Controlling effective interactions and spatial dispersion of nanoparticles in multiblock copolymer melts

The microscopic Polymer Reference Interaction Site Model theory is employed to study, for the first time, the effective interactions, spatial organization, and miscibility of dilute spherical nanoparticles in non‐microphase separating, chemically heterogeneous, compositionally symmetric AB multiblock copolymer melts of varying monomer sequence or architecture. The dependence of nanoparticle wettability on copolymer sequence and chemistry results in interparticle potentials‐of‐mean force that are qualitatively different from homopolymers. An important prediction is the ability to improve nanoparticle dispersion via judicious choice of block length and monomer adsorption‐strengths which control both local surface segregation and chain connectivity induced packing constraints and frustration. The degree of dispersion also depends strongly on nanoparticle diameter relative to the block contour length. Small particles in copolymers with longer block lengths experience a more homopolymer‐like environment which renders them relatively insensitive to copolymer chemical heterogeneity and hinders dispersion. Larger particles (sufficiently larger than the monomer diameter) in copolymers of relatively short block lengths provide better dispersion than either a homopolymer or random copolymer. The theory also predicts a novel widening of the miscibility window for large particles upon increasing the overall molecular weight of copolymers composed of relatively long blocks. The influence of a positive chi‐parameter in the pure copolymer melt is briefly studied. Quantitative application to fullerenes in specific copolymers of experimental interest is performed, and miscibility predictions are made. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1098–1111     

Synthesis and Characterization of 5‐Cyanotetrazolide‐Based Ionic Liquids

New salts based on imidazolium, pyrrolidinium, phosphonium, guanidinium, and ammonium cations together with the 5‐cyanotetrazolide anion [C₂N₅]^? are reported. Depending on the nature of cation–anion interactions, characterized by XRD, the ionic liquids (ILs) have a low viscosity and are liquid at room temperature or have higher melting temperatures. Thermogravimetric analysis, cyclic voltammetry, viscosimetry, and impedance spectroscopy display a thermal stability up to 230 °C, an electrochemical window of 4.5 V, a viscosity of 25 mPa s at 20 °C, and an ionic conductivity of 5.4 mS cm^?1 at 20 °C for the IL 1‐butyl‐1‐methylpyrrolidinium 5‐cyanotetrazolide [BMPyr][C₂N₅]. On the basis of these results, the synthesized compounds are promising electrolytes for lithium‐ion batteries.     

Holography beyond conformal invariance and AdS isometry?

Journal of Experimental and Theoretical Physics - We suggest that the principle of holographic duality be extended beyond conformal invariance and AdS isometry. Such an extension is based on a...     

Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties

The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role.     

Reactions of Aryl Benzoates with Potassium Aryloxides: Solvent Effects on Reaction Pathway and Kinetics

Temperature dependences of the relative reactivity of potassium aryloxides XC₆H₄O^?K⁺ toward 2,4‐dinitrophenyl benzoate in 50 mol% dimethylformamide (DMF)–50 mol% H₂O mixture have been studied using the competitive reactions technique. Correlation analyses of the relative rate constants k_X/k_H and differences in the activation parameters (ΔΔН^≠ and ΔΔS^≠) of the competitive reactions have revealed the existence of two isokinetic series of the reactions of 2,4‐dinitrophenyl benzoate with potassium aryloxides with electron‐donating substituent (EDS) and electron‐withdrawing substituent (EWS), respectively. We have investigated the effect of the substituent X on the activation parameters for each isokinetic series and concluded that the mechanism of the reactions of 2,4‐dinitrophenyl benzoate with potassium aryloxides XC₆H₄O^?K⁺ in 50 mol% DMF–50 mol% H₂O mixture is the same as in DMF. Analysis of the obtained data with using the method of two‐dimensional reaction coordinate diagram leads to the conclusion that the variation of the solvent from DMF to 50 mol% DMF–50 mol% H₂O mixture affects the reaction pathway. The rate constant k_X for the reaction of 3‐nitrophenyl benzoate with potassium 4‐methoxyphenoxide and the relative rate constants k_X/k_H for the reaction of 3‐nitrophenyl benzoate with potassium aryloxides XC₆H₄O^?K⁺ with EDS were measured in 50 mol% DMF–50 mol% H₂O mixtures at 25°C, and it has been shown that the addition of water to DMF does not change the mechanism but slows down these reactions.