A. Türler

Chemical investigation of hassium (element 108).

The periodic table provides a classification of the chemical properties of the elements. But for the heaviest elements, the transactinides, this role of the periodic table reaches its limits because increasingly strong relativistic effects on the valence electron shells can induce deviations from known trends in chemical properties. In the case of the first two transactinides, elements 104 and 105, relativistic effects do indeed influence their chemical properties, whereas elements 106 and 107 both behave as expected from their position within the periodic table. Here we report the chemical separation and characterization of only seven detected atoms of element 108 (hassium, Hs), which were generated as isotopes 269Hs (refs 8, 9) and 270Hs (ref. 10) in the fusion reaction between 26Mg and 248Cm. The hassium atoms are immediately oxidized to a highly volatile oxide, presumably HsO4, for which we determine an enthalpy of adsorption on our detector surface that is comparable to the adsorption enthalpy determined under identical conditions for the osmium oxide OsO4. These results provide evidence that the chemical properties of hassium and its lighter homologue osmium are similar, thus confirming that hassium exhibits properties as expected from its position in group 8 of the periodic table.

Chemical properties of element 106 (seaborgium)

The synthesis, via nuclear fusion reactions, of elements heavier than the actinides, allows one to probe the limits of the periodic table as a means of classifying the elements. In particular, deviations in the periodicity of chemical properties for the heaviest elements are predicted as a consequence of increasingly strong relativistic effects on the electronic shell structure. The transactinide elements have now been extended up to element 112 (ref. 8), but the chemical properties have been investigated only for the first two of the transactinide elements, 104 and 105 (refs 9,10,11,12,13,14,15,16,17,18,19). Those studies showed that relativistic effect render these two elements chemically different from their lighter homologues in the same columns of the periodic table (Fig. 1). Here we report the chemical separation of element 106 (seaborgium, Sg) and investigations of its chemical behaviour in the gas phase and in aqueous solution. The methods that we use are able to probe the reactivity of individual atoms, and based on the detection of just seven atoms of seaborgium we find that it exhibits properties characteristic of the group 6 homologues molybdenum and tungsten. Thus seaborgium appears to restore the trends of the periodic table disrupted by relativistic effects in elements 104 and 105.

Advances in the Production and Chemistry of the Heaviest Elements

Andreas Türler*,†,‡ and Valeria Pershina †Laboratory of Radiochemistry and Environmental Chemistry, Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland ‡Laboratory of Radiochemistry and Environmental Chemistry, Department Biology and Chemistry, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland GSI Helmholtzzentrum für Schwerionenforschung GmbH, Planckstrasse 1, D-64291 Darmstadt, Germany

Chemical identification and properties of element 112

Summary We present results of the second experiment on the chemical identification of element 112. Similar to the first test in 2000, we aimed at the production of the spontaneously fissioning 283112 nuclei with T1/2≈3min. A natU3O8 (with some Nd) target, 2mg of U/cm2 thick, was bombarded with 233-MeV 48Ca ions (the energy in the middle of the target layer). The nuclei recoiling from the target were thermalized in flowing helium. The target chamber was connected through a 25m long capillary to detectors of α-particles and fission fragments. All the equipment and detectors were kept at ambient temperature. According to the test experiments, of all the heavy elements produced in the bombardment, only Hg, Rn and At could be transported to the detectors. The first detecting device was similar to that used earlier – an assembly of 8 pairs of PIPS detectors coated with gold. Here one would observe the decay of element 112 atoms if they like Hg adsorbed on gold. The atoms which were not retained and freely passed through the PIPS detectors entered a new, flow-through ionization chamber, 5000 cm3 in volume, optimized for detecting fission fragments. The PIPS detectors and the ionization chamber were placed inside a large assembly of 3He – filled neutron counters to detect prompt neutrons from the fission events. In 22.5 days, a beam dose of 2.8×1018 ions was accumulated. More than 95 of the simultaneously produced α-active 185Hg (T1/2=49 s) were found deposited already on the first pair of PIPS detectors; meanwhile, all the PIPSs did not detect any fission event. In the ionization chamber, eight fission events were observed in coincidence with neutron counts while the expected background was insignificant. Hence, the spontaneous fissions of the volatile activity can be conclusively attributed to the decay of element 112 produced in the fusion reaction 48Ca+ 238U, and formerly observed in Dubna physical experiments. Evaluation of the experimental data in terms of the adsorption enthalpies indicates much weaker interaction of element 112 with Au than that of Hg. One can conclude that in the given chemical environment, element 112 behaves like Rn rather than like Hg. The formation cross section of 283112 estimated from the data amounts to several pb. The experiments were carried out at the Flerov Laboratory of Nuclear Reactions at JINR in November–December 2001.

Promises of Cyclotron-Produced 44Sc as a Diagnostic Match for Trivalent β−-Emitters: In Vitro and In Vivo Study of a 44Sc-DOTA-Folate Conjugate

In recent years, implementation of 68Ga-radiometalated peptides for PET imaging of cancer has attracted the attention of clinicians. Herein, we propose the use of 44Sc (half-life = 3.97 h, average β+ energy [Eβ+av] = 632 keV) as a valuable alternative to 68Ga (half-life = 68 min, Eβ+av = 830 keV) for imaging and dosimetry before 177Lu-based radionuclide therapy. The aim of the study was the preclinical evaluation of a folate conjugate labeled with cyclotron-produced 44Sc and its in vitro and in vivo comparison with the 177Lu-labeled pendant. Methods: 44Sc was produced via the 44Ca(p,n)44Sc nuclear reaction at a cyclotron (17.6 ± 1.8 MeV, 50 μA, 30 min) using an enriched 44Ca target (10 mg 44CaCO3, 97.00%). Separation from the target material was performed by a semiautomated process using extraction chromatography and cation exchange chromatography. Radiolabeling of a DOTA-folate conjugate (cm09) was performed at 95°C within 10 min. The stability of 44Sc-cm09 was tested in human plasma. 44Sc-cm09 was investigated in vitro using folate receptor–positive KB tumor cells and in vivo by PET/CT imaging of tumor-bearing mice Results: Under the given irradiation conditions, 44Sc was obtained in a maximum yield of 350 MBq at high radionuclide purity (>99%). Semiautomated isolation of 44Sc from 44Ca targets allowed formulation of up to 300 MBq of 44Sc in a volume of 200–400 μL of ammonium acetate/HCl solution (1 M, pH 3.5–4.0) within 10 min. Radiolabeling of cm09 was achieved with a radiochemical yield of greater than 96% at a specific activity of 5.2 MBq/nmol. In vitro, 44Sc-cm09 was stable in human plasma over the whole time of investigation and showed folate receptor–specific binding to KB tumor cells. PET/CT images of mice injected with 44Sc-cm09 allowed excellent visualization of tumor xenografts. Comparison of cm09 labeled with 44Sc and 177Lu revealed almost identical pharmacokinetics. Conclusion: This study presents a high-yield production and efficient separation method of 44Sc at a quality suitable for radiolabeling of DOTA-functionalized biomolecules. An in vivo proof-of-concept study using a DOTA-folate conjugate demonstrated the excellent features of 44Sc for PET imaging. Thus, 44Sc is a valid alternative to 68Ga for imaging and dosimetry before 177Lu-radionuclide tumor therapy.

Thermochromatographic studies of mercury and radon on transition metal surfaces

Abstract In preparation for the experimental investigation of chemical properties of element 112 model studies were conducted based on the assumed similarity of element 112 to either the noble gas Rn or the transition metal Hg, its supposed lighter homologue in group 12. The adsorption behavior of elemental Hg on the transition metals Ag, Au, Ni, Pd, and Pt were investigated experimentally by off-line gas thermochromatography. The deduced adsorption data of Hg were compared with new values calculated using the Eichler–Miedema model. The observed sequence of increasing Hg-metal-interactions for Ag < Ni < Au < Pd < Pt confirms the predicted trend. The only exception was Pd, on which Hg was calculated to adsorb at a higher temperature than on Pt. Difficulties to obtain reproducible clean surfaces of Ag, Ni, Pd, and Pt led to the choice of Au as the best metal surface suitable to adsorb Hg. For fast on-line gas thermochromatography studies on metallic surfaces a new set-up was developed based on the In-situ Volatilization and On-line detection technique (IVO). This set-up was tested in on-line thermochromatographic investigations with short-lived Hg isotopes and 219Rn, using Au or Pd as stationary surfaces. An overall efficiency of about 60% and a transportation time less than 25 s was determined for this newly designed IVO. A separation factor of more than 106 was estimated for non-volatile species.

A Unique Matched Quadruplet of Terbium Radioisotopes for PET and SPECT and for α- and β−-Radionuclide Therapy: An In Vivo Proof-of-Concept Study with a New Receptor-Targeted Folate Derivative

Terbium offers 4 clinically interesting radioisotopes with complementary physical decay characteristics: 149Tb, 152Tb, 155Tb, and 161Tb. The identical chemical characteristics of these radioisotopes allow the preparation of radiopharmaceuticals with identical pharmacokinetics useful for PET (152Tb) and SPECT diagnosis (155Tb) and for α- (149Tb) and β−-particle (161Tb) therapy. The goal of this proof-of-concept study was to produce all 4 terbium radioisotopes and assess their diagnostic and therapeutic features in vivo when labeled with a folate-based targeting agent. Methods: 161Tb was produced by irradiation of 160Gd targets with neutrons at Paul Scherrer Institute or Institut Laue-Langevin. After neutron capture, the short-lived 161Gd decays to 161Tb. 149Tb, 152Tb, and 155Tb were produced by proton-induced spallation of tantalum targets, followed by an online isotope separation process at ISOLDE/CERN. The isotopes were purified by means of cation exchange chromatography. For the in vivo studies, we used the DOTA–folate conjugate cm09, which binds to folate receptor (FR)–positive KB tumor cells. Therapy experiments with 149Tb-cm09 and 161Tb-cm09 were performed in KB tumor–bearing nude mice. Diagnostic PET/CT (152Tb-cm09) and SPECT/CT (155Tb-cm09 and 161Tb-cm09) studies were performed in the same tumor mouse model. Results: Carrier-free terbium radioisotopes were obtained after purification, with activities ranging from approximately 6 MBq (for 149Tb) to approximately 15 GBq (for 161Tb). The radiolabeling of cm09 was achieved in a greater than 96% radiochemical yield for all terbium radioisotopes. Biodistribution studies showed high and specific uptake in FR-positive tumor xenografts (23.8% ± 2.5% at 4 h after injection, 22.0% ± 4.4% at 24 h after injection, and 18.4% ± 1.8% at 48 h after injection). Excellent tumor-to-background ratios at 24 h after injection (tumor to blood, ∼15; tumor to liver, ∼5.9; and tumor to kidney, ∼0.8) allowed the visualization of tumors in mice using PET (152Tb-cm09) and SPECT (155Tb-cm09 and 161Tb-cm09). Compared with no therapy, α- (149Tb-cm09) and β−-particle therapy (161Tb-cm09) resulted in a marked delay in tumor growth or even complete remission (33% for 149Tb-cm09 and 80% for 161Tb-cm09) and a significantly increased survival. Conclusion: For the first time, to our knowledge, 4 terbium radionuclides have been tested in parallel with tumor-bearing mice using an FR targeting agent. Along with excellent tumor visualization enabled by 152Tb PET and 155Tb SPECT, we demonstrated the therapeutic efficacy of the α-emitter 149Tb and β−-emitter 161Tb.

Superheavy Element Flerovium (Element 114) Is a Volatile Metal

The electron shell structure of superheavy elements, i.e., elements with atomic number Z ≥ 104, is influenced by strong relativistic effects caused by the high Z. Early atomic calculations on element 112 (copernicium, Cn) and element 114 (flerovium, Fl) having closed and quasi-closed electron shell configurations of 6d(10)7s(2) and 6d(10)7s(2)7p1/2(2), respectively, predicted them to be noble-gas-like due to very strong relativistic effects on the 7s and 7p1/2 valence orbitals. Recent fully relativistic calculations studying Cn and Fl in different environments suggest them to be less reactive compared to their lighter homologues in the groups, but still exhibiting a metallic character. Experimental gas-solid chromatography studies on Cn have, indeed, revealed a metal-metal bond formation with Au. In contrast to this, for Fl, the formation of a weak bond upon physisorption on a Au surface was inferred from first experiments. Here, we report on a gas-solid chromatography study of the adsorption of Fl on a Au surface. Fl was produced in the nuclear fusion reaction (244)Pu((48)Ca, 3-4n)(288,289)Fl and was isolated in-flight from the primary (48)Ca beam in a physical recoil separator. The adsorption behavior of Fl, its nuclear α-decay product Cn, their lighter homologues in groups 14 and 12, i.e., Pb and Hg, and the noble gas Rn were studied simultaneously by isothermal gas chromatography and thermochromatography. Two Fl atoms were detected. They adsorbed on a Au surface at room temperature in the first, isothermal part, but not as readily as Pb and Hg. The observed adsorption behavior of Fl points to a higher inertness compared to its nearest homologue in the group, Pb. However, the measured lower limit for the adsorption enthalpy of Fl on a Au surface points to the formation of a metal-metal bond of Fl with Au. Fl is the least reactive element in the group, but still a metal.

IVO, a device for in situ Volatilization and On-line detection of products from heavy ion reactions

Abstract A new gaschromatographic separation system to rapidly isolate heavy ion reaction products in the form of highly volatile species is described. Reaction products recoiling from the target are stopped in a gas volume and converted in situ to volatile species, which are swept by the carrier gas to a chromatography column. Species that are volatile under the given conditions pass through the column. In a cluster chamber, which is directly attached to the exit of the column, the isolated volatile species are chemically adsorbed to the surface of aerosol particles and transported to an on-line detection system. The whole set-up was tested using short-lived osmium (Os) and mercury (Hg) nuclides produced in heavy ion reactions to model future chemical studies with hassium (Hs, Z =108) and element 112. By varying the temperature of the isothermal section of the chromatography column between room temperature and −80°C, yield measurements of given species can be conducted, yielding information about the volatility of the investigated species.

Cold fusion reactions with 48Ca

Abstract Fusion reactions of 48 Ca projectiles with 180 Hf, 184 W, 197 Au, 208 Pb and 209 Bi targets were studied. Highest cross sections were found in the 208 Pb( 48 Ca,2n) 254 No channel with σ max 3.2 ± 0.3 μb. The results of the heavier systems are discussed in terms of the extra — push model. For the lighter systems missing cross section is observed if compared to estimates made by the evaporation code HIVAP.