Complexation of Eu(III), Am(III) and Cm(III) with Dicarboxylates: Thermodynamics and Structural Aspects of the Binary and Ternary Complexes

The complexation of Eu(III), Am(III) and Cm(III) with dicarboxylate anions with O, N or S donor groups was measured in I=6.60 mol⋅kg⁻¹ (NaClO₄) at temperatures of 0–60 °C by potentiometry and solvent extraction. The complexation thermodynamics of these complexes show that their stability is due to highly favorable complexation entropies because the complexation enthalpies are endothermic. Luminescence studies with Eu(III) and Cm(III) were used to measure the hydration numbers of the complexes. NMR spectra of ¹H and ¹³C were used to determine the binding modes of La(III) with the ligands. The formation of 1:1:1 ternary complexes of M(EDTA)⁻ with the dicarboxylate ligands was studied to determine changes in coordination of the metal cation with formation of the ternary species. The complexation of ternary complexes changes from bidentate to monodentate as the chain length between the binding sites of the dicarboxylates increases from 1 (malonate) to 4 (adipate). DFT computations were used to confirm the structural aspects of the interaction of these complexes.     

Spectroscopic Studies on the Molecular Complex of the Drug Atenolol with Iodine

Spectroscopic and spectrofluorimetric studies were made of the interaction between the drug atenolol and iodine. The interaction was found to proceed through the initial formation of a charge transfer (CT) complex as an intermediate species. The product of this interaction has been isolated and characterized using UV-Vis, FT-IR and Raman spectroscopic techniques. Formation of the triodide I₃^-\mathrm{I}_{3}^{-} species was confirmed by its electronic and Raman spectra. Peaks appeared in Raman spectrum of the isolated product at 153, 102 and 85 cm⁻¹ that are assigned to ν _as(I-I), ν _s(I-I) and d(I₃^-)\delta(\mathrm{I}_{3}^{-}) respectively, which confirmed the presence of the I₃^-\mathrm{I}_{3}^{-} ion. The stoichiometry of the complex was found to be 1:2. The rate of their reaction has been measured as a function of time and solvent. Pseudo-first-order rate constants for the reaction were measured at various temperatures and the thermodynamic activation parameters (ΔG ^#,ΔS ^# and ΔH ^#) were computed. Preliminary fluorescence quenching studies indicated that the interaction between atenolol and iodine is spontaneous and proceeds through a CT complex, and the quenching of fluorescence of atenolol by iodine increases as the extent of such complexation increases     

Thermodynamic Features of the Complexation of Neodymium(III) and Americium(III) by Lactate in Trifluoromethanesulfonate Media

The protonation of lactate has been studied in a variety of electrolyte solutions using microcalorimetry to reveal a distinct medium influence imposed on the thermochemistry of the equilibrium. The thermochemistry of lactate protonation, when studied directly in 1.0 mol⋅L⁻¹ sodium lactate, agreed well with the studies performed in trifluoromethanesulfonate (triflate). This thermodynamic agreement suggests that the physical chemistry of lactate in the solutions applicable to the TALSPEAK process—a solvent extraction method for separating trivalent actinides from trivalent lanthanides within the scope of used nuclear fuel processing efforts—may be simulated in triflate solutions. Potentiometry, spectrophotometry and microcalorimetry have been subsequently used to study the thermodynamic features of neodymium and americium complexation by lactate using triflate as a strong background electrolyte. Three successive mononuclear lactate complexes were identified for Nd(III) and Am(III). The stability constants for neodymium, β ₁₀₁=2.60±0.01, β ₁₀₂=4.66±0.02 and β ₁₀₃=5.6±0.1, and for americium, β ₁₀₁=2.60±0.06, β ₁₀₂=4.7±0.1 and β ₁₀₃=6.2±0.2, were found to closely agree with the thermodynamic studies reported in sodium perchlorate solutions. Consequently, the thermodynamic medium effect, imposed on the TALSPEAK-related solution equilibria by the presence of strong background electrolytes such as NaClO₄ and NaNO₃, does not significantly impact the speciation in solution.     

Complexation of Sc(III), Ga(III), In(III) and Ln(III) with Eriochrome Red B

Cyclic linear-sweep voltammetry was used to study the complexation of Sc(III), Ga(III), In(III) and Ln(III) with eriochrome red B (ERB). It was established that all metal ions investigated form complex compounds with azodye having a mole ratio, M(III):ERB = 1:2. The hydroxo forms of M(III) ions, which take part in interaction with ERB, were determined by the Nazarenko method. The stability constants for the formation of these chelates are nearly the same. It was shown that the reduction of the ligand in the complex does not only depend on the peculiarities of complexation, but the processes occurring in pre-electrode layer also influence it.     

Studies on Thermodynamics Features of the Interaction between Imidacloprid and Bovine Serum Albumin

At different temperatures, the interactions between imidacloprid （IMI） and bovine serum albumin （BSA） were investigated with a fluorescence quenching spectrum, a synchronous fluorescence spectrum, a three-dimensional fluorescence spectrum and an ultraviolet-visible spectrum. The average values of bonding constants （KLB： 3.424 × 10^4 L,mol^-1）, thermodynamic parameters （△H： 5.188 kJ,mol^-1, △G^（○—）：-26.36 kJ,mol^-1, △S： 103.9 J,K^-1,mol^-1） and the numbers of bonding sites （n： 1.156） could be obtained through Stern-Volmer, Lineweaver-Burk and ther- modynamic equations. It was shown that the fluorescence of BSA could be quenched for its reactions with IMI to form a certain kind of new compound. The quenching belonged to a static fluorescence quenching, with a non-radiation energy transfer happening within a single molecule. The thermodynamic parameters agree with △H〉 0, △S〉0 and△G^（○-）〈0, suggesting that the binding power between IMI and BSA should be mainly a hydrophobic interaction.     

Molecular Dynamics Simulation Studies on the Cooling Process of Polyvinyl Chloride

IntroductionRecently,molecular dynamics(MD)simulationhas been used extensively in the study of polymer sys-tems[1—11].The increased interest in computer simula-tion is assisted by the fast evolution of computer tech-nology,which makes molecular simulatio…     

Spectrophotometric Study of the Complexation of Indium(III) With the α-Diketone Bis(4-Phenyl-3-Thiosemicarbazones) Derived From Glyoxal,Biacetyl and Methylglyoxal

Abstract

Indium(III) reacts with α-diketone bisphenylthiosemicarbazones derived from glyoxal, biacetyl and methylglyoxal to form 1:1 and 1:2 (In: reagent) complexes in acid and basic medium, respectively. The effect of experimental variables was studied in detail on the acid site, and a new method for the spectrophotometric determination of indium(III) with meth-ylglyoxal bis(4-phenyl-3-thiosemicarbazone) (MGBPT) is proposed. The yellow 1:1 In-MGBPT complex is formed at pH 3.5–6 in a solution containing a 60 % V/V of dimethylforrnamide. The nature of the complex (? = 27,100 1 mol^?1 cm^?1 at 465 mm) and the effect of interferences were studied.     

Inclusion Complexation Thermodynamics of Acridine Red and Rhodamine B by Natural and Novel Oligo(ethylenediamine) Tethered Schiff Base β-Cyclodextrin

A series of Schiff base -cyclodextrin derivatives 2–5 with an oligo(ethylenediamine)tether have been newly synthesized and their inclusion complexation behavior has beenassessed and discussed thermodynamically, employing acridine red (AR) and rhodamine B (RhB) as representative guests. Fluorescence spectrophotometric titrations have been performed in methanol-water (1 : 2) phosphate buffer solution (pH = 7.20) at 25.0–45.0 °C in order to obtain the complex stability constants (K_S) and the thermodynamic parameters ( H° and T S°) for the stoichiometric 1 : 1 inclusion complexation of two guests with the native and modified -cyclodextrins ( 1 and 2–5). As compared with theparent -cyclodextrin 1, all of the chemical modifications to the primary side of -cyclodextrins examined led to substantial decreases for rhodamine B and marked increases for acridine red in complex stability, which are elucidated in terms of the induced-fit interaction and the complementary geometrical relationship between the host -cyclodextrins and guest molecules, as well as the length of the linking chain of -CD derivatives. The induced circular dichroism spectral analyses of these -cyclodextrin derivatives indicated that the aromatic moiety in modified -cyclodextrins is not embeded into the hydrophobic cavity ofcyclodextrin. The inclusion complexation of 2–5 with acridine red possess higher binding constants than that with rhodamine B, which are solely attributed to the increased enthalpic gain. Thermodynamically, the inclusion complexation with the modified -cyclodextrins 2–5 is absolutely enthalpy-driven for acridine red, while for complexation with rhodamine B is mainly entropy-driven.     

Molecular Modeling Studies of the β-Cyclodextrin in Monomer and Dimer Form as Hosts for the Complexation of Cholesterol

Molecular modeling studies on the inclusion complex formation ofcholesterol with -cyclodextrin in monomer anddimer form were performed. Monte Carlo docking simulations, moleculardynamics, and non-equilibrium molecular dynamicssimulations were applied to assess the energeticdriving force for the formation of these inclusioncomplexes. Both Monte Carlo docking and moleculardynamics simulations supported the more favorableinclusion complex formation of -cyclodextrindimer. Non-equilibrium molecular dynamics simulationsprovided a direct assessment of the binding force for theinclusion complexes, of which that of dimer form is much greater.     

A Molecular Modeling for the Complexation of Cyclobis(paraquat-p-phenylene) with Substituted Benzenes and Biphenyls

The molecular recognition of cyclobis(paraquat-p-phenylene), 14+, has drawn great attention recently, due to its important applications in the design and synthesis of electrochemically and chemically switchable rotaxanes, photoactive rotaxanes, and other molecular devices1. Usually, this type of molecular recognition was investigated with the methods including X-ray, NMR, UV, and IR. However, since these methods usually have difficulties in providing a detailed understanding of the energeti…     

Studies on Thermodynamics of Micellization and Solvophobic Interactions of Novel Surfactant–Cr(III) Complexes in Non-aqueous Solvents

The critical micelle concentration (CMC) of surfactant–Cr(III)–dodecylamine complexes of the type cis-α-[Cr(trien)(C₁₂H₂₅NH₂)X]²⁺ (where trien = triethylenetetramine; X = F⁻, Cl⁻, Br⁻) has been studied in n-alcohol and in formamide at different temperatures, by electrical conductivity measurements. From the CMC values as a function of temperature, various thermodynamic properties have been evaluated: standard Gibbs energy changes (Δ_mic G ⁰), standard enthalpy changes (Δ_mic H ⁰) and standard entropy changes (Δ_mic S ⁰) for micellization. Critical micelle concentrations have also been measured as a function of the percentage composition of alcohol added. The solvent composition dependences of these thermodynamic parameters were determined. It is suggested that alcohol addition leads to an increase in formamide penetration into the micellar interface that depends on the alcohol’s chain length. The results are discussed in terms of an increased hydrophobic effect, dielectric constant of the medium, the chain length of the alcohols, and the surfactant in the solvent mixture.     

Electrochemical and Spectroscopic Studies on Interaction between Complex of Copper(Ⅱ) with Schiff Base Ligand and DNA

The crystal structure of ( [CuL (H2O) 2 ] (ClO4) 2 · 2H2O, CuL) (L ＝ N- (5-sulfosalicylidene)-4' -bromoaniline) was determined by means of X-ray crystallography. The interaction between CuL and salmon sperm DNA in a 0. 1 mol/L HOAc-NaOAc buffer solution (pH 5.10) was investigated by cyclic voltammetry and UV-Vis spectroscopy. A couple of redox peaks of CuL in the cyclic voltammograms(CV) can be seen at the glassy carbon electrode. It was found that the peak current of CuL decreased significantly with a negative shift of the peak potential in the presence of DNA compared with that in the absence of DNA. In addition,the decreased absorbance of CuL was observed with increasing the concentration of DNA; the absorption spectrum of an ethidium bromide(EB)-DNA system inthe presence of CuL confirms that the binding mode of CuL to DNA is different from the intercalation of EB with DNA. All the experimental results indicate that CuL can bind to DNA by electrostatic binding and form a 1:1 association complex with a binding constant of 2.72×104 L/mol.     

Spectrophotometric and Voltammetric Studies on the Interaction of Heparin with Phenosafranine

The interaction of phenosafranine （PSF） with a glycosaminoglycans of heparin （Hep） in aqueous solution has been characterized by UV-Vis absorption spectrophotometry and cyclic voltammetry in pH 1.5 Britton-Robinson （B-R） buffer solution. The addition of Hep caused decrease of the absorbance of PSF at 532 nm and the redox peak current of PSF. The study showed that an supramolecular complex of PSF-Hep was formed because of the electrostatic attraction of negatively charged Hep with the positively charged PSF, which resulted in the decrease of the equilibrium concentration of PSF in solutions, and the decrease of the absorbance or the peak current of PSF. The stoichiometry of the Hep/PSF complex was further calculated by voltammetric data with the result of 1：1 complex.     

Raman Spectroscopic Studies on the Complexation and Adsorbed Behaviour of Thiourea

Raman spectroscopic studies on thiourea (TU) in highly acidic media (e. g. >3 mol/L HC1O4) show that TU as a solution species is protonated through its sulphur atom and forms complex with anions. However, as an adsorbed species, TU is protonated via the nitrogen atom and adsorbed at the silver electrode surface through the sulphur atom. The distinct effects of pH and anions of the solution on the surface enhanced Raman (SER) spectra of TU were investigated. In acidic and neutral solutions, TU is coadsorbed with anions through its NH3 and - NH2 groups respectively.     

Complexation Studies of Pyridyl Sulfonamide Ligands for Sensing Zinc and Copper Ions

Ligand protonation and stepwise dissociation constants, formation constants and speciation of four pyridyl sulfonamide ligands (Congreeve et al., New J. Chem. 27:98–106, 2003) were assessed, using potentiometric and UV/Visible spectrophotometric pH titrations (in 80% MeOH − 20% H₂O). The suitability of these ligands as Cu(II) and Zn(II) sensors for physiological applications was assessed. Two ligands L¹ and L⁴ were p-toluenesulfonamide derivatives while L² and L³ were triflurosulfonamide derivatives. Additionally L³ and L⁴ were appended with α-methyl groups. The most stable complex was formed by L¹ with Cu(II) owing to the fact that this complex was square planar (log ₁₀  K ₁=12.15±0.004 and log ₁₀  β ₂=15.42±0.006). The rest of the complexes invariably formed distorted tetrahedron geometry and complexation was weaker. Speciation diagrams show the effect of ligand to metal concentration, revealing that the L² and L³ ligands are the most suitable for forming ML₂ complexes at physiological pH.     

Synthesis and Complexation Studies of a Convex Bis-porphyrin Tweezer—A Molecular Capsule Precursor

The synthesis and spectroscopic studies of a convex bis-porphyrin based molecular tweezer are reported. The complexation of small bidentate ligands by metallated derivatives of the bis-porphyrin host were monitored through UV–visible and ¹H NMR spectroscopy and yielded large association constants.     

Complexation between Iron(III) and β-Hydroxyethylimino-N,N-Diethanoic and Dicarboxylic Acids in Aqueous Solutions

The reactions of iron(III) with -hydroxyethylimino-N,N-diethanoic acid (H₂Heida) and dicarboxy-lic acids (oxalic (H₂Ox), malonic (H₂Mal), and succinic (H₂Suc)) are studied using the spectrophotometric method. The equilibrium pattern in the binary and ternary systems is investigated. The complexation processes were shown to be complicated by hydrolysis and to depend strongly on the acidity of the medium. The following complexes were detected: FeHeida⁺, Fe(OH)Heida, Fe(OH)₂Heida^–, Fe(Heida)Ox^–, Fe(OH)(Heida)Ox^2–, Fe(OH)₂(Heida)Ox^3–, Fe(Heida)Mal^–, Fe(OH)(Heida)Mal^2–. Logarithms of the stability constants of these complexes calculated at = 0.1 (NaClO₄) and T = 20 ± 2°C are equal to 11.64 ± 0.05, 22.97 ± 0.05, 31.17 ± 0.05, 18.83 ± 0.03, 28.27 ± 0.02, 36.14 ± 0.02, 17.64 ± 0.03, and 26.39 ± 0.03, respectively.     

Thermodynamics of Formation of Ru(III) and Ru(IV)-μ-Peroxo Complexes

Abstract

Reaction of one half and one equivalents of H₂O₂ with K[Ru^III(pdta-H)Cl].2H₂O gives rise to the μ-peroxo complexes [Ru^III (pdta-H)]₂H₂O₂ and [Ru^IV(pdta-H)]₂O₂, respectively. Equilibrium constants for the formation of the various peroxo species were determined between pH 3-11, in the temperature range 283-313 K and with μ = 0.10 M in KC1. The existence of the various peroxo species was substantiated by potentiometry, spectrophotometry and electrochemical studies. Thermodynamic quantities associated with the formation of the (pdta)Ru^III and (pdta)Ru^IV-μ-peroxo species and their hydrolysis products are reported.