An experimental and theoretical study of butyl methacrylate in situ radical polymerization kinetics in the presence of graphene oxide nanoadditive

The butyl methacrylate radical polymerization kinetics in the presence of graphene oxide nanoadditive is studied both experimentally and theoretically. The experimental study includes the formation of graphite oxide from the oxidation of graphite and its subsequent transformation to graphene oxide (GO) after ultrasonication and in situ polymerization. Monomer conversion versus time was monitored gravimetrically at various reaction temperatures and initial GO fractions. Formation of GO was verified by X‐ray diffraction spectra and the number and weight average molecular weights of the final polymer were obtained from GPC measurements. A detailed theoretical kinetic model was further developed. The model predictions were found to be in satisfactory agreement with the experimental data. The presence of GO was found to result in reduced initiator efficiency verified theoretically and explained through side reactions of primary radicals. Finally, nanocomposites showed enhanced thermal stability compared to neat PBMA. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1433–1441     

Effect of counterions on the thermotropic and thermochromic properties of ionic liquid crystals

Novel liquid crystal materials based on 1-alkyl-4-[5-(dodecylsulphanyl)-1,3,4-oxadiazol-2-yl]pyridinium and bearing bromide, alkyl sulphate or bis(2-ethylhexyl)sulphosuccinate counterions were prepared. Their thermotropic and thermochromic properties were characterized and compared. It was established that the majority of these compounds exhibited SmA mesophases. The observation of thermochromic properties for certain of the compounds is considered to be the consequence of the existence of a charge-transfer complex between the pyridinium cation and its counterion.     

OBSERVATIONS ON THE SYNTHESIS AND in vivo PHOTODYNAMIC ACTIVITY OF SOME BENZOCHLORINS

An improved synthesis of benzochlorins is reported. Demetallation of the meso-hydroxymethylvinyl derivative of octaethylporphyrin, followed by treatment with sulfuric acid results in cyclization to generate the corresponding octaethylbenzochlorin in high yield. Prolonged treatment with acid generates the sulfonated derivative. These sensitizers were shown to be efficient photodynamic agents in vivo. Animals bearing a transplanted N-[4-(5-nitro-2-furyl)-2-thiazoly]formamide induced urothelial tumor were treated with either the benzochlorin or its sulfonated derivative. Irradiation of tumors 24 h later resulted in a significant tumoricidal effect in a short term assay. We conclude that benzochlorins warrant further examination as potential agents for use in photodynamic therapy.     

A technique for speeding up the solution of the Lagrangean dual

We propose techniques for the solution of the LP relaxation and the Lagrangean dual in combinatorial optimization and nonlinear programming problems. Our techniques find the optimal solution value and the optimal dual multipliers of the LP relaxation and the Lagrangean dual in polynomial time using as a subroutine either the Ellipsoid algorithm or the recent algorithm of Vaidya. Moreover, in problems of a certain structure our techniques find not only the optimal solution value, but the solution as well. Our techniques lead to significant improvements in the theoretical running time compared with previously known methods (interior point methods, Ellipsoid algorithm, Vaidya's algorithm). We use our method to the solution of the LP relaxation and the Langrangean dual of several classical combinatorial problems, like the traveling salesman problem, the vehicle routing problem, the Steiner tree problem, thek-connected problem, multicommodity flows, network design problems, network flow problems with side constraints, facility location problems,K-polymatroid intersection, multiple item capacitated lot sizing problem, and stochastic programming. In all these problems our techniques significantly improve the theoretical running time and yield the fastest way to solve them.     

Artificial compressibility, characteristics-based schemes for variable density, incompressible, multi-species flows. Part I. Derivation of different formulations and constant density limit

The paper presents various formulations of characteristics-based schemes in the framework of the artificial-compressibility method for variable-density incompressible flows. In contrast to constant-density incompressible flows, where the characteristics-based variables reconstruction leads to a single formulation, in the case of variable density flows three different schemes can be obtained henceforth labeled as: transport, conservative and hybrid schemes. The conservative scheme results in pseudo-compressibility terms in the (multi-species) density reconstruction. It is shown that in the limit of constant density, the transport scheme becomes the (original) characteristics-based scheme for incompressible flows, but the conservative and hybrid schemes lead to a new characteristics-based variant for constant density flows. The characteristics-based schemes are combined with second and third-order interpolation for increasing the computational accuracy locally at the cell faces of the control volume. Numerical experiments for constant density flows reveal that all the characteristics-based schemes result in the same flow solution, but they exhibit different convergence behavior. The multigrid implementation and numerical studies for variable density flows are presented in Part II of this study.     

Generalized layerwise mechanics for the static and modal response of delaminated composite beams with active piezoelectric sensors

A coupled linear layerwise laminate theory and a beam FE are formulated for analyzing delaminated composite beams with piezoactuators and sensors. The model assumes zig-zag fields for the axial displacements and the electric potential and it treats the discontinuities in the displacement fields due to the delaminations as additional degrees of freedom. The formulation naturally includes the excitation of piezoelectric actuators, their interactions with the composite laminate, and the effect of delamination on the predicted sensory voltage. The quasistatic and modal response of laminated composite Gr/Epoxy beams with active or sensory layers having various delamination sizes is predicted. The numerical results illustrate the strong effect of delamination on the sensor voltage, on through the thickness displacement and on the stress fields. Finally, the effect of delamination on modal frequencies and shapes are predicted and compared with previously obtained experimental results.     

Fouling behavior of microstructured hollow fiber membranes in dead-end filtrations: critical flux determination and NMR imaging of particle deposition

The fouling behavior of microstructured hollow fibers was investigated in constant flux filtrations of colloidal silica and sodium alginate. It was observed that the fouling resistance increases faster with structured fibers than with round fibers. Reversibility of structured fibers' fouling was similar during silica filtrations and better in sodium alginate filtrations when compared with round fibers. The deposition of two different silica sols on the membranes was observed by NMR imaging. The sols had different particle size and solution ionic strength and showed different deposition behaviors. For the smaller particle-sized sol in deionized solution (Ludox-TMA), there was more deposition within the grooves of the structured fibers and much less on the fins. For the alkali-stabilized sol Bindzil 9950, which had larger particles, the deposition was homogeneous across the surface of the structured fiber, and the thickness of the deposit was similar to that on the round fiber. This difference between the deposition behavior of the two sols is explained by differences in the back diffusion, which creates concentration polarization layers with different resistances. The Ludox sol formed a thick polarization layer with very low resistance. The Bindzil sol formed a slightly thinner polarization layer; however, its resistance was much higher, of similar magnitude as the intrinsic membrane resistance. This high resistance of the polarization layer during the Bindzil sol filtration is considered to lead to quick flow regulation toward equalizing the resistance along the fiber surface. The Ludox particles were trapped at the bottom of the grooves as a result of reduced back diffusion. The fouling behavior in sodium alginate filtrations was explained by considering the size-dependent deposition within the broad alginate size distribution. The better reversibility of fouling in the structured fibers is thought to be the result of a looser deposit within the grooves, which is more easily removed than a compressed deposit on the round fibers.     

Ruthenium-catalyzed selective hydrogenation of bis-arylidene tetramic acids. Application to the synthesis of novel structurally diverse pyrrolidine-2,4-diones

Catalytic hydrogenation of 3,5-bis-arylidenetetramic acids, known for their biological activity, has been developed. The chemoselective ruthenium-catalyzed reduction of the exocyclic carbon-carbon double bonds on pyrrolidine-2,4-dione ring system, containing other reducible functions, has been investigated. Depending on the substrate the yield of the hydrogenation process can reach up to 95%. The structural elucidation has been established using NMR and HRMS spectral data.