Crystallographic evidence for different modes of interaction of BF3/BF4 species with water molecules and 18-crown-6

We report the crystal and molecular structures of the complex of 18-C-6 with H₃O⁺BF₄⁻ (I) and the complex of 18-C-6 with BF₃OH₂·H₂O (II). The different modes of appearance of the “BF₃” species as BF₃, BF₃OH₂, BF₃OH₂·H₂O and BF₄⁻, as well as their structurally significant intermolecular and intramolecular interactions, are discussed. In complex I the oxonium ion is bound at the centre of the 18-C-6 macrocycle. The oxonium oxygen is located practically equidistant (2.68–2.73 Å) from the six macrocyclic ethereal oxygens. The BF₄⁻ counter-ion is positioned 7.3 Å away from the oxonium ion in the same general plane of the crown ether. This anion is not involved in any direct intermolecular contacts, a fact that may explain why it is spherically disordered. In complex II there is no guest molecule (or ion) present in the “cavity” of the macrocycle, but there are two hydrogen-bonded systems of BF₃OH₂·H₂O that are interacting with the crown ether on either side of the general macrocyclic plane. Complex II features three types of hydrogen bonds—the O(water)-HO(crown) bonds (2.83 and 2.85 Å), the O(water)H-O(BF₃) bond (2.49 Å) and the O(BF₃)-HO(crown) bond (2.65 Å). The strong intermolecular O(crown)O(water)O(BF₃) and O(crown)O(BF₃) interactions stabilize the normally unstable BF₃OH₂·H₂O species.     

Flow pattern characterization in two phase flow by electrical conductance probe

An improved system of conductance probes is used to identify the flow patterns in two phase horizontal, near horizontal and upward flows. The results show that this system is very well suited to distinguish among flow patterns consistent with visual observations.     

Nonproteolytic cleavage of aspartyl proline bonds in the cellulosomal scaffoldin subunit from Clostridium thermocellum

Previous work from our group [Morag (Morgenstern), E., Bayer, E. A., and Lamed, R. (1991), Appl. Biochem. Biotechnol. 30, 129–136] has demonstrated an anomalous electrophoretic mobility pattern for scaffoldin, the 210-kDa cellulosome-integrating subunit of Clostridium thermocellum. Subsequent evidence [Morag, E., Bayer, E. A., and Lamed, R. (1992), Appl. Biochem. Biotechnol. 33, 205–217] indicated that the effect could be attributed to a nonproteolytic fragmentation of the subunit into a defined series of lowermolecular-weight bands. In the present work, a recombinant segment of the scaffoldin subunit was employed to determine the site(s) of bond breakage. An Asp-Pro sequence within the cohesin domain was identified to be the sensitive peptide bond. This sequence appears quite frequently in the large cellulosomal proteins, and the labile bond may be related to an as yet undescribed physiological role in the hydrolysis of cellulose by cellulosomes.     

The elimination of severe slugging-experiments and modeling

Severe slugging can occur in a pipeline-riser system operating at low liquid and gas rates. The flow of gas into the riser can be blocked by liquid accumulation at the base of the riser. This can cause formation of liquid slugs of a length equal to or longer than the height of the riser. A cyclic process results in which a period of no liquid production into the separator occurs, followed by a period of very high liquid production. This study is an experimental and theoretical investigation of two methods for eliminating this undesirable phenomenon, using choking and gas lift. Choking was found to effectively eliminate or reduce the severity of the slugging. However, the system pressure might increase to some extent. Gas lift can also eliminate severe slugging. While choking reduces the velocities in the riser, gas lift increases the velocities, approaching annular flow. It was found that a relatively large amount of gas was needed before gas injection would completely stabilize the flow through the riser. However, gas injection reduces the slug length and cycle time, causing a more continuous production and a lower system pressure. Theoretical models for the elimination of severe slugging by gas lift and choking have been developed. The models enable the prediction of the flow behavior in the riser. One model is capable of predicting the unstable flow conditions for severe slugging based on a static force balance. The second method is a simplified transient model based on the assumption of a quasi-equilibrium force balance. This model can be used to estimate the characteristics of the flow, such as slug length and cycle time. The models were tested against new severe slugging data acquired in this study. An excellent agreement between the experimental data and the theoretical models was found.     

Synthesis and x-ray crystal structure of anti-dithia[3.3](2.6)triquinacenophane

Synthesis of the title compound ($\text{5}$) is presented herein as part of an approach to the synthesis of substituted dodecahedranes.     

Primal and dual predicted decrease approximation methods

We introduce the notion of predicted decrease approximation (PDA) for constrained convex optimization, a flexible framework which includes as special cases known algorithms such as generalized conditional gradient, proximal gradient, greedy coordinate descent for separable constraints and working set methods for linear equality constraints with bounds. The new scheme allows the development of a unified convergence analysis for these methods. We further consider a partially strongly convex nonsmooth model and show that dual application of PDA-based methods yields new sublinear convergence rate estimates in terms of both primal and dual objectives. As an example of an application, we provide an explicit working set selection rule for SMO-type methods for training the support vector machine with an improved primal convergence analysis.     

Two strong convergence theorems for Bregman strongly nonexpansive operators in reflexive Banach spaces

We study the convergence of two iterative algorithms for finding common fixed points of finitely many Bregman strongly nonexpansive operators in reflexive Banach spaces. Both algorithms take into account possible computational errors. We establish two strong convergence theorems and then apply them to the solution of convex feasibility, variational inequality and equilibrium problems.     

Two Strong Convergence Theorems for a Proximal Method in Reflexive Banach Spaces

Two strong convergence theorems for a proximal method for finding common zeroes of maximal monotone operators in reflexive Banach spaces are established. Both theorems take into account possible computational errors.     

Soft matter dispersions with ordered inner structures, stabilized by ethoxylated phytosterols

This paper describes the formation and characterization of liquid crystalline dispersions based on the hexagonal phase of GMO/tricaprylin/water. As a stabilizer of the soft particles dispersed in the aqueous phase, a non-ionic, non-polymeric surfactant—ethoxylated phytosterol with 30 oxyethylene units (PhEO) was utilized. In contrast to Pluronic copolymers, normally utilized in the stabilization of liquid crystalline dispersions with ordered inner structure, use of such non-polymeric surfactant is not a common practice in this field. We revealed how properties of these particles, such as internal structure, size, and stability, can be rationally modified by the concentration of the stabilizing agent and processing conditions. The physical stability of the hexosomes was further examined by the LUMiFuge technique.Structural effect of PhEO solubilization on the properties of the bulk H_II mesophase system showed that phase behavior was greatly influenced following phase transitions: H_II → H_II + cubic → cubic + L_α → L_α. The decrease of hydrogen bonding of the hydroxyl and carbonyl groups of monoolein with water and simultaneous hydration of EO groups of PhEO appeared to be important for the observed behavior. The use of PhEO as a dispersant resulted in a soft matter multi-phase water dispersion with bimodal distribution of the particle population. Effective stabilization of hexosomes was obtained in an extremely narrow concentration range of PhEO (0.1–0.2 wt%), coexisting with small vesicles and disordered particles. At higher PhEO content, particles had disordered inner structure, and unilamellar and multilamellar vesicles, at the expense of hexosomes in consequence of incorporation of the dispersant into the hexosome structure. PhEO was found to induce lamellar phase formation, introducing disorder into the hexagonal LLC and reducing their domain size.Finally, hexosomes were evaluated as delivery vehicles for the therapeutic peptide desmopressin. Sustained release of this drug was observed during the first 10 h; however, permeation drastically increased in the 10–24 h range.     

Low temperature Fourier transform infrared spectra and hydrogen bonding in polycrystalline uracil and thymine

The FTIR spectra of pure NH and isotopically diluted (NH/ND and ND/NH) polycrystalline uracil and thymine were measured in the range 4000-400 cm(-1) at temperatures from 300 to 10K. For the first time, the essentially narrow bands corresponding to the uncoupled stretching (nu(1)) and out of plane bending (nu(4)) NH proton modes of uracil and thymine were observed in the solid phase. It was found that in the nu(4) region the spectra reveal more details on the H-bond interactions present in both solids than in the nu(1) range. The frequencies of the various bands observed in both spectral regions were used for estimation of the H-bond energy, using empirical correlations between this property and both the red shift of nu(1) and the blue shift of nu(4) that occur upon crystallization due to the establishment of the H-bonds. The results are compared with known thermodynamic, structural and theoretical data. The IR data also suggest that the H-bond networks of both crystals contain, besides the two NH...O=C bonds revealed by X-ray experiments, additional types of H-bonds, which do not show long range periodicity and, thus, cannot be detected by the conventional structural methods. The assignment of some other bands in the spectra of both substances was also reviewed.