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Purpose Thorium-226 (half-life 30.6 m) is a radionuclide of interest for use in targeted alpha therapy applications. Due to its short half-life, 226Th must be provided through a radionuclide generator system from its parent 230U (20.8 d). Furthermore, as the half-life of 226Th is very short, it should be provided in a form that is directly amenable to use in biomedical applications. Methods A reverse radionuclide generator system was developed employing a DGA extraction chromatography column. A 230U/226Th parent/daughter solution in equilibrium is added to a DGA column in >6 M HCl. The parent 230U is eluted first in 0.1 M HNO3 followed by elution of 226Th in 0.1 M citrate buffer pH 5. Results Thorium-226 was recovered from the radionuclide generator column with >96% yield. Greater than 99.5% of the 230U parent was isolated for reuse in the generator. Long term evaluation over six weeks demonstrated consistent supply of 226Th with greater than 99.5% radionuclidic purity. The only contaminant found in the final product was 230U ( Conclusions The reverse radionuclide generator described herein was shown to be a feasible method for providing 226Th in high yield, purity and in a chemical form that is amenable for direct use in biomedical applications.

We report the synthesis and crystal structure of the first quinolino[7,8

Thorium-226 (half-life 30.6 m) is a radionuclide of interest for use in targeted alpha therapy applications. Due to its short half-life,A reverse radionuclide generator system was developed employing a DGA extraction chromatography column. AThorium-226 was recovered from the radionuclide generator column with96% yield. Greater than 99.5% of theThe reverse radionuclide generator described herein was shown to be a feasible method for providing

A major chemical challenge facing implementation of 225Ac in targeted alpha therapy-an emerging technology that has potential for treatment of disease-is identifying an 225Ac chelator that is compatible with in vivo applications. It is unclear how to tailor a chelator for Ac binding because Ac coordination chemistry is poorly defined. Most Ac chemistry is inferred from radiochemical experiments carried out on microscopic scales. Of the few Ac compounds that have been characterized spectroscopically, success has only been reported for simple inorganic ligands. Toward advancing understanding in Ac chelation chemistry, we have developed a method for characterizing Ac complexes that contain highly complex chelating agents using small quantities (μg) of 227Ac. We successfully characterized the chelation of Ac3+ by DOTP8- using EXAFS, NMR, and DFT techniques. To develop confidence and credibility in the Ac results, comparisons with +3 cations (Am, Cm, and La) that could be handled on the mg scale were carried out. We discovered that all M3+ cations (M = Ac, Am, Cm, La) were completely encapsulated within the binding pocket of the DOTP8- macrocycle. The computational results highlighted the stability of the M(DOTP)5- complexes.

Alpha-emitters are radionuclides that decay through the emission of high linear energy transfer α-particles and possess favorable pharmacologic profiles for cancer treatment. When coupled with monoclonal antibodies, peptides, small molecules, or nanoparticles, the excellent cytotoxic capability of α-particle emissions has generated a strong interest in exploring targeted α-therapy in the pre-clinical setting and more recently in clinical trials in oncology. Multiple obstacles have been overcome by researchers and clinicians to accelerate the development of targeted α-therapies, especially with the recent improvement in isotope production and purification, but also with the development of innovative strategies for optimized targeting. Numerous studies have demonstrated the in vitro and in vivo efficacy of the targeted α-therapy. Radium-223 (223Ra) dichloride (Xofigo®) is the first α-emitter to have received FDA approval for the treatment of prostate cancer with metastatic bone lesions. There is a significant increase in the number of clinical trials in oncology using several radionuclides such as Actinium-225 (225Ac), Bismuth-213 (213Bi), Lead-212 (212Pb), Astatine (211At) or Radium-223 (223Ra) assessing their safety and preliminary activity. This review will cover their therapeutic application as well as summarize the investigations that provide the foundation for further clinical development.

Column chromatographic methods have been developed to separate no-carrier-added 111Ag from proton irradiated thorium targets and associated fission products as an ancillary process to an existing 225Ac separation design. Herein we report the separation of 111Ag both prior and subsequent to 225Ac recovery using CL resin, a solvent impregnated resin (SIR) that carries an organic solution of alkyl phosphine sulfides (R3P = S) and alkyl phosphine oxides (R3P = O). The recovery yield of 111Ag was 93 ± 9% with a radiochemical purity of 99.9% (prior) and 87 ± 9% with a radiochemical purity of 99.9% (subsequent to) 225Ac recovery. Both processes were successfully performed with insignificant impacts on 225Ac yields or quality. Measured equilibrium distribution coefficients for silver and ruthenium (a residual contaminant) on CL resin in hydrochloric and nitric acid media are reported, to the best of our knowledge, for the first time. Additionally, measured cross sections for the production of 111Ag and 110mAg for the 232Th(p,f)110m,111Ag reactions are reported within.

Radioisotopes [Formula: see text]Bi and [Formula: see text]Bi were successfully inserted into a water-soluble and tumor-targeting texaphyrin ligand. The reaction with [Formula: see text]Bi(OAc)[Formula: see text] proceeds in about 15 min in aqueous media without the use of any organic base. The Bi(III) texaphyrin complex formed (3) is stable in aqueous media even in the presence of an excess of competitive chelators (EDTA or citric acid), as well as in human blood plasma. These results validate texaphyrins as potential candidates for coordinating bismuth radionuclides and set the stage for their use in targeted alpha therapy (TAT).

Scandium-44g (half-life 3.97h) shows promise for application in positron emission tomography (PET), due to favorable decay parameters. One of the sources of 44gSc is the 44Ti/44gSc generator, which can conveniently provide this radioisotope on a daily basis at a diagnostic facility. Titanium-44 (half-life 60.0 a), in turn, can be obtained via proton irradiation of scandium metal targets. A substantial 44Ti product batch, however, requires high beam currents, long irradiation times and an elaborate chemical procedure for 44Ti isolation and purification. This study describes the production of a combined 175MBq (4.7mCi) batch yield of 44Ti in week long proton irradiations at the Los Alamos Isotope Production Facility (LANL-IPF) and the Brookhaven Linac Isotope Producer (BNL-BLIP). A two-step ion exchange chromatography based chemical separation method is introduced: first, a coarse separation of 44Ti via anion exchange sorption in concentrated HCl results in a 44Tc/Sc separation factor of 102-103. A second, cation exchange based step in HCl media is then applied for 44Ti fine purification from residual Sc mass. In summary, this method yields a 90-97% 44Ti recovery with an overall Ti/Sc separation factor of ≥106.

Actinium-225 and 213Bi have been used successfully in targeted alpha therapy (TAT) in preclinical and clinical research. This paper is a continuation of research activities aiming to expand the availability of 225Ac. The high-energy proton spallation reaction on natural thorium metal targets has been utilized to produce millicurie quantities of 225Ac. The results of sixteen irradiation experiments of thorium metal at beam energies between 78 and 192 MeV are summarized in this work. Irradiations have been conducted at Brookhaven National Laboratory (BNL) and Los Alamos National Laboratory (LANL), while target dissolution and processing was carried out at Oak Ridge National Laboratory (ORNL). Excitation functions for actinium and thorium isotopes, as well as for some of the fission products, are presented. The cross sections for production of 225Ac range from 3.6 to 16.7 mb in the incident proton energy range of 78–192 MeV. Based on these data, production of curie quantities of 225Ac is possible by irradiating a 5.0 g cm−2 232Th target for 10 days in either BNL or LANL proton irradiation facilities.

Scandium-44 g (half-life 3.97 h [1]) shows promise for positron emission tomography (PET) imaging of longer biological processes than that of the current gold standard, 18 F, due to its favorable decay parameters. One source of 44g Sc is the long-lived parent nuclide 44 Ti (half-life 60.0 a). A 44 Ti/ 44g Sc generator would have the ability to provide radionuclidically pure 44g Sc on a daily basis. The production of 44 Ti via the 45 Sc(p,2n) reaction requires high proton beam currents and long irradiation times. Recovery and purification of no-carrier added (nca) 44 Ti from scandium metal targets involves complex separation chemistry. In this study, separation systems based on solid phase extraction chromatography were investigated, including branched diglycolamide (BDGA) resin and hydroxamate based ZR resin. Results indicate that ZR resin in HCl media represents an effective 44 Ti/ 44g Sc separation system.

Targeted alpha therapy (TAT) is a treatment method of increasing interest to the clinical oncology community that utilizes α-emitting radionuclides conjugated to biomolecules for the selective killing of tumor cells. Proton irradiation of thorium generates a number of α-emitting radionuclides with therapeutic potential for application via TAT. In particular, the radionuclide 230Pa is formed via the 232Th(p, 3n) nuclear reaction and partially decays to 230U, an α emitter which has recently received attention as a possible therapy nuclide. In this study, we estimate production yields for 230Pa and other Pa isotopes from proton-irradiated thorium based on cross section measurements. We adopt existing methods for the chromatographic separation of protactinium isotopes from proton irradiated thorium matrices to combine and optimize them for effective fission product decontamination.

The Isotope Production Facility (IPF) at Los Alamos National Laboratory (LANL) is used to produce an array of isotopes for medical, global security, and research applications with an intense beam of protons supplied by the linear accelerator at the Los Alamos Neutron Science Center (LANSCE). An Accelerator Improvement Project (AIP) was recently conducted at IPF to improve facility reliability and reduce programmatic risk while increasing general isotope production capacity and flexibility. This was accomplished through the installation of an improved beam window assembly, more robust beam diagnostics, an active and adjustable collimator , and a new beam rastering system. This paper will highlight the four exciting innovations and how they were designed, validated, and installed in parallel as well as the significant operational advantages they provide to IPF. Key experiments and the increased currents achieved in routine production runs demonstrating the enhanced capability from the AIP will be presented. The most notable capability enhancements include irradiations with beam currents ranging from 100 nA experimental runs up to 300 μ A on routine production targets and utilization of a range of cylindrical target diameters.

Protactinium-230 (t1/2 = 17.4 d) is the parent isotope of 230U (t1/2 = 20.8 d), a radionuclide of interest for targeted alpha therapy (TAT). Column chromatographic methods have been developed to separate no-carrier-added 230Pa from proton irradiated thorium targets and accompanying fission products. Results reported within demonstrate the use of novel sulfur bearing chromatographic extraction resins for the selective separation of protactinium. The recovery yield of 230Pa was 93 ± 4% employing a R3P═S type commercially available resin and 88 ± 4% employing a DGTA (diglycothioamide) containing custom synthesized extraction chromatographic resin. The radiochemical purity of the recovered 230Pa was measured via high purity germanium γ-ray spectroscopy to be >99.5% with the remaining radioactive contaminant being 95Nb due to its similar chemistry to protactinium. Measured equilibrium distribution coefficients for protactinium, thorium, uranium, niobium, radium, and actinium on both the R3P═S type and the DGTA...

The separation of Th, Pa, and U is of high importance in many applications including nuclear power, nuclear waste, environmental and geochemistry, nuclear forensics and nuclear medicine. Diglycolamide (DGA)-based resins have shown the ability to separate many elements, however, these resins consist of non-covalent impregnation of the DGA molecules on the resin backbone resulting in co-elution of the extraction molecule during separation cycles, therefore limiting their long-term and repeated use. Covalently binding the DGA molecules onto silica is one way to overcome this issue. Herein, measured equilibrium distribution coefficients of normal extraction chromatographic DGA resin and a covalently bound form (KIT-6-N-DGA sorbent) are reported. Several differences are observed between the two systems, the most significant being observed for uranium, which demonstrated significantly lower sorption behavior on KIT-6-N-DGA. These results indicate that U can effectively be separated from Th and Pa using KIT-6-N-DGA, a task that could not be completed with the use of normal DGA alone.

Introduction The use of α-emitting isotopes for radionuclide therapy is a promising treatment strategy for small micro-metastatic disease. The radioisotope 213 Bi is a nuclide that has found substantial use for targeted α-therapy (TAT). The relatively unexplored aqueous chemistry of Bi 3+ , however, hinders the development of bifunctional chelating agents that can successfully deliver these Bi radioisotopes to the tumor cells. Here, a novel series of nitrogen-rich macrocyclic ligands is explored for their potential use as Bi-selective chelating agents. Methods The ligands, 1,4,7,10-tetrakis(pyridin-2-ylmethyl)-1,4,7,10-tetraazacyclododecane (L py ), 1,4,7,10-tetrakis(3-pyridazylmethyl)-1,4,7,10-tetraazacyclododecane (L pyd ), 1,4,7,10-tetrakis(4-pyrimidylmethyl)-1,4,7,10-tetraazacyclododecane (L pyr ), and 1,4,7,10-tetrakis(2-pyrazinylmethyl)-1,4,7,10-tetraazacyclododecane (L pz ), were prepared by a previously reported method and investigated here for their abilities to bind Bi radioisotopes. The commercially available and commonly used ligands 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and N -[( R )-2-amino-3-( p -isothiocyanato-phenyl)propyl]- trans -( S,S )- cyclohexane-1,2-diamine- N , N , N ', N ", N "-pentaacetic acid (CHX-A′′-DTPA) were also explored for comparative purposes. Radio-thin-layer chromatography (TLC) was used to measure the binding kinetics and stabilities of the complexes formed. The long-lived isotope, 207 Bi (t 1/2 =32years), was used for these studies. Density functional theory (DFT) calculations were also employed to probe the ligand interactions with Bi 3+ and the generator parent ion Ac 3+ . Results In contrast to DOTA and CHX-A′′-DTPA, these nitrogen-rich macrocycles selectively chelate Bi 3+ in the presence of the parent isotope Ac 3+ . Among the four tested, L py was found to exhibit optimal Bi 3+ -binding kinetics and complex stability. L py complexes Bi 3+ more rapidly than DOTA, yet the resulting complexes are of similar stability. DFT calculations corroborate the experimentally observed selectivity of these ligands for Bi 3+ over Ac 3+ . Conclusion Taken together, these data implicate L py as a valuable chelating agent for the delivery of 213 Bi. Its selectivity for Bi 3+ and rapid and stable labeling properties warrant further investigation and biological studies.

Mechanical testing and microstructural analysis was performed on an Alloy 718 window that was in use at the Los Alamos Neutron Science Center (LANSCE) Isotope Production Facility (IPF) for approximately 5 years. It was replaced as part of the IPF preventive maintenance program. The window was transported to the Wing 9 hot cells at the Chemical and Metallurgical Research (CMR) LANL facility, visually inspected and 3-mm diameter samples were trepanned from the window for mechanical testing and microstructural analysis. Shear punch testing and optical metallography was performed at the CMR hot cells. The 1-mm diameter shear punch disks were cut into smaller samples to further reduce radiation exposure dose rate using Focus Ion Beam (FIB) and microstructure changes were analyzed using a Transmission Electron Microscopy (TEM). Irradiation doses were determined to be ∼0.2–0.7 dpa (edge) to 11.3 dpa (peak of beam intensity) using autoradiography and MCNPX calculations. The corresponding irradiation temperatures were calculated to be ∼34–120 °C with short excursion to be ∼47–220 °C using ANSYS. Mechanical properties and microstructure analysis results with respect to calculated dpa and temperatures show that significant work hardening occurs but useful ductility still remains. The hardening in the lowest dose region (∼0.2–0.7 dpa) was the highest and attributed to the formation of γ ″ precipitates and irradiation defect clusters/bubbles whereas the hardening in the highest dose region (∼11.3 dpa) was lower and attributed mainly to irradiation defect clusters and some thermal annealing.

Proton beam energy, energy straggling, and intensity in thick stacks of target materials at the Los Alamos Isotope Production Facility were investigated using the foil activation technique and computational simulations. Isotopic yield measurements of irradiated foils from several recent experiments used to determine these quantities were compared with the predictions of MCNP6 and TRIM codes, and with Andersen & Ziegler’s semi-empirical formalism. Differences between code predictions and experimental data were examined. Methods for computational simulation of energy propagation agree well with one another and were able to accurately predict the proton beam’s energy for a limited range. Predictions were accurate when degrading from an initial energy of 100 MeV down to approximately 50 MeV, but struggled to represent measured data well at lower energies.

Actinium-225 (t1/2=9.92d) is an α-emitting radionuclide with nuclear properties well-suited for use in targeted alpha therapy (TAT), a powerful treatment method for malignant tumors. Actinium-225 can also be utilized as a generator for (213)Bi (t1/2 45.6 min), which is another valuable candidate for TAT. Actinium-225 can be produced via proton irradiation of thorium metal; however, long-lived (227)Ac (t1/2=21.8a, 99% β(-), 1% α) is co-produced during this process and will impact the quality of the final product. Thus, accurate assays are needed to determine the (225)Ac/(227)Ac ratio, which is dependent on beam energy, irradiation time and target design. Accurate actinium assays, in turn, require efficient separation of actinium isotopes from both the Th matrix and highly radioactive activation by-products, especially radiolanthanides formed from proton-induced fission. In this study, we introduce a novel, selective chromatographic technique for the recovery and purification of actinium isotopes from irradiated Th matrices. A two-step sequence of cation exchange and extraction chromatography was implemented. Radiolanthanides were quantitatively removed from Ac, and no non-Ac radionuclidic impurities were detected in the final Ac fraction. An (225)Ac spike added prior to separation was recovered at ≥ 98%, and Ac decontamination from Th was found to be ≥ 10(6). The purified actinium fraction allowed for highly accurate (227)Ac determination at analytical scales, i.e., at (227)Ac activities of 1-100 kBq (27 nCi to 2.7 μCi).

A new method has been developed for the isolation of 223,224,225Ra, in high yield and purity, from a proton irradiated 232Th matrix. Herein we report an all-aqueous process using multiple solid-supported adsorption steps including a citrate chelation method developed to remove >99.9% of the barium contaminants by activity from the final radium product. A procedure involving the use of three columns in succession was developed, and the separation of 223,224,225Ra from the thorium matrix was obtained with an overall recovery yield of 91 ± 3%, average radiochemical purity of 99.9%, and production yields that correspond to physical yields based on previously measured excitation functions.

Column chromatographic methods have been developed to separate no-carrier-added

The spallation neutron flux produced from proton irradiation of rubidium chloride and gallium targets at the Los Alamos National Laboratory (LANL) Isotope Production Facility (IPF) was investigated using the activation foil technique and computational simulation. Routine irradiations have been found to produce fluxes as high as 1012 n cm−2 s−1, with approximately 50% of the total flux having energy in excess of 1 MeV. Measurements of activation foils are compared with the predicted radionuclide yield using nuclear excitation functions from MCNPX event generators, evaluated nuclear data, and the TALYS nuclear code. Practical application of the secondary neutron flux in the realm of radioisotope production is considered.

Radioactive 82Sr/82Rb produced at Los Alamos National Laboratory is routinely used in generators for hospitals and medical laboratories to support cardiac imaging. The proper quantification of strontium radioisotopes in a sample is important to ensure quality and regulatory compliance. However, the quantification of the impurity 85Sr is difficult, because its primary gamma-ray at 514 keV interferes with the annihilation peak at 511 keV from 82Rb. Synthetic spectra were created as a quality test of several gamma-ray spectral analysis tools’ ability to resolve peaks in the 511/514 keV multiplet. The peak fitting results from the spectroscopy tools (RAYGUN, SPECANAL, GammaVision, UNISAMPO, and GAMANAL) are presented. These spectra can also be useful for other programs to test their annihilation peak analysis procedures.

Accelerator production of 225Ac addresses the global supply deficiency currently inhibiting clinical trials from establishing 225Ac's therapeutic utility, provided that the accelerator product is of sufficient radionuclidic purity for patient use. Two proton activation experiments utilizing the stacked foil technique between 40 and 200 MeV were employed to study the likely co-formation of radionuclides expected to be especially challenging to separate from 225Ac. Foils were assayed by nondestructive γ-spectroscopy and by α-spectroscopy of chemically processed target material. Nuclear formation cross sections for the radionuclides 226Ac and 227Ac as well as lower lanthanide radioisotopes 139Ce, 141Ce, 143Ce, and 140La whose elemental ionic radii closely match that of actinium were measured and are reported. The predictions of the latest MCNP6 event generators are compared with measured data, as they permit estimation of the formation rates of other radionuclides whose decay emissions are not clearly discerned in the complex spectra collected from 232Th(p,x) fission product mixtures.

Rhenium-186g is a radionuclide with a high potential for therapeutic applications. It emits therapeutic β − particles accompanied by low energy γ-rays, which allows for in-vivo tracking of the radiolabeled compound and dosimetry estimates. The current reactor production pathway 185Re(n, γ)186gRe produces low specific activity 186gRe, thereby limiting its therapeutic application. Work is underway to develop an accelerator-based, charged particle induced production method for high specific activity 186gRe from targets of enriched 186W. To optimize the chemical 186gRe recovery method, batch studies have been performed to characterize the adsorption behavior of Re and W on a strongly basic anion exchange resin. An in-depth physicochemical profile was developed for the interaction of Re with resin material, which showed the reaction to be endothermic and spontaneous. Basic (NaOH) and acidic (HNO3) matrices were used to determine the equilibrium distribution coefficients for Re and W. The resin exhibits the best affinity for Re at slightly basic conditions and little affinity above moderately acidic concentrations. Tungsten has low affinity for the resin above moderately basic concentrations. A study was performed to examine the effect of W concentration on Re adsorption, which showed that even a high ionic WO4 2– strength of up to 1.9 mol kg –1 does not significantly compromise ReO4 – retention on the resin.

Scandium-44g (half-life 3.97h) shows promise for application in positron emission tomography (PET), due to favorable decay parameters. One of the sources of

Rhenium-186g (tA target consisting of highly enriched, pressedAWe report a preliminary study of the large-scale production and novel anion exchange based chemical recovery of high specific activity

The rare-earth isotope 163 Ho is of interest for large experiments hoping to improve the precision of neutrino mass measurements to less than 0.1 eV. While a variety of potential production methods exist, production of this isotope in quantities and purities suitable for large-scale neutrino mass measurements is challenging. In particular, the co-production of 166m Ho may limit the utility of a given production method; avoiding this radioactive contaminant is discussed. This work compares available production methods and presents the results of theoretical studies which examine achievable quantity and purity of 163 Ho production in support of the effort to measure neutrino mass.

Rhenium-186g (T 1/2= 89.2 h) is a β − emitter suitable for therapeutic applications. Current production methods rely on reactor production via 185Re(n,γ) which results in low specific activities, thereby limiting its use. Production by p,d activation of enriched 186W results in a 186gRe product with a higher specific activity, allowing it to be used for targeted therapy with limited receptors. A test target consisting of pressed, sintered natWO3 was proton irradiated at Los Alamos (LANL-IPF) to evaluate product yield and impurities, irradiation parameters and wet chemical Re recovery for proof-of-concept for bulk production of 186gRe. We demonstrated isolation of 186gRe in 97% yield from irradiated natWO3 targets within 12 h of end of bombardment (EOB) via an alkaline dissolution followed by anion exchange. The recovery process has potential for automation, and WO3 can be easily recycled for recurrent irradiations. A 186gRe batch yield of 42.7 ± 2.2 μCi/μAh or 439 ± 23 MBq/C was obtained after 24 h in an 18.5 μA proton beam. The target entrance energy was determined to be 15.6 MeV. The specific activity of 186gRe at EOB was measured to be 1.9 kCi (70.3 TBq) mmol−1, which agrees well with the result of a previous 185,186mRe co-production EMPIRE and TALYS modeling study assuming similar conditions. Utilizing enriched 186WO3, we anticipate that a proton beam of 250 μA for 24 h will provide batch yields of 256 mCi (9.5 GBq) of 186gRe at EOB with specific activities even higher than 1.9 kCi (70.3 TBq) mmol−1, suitable for therapy applications.

At the Los Alamos Neutron Science Center (LANSCE) Isotope Production Facility (IPF), radioisotopes are produced for medical, scientific, and industrial applications by irradiating various targets with a 100 MeV, 230 μA proton beam. The medical isotope germanium-68 is produced by irradiating Nb capsules containing molten Ga target material. During irradiation, the Nb is subjected to intense radiation damage, corrosive attack by Ga, and mechanical and thermally-induced stresses for an extended period. Maintaining the structural integrity of the Nb target capsules during irradiation is crucial to contain the molten Ga target and the radioisotope product. In the present work, we focus on potential material related factors and assess the effect of the Nb stock material on target durability. We do so by comparing post-irradiation target mortality information to data collected during pre-irradiation ultrasound testing and X-ray imaging. We also explore possible failure mechanisms by using MCNP6 simulations and ANSYS codes to predict the induced atom displacement levels, hydrogen gas built-up, temperature distribution, and mechanical stresses. Our analysis, performed entirely in the context of an aggressive production program that allows for only limited diagnostic interference, suggests that using Nb stock with reasonably large and uniform grains is the most important factor in reducing early target failure at integrated beam current values

The feasibility of purifying a radioisotopically impure sample of 242Pu using neutron irradiation to “burn up” the plutonium isotopic contaminants 238,239,240,241Pu is investigated. A starting point of 95% 242Pu is assumed, and different neutron energy spectra, fluxes, and irradiation periods representative of the conditions found at available reactors in North America were assessed with Monte Carlo simulation methods to predict the maximum obtainable enrichment of 242Pu. Calculations indicate that radioisotopic purities of 242Pu in excess of 99.5% are achievable with neutron fluxes at Oak Ridge National Laboratory’s High Flux Isotope Reactor, pointing encouragingly to experimental verification of these estimates.

Cross sections for (223,)(225)Ra, (225)Ac and (227)Th production by the proton bombardment of natural thorium targets were measured at proton energies below 200 MeV. Our measurements are in good agreement with previously published data and offer a complete excitation function for (223,)(225)Ra in the energy range above 90 MeV. Comparison of theoretical predictions with the experimental data shows reasonable-to-good agreement. Results indicate that accelerator-based production of (225)Ac and (223)Ra below 200 MeV is a viable production method.

A single terbium foil was irradiated with 800 MeV protons to ascertain the potential for production of lanthanide isotopes of interest in medical, astrophysical, and basic science research and to contribute to nuclear data repositories. Isotopes produced in the foil were quantified by gamma spectroscopy. Cross sections for 36 isotopes produced in the irradiation are reported and compared with predictions by the MCNP6 transport code using the CEM03.03, Bertini, and INCL+ABLA event generators. Our results indicate the need to accurately consider fission and fragmentation of relatively light target nuclei like terbium in the modeling of nuclear reactions at 800 MeV. The predictive power of the code was found to be different for each event generator tested but was satisfactory for most of the product yields in the mass region where spallation reactions dominate. However, none of the event generators' results are in complete agreement with measured data., Comment: 16 pages, 3 figures, 1 tables, only pdf, submitted to Nuclear Physics A

The covalent attachment of tris(allyl)iridium to partially dehydroxylated gamma-alumina is found to proceed via surface hydroxyl group protonation of one allyl ligand to form an immobilized bis(allyl)iridium moiety, (=AlO)Ir(allyl)(2), as characterized by CP-MAS (13)C NMR, inductively coupled plasma-mass spectrometry, and Ir L(3) edge X-ray absorption spectroscopy. Extended X-ray absorption fine-structure (EXAFS) measurements taken on unsupported Ir(allyl)(3) and several associated tertiary phosphine addition complexes suggest that the eta(3)-allyl ligands generally account for an Ir-C coordination number of 2 rather than 3, with an average Ir-C distance of 2.16 A. Using this knowledge, combined EXAFS and X-ray absorption near-edge structure studies reveal that a small amount of Ir(0) is also formed upon reaction of Ir(allyl)(3) with the surface. It was found that the addition of either 2,6-dimethylphenyl isocyanide or carbon monoxide to the supported complex allows spectroscopic identification of the supported bis(allyl)iridium complexes, (=AlO)Ir(allyl)(2)(CNAr) [Ar = 2,6-(CH(3))(2)C(6)H(4)] and (=AlO)Ir(allyl)(2)(CO)(2), respectively. Although samples of the supported bis(allyl)iridium complex are active for the dehydrogenation of cyclohexane to benzene at temperatures between 180 and 220 degrees C, in situ temperature-programmed reaction XAFS and continuous-flow reactor studies suggest that Ir(0) nanoparticles, rather than a well-defined Ir(3+) complex, are responsible for the observed activity.

Ruthenium-103 is the parent isotope of 103mRh (t1/2 56.1 min), an isotope of interest for Auger electron therapy. During the proton irradiation of thorium targets, large amounts of 103Ru are generated through proton induced fission. The development of a two part chemical separation process to isolate 103Ru in high yield and purity from a proton irradiated thorium matrix on an analytical scale is described herein. The first part employed an anion exchange column to remove cationic actinide/lanthanide impurities along with the majority of the transition metal fission products. Secondly, an extraction chromatographic column utilizing diglycolamide functional groups was used to decontaminate 103Ru from the remaining impurities. This method resulted in a final radiochemical yield of 83 ± 5% of 103Ru with a purity of 99.9%. Additionally, measured nuclear reaction cross sections for the formation of 103Ru and 106Ru via the 232Th(p,f)103,106Ru reactions are reported within.

Reaction of two equivalents of [(C 5 [e 4 Et)2U(CH3)(Cl)] (6) or [(C 5 Me 5 ) 2 Th(CH 3 )(Br)] (7) with 1,4-dicyanobenzene leads to the formation of the novel 1,4-phenylenediketimide-bridged bimetallic organoactinide complexes [{(C5Me4Et)2(Cl)U}2(μ-{N=C-(CH3)-C 6 H 4 -(CH3)C=N})] (8) and [{(C 5 Me 5 -) 2 (Br)Th} 2 ,(μ-{N=C(CH 3 )-QH4-(CH 3 )CmN))] (9), respectively. These complexes were structurally characterized by single-crystal X-ray diffraction and NMR spectroscopy. Metal-metal interactions in these isovalent bimetallic systems were assessed by means of cyclic voltammetry, UV-visible/NIR absorption spectroscopy, and variable-temperature magnetic susceptibility. Although evidence for magnetic coupling between metal centers in the bimetallic U IV /U IV (5f 2 -5f 2 ) complex is ambiguous, the complex displays appreciable electronic communication between the metal centers through the π system of the dianionic diketimide bridging ligand, as judged by voltammetry. The transition intensities of the f-f bands for the bimetallic U IV /U IV system decrease substantially compared to the related monometallic ketimide chloride complex, [(C 5 Me 5 ) 2 U(Cl){-N= C(CH3)-(3,4,5-F 3 -C 6 H 2 ))] (11). Also reported herein are new synthetic routes to the actinide starting materials [(C5Me4Et)2U(CH3)(Cl)] (6) and [(C 5 Me 5 ) 2 Th(CH 3 )(Br)] (7) in addition to the syntheses and structures of the monometallic uranium complexes [(C 5 Me 4 Et) 2 UCl 2 ] (3), [(C 5 Me 4 Et) 2 U-(CH 3 ) 2 ) (4), [(C 5 Me 4 Et)2U(-N=C(CH3)-C 6 H 4 -C=N) 2 ) (10), and 11.

Bimetallic ytterbocene complexes with bridging N-heterocylic ligands have been studied extensively in recent years due to their potential applications ranging from molecular wires to single-molecule magnets. Herein, we review our recent results for a series of ytterbocene polypyridyl bimetallic complexes to highlight the versatility and tunability of these systems based on simple changes in bridging ligand geometry. Our work has involved structural, electrochemical, optical, and magnetic measurements with the goal of better understanding the electronic and magnetic communication between the two ytterbium metal centers in this new class of bimetallics.

Two new bimetallic complexes, [Cp*2Yb]2(μ-1,3-(2,2‘-bipyridyl)-5-tBu-C6H3) (1) and [Cp*2Yb]2(μ-1,4-(2,2‘-bipyridyl)-C6H4) (2), and their corresponding two-electron oxidation products [1]2+ and [2]2+ have been synthesized with the aim of determining the impact of the bridging ligand geometry on the electronic and magnetic properties of these materials. Electrochemistry, optical spectroscopy, and bulk susceptibility measurements all support a ground-state electronic configuration of the type [(f)13-(πa*)1-(πb*)1-(f)13]. Density functional theory calculations on the uncomplexed bridging ligands as doubly reduced species also indicate that the diradical electronic configuration is the lowest lying for both meta- and para-bis(bipyridyl) systems. The electrochemical and optical spectroscopic data indicate that the electronic coupling between the metal centers mediated by the diradical bridges is weak, as evidenced by the small separation of the metal-based redox couples and the similarity of the f−f transitions...

Beryllium has been successfully incorporated into a naphthalene containing Schiff base ligand. Evidence from 9Be and 1H NMR data and model compounds indicate that the ligand completely encapsulates the beryllium cation via tetra-dentate tetrahedral coordination using both phenol and imine donors. Calculated 9Be NMR data at the B3LYP/6-311G+(2d,p) DFT level of theory is in agreement with this conclusion.

Nuclear formation cross sections are reported for 26 radionuclides, measured with 40 to 200 MeV proton irradiations of terbium foils. These data are relevant to the production of medically relevant radionuclides (e.g., 152Tb, 155Tb, 155Eu, and 156Eu) and to ongoing efforts to characterize stellar nucleosynthesis routes passing through long-lived intermediaries (e.g., 153Gd). Computational predictions from the ALICE2011, CEM03.03, Bertini, and INCL+ABLA codes are compared with newly measured data to contribute to the ongoing process of code development, and yields are calculated for selected radionuclides using measured data., Comment: 34 pages, 30 figures, 5 tables, submitted to Phys. Rev. C

A systematic study of the novel charge-transfer [(f)14-(pi)0-(f)14 --(f)13-(pi)2-(f)13] electronic state found in 2:1 metal-to-ligand adducts of the type [(Cp)2Yb](BL)[Yb(Cp)2] [BL = tetra(2-pyridyl)pyrazine (tppz) (1), 6',6' '-bis(2-pyridyl)-2,2':4',4'':2'',2'''-quaterpyridine (qtp) (2), 1,4-di(terpyridyl)-benzene (dtb) (3), Cp = (C5Me5)] has been conducted with the aim of determining the effects of increased Yb-Yb separation on the magnetic and electronic properties of these materials. The neutral [(f)13-(pi)2-(f)13], cationic [(f)13-(pi)1-(f)13] and dicationic [(f)13-(pi)0-(f)13] states of these complexes were studied by cyclic voltammetry, UV-vis-NIR electronic absorption spectroscopy, NMR, X-ray crystallography, and magnetic susceptibility measurements. The spectroscopic and magnetic data for the neutral bimetallic complexes is consistent with an [(f)13(pi)2(f)13] ground-state electronic configuration in which each ytterbocene fragment donates one electron to give a singlet dianionic bridging ligand with two paramagnetic Yb(III) centers. The voltammetric data demonstrate that the electronic interaction in the neutral molecular wires 1-3, as manifested in the separation between successive metal reduction waves, is large compared to analogous transition metal systems. Electronic spectra for the neutral and monocationic bimetallic species are dominated by pi-pi and pi-pi transitions, masking the f-f bands that are expected to best reflect the electronic metal-metal interactions. However, these metal-localized transitions are observed when the electrons are removed from the bridging ligand via chemical oxidation to yield the dicationic species, and they suggest very little electronic interaction between metal centers in the absence of pi electrons on the bridging ligands. Analysis of the magnetic data reveals that the qtp complex displays antiferromagnetic coupling of the type Yb(alpha)(alphabeta)Yb(beta) at approximately 13 K.

A new N-heterocyclic complex of ytterbocene (Cp(2)Yb(II), Cp = C(5)Me(5)) has been prepared by the addition of 4'-cyano-2,2':6',2' '-terpyridine (tpyCN) to Cp(2)Yb(II)(OEt(2)) in toluene to give a dark blue species designated as Cp(2)Yb(tpyCN). The effect of the electron-withdrawing group (-CN) on the redox potentials of the charge-transfer form of this complex [in which an electron is transferred from the f(14) metal center to the lowest unoccupied (pi) molecular orbital of the tpyCN ligand to give a 4f(13)-pi(1) electronic configuration] has been quantified by cyclic voltammetry. The tpyCN ligand stabilizes this configuration by 60 mV more than that in the unsubstituted tpy ligand complex and by 110 mV more than that in the unsubstituted bpy ligand complex. Magnetic susceptibility measurements corroborate the enhanced stabilization of the 4f(13)-pi(1) configuration by the substituted terpyridyl ligand complex. Furthermore, the temperature dependence of the magnetic data is most consistent with a thermally induced valence tautomeric equilibrium between this paramagnetic 4f(13)-pi(1) form that dominates near room temperature and the diamagnetic 4f(14)-pi(0) form that dominates at low temperature. Differing coordination modes for the tpyCN ligand to the ytterbocene center have also been confirmed by isolation and X-ray crystallographic characterization of complexes binding through either the cyano nitrogen of tpyCN or the three terpyridyl nitrogen atoms of tpyCN.

The ligand 4,5-dicarboxyimidazole (H(2)DCI) and its methyl derivative 1-methyl-4,5-dicarboxyimidazole (H(2)MDCI) have been shown to bind to Be(II) forming a zwitterionic species that has been structurally characterized. A new dicarboxyimidazole-based polymer has been prepared and its Be-binding properties have been studied using NMR ((1)H and (9)Be) and fluorescence spectroscopy; it represents a rare example of beryllium binding to a polymer. Models of the mononuclear and polymeric Be(II)-binding sites have been studied using density functional theory (DFT), and the (9)Be NMR chemical shifts of these model materials have been calculated for the purpose of direct comparison to experimentally observed values. Differences in the binding modes of the mononuclear and polymeric species are discussed.

Reaction of 2 or 3 equiv of potassium 1,3-bis(trimethylsilyl)allyl (K[1,3-(SiMe3)2C3H3] = K[A‘]) with the triflate salts of Ce, Nd, Eu, Tb, and Yb gives the corresponding neutral bis-(Yb, Eu) and tris-(Ce, Nd, Tb) allyl lanthanide complexes in yields ranging from 40 to 80%. These complexes, which have been crystallographically characterized, initiate the polymerization of methyl methacrylate (MMA), but with poor turnover frequencies when compared with the corresponding salt complexes of the type K[LnA‘3]. K[A‘] itself initiates MMA polymerization, however, and its presence as an ion-pair in the salt complexes may contribute to the activity of heterometallic lanthanide catalysts.

The structures of a series of beryllium containing complexes have been optimized at the B3LYP/6-31G(d) level and their (9)Be magnetic shielding values have been determined using B3LYP/6-311G+g(2d,p) and the gauge-including atomic orbital (GIAO) method. The calculated chemical shifts are in excellent agreement with experimental values. The performance of a variety of NMR methods (SGO, IGAIM, CSGT) were also examined but were found to be inferior to the GIAO method at the chosen level of theory employed. The theoretical method has been utilized to predict the beryllium chemical shifts of structurally characterized complexes for which no measured (9)Be NMR spectrum exists, and to investigate a literature complex with an unusual (9)Be NMR chemical shift. A new standard for beryllium NMR in nonaqueous solvents has been suggested.