Connectivity of Pore Space as a Control on Two-Phase Flow Properties of Tight-Gas Sandstones

We predict capillary-pressure (drainage) curves in tight-gas sandstones which have little matrix or microporosity using a quantitative grain-scale model. The model accounts for the geometric results of some depositional and diagenetic processes important for porosity and permeability reduction in tight-gas sandstones, such as deformation of ductile grains during burial and quartz cementation. The model represents the original sediment as a dense, disordered packing of spheres. We simulated the evolution of this model sediment into a low-porosity sandstone by applying different amounts of ductile grains and quartz precipitation. A substantial fraction of original pore throats in the sediment is closed by the simulated diagenetic alteration. Because the percolation threshold corresponds to closure of half of the pore throats, the pore space in this type of tight-gas sandstone is poorly connected and is often close to being completely disconnected. The drainage curve for different model rocks was computed using invasion percolation in a network taken directly from the grain-scale geometry and topology of the model. Some general trends follow classical expectations and were confirmed by experimental measurements: increasing the amount of cement shifts the drainage curve to larger pressures. This is related to reduction of the connectivity of pore space resulting from closure of throats. Existence of ductile grains in the ductile grain model also reduces the connectivity of pore space but it treats the throats distribution differently causing the drainage curves to be shifted to larger irreducible water saturation when cement is added to the model. The range of porosities in which these connectivity effects are important corresponds to the range of porosities common for tight gas sandstones. Consequently these rocks can exhibit small effective permeability to gas even at large gas saturations. This problem occurs at larger porosities in rocks with significant content of ductile grains because ductile deformation blocks a significant fraction of pore throats even before cementation begins. Predicted drainage curves agree with measurements on two samples with little microporosity, one dominated by rigid grains, the other containing a significant fraction of ductile grains. We conclude that connectivity of the matrix pore space is an important factor for an understanding of flow properties of tight-gas sandstones.     

Naphthoflavone propargyl ether inhibitors of cytochrome P450

Cytochrome P450 enzymes protect the body from foreign substances through a mechanism that involves oxidation of those substances into more readily excretable polar compounds. It has been shown that some naphthoflavones function as substrates of certain P450 enzymes (CYP1A1 and CYP1B1) and with appropriate structural changes may become inhibitors. Moreover, propargyl ether derivatives of adamantane have been shown to function as selective inactivators of some P450 enzymes (CYP2B1 and CYP2B5). In an attempt to improve the potency and selectivity of inhibition, we have designed and synthesized a series of naphthoflavone propargyl ethers. We report here the synthesis, X-ray crystal structures, and inhibition data (IC₅₀ of EROD inhibition in CYP1A1 and CYP1B1 enzymes) of α-naphthoflavone 2′-propargyl ether, β-naphthoflavone 2′-propargyl ether, α-naphthoflavone 4′-propargyl ether, and β-naphthoflavone 4′-propargyl ether. Crystallographic data: α-naphthoflavone 2′-propargyl ether, , a=7.775(1) ?, b=8.062(1) ?, c=13.110(1) ?, α=84.32(1)°, β=75.42(1)°, γ=86.56(1)°, V=790.8(2) ?³; β-naphthoflavone 2′-propargyl ether, , a=7.605(2) ?, b=7.793(1) ?, c=14.167(2) ?, α=77.06(1)°, β=75.41(1)°, γ=89.54(1)°, V=790.9(2) ?³; α-naphthoflavone 4′-propargyl ether, P21/n, a=14.595(2) ?, b=4.708(1) ?, c=24.745(6) ?, β=106.31(2)°, V=1631.8(7) ?³; β-naphthoflavone 4′-propargyl ether, P1, a=4.8871(5) ?, b= 7.9597(7) ?, c=21.788(3) ?, α=81.771(9)°, β=89.918(10)°, γ=72.223(8)°, V= 797.9(2) ?³.     

Application of a new equation of state to energy carriers

A new equation of state (IR EOS) recently reported for liquids and gases has been utilized to predict the densities of some energy carriers at different temperatures, pressures. The ability of IR EOS is examined by comparing its results with experimental data for some energy carriers in homogeneous gas, homogeneous liquid and gas–liquid transition region from low to very high pressures. The IR EOS gives excellent results in homogenous gas and homogeneous liquid region while its predictions in gas–liquid transition have more deviations. The average absolute deviation between calculated and experimental densities for 968 data points of 12 energy carriers is 0.33% over the entire range of data with a maximum pressure of 1000 MPa.     

New metal complexes supported on Fe3O4 magnetic nanoparticles as recoverable catalysts for selective oxidation of sulfides to sulfoxides

Fe₃O₄ nanoparticles were coated with aminopropyltriethoxysilane and subsequently reacted with isatin to obtain imine‐bonded Fe₃O₄ nanoparticles. The addition of ZrOCl₂?8H₂O or CuCl₂ led to the formation of complexes of Zr(IV)/isatin@Fe₃O₄ or Cu (II)/isatin@Fe₃O₄ as new magnetically separable catalysts. The synthesized catalysts were characterized using various techniques. These catalysts are shown to be efficient for chemo‐selective oxidation of sulfides to sulfoxides using hydrogen peroxide as oxidative agent. This system has many advantages, such as excellent level of reusability of magnetic catalysts, high yields, simplicity of separation of catalysts using an external magnet, environmental benignity and ease of handling. Copyright © 2016 John Wiley & Sons, Ltd.     

Selective tetrahydropyranylation of alcohols and phenols using titanium(IV) salophen trifluoromethanesulfonate as an efficient catalyst

Titanium(IV) salophen trifluoromethanesulfonate, [Ti^IV(salophen)(OSO₂CF₃)₂], as a catalyst enables selective tetrahydropyranylation of alcohols and phenols with 3,4‐dihydro‐2H‐pyran. Using this catalytic system, primary, secondary and tertiary alcohols, as well as phenols, were converted to their corresponding tetrahydropyranyl ethers in high yields and short reaction times at room temperature. Investigation of the chemoselectivity of this method showed discrimination between the activity of primary alcohols in the presence of secondary and tertiary alcohols and phenols. This heterogenized catalyst could be reused several times without loss of its catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.