Some probabilistic and extremal results on subdivisions and odd subdivisions of graphs

A probabilistic result of Bollobás and Catlin concerning the largest integer p so that a subdivision of K_p is contained in a random graph is generalized to a result concerning the largest integer p so that a subdivision of A_p is contained in a random graph for some sequence A₁, A₂,… of graphs such that A_i+1 contains a subdivision of A_i. A similar result is proved for subdivisions with odd paths or cycles. The result is applied to disprove a conjecture of Chartrand, Geller, and Hedetniemi. The maximum number of edges in a graph without a subdivision of K_p, p = 4, 5, with odd paths or cycles is determined.     

Speciation in the aqueous H+/H2VO4-/H2O2/picolinate system relevant to diabetes research

A detailed study of the quaternary aqueous H+/H2VO4-/H2O2/picolinate (Pi-) system has been performed at 25 degrees C in 0.150 M Na(Cl) medium using quantitative 51 V NMR (500 MHz) and potentiometric data (glass electrode). In the ternary H+/H2VO4-/Pi- system, six complexes have been found in the pH region 1-10. In the quaternary H+/H2VO4-/H2O2/Pi- system, eight additional complexes have been found. Generally, equilibria are fast in both systems. The rate of peroxide decomposition depends on the species in solution. Chemical shifts, compositions and formation constants for the species are given. Equilibrium conditions and the fit of the model to the experimental data are illustrated in distribution diagrams. Possible formation of mixed ligand species with imidazole, lactic acid and citric acid have been investigated and ruled out under the same experimental conditions. Structural proposals are given, based on 1)C NMR data and available crystal structures.     

The Influence of Cobalt (II) in Carboxymethyl Cellulose Processing

Controlling the reduction in molecular weight of the cellulose chains is essential in the production of carboxymethyl cellulose (CMC). Such a reduction can be achieved by the addition of cobalt during the process of cobalt(II) ions, which act as a catalyst for oxidative cleavage, and the influence thereof has been studied under a variety of conditions. This study has resulted in a model that summarises the effects of the added amount of cobalt, the time for the cobalt reaction, the temperature in the mercerisation stage of the CMC-manufacturing process and finally the effect of the temperature in the etherification stage. It is shown that it is important for cobalt to be present during the mercerisation stage in order to achieve the desired viscosity.     

ABSORPTION SPECTRAL SHIFTS OF CAROTENOIDS RELATED TO MEDIUM POLARIZABILITY

Abstract–Solvent induced absorption spectral shifts of the electronic transition from ground 1 A_g state to the excited 1B_u state in carotenoids have been studied. It is shown that the shift depends only on dispersion interactions in non-polar solvents. In polar media there is just a small extra contribution to the red-shift, due to other forms of interactions. The spectral shifts are well described by the theory, which expresses the shift relative to the gas phase value, as a function of solvent polarizability. The main conclusion is that the dominating mechanism behind the large red-shifted absorbance of carotenoids in the proteinacous environment, in vivo, is the mutual polarizability interactions between the carotenoids and the surrounding medium. The solution-phase values of the dipole moments of the lA_g to 1B_u transitions and the differences of isotropic polarizability between 1B_u and lA_g states of carotenoids in non-polar solvents are calculated and found to be around 13 D and 360 ų respectively. From the great overlap of absorption spectra between carotenoids in quinoline and carotenoids in vivo in purple bacterial antenna complexes, it can be expected that the carotenoids are surrounded by several aromatic amino acids in vivo. Comparisons have been done between the exicted states in carotenoids and in linear conjugated polyenes.     

Unusual effects of separation conditions on chiral separations

Unusual effects in liquid chromatographic separations of enantiomers on chiral stationary phases are reviewed with emphasis on polysaccharide phases. On protein phases and Pirkle phases reversal of the elution order between enantiomers due to variation of temperature and mobile phase composition has been reported. Most of the nonanticipated observations have dealt with the widely used polysaccharide phases. Reversed retention order and other stereoselective effects have been observed by variation of temperature, organic modifier and water content in nonpolar organic mobile phases.     

Dissociative recombination of the weakly bound NO-dimer cation: cross sections and three-body dynamics

Dissociative recombination (DR) of the dimer ion (NO)(2) (+) has been studied at the heavy-ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm. The experiments were aimed at determining details on the strongly enhanced thermal rate coefficient for the dimer, interpreting the dissociation dynamics of the dimer ion, and studying the degree of similarity to the behavior in the monomer. The DR rate reveals that the very large efficiency of the dimer rate with respect to the monomer is limited to electron energies below 0.2 eV. The fragmentation products reveal that the breakup into the three-body channel NO+O+N dominates with a probability of 0.69+/-0.02. The second most important channel yields NO+NO fragments with a probability of 0.23+/-0.03. Furthermore, the dominant three-body breakup yields electronic and vibrational ground-state products, NO(upsilon=0)+N((4)S)+O((3)P), in about 45% of the cases. The internal product-state distribution of the NO fragment shows a similarity with the product-state distribution as predicted by the Franck-Condon overlap between a NO moiety of the dimer ion and a free NO. The dissociation dynamics seem to be independent of the NO internal energy. Finally, the dissociation dynamics reveal a correlation between the kinetic energy of the NO fragment and the degree of conservation of linear momentum between the O and N product atoms. The observations support a mechanism in which the recoil takes place along one of the NO bonds in the dimer.     

The roles of template complexation and ligand binding conditions on recognition in bupivacaine molecularly imprinted polymers

A model for the molecular basis for ligand recognition in bupivacaine imprinted methacrylic acid-ethylene glycol dimethacrylate co-polymers has been developed based upon a series of (1)H-NMR studies in conjunction with HPLC and radioligand binding analyses. (1)H-NMR studies indicated that functional monomer-template complexes survive the polymerisation process, at least up until the stage of gelation. Polymers were synthesised and characterised by surface area analysis (BET), FT-IR and SEM. A combination of zonal and frontal chromatographic studies in aqueous and non-polar media indicate that selectivity arises from a combination of hydrophobic and electrostatic interactions. However, in the concentration regime employed for LC-based studies, ligand recognition in aqueous media was shown to be predominantly non-specific and hydrophobic in character. Radioligand binding studies, in lower ligand binding concentration regimes, permitted closer examination of the higher affinity binding sites. It was shown that the presence of a polar modifier in a non-polar solvent, or an organic modifier in water, produced enhanced selectivity. Variable temperature studies showed that the temperature of binding influences selectivity as well as the apparent number of sites available and that this effect is different in organic and aqueous environments. This indicates that the system studied is more complex in character than is generally appreciated. A comparison of the techniques employed here indicates that although chromatographic studies provide a valuable first-round screen for polymer-ligand selectivities, the level of detail obtainable using radioligand binding studies (lower concentrations and true equilibrium binding) makes them superior for detailed evaluations of molecularly imprinted polymers.     

Reaction of pyridine N-oxides with Grignard reagents: a stereodefined synthesis of substituted dienal oximes

Rapid addition of Grignard reagents to pyridine N-oxides under mild conditions gave stereodefined dienal oximes in good to excellent yields. This reaction provides an efficient access to substituted olefins with defined stereochemistry that are potentially of interest as bioactives themselves or as versatile synthetic intermediates.     

Improved quantification limits in chiral capillary electrochromatography by peak compression effects

The peak compression effect has been applied to improve quantification limits in chiral capillary electrochromatography (CEC). A stationary phase based on the chiral selector vancomycin (Chirobiotic V) was used for separations of the enantiomers of mianserin. By adding solvents with a low dielectric constant, e.g. 2-propanol or tetrahydrofuran, to the sample solution, peak compression could be induced. The plate numbers for the minor enantiomer increased from approximately 100,000 to 1.4-1.6 million plates/m, when the composition of the mobile phase was adjusted so that the analyte eluted within either one of two system zones originating from the sample solution. A 10-fold improvement in the quantification limit for the minor enantiomer was obtained compared to elution under non-focused conditions.