Bargaining sets with small coalitions

We study two alternative definitions of the bargaining set in large (atomless) economies; the local bargaining by MasColell (1989) and the global bargaining set by Vind (1992). We alter these definitions to limit the size of the permitted size of the involved coalitions. It turns out that the local bargaining set becomes very large, whereas the global bargaining set is unaltered.     

A fast-moving [2]rotaxane whose stoppers are remote from the copper complex core

[reaction: see text] A new copper-complexed rotaxane is described. It consists of a two-coordination site ring threaded by a sterically non-hindering 2,2'-bipyridine derivative. An electrochemical signal (oxidation or reduction of the copper center, Cu(I) or Cu(II)) induces rearrangement of the system. By using long and flexible linkers between the stoppers and the central complex, ligand exchange is fast, which leads to short response times (on the millisecond time scale and even below).     

Investigating sorption on iron-oxyhydroxide soil minerals by solid-state NMR spectroscopy: a 6Li MAS NMR study of adsorption and absorption on goethite

High-resolution 2H MAS NMR spectra can be obtained for nanocrystalline particles of goethite (alpha-FeOOH, particle size approximately 4-10 nm) at room temperature, facilitating NMR studies of sorption under environmentally relevant conditions. Li sorption was investigated as a function of pH, the system representing an ideal model system for NMR studies. 6Li resonances with large hyperfine shifts (approximately 145 ppm) were observed above the goethite point of zero charge, providing clear evidence for the presence of Li-O-Fe connectivities, and thus the formation of an inner sphere Li+ complex on the goethite surface. Even larger Li hyperfine shifts (289 ppm) were observed for Li+-exchanged goethite, which contains lithium ions in the tunnels of the goethite structure, confirming the Li assignment of the 145 ppm Li resonance to the surface sites.     

Stabilisation of the transition state of phosphodiester bond cleavage within linear single-stranded oligoribonucleotides

The effect of base sequence on the stability of the transition state (TS) of phosphodiester bond cleavage within linear single-stranded oligoribonucleotides has been studied in order to better understand why the reactivity of some phosphodiester bonds is enhanced compared to an unconstrained linkage. Molecular dynamics simulations of 3.0 ns were carried out for 14 oligonucleotides that contain in the place of the scissile phosphodiester bond a phosphorane structure mimicking the TS of the bond cleavage. The hydrolytic stability of the same oligonucleotides had previously been reported. Both the non-bridging oxyanions and the leaving 5[prime or minute]-oxygen of the pentacoordinated phosphorane moiety were observed to form hydrogen bonds with solvent water molecules in a similar way with all the compounds studied. In addition, water mediated hydrogen bonds between the phosphorane non-bridging oxyanions and the bases of the 3[prime or minute]-flanking sequence were detected with some of the compounds, but not with the most labile ones. Hence, it seems that the enhanced cleavage of some internucleosidic linkages does not result from the TS stabilisation by hydrogen bonding. With heterooligomers, the stacking of bases next to the cleavage site was observed to be enhanced on going from the initial state to the TS, whereas within uracil homooligomer, having initially negligible stacking, no change in the magnitude of stacking was seen. Accordingly, while strong stacking in the initial state is known to retard the phosphodiester bond cleavage, it may in the TS accelerate the reaction. Therefore, enhanced stacking on going from the initial state to transition state appears to be a factor that markedly contributes to the hydrolytic stability of phosphodiester bonds within oligonucleotides and may, at least partly, explain accelerated cleavage compared to fully unconstrained bonds, such as those in polyuridylic acid.     

Acyclic, achiral enamide nucleoside analogues. The importance of the C=C bond in the analogue for its ability to mimic natural nucleosides

The conformations of an acyclic, achiral enamide thymidine analogue 1 have been studied by model building and geometry calculations, as well as by NMR NOE and UV experiments. The results indicate that there are no significant barriers to rotation around any of the sigma bonds, in particular the N1-C1' enamide bond, and that the analogue should be able to accommodate conformations that mimic the conformations of natural nucleosides in A- and B-type helices quite well. For comparison the saturated analogue 2 has been prepared and built into oligonucleotides. It is shown that incorporation of 2 in oligonucleotides results in a much larger depression of the melting temperature (deltaTm -10 to -12.5 degrees C) than does incorporation of 1 (deltaTm -5 to -6.5 degrees C).     

Preparation and antiviral properties of new acyclic, achiral nucleoside analogues: 1- or 9-[3-hydroxy-2-(hydroxymethyl)prop-1-enyl]nucleobases and 1- or 9-[2,3-dihydroxy-2-(hydroxymethyl)propyl]nucleobases

Acyclic, achiral nucleoside derivatives 1b-e of adenine, cytosine, 5-methylcytosine, and guanine, containing a 3-hydroxy-2-(hydroxymethyl)prop-1-enyl group on N-1 or N-9, have been prepared analogously to the previously described thymine derivative 1a. In contrast to the adenine and guanine derivatives, the cytosine derivative 9 was unstable, and was obtained in a low yield due to side reactions. These include cleavage of the propenyl group from the base, and the formation of a bicyclic compound. The thymine derivative, although stable under neutral conditions, likewise underwent a reversible cyclization reaction (Michael addition) in the presence of acids or bases. The 5-methylcytosine derivative was stable under neutral and basic conditions. Four other nucleoside derivatives 26a-d containing a 2,3-dihydroxy-2-(hydroxymethyl)propyl group on N-1 or N-9, three of which are new, have likewise been prepared. All compounds were evaluated as antiviral agents against HIV-1 and HSV-1 but were devoid of antiviral activity.     

Investigation of the muffin-tin approximations for potential and charge density in the MS-Xα method by means of calculations of H2O

By detailed analysis of results for H₂O it is shown that both approximations, the muffin-tin approximation of the potential as well as the muffin-tin approximation of the charge density, severely influence the results. Their effects are of the same order of magnitude. Good results for molecular total energies are achieved by roughly compensating the effects from the two approximations, not by minimizing them. The total energy changes drastically when radius or position of the outer sphere are varied. Equilibrium distances strongly depend on the choice of the atomic sphere radii and always are calculated too large, not due to the charge density approximation, but due to the potential approximation. In order to lay hold of angular properties, the sphere radii have to be chosen in a completely different way than for total energies.     

A glucose dehydrogenase biosensor as an additional signal amplification step in an enzyme-flow immunoassay

Both the antibody affinity and the detectability of the label are essential in deciding the final characteristics of a heterogeneous immunoassay. This paper describes an approach to obtain a supplementary enhancement of the signal generated by using an enzyme label, e.g., by including the product of the enzymatic reaction in an additional amplification cycle during the detection step performed with an amperometric biosensor based on glucose dehydrogenase (GDH). An immunoassay format with a labelled analyte derivative that competes with the analyte present in the sample for a limited amount of antibody binding sites was employed. The beta-galactosidase label hydrolyses the substrate aminophenyl-beta-galactopyranoside, and the generated aminophenol enters then into a bioelectrocatalytic amplification cycle at the GDH biosensor. The principle was applied for determination of 4-nitrophenol, with the best minimal concentration of 1.5 microM and a midpoint of the calibration of 24 microM. The potentials and limitations of such a system are discussed.     

High-performance liquid chromatography on dynamically modified silica : II. Modification of various silica packings with cetyltrimethylammonium bromide

High-performance liquid chromatography on silica using eluents containing cetyltrimethylammonium (CTMA) bromide was investigated, and adsorption isotherms were determined for two silica packings of different pore diameter and surface area. It was found that about one CTMA ion was adsorbed per square nanometer of the silica surface at pH 7.5 and at a concentration of 6 mM CTMA bromide in 50% of methanol.Fourteen different silica packings were compared using a test mixture, and thirteen were found to exhibit the same selectivity towards the test mixture, which included acids, bases and non-ionic compounds, thus providing a chromatographic system that is largely independent of the origin of the column material.The retention mechanisms for the five test compounds are discussed.     

Ein neues,einfaches verfahren zur darstellung von ammonium- und phosphonium- betainen der quadrätsaure

Squaric acid 1 reacts with equimolar amounts of tertiary amines 7 and tertiary phosphines 8 in acetic anhydride to afford the monocondensation-products 4 and 5 , respectively.