoichiometry of extracted complexes has been determined; the effect of HNO₃, HCl, and H₂SO₄ concentration in aqueous phase, extractant structure, and organic solvent nature on the efficiency of ReO₄ ^- ions transfer into organic phase has been considered. It has been shown that Re(VII) can be selectively recovered and concentrated with complexing sorbent obtained by the noncovalent binding of 2-[2-(diphenylphosphoryl)-4-ethylphenoxy]-N,N-dioctylacetamide on the surface of macroporous polymer Amberlite XAD7HP.     

Thermodynamics and kinetics of complexation of iron(III) ion by picolinic and dipicolinic acids

The complexation reactions of iron(III) with 2-pyridine carboxylic acia (picolinic acid) and 2,6-pyridine dicarboxylic acid (dipicolinic acid) in aqueous solutions have been studied by spectrophotometric and stopped flow techniques. Equilibrium constants were determined for the 1 : 1 complexes at temperatures between 25 and 80°C. The values obtained are: Picolinic Acid (HL): Fe³⁺+ H₂L⁺? FeHL³⁺+H+(K₁ = 2.8,ΔH = 2 kcal mole^?1 at 25°C, μ = 2.67 M) Dipicolinic Acid (H₂D): Fe³⁺+H₂D? FeD⁺+2H⁺(K₁K_1A= 227 M, ΔH = 3.4 kcal mole^?1 at 25°C,μ = 1.0 M). The rate constants for the formation of these complexes are also given. The results are used to evaluate the effects of these two acids upon the rate of dissolution of iron(III) from its oxides.     

Microscopic Imaging of Chiral Amino Acids in Agar Gel through Circularly Polarized Luminescence of EuIII Complex

We recently found that [Eu(pda)₂]^? (pda: 1,10‐phenanthroline‐2,9‐dicarboxylic acid), which has an achiral structure in crystals, exhibits circularly polarized luminescence (CPL) in aqueous solutions containing chiral amino acids such as arginine and histidine. CPL measurements were performed for agar gel, which includes an aqueous solution of [Eu(pda)₂]^? and chiral arginine or histidine. The spectral shape, concentration, and pH dependences on CPL intensity in the agar gels were very close to those in aqueous solutions, indicating that the CPL of the Eu^III complex in the agar gels was induced by mechanism similar to that in aqueous solutions. We performed spatially resolved CPL measurements using a laboratory‐built microscopic CPL spectroscopic system for agar‐gel samples, where d ‐ and l ‐ amino acids were separately dispersed. We successfully recorded CPL imaging maps showing spatial dispersions of d ‐ and l ‐amino acid in the agar gels.     

Studies on mixed ligand complexes of samarium(III), europium(III) and dysprosium(III) with 1-nitroso-2-naphthol and trioctylphosphine oxide

The extraction behavior of Sm(III), Eu(III) and Dy(III) with 1-nitroso-2-naphthol (HA) and trioctylphosphine oxide (TOPO) in methyl isobutyl ketone (MIBK) from aqueous NaClO₄ solutions in the pH range 4–9 at 0.1M ionic strength has been studied. The equilibrium concentrations of Sm and Dy were measured using their short-lived neutron activation products,¹⁵⁵Sm and^165mDy, respectively. In the case of Eu, the concentrations were assayed through the^152,154Eu radiotracer. The distribution ratios of these elements were determined as a function of pH, 1-nitroso-2-naphthol and TOPO concentrations. The extractions of Sm, Eu and Dy were found to be quantitative with MIBK solutions in the pH range 5.9–7.5, 5.6–7.5 and 5.8–7.5, respectively. Quantitative extraction of Eu was also obtained between pH 5.8 and 8.8 with chloroform solutions. The results show that these lanthanides (Ln) are extracted as LnA₃ chelates with 1-nitroso-2-naphthol alone, and in the presence of TOPO as LnA₃(TOPO) and LnA₃(TOPO)₂ adducts. The extraction constants and the adduct formation constants of these complexes have been calculated.     

Cationic complexes of Eu(III) and Sr(II) with diphosphine dioxides in organic extracts

IR spectroscopy was used to study the structure and composition of Eu(III) and Sr(II) complexes formed by cation-exchange extraction of these metals from their aqueous nitrate solutions with dichlorethane solutions of mixtures of chlorinated cobalt(III) dicarbollide (CCD) as a superacid with diphenyldiphosphine dioxides containing a methyl (Me-DPDO), ethyl (Et-DPDO), or polyoxyethylene bridge between two phosphorus atoms of phosphine oxide groups. At molar ratios DPDO/CCD ≤ 1, [Eu(H₂O)_nL₄]³⁺ complexes are formed in organic phases, whereas with an excess of DPDO relative to CCD, Eu(NO₃)L ₄ ²⁺ complexes are formed, where L = Me-or Et-DPDO. Polyoxyethylenediphosphine dioxide forms anhydrous complexes of composition Eu:L = 1:1 and 1:2 with Eu(III) and outer-spheric complexes of composition Sr:L = 1:1 and 1:2 with Sr(II), where the organic ligand molecules envelop the hydrated Sr(H₂O) _n ²⁺ cation. The peculiarities of extraction of the complexes are explained based on data about their composition and structure.