A Novel Relative Permeability Model Based on Mixture Theory Approach Accounting for Solid–Fluid and Fluid–Fluid Interactions

A novel model is presented for estimating steady-state co- and counter-current relative permeabilities analytically derived from macroscopic momentum equations originating from mixture theory accounting for fluid–fluid (momentum transfer) and solid–fluid interactions (friction). The full model is developed in two stages: first as a general model based on a two-fluid Stokes formulation and second with further specification of solid–fluid and fluid–fluid interaction terms referred to as \(R_{{i}}\) (i =  water, oil) and R, respectively, for developing analytical expressions for generalized relative permeability functions. The analytical expressions give a direct link between experimental observable quantities (end point and shape of the relative permeability curves) versus water saturation and model input variables (fluid viscosities, solid–fluid/fluid–fluid interactions strength and water and oil saturation exponents). The general two-phase model is obeying Onsager’s reciprocal law stating that the cross-mobility terms \(\lambda _\mathrm{wo}\) and \(\lambda _\mathrm{ow}\) are equal (requires the fluid–fluid interaction term R to be symmetrical with respect to momentum transfer). The fully developed model is further tested by comparing its predictions with experimental data for co- and counter-current relative permeabilities. Experimental data indicate that counter-current relative permeabilities are significantly lower than corresponding co-current curves which is captured well by the proposed model. Fluid–fluid interaction will impact the shape of the relative permeabilities. In particular, the model shows that an inflection point can occur on the relative permeability curve when the fluid–fluid interaction coefficient \(I>0\) which is not captured by standard Corey formulation. Further, the model predicts that fluid–fluid interaction can affect the relative permeability end points. The model is also accounting for the observed experimental behavior that the water-to-oil relative permeability ratio \(\hat{{k}}_{\mathrm{rw}} /\hat{{\mathrm{k}}}_{\mathrm{ro}} \) is decreasing for increasing oil-to-water viscosity ratio. Hence, the fully developed model looks like a promising tool for analyzing, understanding and interpretation of relative permeability data in terms of the physical processes involved through the solid–fluid interaction terms \(R_{{i}}\) and the fluid–fluid interaction term R.     

Synthesis, spectroscopy, and X-ray structures of fac-(CO)3(dppe)MnSC(S)H, fac-(CO)3(dppe)ReSC(S)H, fac-(CO)3(dppp)ReSC(S)H, and fac-(CO)3(dppb)ReSC(S)H

The monodentate dithioformato complexes, fac-(CO)₃(dppe)MnSC(S)H (1), fac- (CO)₃(dppe)ReSC(S)H (2), fac-(CO)₃(dppp)ReSC(S)H (3), and fac-(CO)₃ (dppb)ReSC(S)H (4), where dppe is 1,2-bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, and dppb is 1,4-bis(diphenylphosphino)butane, were synthesized from the treatment of the corresponding hydrides, fac-(CO)₃ (P-P)MSC(S)H with CS₂. Compounds 1–4 crystallize in the monoclinic crystal system: for 1, space group = P2₁/c, a = 15.3139(3) Å, b = 9.7297(4) Å, c = 19.0991(6) Å, = 105.928(1), V = 2736.5 ų, Z = 4; for 2, space group = P2₁/c, a = 15.6395(8) Å, b = 9.8182(5) Å, c = 19.4153(11) Å, = 106.741(1), V = 2854.9(3) ų, Z = 4; for 3, space group = P2₁/n, a = 11.3570(10) Å, b = 19.465(2) Å, c = 15.5702(14) Å, = 104.776(2), V = 3328.3(5) ų, Z = 4; and for 4, space group = C2/c, a = 32.078(2) Å, b = 10.4741(6) Å, c = 19.0608(9) Å, = 94.315(2), V = 6386.1(6) ų, Z = 8.     

Ground state pressure and energy density of an interacting homogeneous Bose gas in two dimensions

We consider an interacting homogeneous Bose gas at zero temperature in two spatial dimensions. The properties of the system can be calculated as an expansion in powers of g, where g is the coupling constant. We calculate the ground state pressure and the ground state energy density to second order in the quantum loop expansion. The renormalization group is used to sum up leading and subleading logarithms from all orders in perturbation theory. In the dilute limit, the renormalization group improved pressure and energy density are expansions in powers of the T ^2B and T ^2Bln(T ^2B), respectively, where T ^2B is the two-body T-matrix. Received 19 April 2002 Published online 13 August 2002     

Absorption studies of neutral retinal Schiff base chromophores

The neutral retinal Schiff base is connected to opsin in UV sensing pigments and in the blue-shifted meta-II signaling state of the rhodopsin photocycle. We have designed and synthesized two model systems for this neutral chromophore and have measured their gas-phase absorption spectra in the electrostatic storage ring ELISA with a photofragmentation technique. By comparison to the absorption spectrum of the protonated retinal Schiff base in vacuo, we found that the blue shift caused by deprotonation of the Schiff base is more than 200 nm. The absorption properties of the UV absorbing proteins are thus largely determined by the intrinsic properties of the chromophore. The effect of approaching a positive charge to the Schiff base was also studied, as well as the susceptibility of the protonated and unprotonated chromophores to experience spectral shifts in different solvents.     

SPECTROSCOPY OF CHLOROPHYLL IN BIOLOGICAL AND SYNTHETIC SYSTEMS*

Abstract. –This review discusses recent spectroscopic studies aimed at discovering the structure, orientation, and function of chlorophyll in vivo. In plant membranes there appear to be at least two distinct types of chlorophyll a. The greater part, over 99%, is antenna chlorophyll which absorbs and transfers radiant energy to a few specialized chlorophyll molecules in a reaction center where the actual charge separation occurs. A dimer-oligomer model for antenna chlorophyll has been proposed on the basis of comparative studies of the absorption spectra of chlorophyll in various dry solvents and in vivo. Unfortunately a similarity between essentially structureless broad spectra is very weak evidence for their original identity. Also the requirement of an anhydrous environment for most of the chlorophyll in biological material is an unlikely postulate. A cross-linked, linear polymer model of chlorophyll in vivo has also been proposed. Recent Resonance Raman spectroscopic results appear to rule out, in large part, either polymer model and once again suggest that it is the various attachments of chlorophyll to proteins which determine its function as antenna pigment in vivo. Circular dichroism measurements of chlorophyll in various plant materials have also led to the conclusion that antenna chlorophyll has strong interaction with protein. However, some doubt still exists as to the interpretation of these CD results. New studies of fluorescence, polarized fluorescence and Resonance Raman spectroscopy of various plant species corroborate the original proposition, based upon deconvolution of absorption spectra, that antenna chlorophyll occurs in vivo in at least five discrete pools, and that each pool is likely to be located in the same environment in different plants. A new model-systems approach to simulating chlorophyll in vivo has come through the use of lipid bilayers and liposomes. Charge transfer has been observed between chlorophyll in a lipid phase and phycobiliproteins or cytochrome c. The most promising, newly synthesized model for the reaction center, P700, is a covalently bound dimeric derivative of pyrochlorophyllide a. Its properties are similar to P700 in several respects except for reversible photooxidation which has not yet been observed. By detergent treatments chlorophyll-protein complexes having about 20–40 chlorophyll a molecules for every P700 have been isolated from different plants, and their spectroscopic properties are under investigation in several laboratories. The several hypotheses to explain the shape of the oxidized minus reduced absorption difference spectrum of P700 have not yet been reconciled. The nature of the photosystem II reaction center chlorophyll, P680, is also a subject of active investigation. Its absorption difference spectrum appears to have two kinetic components.     

Tris­[2‐(benzoyl­amino)­ethyl]­amine

Tris­[2‐(benzoyl­amino)­ethyl]­amine [alternatively, N,N′,N′′‐(nitrilo­tri­ethyl)­tri­benz­amide], C₂₇H₃₀N₄O₃, adopts a folded structure, forming a symmetrical cavity with an average depth of 7.3 Å and width ranging from 4.1–4.4 Å. The folded structure is a result of one intramolecular N—H?O hydrogen bond. A linear chain motif along the c axis best describes the extended intermolecular N—H?O hydrogen bonding.     

Chlovalicin B,a Chlorinated Sesquiterpene Isolated from the Marine Mushroom Digitatispora marina

As part of our search for bioactive metabolites from understudied marine microorganisms, the new chlorinated metabolite chlovalicin B (1) was isolated from liquid cultures of the marine basidiomycete Digitatispora marina, which was collected and isolated from driftwood found at Vannøya, Norway. The structure of the novel compound was elucidated by spectroscopic methods including 1D and 2D NMR and analysis of HRMS data, revealing that 1 shares its molecular scaffold with a previously isolated compound, chlovalicin. This represents the first compound isolated from the Digitatispora genus, and the first reported fumagillin/ovalicin-like compound isolated from Basidiomycota. Compound 1 was evaluated for antibacterial activities against a panel of five bacteria, its ability to inhibit bacterial biofilm formation, for antifungal activity against Candida albicans, and for cytotoxic activities against malignant and non-malignant human cell lines. Compound 1 displayed weak cytotoxic activity against the human melanoma cell line A2058 (~50% survival at 50 µM). No activity was detected against biofilm formation or C. albicans at 50 µM, or against bacterial growth at 100 µM nor against the production of cytokines by the human acute monocytic leukemia cell line THP-1 at 50 µM.