<Superscript>47</Superscript>Sc production development by cyclotron irradiation of <Superscript>48</Superscript>Ca

The therapeutic radionuclide ⁴⁷Sc was produced through the ⁴⁸Ca(p,2n) channel on a proton beam accelerator. The obtained results show that the optimum proton energies are in the range of 24–17 MeV, giving the possibility to produce ⁴⁷Sc radionuclide containing 7.4% of ⁴⁸Sc. After activation, the powdery CaCO₃ target material was dissolved in HCl and scandium isotopes were isolated from the targets. The performed separation experiments indicate that, due to the simplicity of the operations and the chemical purity of the obtained ⁴⁷Sc the best separation process is when scandium radioisotopes are separated on the 0.2 µm filter.     

Marine Exopolysaccharide Complexed With Scandium Aimed as Theranostic Agents

(1) Background: Exopolysaccharide (EPS) derivatives, produced by Alteromonas infernus bacterium, showed anti-metastatic properties. They may represent a new class of ligands to be combined with theranostic radionuclides, such as ⁴⁷Sc/⁴⁴Sc. The goal of this work was to investigate the feasibility of such coupling. (2) Methods: EPSs, as well as heparin used as a drug reference, were characterized in terms of molar mass and dispersity using Asymmetrical Flow Field-Flow Fractionation coupled to Multi-Angle Light Scattering (AF4-MALS). The intrinsic viscosity of EPSs at different ionic strengths were measured in order to establish the conformation. To determine the stability constants of Sc with EPS and heparin, a Free-ion selective radiotracer extraction (FISRE) method has been used. (3) Results: AF4-MALS showed that radical depolymerization produces monodisperse EPSs, suitable for therapeutic use. EPS conformation exhibited a lower hydrodynamic volume for the highest ionic strengths. The resulting random-coiled conformation could affect the complexation with metal for high concentration. The LogK of Sc-EPS complexes have been determined and showing that they are comparable to the Sc-Hep. (4) Conclusions: EPSs are very promising to be coupled with the theranostic pair of scandium for Nuclear Medicine.     

Thermodynamic and Kinetic Study of Scandium(III) Complexes of DTPA and DOTA: A Step Toward Scandium Radiopharmaceuticals

Diethylenetriamine‐N,N,N′,N′′,N′′‐pentaacetic acid (DTPA) and 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid (DOTA) scandium(III) complexes were investigated in the solution and solid state. Three ⁴⁵Sc NMR spectroscopic references suitable for aqueous solutions were suggested: 0.1 M Sc(ClO₄)₃ in 1 M aq. HClO₄ (δ_Sc=0.0 ppm), 0.1 M ScCl₃ in 1 M aq. HCl (δ_Sc=1.75 ppm) and 0.01 M [Sc(ox)₄]^5? (ox^2?=oxalato) in 1 M aq. K₂C₂O₄ (δ_Sc=8.31 ppm). In solution, [Sc(dtpa)]^2? complex (δ_Sc=83 ppm, ?ν=770 Hz) has a rather symmetric ligand field unlike highly unsymmetrical donor atom arrangement in [Sc(dota)]^? anion (δ_Sc=100 ppm, ?ν=4300 Hz). The solid‐state structure of K₈[Sc₂(ox)₇] ? 13 H₂O contains two [Sc(ox)₃]^3? units bridged by twice “side‐on” coordinated oxalate anion with Sc³⁺ ion in a dodecahedral O₈ arrangement. Structures of [Sc(dtpa)]^2? and [Sc(dota)]^? in [(Hguanidine)]₂[Sc(dtpa)] ? 3 H₂O and K[Sc(dota)][H₆dota]Cl₂ ? 4 H₂O, respectively, are analogous to those of trivalent lanthanide complexes with the same ligands. The [Sc(dota)]^? unit exhibits twisted square‐antiprismatic arrangement without an axial ligand (TSA′ isomer) and [Sc(dota)]^? and (H₆dota)²⁺ units are bridged by a K⁺ cation. A surprisingly high value of the last DOTA dissociation constant (pK_a=12.9) was determined by potentiometry and confirmed by using NMR spectroscopy. Stability constants of scandium(III) complexes (log K_ScL 27.43 and 30.79 for DTPA and DOTA, respectively) were determined from potentiometric and ⁴⁵Sc NMR spectroscopic data. Both complexes are fully formed even below pH 2. Complexation of DOTA with the Sc³⁺ ion is much faster than with trivalent lanthanides. Proton‐assisted decomplexation of the [Sc(dota)]^? complex (τ_1/2=45 h; 1 M aq. HCl, 25 °C) is much slower than that for [Ln(dota)]^? complexes. Therefore, DOTA and its derivatives seem to be very suitable ligands for scandium radioisotopes.     

Average cross-sections for (n, α) and (n,p) reactions on titanium in a fission-type reactor spectrum

The average cross-section in a fission-type reactor spectrum was determined experimentally for the reactions:⁴⁶Ti(n,p)⁴⁶Sc,⁴⁷Ti(n,p)⁴⁷Sc,⁴⁸Ti(n,p)⁴⁸Ti(n,α)⁴⁵Ca and⁵⁰Ti(n,α)⁴⁷Ca. In order to obtain the (n,p) cross-sections, reactor irradiation of titanium was followed by measurement of the induced scandium activities with a Ge(Li) detector of calibrated detection efficiency. For this no chemical separations had to be carried out. For the (n,α) reactions, however, the induced calcium activities were separeted and purified by oxalate precipitation, after the bulk of the radioactivity had been removed by precipitation of titanium hydroxide. The⁴⁷Ca disintegration rate was determined in the same way as for the scandium isotopes, whereas for⁴⁵Ca liquid scintillation counting was carried out. The shape of the reactor spectrum was investigated by irradiating reference threshold detectors with different effective threshold energies. To correct for (n,γ) interferences, irradiations were carried out with and without cadmium shielding. On the basis of \(\bar \sigma _F = 0.64\) mb for the reaction²⁷Al(n,α)²⁴Na, the average cross-sections were as follows:⁴⁶Ti(n,p)⁴⁶Sc:10.5±0.4 mb;⁴⁷Ti(n,p)⁴⁷Sc: 16.3±0.6 mb;⁴⁸Ti(n,p)⁴⁸Sc:0.272±0.005 mb;⁴⁸Ti(n,α)⁴⁵Ca: 34μb;⁵⁰Ti(n,α)⁴⁷Ca: 8.1±0.3 μb.     

The determination of stable scandium in plants,animals, sediments,sands, soils,rocks and minerals by neutron-activation analysis

A method is described for the determination of stable scandium in samples of plants, animals, sediments, soils, rocks and minerals. The samples and comparator standards were irradiated in a neutron flux of 5·10¹² n/cm²/sec for 4 h and dissolved and the scandium quantitatively precipitated from 2N nitric acid as scandium phytate; contaminants were rinsed from the precipitate with nitric and hydrochloric acids. The limit of detection was 0.005μg(±10% at the 95% confidence level). The activated ⁴⁶Sc was counted by γ-spectrometry.     

Study of scandium and thorium sorption from uranium leach liquors

Scandium and thorium sorption from simulated uranium leach liquors by phosphorous containing ion exchange resins was studied. Increase of thorium concentration resulted in a decrease of scandium sorption by 26–65%. Tulsion CH 93 resin was chosen for Sc separation from uranium leach liquors. It was shown that 180 g L^?1 Na₂CO₃ allowed for elution 94.1% of Sc and 98.9% of Th in dynamic conditions. Using (NH₄)₂SO₄ (50 g L^?1) + ACBM (180 g L^?1) mixture for primary Sc/Th separation at the resin/eluent ratio of 1:5 resulted in thorium desorption degree as high as 66–69%, whereas scandium loss did not exceed 10%.     

Production of low and high specific activity <Superscript>64</Superscript>Cu in a reactor

Production of radioactive scandium by irradiating natural titanium metal in Pakistan Research Reactor-1 was evaluated. The production rate of ⁴⁷Sc and other radioactive scandium was estimated. High specific activity ⁴⁷Sc can be produced by irradiating enriched ⁴⁷Ti in sufficient quantities needed for therapeutic applications. A new separation technique based on column chromatography was developed. Neutron irradiated titanium was dissolved in hydrofluoric acid, which was evaporated and taken in distilled water. The resulting solution was loaded on silica gel column. The radioactive scandium comes out first and the inactive titanium is removed with 2 M HCl. More than 95% radioactive scandium was recovered, while chemical impurity of titanium determined by optical emission spectroscopy was less than 0.01 μg/mL in final product.     

Evaluation of Vanadium(IV) as a Non-radioactive Surrogate for Technetium(IV) by Comparison of Stability Constants for Polyamino Polycarboxylate Ligand Complexation

The stability constants for the Tc(IV) and V(IV) complexation with the polyamino polycarboxylate ligands IDA, NTA, HEDTA and DTPA were determined using liquid–liquid extraction techniques. These stability constants were then used to evaluate the validity of using V(IV) as a chemical analogue for Tc(IV). Results suggest that Tc(IV), as TcOOH⁺, will form β _1?11 complexes with the selected ligands, while V(IV), as VO²⁺, will form β ₁₀₁ complexes. The values for these determined stability constants are (in log₁₀ unit) 10.9 ± 0.1, 11.4 ± 0.1, 14.9 ± 0.1, and 20.1 ± 0.1 for Tc(IV) in 0.5 mol·L^?1 NaCl at 25 °C, for IDA, NTA, HEDTA and DTPA, respectively, they are 9.3 ± 0.1, 11.6 ± 0.2, 15.8 ± 0.1, and 20.8 ± 0.1 for V(IV) in 0.5 mol·L^?1 NaCl at 25 °C, for the same suite of ligands. The incorporation of a hydroxide into the metal ligand complexes formed by Tc(IV) is proposed as the largest factor differentiating the apparent stability constants of Tc(IV) and V(IV). This work shows that V(IV) is a poor analog for Tc(IV); however, despite the differences in complexation mechanism between V(IV) and Tc(IV), V(IV) still appears to have some use for predicting Tc(IV) complexation behavior.     

Multi-element characterization of high-purity titanium dioxide by neutron activation analysis

A radiochemical neutron activation analysis method for the determination of 34 elements in titanium dioxide has been developed. For the assay of indicator radionuclides with short and with long half-lives, the radiochemical separation was performed by anion exchange on a Dowex 1 × 8 column and by combination of cation and anion exchange on a Dowex 50W × 8 and a Dowex 1 × 8 column from HF- and HF/NH₄F-medium, respectively. With both separation modes, a selective removal of the matrix-produced radionuclides ⁴⁶Sc, ⁴⁷Sc and ⁴⁸Sc was achieved. A selective extraction of copper with dithizone from 15 mol/L HF enabled counting the intensive but unspecific 511-keV rays of ⁶⁴Cu for the determination of Cu. The limits of detection achieved were between 0.004 ng/g for Sm and 0.8 μg/g for Sn (via ¹²⁵Sb). The elements La, Mn and Th were determined by instrumental neutron activation analysis only. These techniques were applied to the analysis of two titanium dioxide samples of different purity grade. The results and limits of detection are compared with those of other methods.     

Anticoincidence counting further improves detection limits of short-lived products by pseudo-cyclic instrumental neutron activation analysis

A systematic investigation was carried out on the merits and limitations of anticoincidence counting for short-lived radionuclides (t _1/2 < 75 s) used in instrumental neutron activation analysis (INAA) and pseudo-cyclic INAA (PC-INAA) methods for single as well as simultaneous multielement determinations in botanical and nutritional reference materials. The list of radionuclides of interest included: ¹⁰⁸Ag, ¹¹⁰Ag, ^165mDy, ²⁰F, ^75mGe, ^179mHf, ^86mRb, ^46mSc, ^77mSe, and ^177mYb. Precision and accuracy of measurements were good, and detection limits were of the order of µg kg^?1.     

Studies of Size-Based Selectivity in Aqueous Ternary Complexes of Americium(III) or Lanthanide(III) Cations

Spectrophotometric and calorimetric titrations were used to determine the equilibrium constants (log₁₀ K ₁₁₁) and enthalpies of formation (ΔH ₁₁₁) for aqueous ternary complexes of the form M(L^a)(L^b) (M = Nd³⁺, Sm³⁺, Tb³⁺, Ho³⁺, Er³⁺, or Am³⁺; L^a = DTPA^5?, DO3A^3?, or CDTA^4?; L^b = oxalate (Ox), malonate (Mal), or iminodiacetate (IDA)). Inner-sphere ternary complexes were readily formed with the septadentate DO3A (1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) and hexadentate CDTA (trans-1,2-diaminocyclohexanetetraacetic acid) ligands, whose binary complexes have residual metal-coordinated water molecules that are readily displaced by the smaller secondary ligands. The stability constants for the formation of lanthanide–CDTA complexes with Ox, Mal, and IDA generally increase with decreasing ionic radius when steric hindrance is minimal, with the trend in the M(CDTA)^? formation constants overshadowing any size-based reversal in the stepwise ternary complexation constants. Similar ternary complexes with DO3A showed little increase in thermodynamic stability compared to analogous CDTA complexes and no preference for larger Ln cations. The octadentate DTPA (diethylenetriaminepentaacetic acid) ligand proved too large to form ternary complexes to a measurable extent with any of the secondary ligands investigated, despite the presence of one residual inner sphere water molecule.     

Determination of zinc in geological samples using Compton suppression with thermal and epithermal instrumental neutron activation analysis

The determination of Zn in geological samples using instrumental neutron activation analysis is usually done using the ⁶⁴Zn(n,γ)⁶⁵Zn reaction and its 244 day half-life. However this analysis has proven to be potentially difficult. This is due to its relatively low neutron absorption cross section and gamma ray intensity, and the relatively high neutron absorption cross section and gamma intensity of ⁴⁶Sc, which has an energy peak that is only 5 keV greater than ⁶⁵Zn. The use of a high resolution detector makes it possible to differentiate between the ⁶⁵Zn and ⁴⁶Sc photopeaks peaks. However, the dominating ⁴⁶Sc gamma ray can even make peak fitting routines unsuccessful in the proper determination of ⁶⁵Zn. The use of a Compton suppression system suppresses the ⁴⁶Sc peak, which has two coincident gamma-rays, and this greatly improves the ratio of the height of the ⁴⁶Sc 1120.5 keV photopeak to the ⁶⁵Zn 1115.4 keV photopeak. Irradiating the sample with epithermal neutrons also improves the measurement since ⁶⁵Zn has a higher cross section for epithermal neutrons rather than thermal neutrons, whereas ⁴⁶Sc has a higher thermal cross section. Another technique to determine zinc is the use of ⁶⁸Zn(n,γ)^69mZn reaction with its 13 h half-life using epithermal neutrons and Compton suppression INAA. However, the 438 keV gamma ray of ^69mZn has no interference with any adjoining photopeak. A critical comparison of these two methods is given.     

Neutron activation analysis of iodine-129 and iodine-127 in environmental samples

The possibilities of reactor induced (n, p) reactions as a tool for neutron activation analysis of titanium in geological samples are discussed. The interference of calcium and scandium is experimentally evaluated. Results for Ti, Ca and Sc in GSP-1 and PCC-1 standard rocks are presented. On the basis of the experimental values, it is concluded that the⁴⁷Ti(n, p)⁴⁷Sc reaction is the most favourable for titanium determination.     

Formation and characterization of the oxygen-rich scandium oxide/dioxygen complexes ScOn (n = 4, 6, 8) in solid argon

The reactions of scandium atoms and O(2) have been reinvestigated using matrix isolation infrared spectroscopy and density functional theory calculations. A series of new oxygen-rich scandium oxide/dioxygen complexes were prepared and characterized. The ground state scandium atoms react with dioxygen to form OSc(eta(2)-O(3)), a side-on bonded scandium monoxide-ozonide complex. The OSc(eta(2)-O(3)) complex rearranges to a more stable Sc(eta(2)-O(2))(2) isomer under visible light irradiation, which is characterized to be a side-on bonded superoxo scandium peroxide complex. The homoleptic trisuperoxo scandium complex, Sc(eta(2)-O(2))(3), and the superoxo scandium bisozonide complex, (eta(2)-O(2))Sc(eta(2)-O(3))(2), are also formed upon sample annealing. The Sc(eta(2)-O(2))(3) complex is determined to have a D(3h) symmetry with three equivalent side-on bonded superoxo ligands around the scandium atom. The (eta(2)-O(2))Sc(eta(2)-O(3))(2) complex has a C(2) symmetry with two equivalent side-on bonded O3 ligands and one side-on bonded superoxo ligand.     

Dissociation Kinetics of Open‐Chain and Macrocyclic Gadolinium(III)‐Aminopolycarboxylate Complexes Related to Magnetic Resonance Imaging: Catalytic Effect of Endogenous Ligands

The kinetics of the metal exchange reactions between open‐chain Gd(DTPA)^2? and Gd(DTPA‐BMA), macrocyclic Gd(DOTA)^? and Gd(HP‐DO3A) complexes, and Cu²⁺ ions were investigated in the presence of endogenous citrate, phosphate, carbonate and histidinate ligands in the pH range 6–8 in NaCl (0.15 M ) at 25 °C. The rates of the exchange reactions of Gd(DTPA)^2? and Gd(DTPA‐BMA) are independent of the Cu²⁺ concentration in the presence of citrate and the reactions occur via the dissociation of Gd³⁺ complexes catalyzed by the citrate ions. The HCO₃^?/CO₃^2? and H₂PO₄^? ions also catalyze the dissociation of complexes. The rates of the dissociation of Gd(DTPA‐BMA), catalyzed by the endogenous ligands, are about two orders of magnitude higher than those of the Gd(DTPA)^2?. In fact near to physiological conditions the bicarbonate and carbonate ions show the largest catalytic effect, that significantly increase the dissociation rate of Gd(DTPA‐BMA) and make the higher pH values (when the carbonate ion concentration is higher) a risk‐factor for the dissociation of complexes in body fluids. The exchange reactions of Gd(DOTA)^? and Gd(HP‐DO3A) with Cu²⁺ occur through the proton assisted dissociation of complexes in the pH range 3.5–5 and the endogenous ligands do not affect the dissociation rates of complexes. More insights into the interaction scheme between Gd(DTPA‐BMA) and Gd(DTPA)^2? and endogenous ligands have been obtained by acquiring the ¹³C NMR spectra of the corresponding diamagnetic Y(III)‐complexes, indicating the increase of the rates of the intramolecular rearrangements in the presence of carbonate and citrate ions. The herein reported results may have implications in the understanding of the etiology of nephrogenic systemic fibrosis, a rare disease that has been associated to the administration of Gd‐containing agents to patients with impaired renal function.     

Acid Dissociation Constants and Rare Earth Stability Constants for DTPA

Diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid (DTPA) is an octadentate aminopolycarboxylate complexing agent whose f-element complexes find important practical applications in nuclear medicine and in advanced nuclear fuel reprocessing. This investigation focuses primarily on the latter application, specifically on characterization of lanthanide–DTPA complexes of relevance to the Trivalent Actinide–Lanthanide Separations by Phosphorus reagent Extraction and Aqueous Komplexants (TALSPEAK) process. To function acceptably, the TALSPEAK process requires the presence of moderate concentrations (0.5–2.0 mol·L^?1) of a (Na⁺/H⁺) lactate (or citrate) buffer. Competition between DTPA, lactate, and the extractant bis(2-ethylhexyl)phosphoric acid (HDEHP) for the lanthanides and trivalent actinides governs the course of the extraction process. To facilitate modeling and to support process improvements, the acid dissociation constants and stability constants for rare earth complexes with DTPA have been determined in 2.0 mol·L^?1 ionic strength (NaClO₄) media. The acid dissociation constants for DTPA and the stability constant for [Eu(DTPA)]^2? also were determined in sodium trifluoromethanesulfonate at 2.0 mol·L^?1 ionic strength to evaluate the potential impact of changing the nature of the electrolyte. The thermodynamic data are compared with earlier reports of similar data at lower ionic strength and used to complete calculations exploring the relative stability of lanthanide–DTPA and lactate complexes under TALSPEAK extraction conditions. Lanthanide–DTPA stability trends are discussed in comparison with literature data on a variety of other metal ions.     

Search of ligands suitable for 212Pb/212Bi in vivo generators

The short half-life of ²¹²Bi and ²¹³Bi limits the application of these radionuclides in α radionuclide therapy. The labeling of biomolecules with ²¹²Pb (mother nuclide of ²¹²Bi) instead of ²¹²Bi or ²¹³Bi has the advantage of obtaining a conjugate with a half-life of 10.6 h, compared with of 60 min for ²¹²Bi or 46 min for ²¹³Bi. Previous attempts to prepare a potential in vivo generator with ²¹²Pb complexed by the DOTA chelator failed, because about 36 % of Bi was reported to escape as a result of the radioactive decay $^{{212}}{\text{Pb}}{\mathop{\longrightarrow}\limits^{\beta ^{ - }}}{^{212}{\text{Bi}}}$ . Herein, we report studies on the stability of the ²¹²Pb complexes with eight selected polydentate ligands, which demonstrate high affinity for 3+ metal cations. From the ligand studied DOTP and BAPTA show a sufficient ²¹²Pb labeling yields but only ²¹²Pb–DOTP complex is stable in isotonic solution of sodium chloride making this way radioactivity level of released ²¹²Bi is below the limit of detection. It should be emphasized that the DOTP complex is stable only in the case when the concentration of free DOTP exceeds 10^?4 M.     

Extraction-chromatographic system TBP-HBr in radiochemical neutron activation analysis of high-purity materials

The extraction and extraction-chromatographic behaviour of a variety of elements in the TBP-HBr system with concentrations from 0.1 to 7M HBr has been studied. The results allowed the development of simple procedures for radiochemical neutron activation determination of 22 impurity elements (Na, K, Sc, Cr, Mn, Fe, Co, Ni, Cu, Ga, As, Se, Rb, Sr, Zn, Mo, Ag, Sb, Te, Ba, La, Hf and W) in high-purity cadmium and indium samples with detection limits from 1 g g^–1 for Fe and Zr to 0.01 ng g^–1 for Na, Sc, Mn with relative standard deviations < 0.15. To increase the selectivity of the extraction-chromatographic separation, use was made of extraction suppression and co-extraction effects. The procedure for the extraction-chromatographic separation of scandium from a number of other elements is described as an example. The procedure can be used for simultaneous quantitative separation of impurity radionuclides from radiation produced long-life scandium radionuclides in the neutron activation analysis of titanium and vanadium.     

Complexation of N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid with Cd(II), Hg(II) and Pb(II) ions in aqueous solution

The persistence of widely used chelating agents EDTA and DTPA in nature has been of concern and there is a need for ligands to replace them. In a search for environmentally friendly metal chelating ligands for industrial applications, complex formation equilibria of N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid (BCA6) with Cd(II), Hg(II) and Pb(II) in aqueous 0.1 M NaNO₃ solution were studied at 25°C by potentiometric titration. Complexation was modeled and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. With all metal ions, stable ML^4? complexes dominated the complex formation. The stabilities of Cd(II), Hg(II) and Pb(II) chelates of BCA6 are remarkably lower than those of EDTA and DTPA. Environmental advantages of the use of BCA6 instead of EDTA and DTPA are better biodegradability and lower nitrogen content with a possibility to save chemicals and process steps in pulp bleaching.     

Stabilities of the Ternary Complexes of Copper(II) with Substituted 1,10-Phenanthrolines and Some Amino Acids in Aqueous Solution

In this study the binary and ternary complexes of copper(II) with substituted 1,10-phenanthrolines [s-phen: 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dmphen) and 5-nitro-1,10-phenanthroline (nphen)] and l-amino acids [aa: l-phenylalanine (phe), l-tyrosine (tyr) and l-tryptophan (trp)] have been investigated using potentiometric methods in 0.1 mol·L^?1 KCl aqueous ionic media at 298.2 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. It was inferred that the aromatic 1,10-phenanthrolines act as a primary ligand in the ternary complexes, while the oxygen and nitrogen donor-containing amino acids are secondary ligands. The observed values of Δlog₁₀ K indicate that the ternary complexes are more stable than the binary ones, suggesting no interaction takes place between the ligands in the ternary complexes. The magnitudes of the measured stability constants of all of the ternary complexes are in the order [Cu(s-phen)(trp)]⁺ > [Cu(s-phen)(tyr)]⁺ > [Cu(s-phen)(phe)]⁺, which is identical to the sequence found for the binary complexes of Cu(II) with the amino acids. When the substituted 1,10-phenanthroline is changed, the stability constants of the ternary complexes decrease in the following order: [Cu(dmphen)(aa)]⁺ > [Cu(phen)(aa)]⁺ > [Cu(nphen)(aa)]⁺.