Characterization of DTPA complexes and conjugated antibodies of astatine

The complex formation of astatine/I/ cation with diethylene triamine pentaacetic acid /DTPA/ and characterization of the complexes were investigated by electromigration in free electrolytes and by gel-chromatography on Sephadex G 25. We describe the conjugation procedure for the production of At-DTPA conjugated polyclonal antibodies.     

Note on the uranyl complexes of EDTA

The nature of the EDTA complex of uranium(VI) is discussed, and it is concluded that there is no need to postulate stabilization of the complex by hydrogen-bonding between a protonated nitrogen atom and the uranyl ion.     

The preparation of astatine labelled tyrosine using an electrophilic reaction

Carrier-free astatotyrosine has been synthesized using an electrophilic reaction in acidic media. Temperature of 150–160°C and reaction time of 20–30 min were chosen as optimal conditions for the synthesis of astatotyrosine. Under the selected conditions the yield was about 90%.     

EDTA and mixed-ligand complexes of tetravalent and trivalent plutonium

EDTA forms stable complexes with plutonium that are integral to nuclear material processing, radionuclide decontamination, and the potentially enhanced transport of environmental contamination. To characterize the aqueous Pu(4+/3+)EDTA species formed under the wide range of conditions of these processes, potentiometry, spectrophotometry, and cyclic voltammetry were used to measure solution equilibria. The results reveal new EDTA and mixed-ligand complexes and provide more accurate stability constants for previously identified species. In acidic solution (pH < 4) and at 1:1 ligand to metal ratio, PuY (where Y4- is the tetra-anion of EDTA) is the predominant species, with an overall formation constant of log beta110 = 26.44. At higher pH, the hydrolysis species, PuY(OH)- and PuY(OH)(2)2-, form with the corresponding overall stability constants log beta(11 - 1) = 21.95 and log beta(11 - 2) = 15.29. The redox potential of the complex PuY at pH = 2.3 was determined to be E(1/2) = 342 mV. The correlation between redox potential, pH, and the protonation state of PuY- was derived to estimate the redox potential of the Pu(4+/3+)Y complex as a function of pH. Under conditions of neutral pH and excess EDTA relative to Pu4+, PuY(2)4- forms with an overall formation constant of log beta120 = 35.39. In the presence of ancillary ligands, mixed-ligand complexes form, as exemplified by the citrate and carbonate complexes PuY(citrate)3- (log beta1101 = 33.45) and PuY(carbonate)2- (log beta1101 = 35.51). Cyclic voltammetry shows irreversible electrochemical behavior for these coordinatively saturated Pu4+ complexes: The reduction wave is shifted approximately -400 mV from the reduction wave of the complex PuY, while the oxidation wave is invariant.     

Anomalous solvent extraction behavior of astatine

We studied the solvent extraction behavior of astatine and found the anomalous behavior of this element similar to radioiodine. Astatine was extracted into CS₂ from acidic solution over a wide range of carrier iodine concentration. The distribution ratios of astatine were determined by measuring the -ray from 210 At with a Nal(TI) detector. A drastic change was observed around at 10^–4 mol/l as in the case of 131 I. This tendency is well explained by the kinematics of the chemical reactions concemed.     

NMR study of intramolecular processes in EDTA metal complexes

The kinetics of the intramolecular acetate scramblings occurring in thirteen ethylenediaminetetraacetate (EDTA) complexes has been studied by analyzing the modification observed in the NMR spectra of their D₂O solutions, when temperature is changed. The experimental results indicate that the Δ, Λ conversion is a fast process on the NMR time scale for each of the complexes considered, whereas the nitrogen inversion occurs at an observable rate in the case of the Cd(II), In(III), Sc(III), Y(III) and Lu(III) chelates and is too rapid in the other complexes. Computer analysis of the experimental NMR spectra has been performed in order to obtain enthalpy, entropy and free energy of activation concerning the N inversion of the cited chelates. Twist and bond breaking mechanisms are discussed with reference to both scrambling processes.     

The mechanism of the reaction of elementary astatine with organic solvents

The mechanism of the reaction of elementary astatine with benzene, toluene and monochlorobenzene were studied by means of radiogaschromatography. The reaction proceeds in two steps with benzene and toluene. In Step 1 the chemical bond of At₂ is cleaved by the disintegration of either astatine and the remained astatine reacts immediately with solvent. At Step 2 the compound produced at Step 1 is started to decompose by the decay of astatine. But this mechanism could not be applied to the astatine-monochlorobenzene system.     

An expanded halogen bonding scale using astatine

As a non-covalent interaction, halogen bonding is now acknowledged to be useful in all fields where the control of intermolecular recognition plays a pivotal role. Halogen-bond basicity scales allow quantification of the halogen bonding of referential donors with organic functional groups from a thermodynamic point of view. Herein we present the pK_BAtI basicity scale to provide the community an overview of halogen-bond acceptor strength towards astatine, the most potent halogen-bond donor element. This experimental scale is erected on the basis of complexation constants measured between astatine monoiodide (AtI) and sixteen selected Lewis bases. It spans over 6 log units and culminates with a value of 5.69 ± 0.32 for N,N,N′,N′-tetramethylthiourea. On this scale, the carbon π-bases are the weakest acceptors, the oxygen derivatives cover almost two-thirds of the scale, and sulphur bases exhibit the highest AtI basicity. Regarding the applications of ²¹¹At in targeted radionuclide therapy, stronger labelling of carrier agents could be envisaged on the basis of the pK_BAtI scale.

Based on the halogen bonding between astatine monoiodide (AtI) and 16 Lewis bases, the newly established pK_BAtI scale indicates that the halogen bond basicity of AtI follows the order C ≤ O ≤ S ≈ Se for the acceptor atomic site.     

The stability of some metal EDTA, DTPA and DOTA complexes: Application as tracers in groundwater studies

Studies of the stability of various metal EDTA, DTPA and DOTA complexes in order to evaluate their applicability as non-sorbing tracers have been performed. In laboratory tests, the stability generally increases for the individual metal ions in the EDTA<DTPA<DOTA order. For most metal ions, the same trend can be observed for the thermodynamic stability constants. In the in situ experiment, various metal EDTA tracers were used in very low concentrations; YbEDTA⁻, for example had a breakthrough and recovery which were very similar to the non-sorbing tracers used. According to the extremely low tracers concentrations used, thermodynamic data indicate that all metal EDTA tracers should have been decomplexed as a result of the competition with the naturally occurring cations in the groundwater. This was not found, which indicates that the decomplexation rate and sorption mechanism are important in estimating the applicability of the metal complexes as tracers. The DOTA complexes of elements in the middle of the lanthanide series have indicated high stability in the laboratory tests and therefore appear to be good candidates as non-sorbing tracers. However, in contrary to the metal EDTA, tracers, the DOTA complexes of La³⁺ and Lu³⁺ seemed to be slightly delayed in the in situ experiment.     

Distribution behavior of astatine: Solvent extraction and back extraction

The distribution behavior of astatine was studied at tracer concentrations and over a wide range of carrier iodide concentration in both solvent extraction and back extraction processes. Astatine compounds were extracted instantly into the organic solvent, CS₂ from the carrier free and carrier iodide containing solutions. Back extraction of astatine with various NaOH solutions followed by solvent extraction caused the hydrolysis of astatine. The distribution behavior of astatine was explained by the extraction reaction schemes.     

Vibrational spectra of two Fe(III)/EDTA complexes useful for iron supplementation

The infrared and Raman spectra of Na[FeEDTA(H₂O)]·2H₂O and Na₄[(FeEDTA)₂O]·3H₂O (EDTA = tetra anion of ethylenediaminetetraacetic acid), two complexes proposed as adequate for iron supplementation, were recorded and analyzed in relation to its structural peculiarities. Some comparisons between the recorded spectra are also presented, and the characteristics of the carboxylate motions as well as those of the metal-to-ligand vibrations are discussed in detail.     

Chemical properties of positive singly charged astatine ion in aqueous solution

The mobility of oxidized astatine in solutions H(Na)ClO₄ (=0.4 M) – 1·10^–4M K₂Cr₂O₇ has been measured at 25°C in the interval 0.63pH1.68. Under these conditions astatine migrates to the cathode only. The speed of the migration depends upon the concentration of hydrogen ions in solution: pH 1.68 U_c = 1.17 · 10^-4 cm² V^-1 s^-1 pH 0.63 U_c = 2.67 · 10^-4 cm² V^-1 s^-1 The effect agrees with the opinion that the singly charged cation of astatine formed in acidic solutions is a strong aquacomplex [(H₂O)_xAt]⁺ (x=1–2) (protonated hypoastatic acid). Deprotonation constant of this cation is K_dp=0.032±0.005. Specific properties of the astatine cation are given. They can be explained, probably, through the peculiarities of its structure.     

The interaction of EDTA with barium sulfate

Ethylenediaminetetraacetic acid (EDTA) is a known complexing agent that interacts with a host of cations. In this paper, various techniques are used to elucidate the mechanism of interaction between EDTA and barium sulfate surfaces. It is shown that complexation with metal ions is not sufficient to explain the inhibition of barite crystallization but that other processes such as chemisorption must also occur. EDTA is shown to always adsorb as the mono-protonated species - suggesting that the molecule is able to lose a proton when it adsorbs at lower pH. Molecular modelling shows that the interaction of the surface barium ions with the carboxylate group is an important one. Finally, in situ turbidity measurements provide information about the mechanism of nucleation/growth modification. It is found that the EDTA molecule inhibits barium sulfate nucleation and that this could be its primary means of inhibiting precipitation of barium sulfate.     

Fast kinetic studies of reduction of ferricytochrome c by a series of Fe(EDTA)-type complexes

The reductions of cytochrome c by a series of derivatives of Fe(EDTA)2- complex have been studied by a stopped-flow technique. The reactions of cytochrome c with Fe(EDTA)2-, Fe (CDTA)2- and Fe(IDA)22- present typical outer sphere mechanism, meanwhile the cytochrome c(III) and Fe(NTA)- system shows abnormal kinetic behavior, including the rate saturation, big negative entropy and lower overall charge and binding site charge calculated from the dependence of electron transfer rate on ionic strength. On the basis of these observations a semi-inner-sphere mechanism is proposed to illustrate the kinetics.     

Studies on metallochromic indicators--II. Zincon and its mercury and zinc complexes as indicators in EDTA titrations

Zincon has been found to be an excellent indicator in the titration of mercury(II) with EDTA at pH 5.5-7. Moreover the mercury(II)-Zincon and zinc-Zincon systems have been found to be suitable indicators in the direct EDTA titrations of Pb(2+), Cd(1+) and Ca(2+). Interference studies of a number of cations and anions have been made. Chloride and bromide can be tolerated in the titration of mercury(II), up to equivalent concentrations.     

Synthesis and characterization of cationic astatine compounds with sulphur-containing ligands stable in aqueous solutions

The formation of cationic astatine compounds with thiourea, thiourea derivatives and some N-acylthioureas was investigated in aqueous solutions. The ion mobilities in free electrolytes were determined for the detection of carrier-free astatine compounds and their characterization. Informations about the stability of this group of compounds could be given after investigations in the presence of halogenide and pseudo halogenide ions /Cl^–, Br^–, I^–, SCN^–/. First results on the reaction of At//⁺ with thiourea derivatives and N-acylthioureas in acid and neutral solutions are reported. The cationic astatine compound formation with representatives of this group is shown.