Perfluorobiphenyls and perfluorobiphenyl ethers

Nucleophilic attack by various polyfluoro- and perfluoro-phenoxides upon decafluorobiphenyl, perfluoro-4-methylbiphenyl and perfluoro-4,4′-dimethylbiphenyl in dimethylacetamide solution gave a number of high boiling aryl ethers by mono- and di-substitution. The disodium salt of octafluoro-4-4′-dihydroxybiphenyl with octafluoroanisole in dimethylacetamide gave another aryl ether containing four rings, but the dipotassium salt of hexafluoro-3,3′-dihydroxy-4,4t?-bis(trifluoromethyl)biphenyl (prepared by the action of potassium hydroxide upon perfluoro-4,4′-dimethylbiphenyl) with octafluorotoluene gave a complex mixture of products. The syntheses of various new compounds used as intermediates are described.     

Reply to comment on the possible role of the reaction H+H2O→H2+OH in the radiolysis of water at high temperatures

In reply to “Comment on the possible role of reaction H+H₂O→H₂+OH in the radiolysis of water at high temperatures” (Bartels, 2009 Comment on the possible role of the reaction H+H₂O→H₂+OH in the radiolysis of water at high temperatures. Radiat. Phys. Chem. 78, 191–194) we present an alternative thermodynamic estimation of the reaction rate constant k. Based on the non-symmetric standard state convention we have calculated that the Gibbs energy of reaction Δ_rG=57.26 kJ mol^?1 and the reaction rate constant k=7.23×10^?5 M^?1 s^?1 at ambient temperature. Re-analysis of the thermodynamic estimation (Bartels, 2009 Comment on the possible role of the reaction H+H₂O→H₂+OH in the radiolysis of water at high temperatures. Radiat. Phys. Chem. 78, 191–194) showed that the upper limit for the rate constant at 573 K is k=1.75×10⁴ M^?1 s^?1 compared to the value predicted by the diffusion-kinetic modelling (3.18±1.25)×10⁴ M^?1 s^?1 (Swiatla-Wojcik, D., Buxton, G.V., 2005. On the possible role of the reaction H+H₂O→H₂+OH in the radiolysis of water at high temperatures. Radiat. Phys. Chem. 74(3–4), 210–219). The presented thermodynamic evaluation of k(573) is based on the assumption that k can be calculated from Δ_rG and the rate constant of the reverse reaction which, as discussed, are both uncertain at high temperatures.     

Sulpholane as a solvent for titration of barbiturates and sulpha drugs

Sulpholane (tetramethylenesulphone) has been used as the medium for non-aqueous potentiometric titration of barbiturates and sulpha drugs with tetrabutylammonium hydroxide. Recoveries for 0.1-0.3 mmole of barbituric acid, phenobarbital, amobarbital, barbital, secobarbital, sulphapyridine, sulphadiazine and sulphamerazine were generally in the range 99-101%. A glass-calomel electrode system was used: common acid-base indicators give no colour change in the medium used.     

Modeling the morphology and mechanical properties of sheared ternary mixtures

Through a combination of simulation techniques, we determine both the structural evolution and mechanical properties of blends formed from immiscible ternary mixtures. In this approach, we first use the lattice Boltzmann method to simulate the phase separation dynamics of A/B/C fluid mixtures for varying compositions within the spinodal region. We also investigate the effect of an imposed shear on the phase ordering of the mixture. We assume that the fluid is quenched sufficiently rapidly that the phase-separated structure is preserved in the resultant solid. Then, the output from our morphological studies serves as the input to the lattice spring model, which is used to simulate the elastic response of solids to an applied deformation. These simulations reveal how the local stress and strain fields and the global Young's modulus depend on the composition of the blend and the stiffness of the components. By comparing the results for the sheared and unsheared cases, we can isolate optimal processing conditions for enhancing the mechanical performance of the blends. Overall, the findings provide fundamental insight into the relationship between structure, processing, and properties for heterogeneous materials and can yield guidelines for formulating blends with the desired macroscopic mechanical behavior.     

Bio-Templated Chiral Zeolitic Imidazolate Framework for Enantioselective Chemoresistive Sensing

Chiral metal–organic frameworks (MOFs) have gained rising attention as ordered nanoporous materials for enantiomer separations, chiral catalysis, and sensing. Among those, chiral MOFs are generally obtained through complex synthetic routes by using a limited choice of reactive chiral organic precursors as the primary linkers or auxiliary ligands. Here, we report a template-controlled synthesis of chiral MOFs from achiral precursors grown on chiral nematic cellulose-derived nanostructured bio-templates. We demonstrate that chiral MOFs, specifically, zeolitic imidazolate framework (ZIF), unc -[Zn(2-MeIm)₂, 2-MeIm=2-methylimidazole], can be grown from regular precursors within nanoporous organized chiral nematic nanocelluloses via directed assembly on twisted bundles of cellulose nanocrystals. The template-grown chiral ZIF possesses tetragonal crystal structure with chiral space group of P4₁, which is different from traditional cubic crystal structure of I-43 m for freely grown conventional ZIF-8. The uniaxially compressed dimensions of the unit cell of templated ZIF and crystalline dimensions are signatures of this structure. We observe that the templated chiral ZIF can facilitate the enantiotropic sensing. It shows enantioselective recognition and chiral sensing abilities with a low limit of detection of 39 μM and the corresponding limit of chiral detection of 300 μM for representative chiral amino acid, D- and L- alanine.     

Experimental measurement of wall shear stress in strongly disrupted flows

Mean and fluctuating wall shear stress is measured in strongly disrupted cases generated by various low-porosity wall-mounted single- and multi-scale fences. These grids generate a highly turbulent wake which interacts with the wall-bounded flow modifying the wall shear stress properties. Measurement methods are validated first against a naturally growing zero pressure gradient turbulent boundary layer showing accuracies of 1% and 4% for extrapolation and direct measurement of the mean shear stress respectively. Uncertainty associated with the root mean square level of the fluctuations is better than 2% making it possible to measure small variations originating from the different fences. Additionally, probability density functions and spectra are also measured providing further insight into the flow physics. Measurement of shear stress in the disrupted cases (grid+TBL) suggest that the flow characteristics and turbulence mechanisms remain unaltered far from the grid even in the most disrupted cases. However, a different root mean square level of the fluctuations is found for different grids. Study of the probability density functions seem to imply that there are different degrees of interaction between the inner and outer regions of the flow.     

Stability of a microwave heated fluid Layer

When a time harmonic electromagnetic wave impinges on a slaba certain portion of the wave creates heat within the slab throughdipolar and ohmic heating. The electrical and thermal propertiesof the material dictate the dynamical nature of the heatingprocess, as well as the steady-state temperature profile. Thematerial considered here is a slab of fluid. We consider thecase where the fluid is bounded by thin rigid layers of transparentmaterial. The steady-state heating profile governs the typesof convective motions that can occur and also affects the stabilitycharacteristics of temperature, pressure and velocity perturbationsintroduced in the slab. The main objective here is to examinesuch stability characteristics, initially in the linear regime.Both rigid-rigid and rigid-free configurations are considered.