Molecular interaction between perthiolated [beta]-cyclodextrin (CD) and the guests molecules adamantaneacetic acid (AD) and ferroceneacetic acid (FC); and the effect of the interaction on the electron transition of CD anchored particles

The molecular interactions between the host molecule, perthiolated beta-cyclodextrin (CD), and the guest molecules, adamantaneacetic acid (AD) and ferroceneacetic acid (FC), have been inestigated theoretically in both the gas and aqueous phases. The major computations have been carried out at the theoretical levels, RHF/6-31G and B3LYP/6- 31G. MP2 electronic energies were also computed based at the geometries optimized by both the RHF and B3LYP methods in the gas phase to establish a better estimate of the correlation effect. The solvent phase computations were completed at the RHF/6-31G and B3LYP/6-31G levels using the PCM model. The most stable structures optimized in gas phase by both the RHF and B3LYP methods were used for the computations in solution. A method to systematically manipulate the relative position and orientation between the interacting molecules is proposed. In the gas phase, six trials with different host-guest relative positions and orientations were completed successfully with the B3LYP method for both the CD-AD and CD-FC complexes. Only four trials were completed with RHF method. In the gas phase, the best results from the RHF method gives for the association Gibbs free energy (ΔG°) values equal to -32.21kj/mol for CD-AD and -25.73kj/mol for CD-FC. And the best results from the B3LYP method have ΔG° equal to -47.57kj/mol for CD-AD and -41.09kj/mol for CD-FC. The MP2 correction significantly lowers ΔG° based on the geometries from both methods. For the RHF structure, the MP2 computations lowered ΔG° to -60.64kj/mol for CD-AD and -54.10 for CD-FC. For the structure from the B3LYP method, it was reduced to -59.87 kj/mol for CD-AD and -54.84 kj/mol for CDFC. The RHF solvent phase calculations yielded following results: ΔG°(aq) equals 107.2kj/mol for CD-AD and 111.4kj/mol for CD-FC. Compared with the results from the RHF method, the B3LYP method provided clearly better solvent phase results with ΔG° (aq) equal to 38.64kj/mol for CD-AD and 39.61kj/mol for CD-FC. These results qualitatively explain the experimental observations. However quantitatively they are in poor agreement with the experimental values available in the literature and those recently published by Liu et al. And the reason is believed to be omission of hydrophobic contribution to the association. Determining the global geometrical minima for these very large systems was very difficult and computationally time consuming, but after a very thorough search, these were identified. A relevant result of this search is that when the complexes, CD-AD and CD-FC, are formed, the AD and FC molecules are only partially embedded inside the CD cavity. The totally embedded complexes were found to have significantly higher energies. The semiempirical method, ZINDO, was employed to investigate the effect of complexation on the first electronic excitation of CD anchored to a metal nano-particle. The computational results revealed that after complexation to FC, the transition intensity declines to about 25% of the original value, and after complexation with AD, the intensity drops almost 50%. The tighter binding and transition intensity of CD-AD qualitatively agrees with the experimental result that the addition of AD to a solution of CD and FC restores the fluorescence of CD that was quenched by the addition of FC. A method to evaluate the “hydrophobic force” effect is proposed for future work.

The abundance and isotopic composition of Cd in iron meteorites

Cadmium is a highly volatile element and its abundance in meteorites may help better understand volatility-controlled processes in the solar nebula and on meteorite parent bodies. The large thermal neutron capture cross section of 113Cd suggests that Cd isotopes might be well suited to quantify neutron fluences in extraterrestrial materials. The aims of this study were (1) to evaluate the range and magnitude of Cd concentrations in magmatic iron meteorites, and (2) to assess the potential of Cd isotopes as a neutron dosimeter for iron meteorites. Our new Cd concentration data determined by isotope dilution demonstrate that Cd concentrations in iron meteorites are significantly lower than in some previous studies. In contrast to large systematic variations in the concentration of moderately volatile elements like Ga and Ge, there is neither systematic variation in Cd concentration amongst troilites, nor amongst metal phases of different iron meteorite groups. Instead, Cd is strongly depleted in all iron meteorite groups, implying that the parent bodies accreted well above the condensation temperature of Cd (i.e., ≈650 K) and thus incorporated only minimal amounts of highly volatile elements. No Cd isotope anomalies were found, whereas Pt and W isotope anomalies for the same iron meteorite samples indicate a significant fluence of epithermal and higher energetic neutrons. This observation demonstrates that owing to the high Fe concentrations in iron meteorites, neutron capture mainly occurs at epithermal and higher energies. The combined Cd-Pt-W isotope results from this study thus demonstrate that the relative magnitude of neutron capture-induced isotope anomalies is strongly affected by the chemical composition of the irradiated material. The resulting low fluence of thermal neutrons in iron meteorites and their very low Cd concentrations make Cd isotopes unsuitable as a neutron dosimeter for iron meteorites.

Der Weg des Landes Appenzell in die Eidgenossenschaft: Das Bündnis von 1513 und seine Vorgeschichte. CD-ROM mit interaktiven Leseübungen und Kommentaren zu Schriftdokumenten im Zusammenhang mit der Aufnahme des Landes Appenzell in die Eidgenossenschaft vor 500 Jahren

Die CD bietet als erste Publikation überhaupt die Möglichkeit, anhand wichtiger Quellen den Weg des Landes Appenzell in die Eidgenossenschaft nachzuvollziehen. Die Dokumente zeigen die Vorgeschichte des Bündnisses vom 17. Dezember 1513, mit welchem Appenzell als 13. Ort in die Eidgenossenschaft aufgenommen wurde. Zudem kann mit der CD ROM das Lesen alter Handschriften erlernt werden. Das bietet die CD ROM nicht nur das Bild und den gesamten Wortlaut der Urkunde von 1513, sondern auch eine Audio-Datei des Dokuments und erstmals auch eine Übertragung des Urkundentexts in modernes Deutsch.

Selective uptake, distribution, and redistribution of Cd-109, Co-57, Zn-65, Ni-63, and Cs-134 via xylem and phloem in the heavy metal hyperaccumulator Solanum nigrum L

The focus of this article was to explore the translocation of Cd-109, Co-57, Zn-65, Ni-63, and Cs-134 via xylem and phloem in the newly found hyperaccumulator Solanum nigrum L. Two experiments with the uptake via the roots and transport of Cd-109, Co-57, and Zn-65 labeled by roots, and the redistribution of Cd-109, Zn-65, Co-57, Ni-63, and Cs-134 using flap label in S. nigrum in a hydroponic culture with a standard nutrient solution were conducted. The results showed that Cd-109 added for 24 h to the nutrient medium of young plants was rapidly taken up, transferred to the shoot, and accumulated in the cotyledons and the oldest leaves but was not efficiently redistributed within the shoot afterward leading to a rather low content in the fruits. In contrast, Co-57 was more slowly taken up and released to the shoot, but afterward, this element was redistributed from older leaves to younger leaves and maturing fruits. Zn-65 was rapidly taken up and transferred to the shoot (mainly to the youngest leaves and not to the cotyledons). Afterward, this radionuclide was redistributed within the shoot to the youngest organs and finally accumulated in the maturing fruits. After flap labeling, all five heavy metals tested (Cd-109, Co-57, Zn-65, Ni-63, Cs-134) were exported from the labeled leaf and redistributed within the plant. The accumulation in the fruits was most pronounced for Ni-63 and Zn-65, while a relatively high percentage of Co-57 was finally found in the roots. Cs-134 was roughly in the middle of them. The transport of Cd-109 differed from that previously reported for wheat or lupin and might be important for the potential of S. nigrum to hyperaccumulate cadmium.

Ice-Core Based Assessment of Historical Anthropogenic Heavy Metal (Cd, Cu, Sb, Zn) Emissions in the Soviet Union

The development of strategies and policies aiming at the reduction of environmental exposure to air pollution requires the assessment of historical emissions. Although anthropogenic emissions from the extended territory of the Soviet Union (SU) considerably influenced concentrations of heavy metals in the Northern Hemisphere, Pb is the only metal with long-term historical emission estimates for this region available, whereas for selected other metals only single values exist. Here we present the first study assessing long-term Cd, Cu, Sb, and Zn emissions in the SU during the period 1935–1991 based on ice-core concentration records from Belukha glacier in the Siberian Altai and emission data from 12 regions in the SU for the year 1980. We show that Zn primarily emitted from the Zn production in Ust-Kamenogorsk (East Kazakhstan) dominated the SU heavy metal emission. Cd, Sb, Zn (Cu) emissions increased between 1935 and the 1970s (1980s) due to expanded non-ferrous metal production. Emissions of the four metals in the beginning of the 1990s were as low as in the 1950s, which we attribute to the economic downturn in industry, changes in technology for an increasing metal recovery from ores, the replacement of coal and oil by gas, and air pollution control.

The role of chronic irritation and inflammation in tumor promotion in CD-1 mice by petroleum middle distillates

An initiation-promotion bioassay in CD-1 mice was used to examine the role of chronic irritation and inflammation in tumor promotion by petroleum middle distillates. A representative hydrodesulfurized middle distillate (API 81-07) was selected as the test article. Test groups (54 mice per group) were initiated once with 50 ug of 7,12-dimethylbenzanthracene (DMBA). Promotion with API 81-07 consisted of twice weekly treatments for 25 weeks with either 25 ul, 50 ul, 50 ul + daily treatment with 15 ug dexamethasone, 50 ul + post-application washings, and 100 ul. Three mice from each group were sacrificed at 21 day intervals (24 total per group). The skin from interim sacrificed (IS) mice was examined histopathologically for tumor, acanthosis, hyperkeratosis, pseudo-epitheliomatous hyperplasia, epidermal crusting, and subacute inflammation. In-life observations included examination of all mice for erythema and edema for 8 weeks following the first promotion treatment. Tumor incident at study termination was as follows: 25 ul (45%), 50 ul (43%), 50 ul + dexamethasone (0%), 50 ul + washing (70%), and 100 ul (81%). An overall correlation of $>$0.90 between tumor incidence and group means for acanthosis and hyperkeratosis was observed in IS mice at all intervals. Correlations of $<$0.75 were observed for other group mean histopathological parameters and tumor incidence. The overall correlation of group mean erythema and edema with tumor incident was $>$0.90. The results of this study support the hypothesis that induction of a lasting, albeit mild, hyperplasia is an essential, but not sufficient requirement, for tumor promotion. Furthermore, subacute inflammation does not appear to be a significant factor in tumor promotion by petroleum middle distillates. However, inflammation may be a factor in tumor progression. ^

BENZENE MYELOCLASTOGENICITY AND METABOLISM IN CD-1 MICE: A CORRELATION

Benzene was studied in its target organ of effect, the bone marrow, with the micronucleus test and metaphase chromosomal analysis. Groups of 5 or 10, male and female CD-1 mice were treated with one or two p.o. or i.p. doses of benzene (440 mg/kg) or toluene (430, 860 or 1720 mg/kg) or both, and sacrificed 30 or 54h after the first dose. Benzene-treated animals were pretreated with phenobarbital (PB), 3-methylcholanthrene (3MC), (beta)-naphthoflavone ((beta)NF), SKF-525A, or Aroclor 1254. Toluene showed no clastogenic activity and reduced the clastogenic effect of co-administered benzene. None of the pretreatments protected against benzene clastogenicity. 3MC and (beta)NF greatly promoted benzene myeloclastogenicity. Dose response curves for benzene myeloclastogenicity were much steeper with 3MC induction than without. Micronuclei (MN) were 4-6 times higher by p.o. than i.p. benzene administration. This was not due to bacterial flora since no difference was found between germ-free and conventional males gavaged with benzene. A sensitive high-pressure liquid chromatographic method was developed and used to explore the relation between metabolic profiles of benzene in urine and MN after various pretreatments. Phenol (PH), trans-trans-muconic acid (MA) and hydroquinone (HQ) in the 48h male mouse urine accounted, respectively, for 12.8-22.8, 1.8-4.7 and 1.5-3.7% of the single oral dose of benzene (880, 440 and 220 mg/kg). Catechol (CT) was seen in trace amounts. MA was identified by ultraviolet and infrared spectroscopy and elemental analysis. Urinary metabolites--especially MA, HQ, and phenol glucuronide--correlated well with MN and were dependent on both the dose and the metabolism of benzene. Benzene metabolism was most inducible by cytochrome P-448 enzyme inducers, by p.o. > i.p., in males > females, and inhibited by toluene. Ph, CT or HQ administered p.o., 250, 150 and 250 mg/kg, respectively, or at 150 mg/kg x 2 after 3MC pretreatment, failed to reproduce the potent myeloclastogenicity of benzene. In fact, only HQ was mildly clastogenic. ^

Ground truthing the Cd/Ca-carbon isotope relationship in foraminifera of the Greenland-Iceland-Norwegian Seas

In order to examine whether the paleoceanographic nutrient proxies, d13C and cadmium/calcium in foraminiferal calcite, are well coupled to nutrients in the region of North Atlantic Deep Water formation, we present da ta from two transects of the Greenland-Iceland-Norwegian Seas. Along Transect A (74.3°N, 18.3°E to 75.0°N, 12.5°W, 15 stations), we measured phosphate and Cd concentrations of modern surface sea water. Along Transect B (64.5°N, 0.7°W to 70.4°N, 18.2°W, 14 stations) we measured Cd/Ca ratios and d13C of the planktonic foraminifera Neogloboquadrina pachyderma sinistral in core top sediments. Our results indicate that Cd and phosphate both vary with surface water mass and are well correlated along Transect A. Our planktonic foraminiferal d13C data indicate similar nutrient variation with water mass along Transect B. Our Cd/Ca data hint at the same type of nutrient variability, but interpretations are hampered by low values close to the detection limit of this technique and therefore relatively large error bars. We also measured Cd and phosphate concentrations in water depth profiles at three sites along Transect A and the d13C of the benthic foraminifera Cibicidoides wuellerstorfi along Transect B. Modern sea water depth profiles along Transect A have nutrient depletions at the surface and then constant values at depths greater than 100 meters. The d13C of planktonic and benthic foraminifera from Transect B plotted versus depth also reflect surface nutrient depletion and deep nutrient enrichment as seen at Transect A, with a small difference between intermediate and deep waters. Overall we see no evidence for decoupling of Cd/Ca ratio and d13C in foraminiferal calcite from water column nutrient concentrations along these transects in a region of North Atlantic Deep Water formation.