A vector percolation modeling of oil–gas relative permeabilities

We presented exact analytical formulae and numerical calculation of diffusitivity curves with different law for a local pore behavior and have obtained critical exponent, different from conductivity. The connectivity percolation theory was built only on the conductivity, (the diffusion critical exponent was supposed to be equal to the conductivity exponent) and therefore sees only one side of problem-the scalar side. In many topological problems involving mechanical properties and fluid flow the connectivity scalar percolation geometry does not enough to apply.

One of the most useful aspects of percolation is that many very complicated systems have the same behavior with the same critical exponents. Universality of vector percolation is shown in the coincidence between the experimental measured relative hydraulic permeability of fluid and gas flow through unconsolidated sand and effective conductivity and diffusitivity curves of the bond–site percolation models. Comparisons of our calculation results to natural matches are quite good. We have argued that experimental data may be interpreted as a variant of pure vector percolation and to belong to the same universality class.     

Concurrent combined verification: reducing false positives in automated NMR structure verification through the evaluation of multiple challenge control structures

Automated structure verification using ¹H NMR data or a combination of ¹H and heteronuclear single‐quantum correlation (HSQC) data is gaining more interest as a routine application for qualitative evaluation of large compound libraries produced by synthetic chemistry. The goal of this automated software method is to identify a manageable subset of compounds and data that require human review. In practice, the automated method will flag structure and data combinations that exhibit some inconsistency (i.e. strange chemical shifts, conflicts in multiplicity, or overestimated and underestimated integration values) and validate those that appear consistent. One drawback of this approach is that no automated system can guarantee that all passing structures are indeed correct structures. The major reason for this is that approaches using only ¹H or even ¹H and HSQC spectra often do not provide sufficient information to properly distinguish between similar structures. Therefore, current implementations of automated structure verification systems allow, in principle, false positive results. Presented in this work is a method that greatly reduces the probability of an automated validation system passing incorrect structures (i.e. false positives). This novel method was applied to automatically validate 127 non‐proprietary compounds from several commercial sources. Presented also is the impact of this approach on false positive and false negative results. Copyright © 2012 John Wiley & Sons, Ltd.     

Characterization of a didehydrobenzoxazine intermediate in a novel carbene-to-carbene transformation

Irradiation of N(2) matrix-isolated 3-chloro-3-(2-benzoxazolyl)diazirine gives a mixture of syn- and anti-benzoxazolylchlorocarbenes which could be characterized by IR, UV/vis, and B3LYP modeling. Subsequent irradiation of the carbene caused ring opening to the corresponding quinoimine, which was similarly characterized. In turn, the quinoimine photochemically underwent ring-closure to a novel, highly strained cyclic ketenimine. Unrestricted singlet DFT calculations were required to fit the IR spectrum of the ketenimine, suggesting significant diradical character. Photolysis of the ketenimine led to ring cleavage in yet another fashion, to give an isonitrile-phenoxychlorocarbene, whose spectra were similar to those of the previously characterized phenoxychlorocarbene. Finally, at shorter wavelengths, the phenoxycarbene underwent the expected rearrangement to the corresponding benzoyl chloride.     

Protein immobilization on epoxy-activated thin polymer films: effect of surface wettability and enzyme loading

A series of epoxy-activated polymer films composed of poly(glycidyl methacrylate/butyl methacrylate/hydroxyethyl methacrylate) were prepared. Variation in comonomer composition allowed exploration of relationships between surface wettability and Candida antartica lipase B (CALB) binding to surfaces. By changing solvents and polymer concentrations, suitable conditions were developed for preparation by spin-coating of uniform thin films. Film roughness determined by AFM after incubation in PBS buffer for 2 days was less than 1 nm. The occurrence of single CALB molecules and CALB aggregates at surfaces was determined by AFM imaging and measurements of volume. Absolute numbers of protein monomers and multimers at surfaces were used to determine values of CALB specific activity. Increased film wettability, as the water contact angle of films increased from 420 to 550, resulted in a decreased total number of immobilized CALB molecules. With further increases in the water contact angle of films from 55 degrees to 63 degrees, there was an increased tendency of CALB molecules to form aggregates on surfaces. On all flat surfaces, two height populations, differing by more than 30%, were observed from height distribution curves. They are attributed to changes in protein conformation and/or orientation caused by protein-surface and protein-protein interactions. The fraction of molecules in these populations changed as a function of film water contact angle. The enzyme activity of immobilized films was determined by measuring CALB-catalyzed hydrolysis of p-nitrophenyl butyrate. Total enzyme specific activity decreased by decreasing film hydrophobicity.     

MoS2‐on‐MXene Heterostructures as Highly Reversible Anode Materials for Lithium‐Ion Batteries

Two‐dimensional (2D) heterostructured materials, combining the collective advantages of individual building blocks and synergistic properties, have spurred great interest as a new paradigm in materials science. The family of 2D transition‐metal carbides and nitrides, MXenes, has emerged as an attractive platform to construct functional materials with enhanced performance for diverse applications. Here, we synthesized 2D MoS₂‐on‐MXene heterostructures through in situ sulfidation of Mo₂TiC₂T_x MXene. The computational results show that MoS₂‐on‐MXene heterostructures have metallic properties. Moreover, the presence of MXene leads to enhanced Li and Li₂S adsorption during the intercalation and conversion reactions. These characteristics render the as‐prepared MoS₂‐on‐MXene heterostructures stable Li‐ion storage performance. This work paves the way to use MXene to construct 2D heterostructures for energy storage applications.     

Study of charge storage in the nanofibrous poly(ethylene terephthalate) electrets prepared by electrospinning or by corona discharge method

In this paper, the charge storage performance of electrospun poly(ethylene terephthalate) (PET) mats with high specific surface area was evaluated in comparison to that of PET film electrets. Corona discharge method was used to charge the electrospun PET mats and PET films. The surface potential decay measurements revealed that the corona charged РЕТ mats had higher initial values for the normalized surface potential compared to the РЕТ electret films. A tendency for stabilization of the electret charge to one and the same value for all charged samples (mats and films) after the 50th day was observed. The peaks at 90 °C in the thermally stimulated current (TSC) spectra of uncharged and charged in corona discharge electrospun PET mats were observed and attributed to a relaxation of the separated space charges, the dipole disorientation or injected charges within the bulk. It was found that the value of the storage charge in a corona charged electrospun PET mats was higher than that in PET mats prepared by electrospinning.     

Direct synthesis, crystal structures, high-field EPR, and magnetic studies of heterometallic polymers containing manganese(II) carboxylates interconnected by [Cu(en)2]2+

Two heterometallic polymers containing cations [Cu(en)2]2+ and either the [Mn(mal)2(H2O)2]2- (1) or [Mn2(succ)2Cl2]n2n- (2) anions (mal=malonate and succ=succinate) were investigated by X-ray crystallography, high-field electron paramagnetic resonance (EPR) spectroscopy, and magnetic susceptibility measurements. Magnetic susceptibility and EPR spectra characteristic of antiferromagnetically coupled Mn2+-Mn2+ pairs were observed in 2, and the exchange integral J=31 cm(-1) (H=JS1S2) as well as the zero-field-splitting parameter D=-3.046 cm(-1) in the triplet state of the dimanganese entity was determined.     

N22C2 versus N24: role of molecular curvature in determining isomer stability

Three-dimensional N(22)C(2) cages are examined by theoretical calculations to determine relative stability among various isomers. Stability as a function of cage shape and stability as a function of carbon location are calculated and discussed. The results are compared to isomers of N(24) to determine the effects of carbon substitution into the cage structure. Further, since the various cage shapes in this study vary by degree of curvature, model calculations are carried out to determine the energetic consequences of curving the local structure around nitrogen and carbon. The model calculations are compared to the actual results on the larger cages to determine how well curvature effects explain the relative stability of N(22)C(2) isomer as compared to the corresponding N(24).     

Percolation Approach to the Anisotropy Factor in an Unsaturated Porous Medium

The anisotropy factor is defined as the ratio of the effective (macroscopic) conductivities parallel to the bedding plane and perpendicular to it. The anisotropy factor A(p,a) is a function of both the saturation degree, p, in the void space of the disordered medium and the anisotropy parameter, a, that characterizes the ratio of the local conductivities parallel and normal to the bedding plane. There are two opposite behaviors of the anisotropy factor as a function of the saturation degree described in literature. One presents the anisotropy factor as a curve with a maximum and the other as a curve with a minimum. The main result of calculating the conductivities of a uniaxial percolation anisotropic model is that at the saturation threshold value, p_c, A(p_c, a) = 1, wherefrom it increases at a >1 (or decreases at a < 1) with saturation. An extension of the computed results below the threshold is also proposed.     

Geometry and aromaticity in highly strained heterocyclic allenes: characterization of a 2,3-didehydro-2H-thiopyran

[reaction: see text] The highly strained cyclic allene 2,3-didehydro-2H-thiopyran was generated by irradiation of matrix-isolated 2-benzothienylchlorocarbene and characterized by IR and UV/vis spectroscopy, in situ trapping, and DFT modeling. Calculations indicate that the allenic moiety in this system, although less aromatic in character, is relatively more stable than in the corresponding oxa system. It is suggested that the thio ring system can more readily accommodate the allenic geometry.