Synthesis of ion exchange film based on chemical grafting of styrene onto polyethylene/EPDM rubber blend for thorium removal.

Chemical grafting of low-density polyethylene film blended with ethylene propylene diene monomer rubber (PE/EPDM) using styrene monomer followed by a sulfonation process was investigated. Different factors affecting the grafting process, such as monomer and initiator concentrations, time of reaction, and grafting temperature, were studied. Sulfonation of the grafted films was carried out using chlorosulfonic acid in dichloromethane. Characterization of the grafted and sulfonated films was performed using ATR-FTIR, SEM, TGA, and XRD instruments. The grafting was successfully performed in aqueous media using sodium bisulfite as initiator, reaching a grafting yield of 130% and an ion exchange capacity of 1.2 meq/g. The removal of thorium ions from aqueous solution was studied using the obtained ion exchange films. The results showed that the maximum adsorption capacity of Th(IV) was 177.5 mg. g-1 (pH = 3, 298 K and 60 min). Removal isotherm and Kinetics were investigated, and the results revealed that the adsorption process was chemisorption homogeneous monolayer adsorption, exothermic, and spontaneous.

Biosorption of thorium onto Chlorella Vulgaris microalgae in aqueous media.

Thorium biosorption by a green microalga, Chlorella Vulgaris, was studied in a stirred batch reactor to investigate the effect of initial solution pH, metal ion concentration, biomass dosage, contact time, kinetics, equilibrium and thermodynamics of uptake. The green microalgae showed the highest Th adsorption capacity at 45 °C for the solution with a thorium concentration of 350 mg L-1 and initial pH of 4. The amount of uptake raised from 84 to 104 mg g-1 as the temperature increased from 15 to 45 °C for an initial metal concentration of 75 mg L-1 at pH 4. Transformation Infrared Spectroscopy (FTIR) was employed to characterize the vibrational frequency changes for peaks related to surface functional groups. Also, the scanning electron microscope (SEM) and energy-dispersive X-ray spectroscopy (EDX) were used to determine the morphological changes and elemental analysis of the biosorbent before and after the sorption process. The Langmuir isotherm was in perfect agreement with the equilibrium empirical data of thorium biosorption and the highest sorption capacity of the Chlorella Vulgaris microalgae was determined as 185.19 mg g-1. Also, the results of kinetic studies show that the thorium biosorption process follows a pseudo-second-order kinetic model. The negative value of ΔG0 indicates spontaneity and the positive values of ΔH0 indicate the endothermic nature of the adsorption process.

Hydrophilic interaction liquid chromatography: An efficient tool for assessing thorium interaction with phosphorylated biomimetic peptides.

In the field of nuclear toxicology, the knowledge of the interaction of actinides (An) with biomolecules is of prime concern in order to elucidate their toxicity mechanism and to further develop selective decorporating agents. In this work, we demonstrated the great potential of hydrophilic interaction liquid chromatography (HILIC) to separate polar thorium (Th) biomimetic peptide complexes, as a key starting point to tackle these challenges. Th4+ was used as plutonium (Pu4+) analogue and pS16 and pS1368 as synthetic di- and tetra-phosphorylated peptides capable of mimicking the interaction sites of these An in osteopontin (OPN), a hyperphosphorylated protein. The objective was to determine the relative affinity of pS16 and pS1368 towards Th4+, and to evaluate the pS1368 selectivity when Th4+ was in competition complexation reaction with UO22+ at physiological pH. To meet these aims, HILIC was simultaneously coupled to electrospray ionization mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS), which allowed to identify online the molecular structure of the separated complexes and quantify them, in a single step. Dedicated HILIC conditions were firstly set up to separate the new dimeric Th2(peptide)2 complexes with good separation resolution (peptide = pS16 or pS1368). By adding pS16 and pS1368 in different proportions relatively to Th4+, we found that lower or equal proportions of pS16 with respect to pS1368 were not sufficient to displace pS1368 from Th2pS13682 and pS16 proportion higher than pS1368 led to the formation of a predominant ternary complex Th2(pS16)(pS1368), demonstrating preferential Th4+ binding to the tetra-phosphorylated peptide. Finally, online identification and quantification of the formed complexes when Th4+ and UO22+ were mixed in equimolar ratio relatively to pS1368 showed that in spite of pS1368 has been specifically designed to coordinate UO22+, pS1368 is also Th4+-selective and exhibits stronger affinity for this latter than for UO22+. Hence, the results gathered through this approach highlight the impact of Th4+ coordination chemistry on its interaction with pS1368 and more widely to its affinity for biomolecules.

Functionalization of MXene using iota-carrageenan, maleic anhydride, and N,N'-methylene bis-acrylamide for high-performance removal of thorium (IV), uranium (IV), sulfamethoxazole, and levofloxacin.

An increasing quantity of pollutants has been discharged into the aquatic media, posing a serious hazard to public health. To address this issue, a new sorbent material, MXene@i.Carr@MaMb, was developed through the functionalization of the MXene surface using iota-carrageenan (i.Carr), maleic anhydride, and N, N'-methylene bis-acrylamide. This sorbent material was designed to remove thorium (Th (IV)) effectively, uranium (U (IV)), sulfamethoxazole (SMX), and levofloxacin (LEV) from wastewater. The MXene@i.Carr@MaMb composite incorporated significant functional groups, including OH, F, and O from MXene, oxygen and ester sulfate groups from iota-carrageenan (i.Carr), and OH, NH, and CO groups from N, N'-methylene bis-acrylamide, and maleic anhydride, which interacted with the UV (IV), Th (IV), SMX, and LEV pollutants through electrostatic interaction, complexation, and hydrogen bonding. MXene@i.Carr@MaMb composite exhibited excellent sorption capacities for Th (IV) (3.6 ± 0.03 mmol g-1), U (IV) (3.7 ± 0.09 mmol g-1), SMX (5.8 ± 0.03 mmol g-1), and LEV (5.9 ± 0.05 mmol g-1) at 323.15 K. The sorption kinetics and isotherms of radioactive metals and antibiotics can be well-described using pseudo-first-order kinetic models and Langmuir and Sips isothermal equations. This study presented a novel sorbent material for efficiently removing radioactive metals and antibiotics from wastewater.

The effect of extracellular polymeric substances on MICP solidifying rare earth slags and stabilizing Th and U.

Microbially induced carbonate precipitation (MICP) has been used to cure rare earth slags (RES) containing radionuclides (e.g. Th and U) and heavy metals with favorable results. However, the role of microbial extracellular polymeric substances (EPS) in MICP curing RES remains unclear. In this study, the EPS of Lysinibacillus sphaericus K-1 was extracted for the experiments of adsorption, inducing calcium carbonate (CaCO3) precipitation and curing of RES. The role of EPS in in MICP curing RES and stabilizing radionuclides and heavy metals was analyzed by evaluating the concentration and morphological distribution of radionuclides and heavy metals, and the compressive strength of the cured body. The results indicate that the adsorption efficiencies of EPS for Th (IV), U (VI), Cu2+, Pb2+, Zn2+, and Cd2+ were 44.83%, 45.83%, 53.7%, 61.3%, 42.1%, and 77.85%, respectively. The addition of EPS solution resulted in the formation of nanoscale spherical particles on the microorganism surface, which could act as an accumulating skeleton to facilitate the formation of CaCO3. After adding 20 mL of EPS solution during the curing process (Treat group), the maximum unconfined compressive strength (UCS) of the cured body reached 1.922 MPa, which was 12.13% higher than the CK group. The contents of exchangeable Th (IV) and U (VI) in the cured bodies of the Treat group decreased by 3.35% and 4.93%, respectively, compared with the CK group. Therefore, EPS enhances the effect of MICP curing RES and reduces the potential environmental problems that may be caused by radionuclides and heavy metals during the long-term sequestration of RES.

Eco-friendly and cost-effective adsorbent derived from blast furnace slag with black liquor waste for hazardous remediation.

The current investigation concerns with preparation eco-friendly and cost-effective adsorbent (mesoporous silica nanoparticles (SBL)) based on black liquor (BL) containing lignin derived from sugarcane bagasse and combining it with sodium silicate derived from blast furnace slag (BFS) for thorium adsorption. Thorium ions were adsorbed from an aqueous solution using the synthesized bio-sorbent (SBL), which was then assessed by X-ray diffraction, BET surface area analysis, scanning electron microscopy with energy dispersive X-ray spectroscopy (EDX), and Fourier transforms infrared spectroscopy (FTIR). Th(IV) sorption properties, including the pH effect, uptake rate, and sorption isotherms across various temperatures were investigated. The maximum sorption capacity of Th(IV) on SBL is 158.88 mg/L at pH value of 4328 K, and 60 min contact time. We demonstrated that the adsorption processes comport well with pseudo-second-order and Langmuir adsorption models considering the kinetics and equilibrium data. According to thermodynamic inspections results, the Th(IV) adsorption process exhibited endothermic and random behavior suggested by positive ΔH° and ΔS° values, while the negative ΔG° values indicated a spontaneous sorption process. The maximum Th(IV) desorption from the loaded SBL (Th/SBL) was carried out at 0.25 M of NaHCO3 and 60 min of contact. Sorption/desorption processes have five successive cycles. Finally, this study suggests that the recycling of BFS and BL can be exploited for the procurement of a promising Th(IV) adsorbents.

Interaction Between the Transferrin Protein and Plutonium (and Thorium), What's New?

Transferrin (Tf) is a glycoprotein that transports iron from the serum to the various organs. Several studies have highlighted that Tf can interact with metals other than Fe(III), including actinides that are chemical and radiological toxics. We propose here to report on the behavior of Th(IV) and Pu(IV) in comparison with Fe(III) upon Tf complexation. We considered UV-Vis and IR data of the M2 Tf complex (M=Fe, Th, Pu) and combined experimental EXAFS data with MD models. EXAFS data of the first M-O coordination sphere are consistent with the MD model considering 1 synergistic carbonate. Further EXAFS data analysis strongly suggests that contamination by Th/Pu colloids seems to occur upon Tf complexation, but it seems limited. SAXS data have also been recorded for all complexes and also after the addition of Deferoxamine-B (DFOB) in the medium. The Rg values are very close for apoTf, ThTf and PuTf, but slightly larger than for holoTf. Data suggest that the structure of the protein is more ellipsoidal than spherical, with a flattened oblate form. From this data, the following order of conformation size might be considered:holoTf

Ultra-effective modified clinoptilolite adsorbent for selective thorium removal from radioactive residue.

This study investigated the efficacy of using phosphate-modified zeolite (PZ) as an adsorbent for removing thorium from aqueous solutions. The effects of various factors such as contact time, adsorbent mass, initial thorium concentration, and pH value of the solution on the removal efficiency were analyzed using the batch technique to obtain optimum adsorption condition. The results revealed that the optimal conditions for thorium adsorption were a contact time of 24 h, 0.03 g of PZ adsorbent, pH 3, and a temperature of 25 °C. Isotherm and kinetics parameters of the thorium adsorption on PZ were also determined, with equilibrium studies showing that the experimental data followed the Langmuir isotherm model. The maximum adsorption capacity (Qo) for thorium was found to be 17.3 mg/g with the Langmuir isotherm coefficient of 0.09 L/mg. Using phosphate anions to modify natural zeolite increased its adsorption capacity. Furthermore, adsorption kinetics studies demonstrated that the adsorption of thorium onto PZ adsorbent fitted well with the pseudo-second-order model. The applicability of the PZ adsorbent in removing thorium from real radioactive waste was also investigated, and nearly complete thorium removal was achieved (> 99%) from the leached solution obtained from cracking and leaching processes of rare earth industrial residue under optimized conditions. This study elucidates the potential of PZ adsorbent for efficient removal of thorium from rare earth residue via adsorption, leading to a reduction in waste volume for ultimate disposition.

Adsorption of thorium (IV) ions using a novel borate-based nano material Ca3Y2B4O12: Application of response surface methodology and Artificial Neural Network.

Since nuclear wastes are the most important wastes in terms of health and the environment, they are evaluated differently within nuclear reactors as well as in terms of their use in medical and industrial applications. In some cases, emergency intervention is necessary due to the amount of radioactivity or the physical and/or chemical conditions. . The purpose of this study is to investigate the adsorption properties of nano Ca3Y2B4O12 (CYBO) material synthesized by the sol-gel combustion method for the adsorption of Thorium (IV) from an aqueous medium. We tested how pH (3-8), the concentration of Th (IV) (25-125 mg/L), amount of adsorbent value (0.005-0.08 g) and temperature (20-60 °C), affect adsorption efficiency. The best possible combinations of these parameters were examined by Response Surface Methodology (RSM) and Artificial Neural Network (ANN). R2 values for RSM and ANN were 0.9964 and 0.9666, respectively. According to the models, the adsorption capacity under the optimum conditions determined for the RSM and ANN model was found to be 134.62 mg/g and 125.12 mg/g, respectively.

Humic acid attachment on chitosan-modified silica gel as an economical, efficient, and selective adsorbent for thorium and uranium removal.

A novel, low-cost adsorbent material was prepared by the immobilization of humic acid on a silica gel surface coated with cross-linked chitosan (SiChiHA). The adsorbent was developed to remove selectively of Th(IV) and U(VI) from aqueous solution, including their pre-concentration and separation from lanthanides and high salinity conditions. A simple waste-less humic acid immobilization method was shown to be successful based on FT-IR, SEM-EDS, and zeta potential characterization results. The adsorbent was found to be stable over a wide pH range, with the highest capacities obtained at pH 3.5 (Th(IV)) and pH 5 (U(VI)). Langmuir model calculations yielded a maximum capacity of 30.6 mg g-1 and 75.4 mg g-1 for Th(IV) and U(VI). The adsorption process was found to be rapid (half concentration was removed within 10 min) and best described by a pseudo-second order rate equation. Increasing NaCl concentration up to 2 mol L-1 or lanthanide concentration up to 100 times did not significantly affect the removal efficiency for either Th(IV) of U(VI). Both elements could be sequentially separated by elution with ammonium citrate and nitric acid, respectively. The adsorption-desorption experiment showed that the adsorbent could be used for at least five cycles without significant capacity loss. This study provides insight into the development of low-cost adsorbent with practical functionality, including separation and regeneration ability, the advantageous properties scarcely reported in low-cost adsorbent literature.

Radiochemical Quality Control Methods for Radium-223 and Thorium-227 Radiotherapies.

Background: The majority of radiopharmaceuticals for use in disease detection and targeted treatment undergo a single radioactive transition (decay) to reach a stable ground state. Complex emitters, which produce a series of daughter radionuclides, are emerging as novel radiopharmaceuticals. The need for validation of chemical and radiopurity with such agents using common quality control instrumentation is an area of active investigation. Here, we demonstrate novel methods to characterize 227Th and 223Ra. Materials and Methods: A radio-TLC scanner and a γ-counter, two common and widely accessible technologies, as well as a solid-state α-particle spectral imaging camera were evaluated for their ability to characterize and distinguish 227Th and 223Ra. We verified these results through purity evaluation of a novel 227Th-labeled protein construct. Results: The γ-counter and α-camera distinguished 227Th from 223Ra, enabling rapid and quantitative determination of radionuclidic purity. The radio-TLC showed limited ability to describe purity, although use under α-particle-specific settings enhanced resolution. All three methods were able to distinguish a pure from impure 227Th-labeled protein. Conclusions: The presented quality control evaluation for 227Th and 223Ra on three different instruments can be applied to both research and clinical settings as new alpha particle therapies are developed.

Actinide-Oxygen Multiple Bonds from Air: Synthesis and Characterization of a Thorium Oxo Supported by Redox-Active Ligands.

The first non-uranyl, f-element oxo complex synthesized from dioxygen in dry air is presented in this work. The synthesis was accomplished by treating the redox-active thorium amidophenolate complex, [Th(dippap)3][K(15-c-5)2]2 (1-ap crown), with dioxygen in dry air, forming a rare terminal thorium oxo, [O═Th(dippisq)2(dippap)][K(15-c-5)2]2 (2-oxo). Compound 1-ap crown was regenerated by treating 2-oxo with potassium graphite. X-ray crystallography of 2-oxo revealed a comparatively longer bond length for the thorium-oxygen double bond when compared to other thorium oxos. As such, several thorium-oxygen single bonds were synthesized for comparison, including Th(dippisq)2(OSiMe3)2(THF) (4-OSiMe3), Th(OSiMe3)4(bipy)2 (5-OSiMe3), and [Th(OH)2 (dippHap)4][K(15-c-5)2]2 (6-OH). Full spectroscopic and structural characterization of the complexes was performed via 1H NMR spectroscopy, X-ray crystallography, EPR spectroscopy, and electronic absorption spectroscopy as well as SQUID magnetometry, which all confirmed the electronic structure of these complexes.

An alternative radiochemical separation strategy for isolation of Ac and Ra isotopes from high energy proton irradiated thorium targets for further application in Targeted Alpha Therapy (TAT).

Targeted Alpha Therapy (TAT) has shown very high potential for the treatment of cancers that were not responsive to other therapy options (e.g., ß- therapy and chemotherapy). The main constraint to the widespread use of TAT in clinics is the limited availability of alpha-emitting radionuclides. One of the most promising candidates for TAT is 225Ac (t1/2 = 9.92 days), which can be used directly in combination with selective biomolecules (e.g., antibodies, peptides, etc.) or be a generator source of 213Bi (t1/2 = 45.6 min), another shorter-lived TAT radionuclide. Several strategies are currently under investigation to increase the supply of 225Ac. One of the most attractive options is the irradiation of natural thorium-232 targets with high-energy protons (≥100 MeV). However, there are several challenges associated with this production method including the development of an efficient radiochemical purification method. During irradiation of natural thorium with proton energy above 100 MeV, several Ra isotopes (223,224,225Ra) are produced. 223Ra (t1/2 = 11.43 days) is used for the treatment of bone metastases and can also be used as a generator source for 211Pb. Additionally, 225Ra (t1/2 = 14.9 days) can be a valuable source of isotopically pure 225Ac. In the present work, we address the radiochemical separation aspects of isolating Ac and Ra isotopes from irradiated thorium targets.

Porphyrinoid actinide complexes.

The diverse coordination modes and electronic features of actinide complexes of porphyrins and related oligopyrrolic systems (referred to as "porpyrinoids") have been the subject of interest since the 1960s. Given their stability and accessibility, most work with actinides has focused on thorium and uranium. This trend is also seen in the case of porphyrinoid-based complexation studies. Nevertheless, the diversity of ligand environments provided by porphyrinoids has led to the stabilization of a number of unique complexes with the early actinides that are often without structural parallel within the broader coordination chemical lexicon. This review summarizes key examples of prophyrinoid actinide complexes reported to date, including the limited number of porphyrinoid systems involving transuranic elements. The emphasis will be on synthesis and structure; however, the electronic features and reactivity pattern of representative systems will be detailed as well. Coverage is through December of 2021.

Hydroxypyridinones as a Very Promising Platform for Targeted Diagnostic and Therapeutic Radiopharmaceuticals.

Hydroxypyridinones (HOPOs) have been used in the chelation therapy of iron and actinide metals. Their application in metal-based radiopharmaceuticals has also been increasing in recent years. This review article focuses on how multidentate HOPOs can be used in targeted radiometal-based diagnostic and therapeutic radiopharmaceuticals. The general structure of radiometal-based targeted radiopharmaceuticals, a brief description of siderophores, the basic structure and properties of bidentate HOPO, some representative HOPO multidentate chelating agents, radiopharmaceuticals based on HOPO multidentate bifunctional chelators for gallium-68, thorium-227 and zirconium-89, as well as the future prospects of HOPO multidentate bifunctional chelators in other metal-based radiopharmaceuticals are described and discussed in turn. The HOPO metal-based radiopharmaceuticals that have shown good prospects in clinical and preclinical studies are gallium-68, thorium-227 and zirconium-89 radiopharmaceuticals. We expect HOPO multidentate bifunctional chelators to be a very promising platform for building novel targeted radiometal-based diagnostic and therapeutic radiopharmaceuticals.

A Uranium(II) Arene Complex That Acts as a Uranium(I) Synthon.

Two-electron reduction of the amidate-supported U(III) mono(arene) complex U(TDA)3 (2) with KC8 yields the anionic bis(arene) complex [K[2.2.2]cryptand][U(TDA)2] (3) (TDA = N-(2,6-di-isopropylphenyl)pivalamido). EPR spectroscopy, magnetic susceptibility measurements, and calculations using DFT as well as multireference CASSCF methods all provide strong evidence that the electronic structure of 3 is best represented as a 5f4 U(II) metal center bound to a monoreduced arene ligand. Reactivity studies show 3 reacts as a U(I) synthon by behaving as a two-electron reductant toward I2 to form the dinuclear U(III)-U(III) triiodide species [K[2.2.2]cryptand][(UI(TDA)2)2(µ-I)] (6) and as a three-electron reductant toward cycloheptatriene (CHT) to form the U(IV) complex [K[2.2.2]cryptand][U(η7-C7H7)(TDA)2(THF)] (7). The reaction of 3 with cyclooctatetraene (COT) generates a mixture of the U(III) anion [K[2.2.2]cryptand][U(TDA)4] (1-crypt) and U(COT)2, while the addition of COT to complex 2 instead yields the dinuclear U(IV)-U(IV) inverse sandwich complex [U(TDA)3]2(µ-η8:η3-C8H8) (8). Two-electron reduction of the homoleptic Th(IV) amidate complex Th(TDA)4 (4) with KC8 gives the mono(arene) complex [K[2.2.2]cryptand][Th(TDA)3(THF)] (5). The C-C bond lengths and torsion angles in the bound arene of 5 suggest a direduced arene bound to a Th(IV) metal center; this conclusion is supported by DFT calculations.

Early, intensive marine resource exploitation by Middle Stone Age humans at Ysterfontein 1 rockshelter, South Africa.

Modern human behavioral innovations from the Middle Stone Age (MSA) include the earliest indicators of full coastal adaptation evidenced by shell middens, yet many MSA middens remain poorly dated. We apply 230Th/U burial dating to ostrich eggshells (OES) from Ysterfontein 1 (YFT1, Western Cape, South Africa), a stratified MSA shell midden. 230Th/U burial ages of YFT1 OES are relatively precise (median ± 2.7%), consistent with other age constraints, and preserve stratigraphic principles. Bayesian age-depth modeling indicates YFT1 was deposited between 119.9 to 113.1 thousand years ago (ka) (95% CI of model ages), and the entire 3.8 m thick midden may have accumulated within ∼2,300 y. Stable carbon, nitrogen, and oxygen isotopes of OES indicate that during occupation the local environment was dominated by C3 vegetation and was initially significantly wetter than at present but became drier and cooler with time. Integrating archaeological evidence with OES 230Th/U ages and stable isotopes shows the following: 1) YFT1 is the oldest shell midden known, providing minimum constraints on full coastal adaptation by ∼120 ka; 2) despite rapid sea-level drop and other climatic changes during occupation, relative shellfish proportions and sizes remain similar, suggesting adaptive foraging along a changing coastline; 3) the YFT1 lithic technocomplex is similar to other west coast assemblages but distinct from potentially synchronous industries along the southern African coast, suggesting human populations were fragmented between seasonal rainfall zones; and 4) accumulation rates (up to 1.8 m/ka) are much higher than previously observed for dated, stratified MSA middens, implying more intense site occupation akin to Later Stone Age middens.

How Does Iron Storage Protein Ferritin Interact with Plutonium (and Thorium)?

The impact of the contamination of living organisms by actinide elements has been a constant subject of attention since the 1950s. But to date still little is understood. Ferritin is the major storage and regulation protein of iron in many organisms, it consists of a protein ring and a ferrihydric core at the center. This work sheds light on the interactions of early actinides (Th, Pu) at oxidation state +IV with ferritin and its ability to store those elements at physiological pH compared to Fe. The ferritin-thorium load curve suggests that ThIV saturates the protein (2840 Th atoms per ferritin) in a similar way that Fe does on the protein ring. Complementary spectroscopic techniques (spectrophotometry, infrared spectroscopy, and X-ray absorption spectroscopy) were combined with molecular dynamics to provide a structural model of the interaction of ThIV and PuIV with ferritin. Comparison of spectroscopic data together with MD calculations suggests that ThIV and PuIV are complexed mainly on the protein ring and not on the ferrihydric core. Indeed from XAS data, there is no evidence of Fe neighbors in the Th and Pu environments. On the other hand, carboxylates from amino acids of the protein ring and a possible additional carbonate anion are shaping the cation coordination spheres. This thorough description from a molecular view point of ThIV and PuIV interaction with ferritin, an essential iron storage protein, is a cornerstone in comprehensive nuclear toxicology.

MD simulation reveals differential binding of Cm(III) and Th(IV) with serum transferrin at acidic pH.

The iron carrier human serum transferrin (sTf) is known to transport other metals, including some actinides (An). Radiotoxic An are routinely involved in the nuclear fuel cycle and the possibility of their accidental exposure cannot be ruled out. Understanding An interaction with sTf assumes a greater significance for the development of safe and efficacious chelators for their removal from the blood stream. Here we report several 100 ns equilibrium MD simulations of Cm(III)- and Th(IV)-loaded sTf at various protonation states of the protein to explore the possibility of the two An ions release and speciation. The results demonstrate variation in protonation state of dilysine pair (K206 and K296) and the tyrosine (Y188) residue is necessary for the opening of Cm(III)-bound protein and the release of the ion. For the tetravalent thorium, protonation of dilysine pair suffices to cause conformational changes of protein. However, in none of the protonation states, Th(IV) releases from sTf because of its strong electrostatic interaction with D63 in the first shell of the sTf binding cleft. Analysis of hydrogen bond, water bridge, and the evaluation of potential of mean forces of the An ions' release from sTf, substantiate the differential behavior of Cm(III) and Th(IV) at endosomal pH. The results provide insight in the regulation of Cm(III) and Th(IV) bioavailability that may prove useful for effective design of their decorporating agents and as well may help the future design of radiotherapy based on tetravalent ions.

Construction of a thorium/actinium generator at the Canadian Nuclear Laboratories.

Targeted Alpha Therapy (TAT) has demonstrated considerable promise in the treatment of a range of cancers in both preclinical and, more recently clinical research. In particular, work with the alpha-emitting radionuclide 225Ac has been effectively employed due to the relatively rapid decay cascade that leads to 4 alpha and 2 beta emissions. One limitation for TAT has been caused by access to the vital radionuclide. Traditionally, 225Ac has been sourced from thorium/actinium generators based on the alpha decay of stockpiles of 229Th. 229Th is itself the alpha-decay product from 233U. Due to proliferation issues associated with 233U, only three thorium/actinium generators have been reported in the literature, capable of supporting clinical research. This paper describes the construction and operation of a thorium/actinium radionuclide generator at the Canadian Nuclear Laboratories, capable of supporting preclinical and limited clinical research in the area of TAT. Thorium was recovered and purified by a combination of anion exchange and extraction chromatography from aged 233U stockpiles. A separation scheme for 225Ra and 225Ac has been developed, based upon the chemical composition of the thorium material to allow for regular, routine milkings capable of supplying up to 3.7 GBq (100 mCi) of radiochemically pure 225Ac annually. This routine separation is accomplished using a combination of anion exchange chromatography to separate Ac and Ra isotopes from Th and extraction chromatography employing TEVA and DGA-N resins to separate actinium from radium and breakthrough thorium.