Base-mediated transformation of the agostic (π-allyl)-closo-rhodacarboranes into complexes with an open (1-5-η5)-pentadienyl ligand.

The reactions of agostic (CH3···Rh) complexes [3-{(1-3-η(3))-1,1,2-trimethylallyl}-1-R-2-R'-closo-3,1,2-RhC2B9H9] [1: R = R' = Me; 2: R,R' = µ-(ortho-xylylene); 3: R = Ph, R' = Me] in a cooled (+5 °C) toluene solution with the strong non-nucleophilic base N,N,N',N'-tetramethylnaphthalene-1,8-diamine (tmnd) formally involve a linear coupling of the π-allyl ligand of one molecule of the complex to the π-allyl ligand of the second molecule of the complex, ultimately forming the structurally novel mononuclear species [3-{(1-5-η(5))-2,3-dimethyl-5-(3-methylbuten-2-yl)pentadienyl}-1-R-2-R'-closo-3,1,2-RhC2B9H9] (4, 5) and (6a,b, a mixture of diastereomers). Complexes 5 and 6a,b were also prepared using weaker bases such as PPh3 or even EtOH instead of tmnd. All new complexes 4-6 were characterized by a combination of analytical and multinuclear NMR data, as well as by single-crystal X-ray diffraction studies of two selected species 5 and the major diastereomer of 6, which revealed an open η(5)-pentadienyl coordination mode of the hydrocarbon ligands in these complexes.

Estimating the exposure of small mammals at three sites within the Chernobyl exclusion zone--a test application of the ERICA Tool.

An essential step in the development of any modelling tool is the validation of its predictions. This paper describes a study conducted within the Chernobyl exclusion zone to acquire data to conduct an independent test of the predictions of the ERICA Tool which is designed for use in assessments of radiological risk to the environment. Small mammals were repeatedly trapped at three woodland sites between early July and mid-August 2005. Thermoluminescent dosimeters mounted on collars were fitted to Apodemus flavicollis, Clethrionomys glareolus and Microtus spp. to provide measurements of external dose rate. A total of 85 TLDs were recovered. All animals from which TLDs were recovered were live-monitored to determine (90)Sr and (137)Cs whole-body activity concentrations. A limited number of animals were also analysed to determine (239,240)Pu activity concentrations. Measurements of whole-body activity concentrations and dose rates recorded by the TLDs were compared to predictions of the ERICA-Tool. The predicted (90)Sr and (137)Cs mean activity concentrations were within an order of magnitude of the observed data means. Whilst there was some variation between sites in the agreement between measurements and predictions this was consistent with what would be expected from the differences in soil types at the sites. Given the uncertainties of conducting a study such as this, the agreement observed between the TLD results and the predicted external dose rates gives confidence to the predictions of the ERICA Tool.

Exposure to chronic, low-dose rate gamma-radiation at Chornobyl does not induce point mutations in Big Blue mice.

Empirical genetic effects resulting from low-dose rate irradiation and chronic, cumulative exposure are poorly characterized. Expected effects are based on epidemiological studies and downward, linear extrapolations from nonthreshold models derived from acute, high-dose exposures. These extrapolations and their associated risk coefficients have no experimental support, and because of their inherent uncertainty they are the subject of considerable debate. The expectation of deleterious genetic effects resulting from low-dose rate irradiation and chronic exposure is in need of empirical assessment because this type of exposure is typical of those encountered in occupational, residential, and environmental settings. Recent acute low-dose (<10 cGy) studies using cytogenetic and point mutation endpoints indicate that observed effects range from those lower than spontaneous to an increase in the frequency of point mutations. Using the Big Blue assay, we examined the ability of chronic, continuous gamma-irradiation (2.3 x 10(-3) cGy/min) in the Chornobyl environment to induce point mutations. This system has demonstrated a significant point mutation sensitivity (4.5-fold increase) to acute, high-dose (1-3 Gy) gamma-radiation. Mutant frequencies and the mutation spectra were examined in exposed and reference samples of Big Blue mice following 90 days exposure (cumulative absorbed dose = 3 Gy) to the Chornobyl environment. No significant increase in the mutant frequency or bias in the mutational spectrum was observed in exposed individuals. This finding suggests that low-dose rate gamma-irradiation at Chornobyl does not induce point mutations and that cumulative, chronically absorbed doses do not induce the same genetic effects as acute doses of the same magnitude.

Crown compounds for anions: sandwich and half-sandwich complexes of cyclic trimetric perfluoro-o-phenylenemercury with polyhedral closo-[B10H10]2- and closo-[B12H12]2- anions.

It has been shown by IR and NMR spectroscopy that cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4-Hg)3 (1) is capable of binding closo-[B10H10]2- and closo-[B12H12]2- anions to form complexes [[(o-C6F4Hg)3](B10-H10)]2- (2), [[(o-C6F4Hg)3]2(B10H10)]2-(3), [[(o-C6F4Hg)3](B12H12)]2- (4), and [[(o-C6F4Hg)3]2(B12H12)]2- (5). According to IR data, the bonding of the [B10H10]2- and [B12H12]2- ions to the macrocycle in these complexes is accomplished through the formation of B-H-Hg bridges. Complexes 2, 3, and 5 have been isolated in analytically pure form and have been characterized by spectroscopic means. X-ray diffraction studies of 3 and 5 have revealed that these compounds have unusual sandwich structures, in which the polyhedral di-anion is located between the planes of two molecules of 1 and is bonded to each of them through two types of B-H-Hg bridges. One type is the simultaneous coordination of a B-H group to all three Hg atoms of the macrocycle. The other type is the coordination of a B-H group to a single Hg atom of the cycle. According to X-ray diffraction data, complex 2 has an analogous but half-sandwich structure. The obtained complexes 2-5 are quite stable; their stability constants in THF/acetone (1:1) at 20 degrees C have been determined as 1.0 x 10(2)Lmol(-1), 2.6 x 10(3)L(2)mol(2), 0.7 x 10(2)Lmol(-1), and 0.98 x 10(3)L(2)mol(-2), respectively.

Accumulation of 137Cesium and 90Strontium from abiotic and biotic sources in rodents at Chornobyl, Ukraine.

Bank voles (Clethrionomys glareolus) and laboratory strains of house mice (Mus musculus BALB and C57BL) were relocated into enclosures in a highly contaminated area of the Red Forest near the Chornobyl (Ukraine) Reactor 4 to evaluate the uptake rates of 137Cs and 90Sr from abiotic sources. Mice were provided with uncontaminated food supplies, ensuring that uptake of radionuclides was through soil ingestion, inhalation, or water. Mice were sampled before introduction and were reanalyzed every 10 d for 137Cs uptake. Levels of 90Sr were assessed in subsamples from the native populations and in experimental animals at the termination of the study. Uptake rates in house mice were greater than those in voles for both 137Cs and 90Sr. Daily uptake rates in house mice were estimated at 2.72 x 10(12) unstable atoms per gram (whole body) for 137Cs and 4.04 x 10(10) unstable atoms per gram for 90Sr. Comparable rates in voles were 2.26 x 10(11) unstable atoms per gram for 137Cs and 1.94 x 10(10) unstable atoms per gram for 90Sr. By comparing values from voles in the enclosures to those from wild voles caught within 50 m of the enclosures, it was estimated that only 8.5% of 137Cs was incorporated from abiotic sources, leaving 91.5% being incorporated by uptake from biotic materials. The fraction of 90Sr uptake from abiotic sources was at least 66.7% (and was probably much higher). Accumulated whole-body doses during the enclosure periods were estimated as 174 mGy from intramuscular 137Cs and 68 mGy by skeletal 90Sr in house mice over 40 d and 98 mGy from 137Cs and 19 mGy from 90Sr in voles over 30 d. Thus, uptake of radionuclides from abiotic materials in the Red Forest at Chornobyl is an important source of internal contamination.