Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

Self‐assembly of AB₂ and AB₃ type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model.     

Combustion properties of H2/N2/O2/steam mixtures

The present work reports new experimental and numerical results of the combustion properties of hydrogen based mixtures diluted by nitrogen and steam. Spherical expanding flames have been studied in a spherical bomb over a large domain of equivalence ratios, initial temperatures and dilutions at an initial pressure of 100 kPa (T_ini = 296, 363, 413 K; N₂/O₂ = 3.76, 5.67, 9; %Steam = 0, 20, 30). From these experiments, the laminar flame speed $S_L^0$, the Markstein length L’, the activation energy Ea and the Zel'dovich β number have been determined. These parameters were also simulated using COSILAB^® in order to verify the validity of the Mével et al. [1] detailed kinetic mechanism. Other parameters as the laminar flame thickness δ and the effective Lewis number Le_eff were also simulated. These new results aim at providing an extended database that will be very useful in the hydrogen combustion hazard assessment for nuclear reactor power plant new design.     

Polypyrrole Shell@3D‐Ni Metal Core Structured Electrodes for High‐Performance Supercapacitors

Three‐dimensional (3D) nanometal films serving as current collectors have attracted much interest recently owing to their promising application in high‐performance supercapacitors. In the process of the electrochemical reaction, the 3D structure can provide a short diffusion path for fast ion transport, and the highly conductive nanometal may serve as a backbone for facile electron transfer. In this work, a novel polypyrrole (PPy) shell@3D‐Ni‐core composite is developed to enhance the electrochemical performance of conventional PPy. With the introduction of a Ni metal core, the as‐prepared material exhibits a high specific capacitance (726 F g^?1 at a charge/discharge rate of 1 A g^?1), good rate capability (a decay of 33 % in C_sp with charge/discharge rates increasing from 1 to 20 A g^?1), and high cycle stability (only a small decrease of 4.2 % in C_sp after 1000 cycles at a scan rate of 100 mV s^?1). Furthermore, an aqueous symmetric supercapacitor device is fabricated by using the as‐prepared composite as electrodes; the device demonstrates a high energy density (≈21.2 Wh kg^?1) and superior long‐term cycle ability (only 4.4 % and 18.6 % loss in C_sp after 2000 and 5000 cycles, respectively).     

Synthesis of self‐healing polyurethane urea‐based supramolecular materials

Supramolecular polyurethane ureas are expected to have superior mechanical properties primarily due to the reversible, noncovalent interactions such as hydrogen bonding interactions. We synthesized polyurethane prepolymers from small molecular weight of poly(tetramethylene ether)glycol and isophorone diisocyanates, which were end capped with propylamine to synthesize polyurethane ureas with high contents of urea and urethane groups for hydrogen‐bonding formations to facilitate self‐healing. The effects of polyurethane urea molecular weight (3000 ≤ M_n ≤ 9000), crosslinking, and cutting direction were studied in terms of thermal, mechanical, and morphological properties with an emphasis on the self‐healing efficiency. It was found that the thermal self‐healability was more pronounced as the molecular weight of polyurethane urea decreased, showing a maximum of more than 96% with 3000 M_n when the sample was cut along the stretch direction. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 468–474     

Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline‐2,3‐diyl)s

The development of synthetic routes which lead to five new diisocyanide monomers with one or two phenolic groups is described. Their polymerization behavior is studied with Pd‐ and Ni‐based initiators, as well as under microwave irradiation. The polymerizability is mainly dominated by steric effects as is concluded from experiments using different protecting groups. Chiroptical properties of these new polymers are studied by CD‐spectroscopy. After deprotection, helically chiral poly(quinoxalin‐2,3‐diyl)s are obtained which display a Brønsted function attached to a stereolabile biaryl axis whose configuration should be influenced by the chiral polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1320–1329     

Roles of SiH4 and SiF4 in growth and structural changes of poly-Si films

The structural properties of polycrystalline silicon films, prepared by plasma enhanced chemical vapor deposition system, with different flow rates of SiH₄/SiF₄ mixtures at 300 °C were investigated. This study indicates that the low hydrogen coverage on the growing surface, under optimum fluorine radicals, will be leaded to an improvement of crystallized area as compared with case of high hydrogen coverage surface. Moreover, the studies of the role of SiH₄ and SiF₄ radicals show that the SiH₄ radicals are important in the nucleation and growth of grains. However, SiF₄ radicals are effective in the structural change of grain boundaries regions and by this way, in the present system, establish the growth of grains under the dominant 〈1 1 0〉 direction. The stress investigation indicates that addition of high flow rate of SiF₄ in amorphous film, results in the nearly stress free films. Finally, we found that the changes in g-value reflect the changes in the intrinsic compressive and tensile stress in the both polycrystalline and amorphous silicon films.     

对位酚类衍生物作为化学发光分析的增强剂研究

在化学发光分析中，常常要用到碱性条件下鲁米诺与过氧化氢的反应系统，通过催化剂辣根过氧化物酶使反应顺利进行。如果再加入适当的增强剂，则灵敏度提高且发光时间延长，可改善测定的重现性。实验证明，对位酚类衍生物，如：对叔丁基苯酚，对甲苯酚的发光增强作用明显，其发光效率可上升几十倍，发光时间也获得有效延长。     

Preparation, structure and properties of novel 1,3-dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units

1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts.