Nanocatalosomes as Plasmonic Bilayer Shells with Interlayer Catalytic Nanospaces for Solar-Light-Induced Reactions

Interest and challenges remain in designing and synthesizing catalysts with nature-like complexity at few-nm scale to harness unprecedented functionalities by using sustainable solar light. We introduce “nanocatalosomes”—a bio-inspired bilayer-vesicular design of nanoreactor with metallic bilayer shell-in-shell structure, having numerous controllable confined cavities within few-nm interlayer space, customizable with different noble metals. The intershell-confined plasmonically coupled hot-nanospaces within the few-nm cavities play a pivotal role in harnessing catalytic effects for various organic transformations, as demonstrated by “acceptorless dehydrogenation”, “Suzuki–Miyaura cross-coupling” and “alkynyl annulation” affording clean conversions and turnover frequencies (TOFs) at least one order of magnitude higher than state-of-the-art Au-nanorod-based plasmonic catalysts. This work paves the way towards next-generation nanoreactors for chemical transformations with solar energy.     

Study of spin–phonon coupling in LiFe1 − xMnxPO4olivines

LiFe_{1 − x}Mn_xPO₄ olivines are promising material for improved performance of Li‐ion batteries. Spin–phonon coupling of LiFe_{1 − x}Mn_xPO₄ (x = 0, 0.3, 0.5) olivines is studied through temperature‐dependent Raman spectroscopy. Among the observed phonon modes, the external mode at ~263 cm⁻¹ is directly correlated with the motions of magnetic Fe²⁺/Mn²⁺ ions. This mode displays anomalous temperature‐dependent behavior near the Néel temperature, indicating a coupling of this mode with spin ordering. As Mn doping increases, the anomalous behavior becomes clearly weaker, indicating the spin–phonon coupling quickly decreases. Our analyses show that the quick decrease of spin–phonon coupling is due to decrease of the strength of spin–phonon coupling, but not change of spin‐ordering feature with Mn doping. Importantly, we suggest that the low electrochemical activity of LiMnPO₄ is correlated with the weak spin–phonon coupling strength, but not with the weak ferromagnetic ground state. Our work would play an important role as a guide in improving the performances of future Li‐ion batteries. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects of the cinnamoyl group on liquid crystal aligning capabilities on PCEMA surfaces

Four kinds of poly(4-methacryloyloxychalcone) (PCEMA) photo-alignment materials were synthesized. The effect of the cinnamoyl group on liquid crystal (LC) aligning capabilities and electro-optical characteristics of photo-aligned twisted nematic (TN) liquid crystal displays (LCDs) was investigated by photo-dimerization. Uniform NLC alignment by linearly polarized UV exposure at normal incidence on the PCEMA surfaces having a high density of cinnamoyl groups was observed. Also, excellent voltage-transmittance (V-T) curves for the photo-aligned TN-LCDs on the PCEMA surfaces was achieved. We find that the V-T and response time characteristics can be improved by increasing the density of cinnamoyl groups.     

Synthesis and characterization of highly hindered and thermally stable poly(1,4‐spirobifluorenylenevinylene) derivative

A new poly(1,4‐spirobifluorenylenevinylene) having advantage PPV and spirobifluorene as new emissive family was synthesized. Compared with PPV derivatives that usually have a tolane bisbenzyl defect, the polymer has the defect free structure because of the steric hindrance of the asymmetric bulky spirobifluorenyl group. Compared with spirobifluorene derivatives that usually have a low solubility, the polymer has the good solubility in common organic solvents. The polymer was amorphous and showed high PL quantum efficiency and high thermal stability with high T_g. The PL emission peaks were shown at 480–490 nm in solution and film, respectively, which may represent the bluest emission peak reported for fully conjugated PPV derivatives. The study of thermal annealing of PL spectrum showed excimer formation inhibited. The thermal and optoelectronic properties of the polymer imply that it is a promising material for the PLED application. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 900–907, 2007.     

New family of highly emissive,soluble poly(1,4‐fluorenylenevinylene) derivatives: Synthesis and characterization

A new poly(arylene vinylene) derivative, poly(1,4‐fluorenylenevinylene), with the advantages of poly(p‐phenylene vinylene) and polyfluorene (PF), was designed, synthesized, and characterized. The polymer showed a defect‐free structure and a number‐average molecular weight of 32,600. The resulting polymer was thermally stable with a high glass‐transition temperature (200 °C) and was readily soluble in common organic solvents. The polymer film showed a maximum emission at 515 nm and had a photoluminescence quantum yield of 58 ± 5%. A cyclic voltammetry study revealed that the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of the polymer were 2.9 and 5.51 eV, respectively. The double‐layer light‐emitting‐diode devices fabricated from the polymer emitted bright green light with a maximum around 515 nm. The device showed a maximum luminous efficiency of 0.13 cd/A and a maximum luminance value of 600 cd/m² at 17 V. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6515–6523, 2005     

Synthesis of core‐shell silver–polyaniline nanocomposites by gamma radiolysis method

Core‐shell silver (Ag)–polyaniline (PAni) nanocomposites have been synthesized by the in‐situ gamma radiation‐induced chemical polymerization method. Aqueous solution of aniline, a free‐radical oxidant, and/or silver metal salt were irradiated by γ‐rays. Reduction of the silver salt in aqueous aniline leads to the formation of silver nanoparticles which in turn catalyze oxidation of aniline to polyaniline. The resultant Ag‐PAni nanocomposites were characterized by using different spectroscopy analyses like X‐ray photoelectron, UV–visible, and infrared spectroscopy. The optical absorption bands revealed that the bands at about 400 nm are due to the presence of nanosilver and the blue‐shifted peak at ～ 555 nm is due to the presence of metallic silver within the PAni matrix. X‐ray diffraction pattern clearly indicates the broad amorphous polymer and the sharp metal peaks. Scanning electron microscopy and transmission electron microscopy of the nanocomposite showed a uniform size distribution with spherical and granular morphology. Thermogravimetric analysis revealed that the composites have a higher degradation temperature than polyaniline alone. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5741–5747, 2007     

Preparation of gradient copolymers via ATRP in miniemulsion. II. Forced gradient

A series of forced gradient copolymers with different controlled distribution of monomer units along the copolymer backbone were successfully prepared by atom transfer radical polymerization in miniemulsion. The newly developed initiation technique, known as activators generated by electron transfer, was beneficial for forced gradient copolymers preparation because all polymer chains were initiated within the miniemulsion droplets and the miniemulsion remained stable throughout the entire polymerization. Various monomer pairs with different reactivity ratios were examined in this study, including n‐butyl acrylate/t‐butyl acrylate, n‐butyl methacrylate/methyl methacrylate, and n‐butyl acrylate/styrene. In each case, the added monomer diffused across the aqueous suspending medium and gradient copolymers with different forced distributions of comonomer units along the polymer backbone were obtained. The shape of the gradient along the backbone of the copolymers was influenced by the molar ratio of the monomers, the reactivity ratio of the comonomers as well as the feeding rate. The shape of the gradient was also affected by the relative hydrophobicities of the comonomers. Copolymerizations exhibited good control for all feeding rates and comonomer feeding ratios, as evidenced by narrow molecular weight distribution (M_w/M_n = 1.20–1.40) and molecular weight increasing smoothly with polymer yield, indicating high initiation efficiency. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1413–1423, 2007     

Crystal graphs for Lie superalgebras and Cauchy decomposition

We discuss Cauchy type decompositions of crystal graphs for general linear Lie superalgebras. More precisely, we consider bicrystal graph structures on various sets of matrices of non-negative integers, and obtain their decompositions with explicit combinatorial isomorphisms.This research was supported by 2005 research fund of University of Seoul.     

Regular orientable embeddings of complete bipartite graphs

In this paper, it will be shown that the isomorphism classes of regular orientable embeddings of the complete bipartite graph K_n,n are in one‐to‐one correspondence with the permutations on n elements satisfying a given criterion, and the isomorphism classes of them are completely classified when n is a product of any two (not necessarily distinct) prime numbers. For other n, a lower bound of the number of those isomorphism classes of K_n,n is obtained. As a result, many new regular orientable embeddings of the complete bipartite graph are constructed giving an answer of Nedela‐?koviera's question raised in 12 . © 2005 Wiley Periodicals, Inc. J Graph Theory