Wetting Phase Bridges Establish Capillary Continuity Across Open Fractures and Increase Oil Recovery in Mixed-Wet Fractured Chalk

The effect of fractures on oil recovery and in situ saturation development in fractured chalk has been determined at near neutral wettability conditions. Fluid saturation development was monitored both in the matrix and in the fractures and the mechanisms of fracture crossing were determined using high spatial resolution MRI. Capillary continuity across open oil-filled fractures was verified by imaging the water bridges established within the fracture. Despite an alternate escape fracture for the water, separate water bridges were shown to be stable for the entire duration of the experiments. The established capillary contact resulted in oil recovery exceeding the spontaneous imbibition potential in the outlet-isolated cores by ca. 10% PV. This is explained by viscous recovery provided by water bridges across open fractures. The size of the bridges seemed to be controlled by the wettability of the rock and not by the differential pressure applied across the open fracture.     

Energy-Preserving Integrators Applied to Nonholonomic Systems

We introduce energy-preserving integrators for nonholonomic mechanical systems. We will see that the nonholonomic dynamics is completely determined by a triple \(({{\mathcal {D}}}^*, \varPi , \mathcal {H})\), where \({{\mathcal {D}}}^*\) is the dual of the vector bundle determined by the nonholonomic constraints, \(\varPi \) is an almost-Poisson bracket (the nonholonomic bracket) and \( \mathcal {H}: {{\mathcal {D}}}^*\rightarrow \mathbb {R}\) is a Hamiltonian function. For this triple, we can apply energy-preserving integrators, in particular, we show that discrete gradients can be used in the numerical integration of nonholonomic dynamics. By construction, we achieve preservation of the constraints and of the energy of the nonholonomic system. Moreover, to facilitate their applicability to complex systems which cannot be easily transformed into the aforementioned almost-Poisson form, we rewrite our integrators using just the initial information of the nonholonomic system. The derived procedures are tested on several examples: a chaotic quartic nonholonomic mechanical system, the Chaplygin sleigh system, the Suslov problem and a continuous gearbox driven by an asymmetric pendulum. Their performance is compared with other standard methods in nonholonomic dynamics, and their merits verified in practice.

     

Determination of free chromate in lignosulfonate dispersants by ion chromatography with atomic absorption spectrometric detection

Free chromate in lignosulfonates is determined by ion chromatography with a suppressor column. An interfering peak appears when the standard conductivity detector is used. With an on-line atomic absorption spectrometric detector, the chromatograms show two chromium-containing peaks, the second of which can be linearly related to chromate. The first peak is probably related to an unidentified anionic complex of Cr(III) with lignosulfonate.     

A simple and effective method for producing nonrandom peptide libraries using cotton as a carrier in continuous flow peptide synthesizers

A method has been developed for generating nonrandom peptide libraries on cotton. Disks of cotton fabric were chemically modified to enable peptide synthesis. Incorporation of a 6-aminocaproic acid residue handle on the cellulose turned out to be advantageous. Disks were labeled with silver ink, stacked one on top of another in a continuous flow peptide synthesizer column, and simultaneously subjected to automated synthesis procedures. Depending on the sequences to be synthesized, the automatic synthesis procedure was stopped, and the disks were removed from the column, sorted, and reapplied to subsequent synthesis steps. In this way, individual peptides could be easily prepared in milligram quantities on each of the cotton disks.     

Synthesis of (+)-goniothalamin and its enantiomer by combination of lipase catalyzed resolution and alkene metathesis

(+)-Goniothalamin has been synthesized by lipase catalyzed resolution of (1E)-1-phenylhexa-1,5-dien-3-ol using vinyl acrylate as acyl donor followed by ring closing metathesis of the formed (1R)-1-[(E)-2-phenylvinyl]but-3-enyl acrylate. The unreacted alcohol from the resolution, (1E,3S)-1-phenylhexa-1,5-dien-3-ol, was esterified non-enzymatically, and used for synthesis of (−)-goniothalamin.     

Aspects on the interaction between sodium carboxymethylcellulose and calcium carbonate and the relationship to specific site adsorption

The mechanisms of adsorption and association for sodium carboxymethylcellulose (NaCMC) in calcium carbonate suspensions have been determined from isothermal calorimetry and adsorption measurements. The equilibrium adsorption isotherms were determined by two different methods of separation; a depletion method and a serum exchange method. The enthalpy of dilution for NaCMC was determined on supernatants obtained from the calcium carbonate suspensions in order to investigate the interaction between NaCMC and dissolved species from the mineral. For comparison, NaCMC was injected into CaCl(2) solutions in order to determine the role of calcium ions in the adsorption process. The initial part of the adsorption isotherm showed a quasi-infinite slope indicating a high affinity for the NaCMC to the calcium carbonate surface, which was significantly reduced when anionic sodium polyacrylate was preadsorbed onto the calcium carbonate implying competitive adsorption. An endothermic enthalpy change was observed between the NaCMC and the calcium carbonate surface, suggesting attachment of the carboxylic acid groups onto the hydrated calcium sites. A similar endothermic enthalpy was observed when NaCMC was injected into CaCl(2) solutions or supernatants obtained from the calcium carbonate suspensions, indicating a complexation of carboxylic acid groups and hydrated calcium ions. It was concluded that the mechanisms of interaction of NaCMC in calcium carbonate suspensions are primarily an association between NaCMC and Lewis acid sites on the calcium carbonate surface and the formation of NaCMC-Ca(2+) complexes in the bulk solution, both of which will be affected by the amount of anionic sodium polyacrylate present.     

Hierachically porous nanocrystalline cobalt oxide monoliths through nanocasting

Nanocrystalline cobalt oxide, Co(3)O(4), monoliths exhibiting hierarchical bimoidal porosity have been prepared by nanocasting of porous silica monoliths.     

High ionic strength electrokinetics

The electrokinetic potentials at high ionic strengths can be measured by means of electroacoustic method. The reported values are surprisingly high: up to 25 mV in 1 mol dm(-3) 1:1 electrolyte solution. The IEP of metal oxides in concentrated solutions of 1:1 electrolytes shifts to substantially higher pH values with respect to the pristine value, although these electrolytes are inert at low concentration. The shift in the IEP is salt-specific, and it is correlated with the hard-soft character of the anion and of the cation.     

Synthesis and applications of chiral phosphite ligands derived from incompletely condensed silsesquioxane backbones

The synthesis of novel chiral tri- and bidentate phosphites 2, 5, 6 and 8, derived from incompletely condensed silsesquioxane backbones and binaphthol, is described. These compounds can be obtained in good yield and are characterized by multinuclear NMR spectroscopy, mass spectrometry and elemental analyses. The complexation with [Rh(cod)₂]BF₄ has been studied for all bidentate ligands. These nanosized ligands have been applied in the rhodium-catalyzed asymmetric hydroformylation of vinyl acetate and in the rhodium-catalyzed hydrogenation of methyl-(Z)-2-acetamidocinnamate.     

Superlinear scaling in master-slave quantum chemical calculations using in-core storage of two-electron integrals

We describe the implementation of a parallel, in-core, integral-direct Hartree-Fock and density functional theory code for the efficient calculation of Hartree-Fock wave functions and density functional theory. The algorithm is based on a parallel master-slave algorithm, and the two-electron integrals calculated by a slave are stored in available local memory. To ensure the greatest computational savings, the master node keeps track of all integral batches stored on the different slaves. The code can reuse undifferentiated two-electron integrals both in the wave function optimization and in the evaluation of second-, third-, and fourth-order molecular properties. Superlinear scaling is achieved in a series of test examples, with speedups of up to 55 achieved for calculations run on medium-sized molecules on 16 processors with respect to the time used on a single processor.