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Distribution by Scientific Domains

Life Sciences	50%
Chemistry	50%

Selected Abstracts

Non-Covalent Interactions of Organic Halogen Compounds with Aromatic Systems , Analyses of Crystal Structure Data

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2005
Dariusz Swierczynski
Abstract The Cambridge Structural Database showed in mid 2002 about 20.000 structures containing halogen atoms and aryl rests with distances d between the aryl center and the halogen atom, which would allow both hydrogen bonds with the aromatic hydrogens and/or van der Waalsinteractions with the ,-cloud. The latter are characterized by short distances d and by small angles , between the vector along the aryl centroid,halogen line and the perpendicular vector originating in the aryl center (the plane normal). The cases with d < 3.0 Å for F; and d < 3.5 Å for Cl, Br or I (outliers neglected), and , , 10 ± 5°, indicating predominating van der Waals forces, amount to several hundreds. The majority of fragments exhibit larger d and , values, in line with avoidance of electrostatic repulsion between the negative partial charges of the halogens and the ,-cloud center, and with an increasing electrostatic attraction with the aromatic hydrogen atoms. The corresponding hydrogen bonds are characterized by longer distances d and by angle values of , > 60° (about 40 % of the fragments), with only very few cases close to linear hydrogen bonds (then with , = 90°). Compounds containing metal,halogen bonds were omitted in view of possible strong orientational interferences. The structures were screened with four different halogen binding modes, all of them containing the halogen attached to a carbon atom, but with different hybrizations at the connecting carbon centers. The results show only small differences in the distance distributions, with a slight preference for smaller , values for sp2 frameworks. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Prey switching in four species of carnivorous stoneflies

FRESHWATER BIOLOGY, Issue 6 2004
J. M. Elliott
Summary 1. Previous studies compared the functional responses to their prey, and both intraspecific and interspecific interference, in mature larvae of Dinocras cephalotes, Perla bipunctata, Isoperla grammatica and Perlodes microcephalus. The present study examines switching by larvae of the same species presented with different proportions of two contrasting prey types; larvae of Baetis rhodani and Chironomus sp. In each experiment, 200 prey were arranged in nine different combinations of the two prey types (20 : 180, 40 : 160, 60 : 140, 80 : 120, 100 : 100, 120 : 80, 140 : 60, 160 : 40, 180 : 20). Prey were replaced as they were eaten. A model predicted the functional response in the absence of switching and provided a null hypothesis against which any tendency for switching could be tested. 2. No evidence for prey switching by Dinocras and Perla was obtained, both species showing a slight preference for Baetis over Chironomus. Prey switching occurred in Isoperla and Perlodes. As the relative abundance of one prey type increased in relation to the alternative, the proportion eaten of the former prey changed from less to more than expected from its availability, the relationship being described by an S-shaped curve. Isoperla and Perlodes switched to a preference for Baetis when its percentage of the total available prey exceeded 57 and 42%, respectively. Equivalent values for Chironomus were 43 and 58% for Isoperla and Perlodes, respectively. Switching was strongest in Perlodes. 3. Non-switching in Dinocras and Perla was related to their feeding strategy, both species being more successful when using a non-selective ambush strategy at dusk and dawn rather than a search strategy during the night. Both Isoperla and Perlodes used a search strategy. The smaller Isoperla fed chiefly at dusk and dawn, and preferred Chironomus larvae, whereas most of the larger Perlodes fed continuously from dusk to dawn and preferred Baetis larvae. [source]

FEEDING PREFERENCES OF THE MONKEY MIA DOLPHINS: RESULTS FROM A SIMULTANEOUS CHOICE PROTOCOL

MARINE MAMMAL SCIENCE, Issue 4 2003
Lawrence M. Dill
Abstract The semiwild beach-feeding bottlenose dolphins (Tursiops aduncus) of Monkey Mia, Western Australia, provide an unparalleled opportunity to examine prey preference of this species. In a series of binary-choice feeding experiments, we took advantage of the animals' willingness to be fed by hand, to explore their preferences for fish species, size, and state (freshly caught or previously frozen). At the end of each beach visit, each dolphin was provided with a pair of fish but allowed to eat only the first one chosen. The dolphins appeared indifferent among the three species of fish offered to them (yellowtail trumpeter, Amniataba caudovittatus; striped trumpeter, Pelates sexlineatus; and western butterfish, Pentapodus vitta), which were of similar body form and matched for mass. Overall, the dolphins showed a slight preference for the larger of two yellowtail trumpeter offered, suggesting the capability for rational choice when there was a basis for it (most likely energy in this case), although there was considerable individual variation. The dolphins did not distinguish between freshly caught and previously frozen yellowtail. The methodology we describe can be used to generate data of potential value for understanding food and habitat selection of wild dolphins, and for modifying management practices for semiwild dolphins at Monkey Mia and elsewhere. [source]

Alkali Metal Complexes of the Dipeptides PheAla and AlaPhe: IRMPD Spectroscopy,

CHEMPHYSCHEM, Issue 4 2008
Nick C. Polfer, Prof.
Abstract Complexes of PheAla and AlaPhe with alkali metal ions Na+ and K+ are generated by electrospray ionization, isolated in the Fourier-transform ion cyclotron resonance (FT,ICR) ion trapping mass spectrometer, and investigated by infrared multiple-photon dissociation (IRMPD) using light from the FELIX free electron laser over the mid-infrared range from 500 to 1900 cm,1. Insight into structural features of the complexes is gained by comparing the obtained spectra with predicted spectra and relative free energies obtained from DFT calculations for candidate conformers. Combining spectroscopic and energetic results establishes that the metal ion is always chelated by the amide carbonyl oxygen, whilst the C-terminal hydroxyl does not complex the metal ion and is in the endo conformation. It is also likely that the aromatic ring of Phe always chelates the metal ion in a cation-, binding configuration. Along with the amide CO and ring chelation sites, a third Lewis-basic group almost certainly chelates the metal ion, giving a threefold chelation geometry. This third site may be either the C-terminal carbonyl oxygen, or the N-terminal amino nitrogen. From the spectroscopic and computational evidence, a slight preference is given to the carbonyl group, in an ROaOt chelation pattern, but coordination by the amino group is almost equally likely (particularly for K+PheAla) in an ROaNt chelation pattern, and either of these conformations, or a mixture of them, would be consistent with the present evidence. (R represents the , ring site, Oa the amide oxygen, Ot the terminal carbonyl oxygen, and Nt the terminal nitrogen.) The spectroscopic findings are in better agreement with the MPW1PW91 DFT functional calculations of the thermochemistry compared with the B3LYP functional, which seems to underestimate the importance of the cation,, interaction. [source]