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.     

Discovery of a substrate selectivity switch in tyrosine ammonia-lyase, a member of the aromatic amino acid lyase family

Tyrosine ammonia-lyase (TAL) is a recently described member of the aromatic amino acid lyase family, which also includes phenylalanine (PAL) and histidine ammonia-lyases (HAL). TAL is highly selective for L-tyrosine, and synthesizes 4-coumaric acid as a protein cofactor or antibiotic precursor in microorganisms. In this report, we identify a single active site residue important for substrate selection in this enzyme family. Replacing the active site residue His89 with Phe in TAL completely switched its substrate selectivity from tyrosine to phenylalanine, thereby converting it into a highly active PAL. When a corresponding mutation was made in PAL, the enzyme lost PAL activity and gained TAL activity. The discovered substrate selectivity switch is a rare example of a complete alteration of substrate specificity by a single point mutation. We also show that the identity of the amino acid at the switch position can serve as a guide to predict substrate specificities of annotated aromatic amino acid lyases in genome sequences.     

DFTMP, an NMR reagent for assessing the near-neutral pH of biological samples

A new NMR chemical shift standard and pH indicator, difluorotrimethylsilanylphosphonic acid (DFTMP), is described, and the utility of this reagent is demonstrated for in situ determination of pH in complex biofluids. The pH dependence of this reagent allows accurate in situ determination of aqueous solution pH to within an RMSE of 0.02 pH units over a pH range of 5 to 8. Advantages of this reagent over previously described pH-sensitive components include (1) lack of metal binding affinity, (2) minimal disturbance of endogenous spectral regions, and (3) the potential to function as a multinuclear pH indicator and chemical shift reference point for 19F, 1H, and 31P nuclei. This reagent will be generally useful for NMR experiments on biological systems where the pH needs to be accurately measured at the moment of data acquisition.     

C-H activation as a strategic reaction: enantioselective synthesis of 4-substituted indoles

A method is described for the asymmetric synthesis of 4-substituted indoles from the Rh2(S-DOSP)4-catalyzed decomposition of vinyldiazoacetates in the presence of N-Boc-4-acetoxy-6,7-dihydroindole. The reaction proceeds via a combined C-H activation/Cope rearrangement-elimination mechanism resulting in good yields and very high asymmetric induction.     

Eine Notiz zur Methoxyl-Bestimmung

Ohne Zusammenfassung     

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     

Synthesis of tetrahydropyridazino[1,2-a][1,2,4] benzotriazin-6-one derivatives. A novel heterocyclic system

Synthesis of pyridazino[1,2-a][1,2,4]benzotriazin-6-one derivatives involving reaction of either 1,2,3,6-tetra-hydropyridazine ( 9 ) or hexahydropyridazine 14 with 2-fluoro-5-nitrophenylisocyanate ( 5 ) to give, via intramolecular cyclization, 3a and 16 respectively is described. Compound 3a was converted to 18 via methylation and hydroxylation to give 20 followed by conversion to the acetonide derivative 18 . Both 16 and 18 were reduced to the amino derivatives 17 and 19 respectively.     

Ozone Decomposition Data for Kinetics Exercises

The goal of this paper is to provide data that can be used in a variety of exercises ranging from kinetics in general chemistry to advanced problems in physical chemistry. The data provided relates to ozone-decay kinetics in various atmospheres (O₂, N₂, Ar) as measured by ultraviolet/visible absorbance spectroscopy (UV/vis) at 254 nm. The absorbance of ozone is monitored over a 75-min time period, and by using Beers law the concentration is calculated. Nine data sets, each repeated three times, of absorbance measurements are provided for student exercises, and prelaboratory and postlaboratory questions are suggested.     

A STUDY OF THE PHOTODYNAMIC EFFICIENCIES OF SOME EYE LENS CONSTITUENTS

We have studied the photochemical quantum yields of singlet oxygen production (using the RNO bleaching method) and superoxide production (using the EPR-spin trapping method and the SOD-inhibitable ferricytochrome c reduction spectral assay) of kynurenine (Ky), N-formylkynurenine (NFK), 3-hydroxykynurenine (3HK), kynurenic acid (KUA), and the flavins, riboflavin (RF) and flavin mononucleotide (FMN). Such a study of the photodynamic efficiencies is important since these compounds appear endogenously in the eye. The singlet oxygen quantum yields of the flavins and KUA are high, while Ky and 3HK generate no detectable amounts of singlet oxygen. The superoxide quantum yields of the sensitizers are low compared to their singlet oxygen, and Ky and 3HK produce no detectable amounts of superoxide. The production of the superoxide radical is enhanced in the presence of electron donor molecules such as EDTA and NADH. These results suggest that the production of oxyradicals in the lens may be modulated by the presence of endogenous electron donor molecules such as the coenzymes NADH and NADPH, which are present in significant amounts in some lenses. They also suggest that Ky and 3HK, which are known to be present in aged lenses, might play a protective rather than a deleterious role in the eye.