Photocurrent generation in multilayer self-assembly films fabricated from water-soluble poly(phenylene vinylene)

A novel, water-soluble, cationic PPV derivative poly[(2,5-bis(3-bromotrimethylammoniopropoxy)-phenylene-1,4-divinylene)-alt-1,4-(2,5-bis(2-(2-hydroxyethoxy)ethoxy))phenylene vinylene] (BH-PPV) has been synthesized by a Heck coupling reaction. Multilayered assemblies of the BH-PPV and the sodium salt of hexa(sulfobutyl)fullerenes (C(60)-HS) were fabricated successfully by an alternate deposition technique. The multilayer structures were studied by UV/Vis spectroscopy, small angle X-ray diffraction, and atomic force microscopy. The photoinduced charge transfer property of the self-assembled multilayer film was also measured by a three-electrode cell technique. A steady and rapid cathodic 5.5 microA cm(-2) photocurrent response was measured as the irradiation of the multilayer film was switched on and off. Importantly, the response of on/off cycling is prompt and reproducible. A possible mechanism for the electron-transfer process is proposed.     

Rigid rod anchored to infinite membrane

We investigate the shape deformation of an infinite membrane anchored by a rigid rod. The density profile of the rod is calculated by the self-consistent-field theory and the shape of the membrane is predicted by the Helfrich membrane elasticity theory [W. Helfrich, Z. Naturforsch. 28c, 693 (1973)]. It is found that the membrane bends away from the rigid rod when the interaction between the rod and the membrane is repulsive or weakly attractive (adsorption). However, the pulled height of the membrane at first increases and then decreases with the increase of the adsorption strength. Compared to a Gaussian chain with the same length, the rigid rod covers much larger area of the membrane, whereas exerts less local entropic pressure on the membrane. An evident gap is found between the membrane and the rigid rod because the membrane's curvature has to be continuous. These behaviors are compared with that of the flexible-polymer-anchored membranes studied by previous Monte Carlo simulations and theoretical analysis. It is straightforward to extend this method to more complicated and real biological systems, such as infinite membrane/multiple chains, protein inclusion, or systems with phase separation.     

Boomerang‐Type Substitution Reaction: Reactivity of Fullerene Epoxides and a Halofullerenol

The C_s‐symmetric fullerene chlorohydrin C₆₀(Cl)(OH)(OOtBu)₄ reacts with 4‐dimethylaminopyridine (DMAP) and 1,4‐diazabicyclo[2.2.2]octane (DABCO) to yield two isomers with the formula C₆₀(O)(OOtBu)₄ in good yields. These isomers differ with respect to the location of the epoxy functionality. The one from DMAP is C_s symmetric, whereas that from DABCO is C₁ symmetric with the epoxy group on the central pentagon. Two different mechanisms are proposed to explain the chemoselectivity of these reactions. The reaction with DMAP involves single‐electron transfer as the key step; DMAP acts as the electron donor. A combination of an oxygen‐atom shift and S_N2′′ processes (boomerang substitution) are responsible for the formation of isomer with DACBO. Various related reactions support the proposed mechanisms. The structures of new fullerene derivatives were determined by spectroscopy, single‐crystal X‐ray analysis, and chemical correlation experiments.     

Synthesis of oligo(p-phenylene vinylene)-porphyrin-oligo(p-phenylene vinylene) triads as antenna molecules for energy transfer

The oligo(p-phenylene vinylene)-porphyrin-oligo(p-phenylene vinylene) (P-OPVn, n=2, 4, where n is the number of phenyl rings) and the complex with Zn²⁺ based on P-OPVn were synthesized for investigating their photophysical properties via UV-vis, voltammetry, steady-state and time-resolved fluorescence spectra. In these molecules two OPV moieties as energy donors were linked to porphyrin center by virtue of Wittig reaction. The detailed studies of photophysical properties indicate that OPV group can act as an antenna unit for effective intramolecular energy transfer.     

Effect of graft polymer prepared by living radical polymerisation on electro-optical properties of polymer dispersed liquid crystal

In this study, a graft polymer matrix prepared by living radical polymerisation had been incorporated into polymer dispersed liquid crystals (PDLCs). The electro-optical properties of the PDLCs were investigated. The results showed that the length and density of graft chain had a great influence on the memory effect of the PDLCs. Low-driving-voltage and weak-memory-effect PDLCs could easily be obtained with a graft polymer matrix.     

Effect of rGO on polymer-dispersed liquid crystal fabricated by RAFT polymerisation

In this study, we demonstrated that doping polymer matrix with a small amount of reduced graphene oxide (rGO) component (0.05–0.2%) had significant influence on the polymerisation kinetics and electro-optical performances of polymer-dispersed liquid crystal films (PDLCs) fabricated with macro reversible addition-fragmentation chain transfer agents. The effects of rGO content were studied in terms of morphology, compound viscosity, polymer conductivity, polymerisation kinetics and driving voltage of PDLCs. The results exhibited that higher rGO content increased the compound viscosity and the entire process proceeded slowly. Furthermore, the addition of rGO increased the polymer conductivity and local electric field, and reduced the saturation voltage as well as the threshold voltage from 27.3 to 19.5 V and 13.2 to 6.41 V, respectively.     

Intermetallic Compounds: Liquid-Phase Synthesis and Electrocatalytic Applications

Characterized by long-range atomic ordering, well-defined stoichiometry, and controlled crystal structure, intermetallics have attracted increasing attention in the area of chemical synthesis and catalytic applications. Liquid-phase synthesis of intermetallics has arisen as the promising methodology due to its precise control over size, shape, and resistance toward sintering compared with the traditional metallurgy. This short review tends to provide perspectives on the liquid-phase synthesis of intermetallics in terms of both thermodynamics and methodology, as well as its applications in various catalytic reactions. Specifically, basic thermodynamics and kinetics in the synthesis of intermetallics will be first discussed, followed by discussing the main factors that will affect the formation of intermetallics during synthesis. The application of intermetallics in electrocatalysis will be demonstrated case by case at last. We conclude the review with perspectives on the future developments with respect to both synthesis and catalytic applications.     

Themed Issue on Graphdiyne

Graphdiyne(GDY)has characteristics of one-atom-thick two-dimensional layers comprising of sp and sp2 hybridized carbon atoms.The chemical and electronic structure gives GDY many unique and fascinating properties,such as rich chemical bonds,highly conjugated and super-large π structures,infinitely distributed pores and high inhomogeneity of charge distribution,etc.     

Large‐Area Aminated‐Graphdiyne Thin Films for Direct Methanol Fuel Cells

A two‐dimensional (2D) carbon nanofilm with uniform artificial nanopores is an ideal material to ultimately suppress the fuel permeation in the proton exchange membrane fuel cells. Graphdiyne has great mechanical strength, high dimensional stability, and controllable nanopores, and has good prospects to play this crucial role. It is found that graphdiyne nanofilm with amino groups and natural nanopores can be easily prepared with high integrity. The aminated graphdiyne has good compatibility with the Nafion matrix owing to the acid–base interaction between them. The excellent comprehensive properties of graphdiyne in selectivity, dimensional stability, and integrity effectively improve the power performance and stability of fuel cells at wide temperature. Our results can be developed into a universal method that can easily realize the selective separation of ions and small molecules, and open a new way for the emerging applications in green energy.