Stability and Cooling of the C_{7}

We have studied the stability of the smallest long-lived all carbon molecular dianion (C_{7}^{2-}) in new time domains and with a single ion at a time using a cryogenic electrostatic ion-beam storage ring. We observe spontaneous electron emission from internally excited dianions on millisecond timescales and monitor the survival of single colder C_{7}^{2-} molecules on much longer timescales. We find that their intrinsic lifetime exceeds several minutes-6 orders of magnitude longer than established from earlier experiments on C_{7}^{2-}. This is consistent with our calculations of vertical electron detachment energies predicting one inherently stable isomer and one isomer which is stable or effectively stable behind a large Coulomb barrier for C_{7}^{2-}→C_{7}^{-}+e^{-} separation.

60Fe deposition during the late Pleistocene and the Holocene echoes past supernova activity.

Nuclides synthesized in massive stars are ejected into space via stellar winds and supernova explosions. The solar system (SS) moves through the interstellar medium and collects these nucleosynthesis products. One such product is 60Fe, a radionuclide with a half-life of 2.6 My that is predominantly produced in massive stars and ejected in supernova explosions. Extraterrestrial 60Fe has been found on Earth, suggesting close-by supernova explosions ∼2 to 3 and ∼6 Ma. Here, we report on the detection of a continuous interstellar 60Fe influx on Earth over the past ∼33,000 y. This time period coincides with passage of our SS through such interstellar clouds, which have a significantly larger particle density compared to the local average interstellar medium embedding our SS for the past few million years. The interstellar 60Fe was extracted from five deep-sea sediment samples and accelerator mass spectrometry was used for single-atom counting. The low number of 19 detected atoms indicates a continued but low influx of interstellar 60Fe. The measured 60Fe time profile over the 33 ky, obtained with a time resolution of about ±9 ky, does not seem to reflect any large changes in the interstellar particle density during Earth's passage through local interstellar clouds, which could be expected if the local cloud represented an isolated remnant of the most recent supernova ejecta that traversed the Earth ∼2 to 3 Ma. The identified 60Fe influx may signal a late echo of some million-year-old supernovae with the 60Fe-bearing dust particles still permeating the interstellar medium.

233U/236U signature allows to distinguish environmental emissions of civil nuclear industry from weapons fallout.

Isotopic ratios of radioactive releases into the environment are useful signatures for contamination source assessment. Uranium is known to behave conservatively in sea water so that a ratio of uranium trace isotopes may serve as a superior oceanographic tracer. Here we present data on the atomic [Formula: see text]U/[Formula: see text]U ratio analyzed in representative environmental samples finding ratios of (0.1-3.7)[Formula: see text]10[Formula: see text]. The ratios detected in compartments of the environment affected by releases of nuclear power production or by weapons fallout differ by one order of magnitude. Significant amounts of [Formula: see text]U were only released in nuclear weapons fallout, either produced by fast neutron reactions or directly by [Formula: see text]U-fueled devices. This makes the [Formula: see text]U/[Formula: see text]U ratio a promising new fingerprint for radioactive emissions. Our findings indicate a higher release of [Formula: see text]U by nuclear weapons tests before the maximum of global fallout in 1963, setting constraints on the design of the nuclear weapons employed.

Radiocarbon concentration in tree-ring samples collected in the south-west Slovakia (1974-2013).

Radiocarbon measurements of tree-ring samples collected in Vysoká pri Morave were compared with tree-ring data of the Zlkovce monitoring station situated 5km south-east from the Jaslovské Bohunice Nuclear Power Plant (NPP). Radiocarbon concentrations in Vysoká pri Morave and in Zlkovce tree rings were decreasing exponentially with decay constants of 14.48±1.23 y and 17.96±1.97 y, respectively, in agreement with similar results obtained at other radiocarbon stations. The Suess effect, represented by a dilution in 14C levels by fossil fuel CO2 emissions, was observed in both tree-ring data sets. The Vysoká pri Morave 14C data were during 1974-1995 systematically lower by about 50‰ than the Schauinsland (Germany) clean air reference values due to a regional fossil-fuel impact. However, after 1996 the Vysoká pri Morave 14C data were closer to the Schauinsland data due to lower CO2 emissions as a result of closing some of the heavy industry technologies in the region.

Recent near-Earth supernovae probed by global deposition of interstellar radioactive (60)Fe.

The rate of supernovae in our local Galactic neighbourhood within a distance of about 100 parsecs from Earth is estimated to be one every 2-4 million years, based on the total rate in the Milky Way (2.0 ± 0.7 per century). Recent massive-star and supernova activity in Earth's vicinity may be traced by radionuclides with half-lives of up to 100 million years, if trapped in interstellar dust grains that penetrate the Solar System. One such radionuclide is (60)Fe (with a half-life of 2.6 million years), which is ejected in supernova explosions and winds from massive stars. Here we report that the (60)Fe signal observed previously in deep-sea crusts is global, extended in time and of interstellar origin from multiple events. We analysed deep-sea archives from all major oceans for (60)Fe deposition via the accretion of interstellar dust particles. Our results reveal (60)Fe interstellar influxes onto Earth at 1.5-3.2 million years ago and at 6.5-8.7 million years ago. The signal measured implies that a few per cent of fresh (60)Fe was captured in dust and deposited on Earth. Our findings indicate multiple supernova and massive-star events during the last ten million years at distances of up to 100 parsecs.

Stable platinum isotope measurements in presolar nanodiamonds by TEAMS.

Nanodiamonds are stardust grains commonly found in primitive meteorites. They survived the formation of the solar system and kept their own individuality. Measurements of trace-element isotopic signatures in these grains will help understanding heavy element nucleosynthesis in massive stars and dust formation from their ejecta. We have continued previous attempts to search for stable Pt isotope anomalies in nanodiamonds via trace element accelerator mass spectrometry (TEAMS). The installation of a new injector beam line at the VERA facility allowed studying low traces of stable elements in different materials. Moreover, recent experiments showed that VERA provides the required measurement precision together with a low Pt machine background. Here, we observed for the first time an indication for enhancements of 198Pt/195Pt isotope ratios in two diamond residues prepared by different chemical separation techniques from the Allende meteorite. Variations in other isotopic ratios were within analytical uncertainty, and no anomaly was identified in a third diamond fraction.

Structure and stability of the negative hydrogen molecular ion.

We present the results of a Coulomb explosion experiment that allows for the imaging of the rovibrational wave function of the metastable H2- ion. Our measurements confirm the predicted large internuclear separation of 6 a.u., and they show that the ion decays by autodetachment rather than by spontaneous dissociation. Imaging of the resulting H2 products reveals a large angular momentum of J = 25 ± 2, quantifying the rotation that leads to the metastability of this most fundamental molecular anion.

Calorimetric low temperature detectors for low-energetic heavy ions and their application in accelerator mass spectrometry.

The energy-sensitive detection of heavy ions with calorimetric low temperature detectors was investigated in the energy range of E=0.1-1 MeV/amu, commonly used for accelerator mass spectrometry (AMS). The detectors used consist of sapphire absorbers and superconducting aluminum transition edge thermometers operated at T approximately 1.5 K. They were irradiated with various ion beams (13C, 197Au, 238U) provided by the VERA tandem accelerator in Vienna, Austria. The relative energy resolution obtained was DeltaE/E=(5-9) x 10(-3), even for the heaviest ions such as 238U. In addition, no evidence for a pulse height defect was observed. This performance allowed for the first time to apply a calorimetric low temperature detector in an AMS experiment. The aim was to precisely determine the isotope ratio of 236U/238U for several samples of natural uranium, 236U being known as a sensitive monitor for neutron fluxes. Replacing a conventionally used detection system at VERA by the calorimetric detector enabled to substantially reduce background from neighboring isotopes and to increase the detection efficiency. Due to the high sensitivity achieved, a value of 236U/238U=6.1 x 10(-12) could be obtained, representing the smallest 236U/238U ratio measured at the time. In addition, we contributed to establishing an improved material standard of 236U/238U, which can be used as a reference for future AMS measurements.

Experimental and theoretical evidence for long-lived molecular hydrogen anions H2- and D2-.

The existence of (metastable) molecular hydrogen anions H2(-), D2(-), and H3(-) is demonstrated. These anion species were produced by sputtering of TiH2 and TiD2 targets with Cs+ ions and were identified by accelerator mass spectrometry. From the respective flight times through the spectrometer, lifetimes for H2(-) and D2(-) of at least 3 micros and 4 micros, respectively, can be inferred. Theoretical calculations within the nonlocal resonance model predict the existence of highly rotationally excited anions with lifetimes in the micros range. It is proposed that in sputtering molecular hydrogen species with high rotational and vibrational excitation are formed that are stable on the time scale of the experiment.

Interaction of endothelial and neuronal nitric-oxide synthases with the bradykinin B2 receptor. Binding of an inhibitory peptide to the oxygenase domain blocks uncoupled NADPH oxidation.

Endothelial nitric-oxide synthase (type III) (eNOS) was reported to form an inhibitory complex with the bradykinin receptor B2 (B2R) from which the enzyme is released in an active form upon receptor activation (Ju, H., Venema, V. J., Marrero, M. B., and Venema, R. C. (1998) J. Biol. Chem. 273, 24025-24029). Using a synthetic peptide derived from the known inhibitory sequence of the B2R (residues 310-329) we studied the interaction of the receptor with purified eNOS and neuronal nitric-oxide synthase (type I) (nNOS). The peptide inhibited formation of L-citrulline by eNOS and nNOS with IC(50) values of 10.6 +/- 0.4 microM and 7.1 +/- 0.6 microM, respectively. Inhibition was not due to an interference of the peptide with L-arginine or tetrahydrobiopterin binding. The NADPH oxidase activity of nNOS measured in the absence of L-arginine was inhibited by the peptide with an IC(50) of 3.7 +/- 0.6 microM, but the cytochrome c reductase activity of the enzyme was much less susceptible to inhibition (IC(50) >0.1 mM). Steady-state absorbance spectra of nNOS recorded during uncoupled NADPH oxidation showed that the heme remained oxidized in the presence of the synthetic peptide consisting of amino acids 310-329 of the B2R, whereas the reduced oxyferrous heme complex was accumulated in its absence. These data suggest that binding of the B2R 310-329 peptide blocks flavin to heme electron transfer. Co-immunoprecipitation of B2R and nNOS from human embryonic kidney cells stably transfected with human nNOS suggests that the B2R may functionally interact with nNOS in vivo. This interaction of nNOS with the B2R may recruit the enzyme to allow for the effective coupling of bradykinin signaling to the nitric oxide pathway.

Chemical syntheses and biological studies on dimeric chimeras of oxytocin and the V(2)-antagonist, d(CH(2))(5)[D-Ile(2), Ile(4)]arginine vasopressin.

Parallel and antiparallel heterodimers have been synthesized that combine into a single molecule the neurohypophyseal hormone oxytocin and the potent vasopressin V(2)-antagonist d(CH(2))(5)[D-Ile(2), Ile(4)]arginine vasopressin. Solid-phase synthesis with N(alpha)-9-fluorenylmethyloxycarbonyl (Fmoc) chemistry, featuring appropriate combinations of orthogonal protecting groups for the thiols [S-(N-methyl-N-phenylcarbamoyl)sulfenyl (Snm); S-acetamidomethyl (Acm); S-triphenylmethyl (Trt)], was used to assemble the required linear nonapeptide amide monomer intermediates, which were then brought together in defined ways by solution reactions to provide the two heterodimers. The first disulfide bridge was formed by a directed approach involving attack by the free thiol of the 1-beta-mercapto-beta, beta-cyclopentamethylenepropionic acid (Pmp) residue of one monomer onto the Snm group of a cysteine residue on the other monomer; the inverse directed strategy failed due to steric hindrance. The second disulfide bridge was formed by iodine co-oxidation of Cys(Acm) residues on adjacent chains. Biological studies revealed that both the parallel and antiparallel chimeras lack pressor activity, have low uterotonic activity, and have diuretic activities comparable to that of the monomeric V(2)-antagonist. Sodium excretion depends on experimental conditions. Thus, with a 4% water load, both chimeras display effects similar to that of an equimolar mixture of oxytocin and V(2)-antagonist, i.e., lower sodium excretion than that resulting from administration of oxytocin alone but higher than that when V(2)-antagonist was administered alone. However, when no water load was used, the parallel chimera proved to be more effective in promoting sodium excretion than either oxytocin alone or an equimolar mixture of oxytocin and V(2)-antagonist.