Simulation of three-phase displacement experiments

Three-phase displacement experiments for a water-benzyl alcohol-decane system are simulated. Literature experimental three-phase relative permeabilities for the system are used to describe the relative permeabilities in the three-phase region for different three-phase relative permeability models. Saturation trajectories and elliptical regions are mapped in the three-phase region. Simulations are performed to model displacement experiments including breakthrough and the formation of multiple shocks. The model can be used to predict the results for other displacements. In an experiment where significant gravity segregation is present, the displacement is more accurately modeled by assuming a uniform initial condition than by using the actual vertical saturation and assuming no cross flow. It is shown how different residual saturation values can be measured in the laboratory depending on the initial saturation conditions in the core. The experimental residual saturations can be significantly different than the ‘theoretical’ or model values.     

On the use of pseudocontact shifts in the structure determination of metalloproteins

The utility of pseudocontact shifts in the structure refinement of metalloproteins has been evaluated using a native, paramagnetic Cu(2+) metalloprotein, plastocyanin from Anabaena variabilis (A.v.), as a model protein. First, the possibility of detecting signals of nuclei spatially close to the paramagnetic metal ion is investigated using the WEFT pulse sequence in combination with the conventional TOCSY and (1)H-(15)N HSQC sequences. Second, the importance of the electrical charge of the metal ion for the determination of correct pseudocontact shifts from the obtained chemical shifts is evaluated. Thus, using both the Cu(+) plastocyanin and Cd(2+)-substituted plastocyanin as the diamagnetic references, it is found that the Cd(2+)-substituted protein with the same electrical charge of the metal ion as the paramagnetic Cu(2+) plastocyanin provides the most appropriate diamagnetic reference signals. Third, it is found that reliable pseudocontact shifts cannot be obtained from the chemical shifts of the (15)N nuclei in plastocyanin, most likely because these shifts are highly dependent on even minor differences in the structure of the paramagnetic and diamagnetic proteins. Finally, the quality of the obtained (1)H pseudocontact shifts, as well as the possibility of improving the accuracy of the obtained structure, is demonstrated by incorporating the shifts as restraints in a refinement of the solution structure of A.v. plastocyanin. It is found that incorporation of the pseudocontact shifts enhances the precision of the structure in regions with only few NOE restraints and improves the accuracy of the overall structure.     

The computational complexity of knot genus and spanning area

We show that the problem of deciding whether a polygonal knot in a closed three-dimensional manifold bounds a surface of genus at most is NP-complete. We also show that the problem of deciding whether a curve in a PL manifold bounds a surface of area less than a given constant is NP-hard.

     

Solubility and partial molar volume of carbon dioxide and ethane in crosslinked poly(ethylene oxide) copolymer

Experimental solubility and sorptive dilation data are reported for carbon dioxide and ethane in a crosslinked poly(ethylene oxide) (XLPEO) rubbery copolymer. Five different temperatures (253 ≤ T(K) ≤ 308) were considered, with a maximum gas pressure of 2.09 MPa (20.6 atm). The polymer was prepared by photopolymerization of a solution containing 70 wt % poly(ethylene glycol) methyl ether acrylate (PEGMEA) and 30 wt % poly(ethylene glycol) diacrylate (PEGDA). Sorption isotherms were described by the Flory‐Huggins model. For each gas, the Flory‐Huggins interaction parameter was a decreasing function of temperature and did not show a composition dependence. Dilation and sorption data were combined to calculate the partial molar volume (PMV) of the gases in the polymer, which was an increasing function of temperature. Based on a comparison with literature data for a XLPEO homopolymer prepared from pure PEGDA over the same range of operating conditions, an effect of the network composition on both gas solubility and PMV was found. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 456–468, 2010     

Mass-analyzed ion kinetic energy spectra of the [M + 1]+ ions of aliphatic esters produced by chemical ionization

To test the similarity of chemical ionization (CI) spectra of esters to the collision-induced decomposition mass-analyzed ion kinetic energy (CID-MIKE) spectra of protonated esters, the CID-MIKE spectra of the [M + 1]⁺ ions of nineteen aliphatic esters were studied. The major fragments produced in the two kinds of experiment are similar, but there are significant differences in the ions of high mass, which would reduce the usefulness of library searches of CI spectra to identify MIKE spectra of [M + 1]⁺ ions.     

A theoretical study on the protonation of cycloalkanes CnH2n (n = 3 to 6)

Ab initio self-consistent-field molecular orbital calculations have been carried out for the C_nH_2n (n = 3 to 6) cycloalkanes and various conformers of their protonated forms. The calculated protonation energies for the sequence of conformers of the protonated forms follow the experimentally observed trend. Correlations between optimum C? C? C bond angles at the protonation site and the calculated protonation energies have been observed, and these correlations may be of some use in estimating protonation energy-bond angle relations in other (strained) cyclic compounds when the central carbon atom of a C? C? C moiety is protonated.