Product Selectivity in Semiconductor-Mediated Dehydrazonation of Benzophenone Hydrazone

Secondary amines are obtained in moderate-good yields by reduction of crude imines prepared from N-alkyltriethoxyiminophosphoranes and aldehydes via the aza-Wittig reaction. N-Alkyltriethoxyiminophosphoranes are synthesized by one-pot azidation of alkyl bromides followed by Staudinger reaction.     

Graphene Oxide as a Mediator in Organic Synthesis: a Mechanistic Focus

Graphene oxide (GO) is experiencing growing interest by synthetic organic chemists as a promoter of chemical transformations. The synergistic role of the multiple functionalities featuring the nanostructured carbon materials and their π-domains enables the interplay of specific activation modes towards organic compounds that can explore unprecedented chemical modifications. A detailed comprehension of the mechanistic details that govern the transformations guided by GO is a not fully solved task in the field. In this direction, more sophisticated and diversified techniques are employed, providing insights towards intriguing activation modes exerted by the π-matrix and the oxygenated/sulfonate groups decorating the functionalized nano-carbon material. The present Minireview accounts for a critical survey of the most recent developments in the area of GO-mediated organic transformations with a specific focus on mechanist aspects.     

Sliding threshold of spike‐rate dependent plasticity of a semiconducting polymer/electrolyte cell

Spike‐rate dependent plasticity, one of the conventional learning protocols in neuroscience, has been achieved in semiconducting polymer/electrolyte cells. The frequency threshold θ_m of spike‐rate dependent plasticity is sliding in requirement of stability. In this work, various prior signal inputs are applied to poly[2‐methoxy‐5‐(2‐ethylhexyloxy)?1,4‐phenylenevinylene]/polyethylene oxide ‐Nd³⁺ cells to explore their effects on θ_m.The study find that a prior inhibitory input, i.e., a weak stimulation, moves θ_m in the low frequency direction, while a prior excitatory input, i.e., an intensive stimulation, moves θ_m in the high frequency direction. Our results demonstrate the adaptivity of ionic kinetics in macromolecules systems for signal handling and learning. We suggest that a sliding threshold is due to the variable active ionic domains depending on stimulation strength and history. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2412–2417     

Host-Guest Interaction in Ethylene and Ethane Separation on Zeolitic Imidazolate Frameworks as Revealed by Solid-State NMR Spectroscopy

The separation of ethane/ethylene mixture by using metal-organic frameworks (MOFs) as adsorbents is strongly associated with the pore size-sieving effect and the adsorbent-adsorbate interaction. Herein, solid-state NMR spectroscopy is utilized to explore the host-guest interaction and ethane/ethylene separation mechanism on zeolitic imidazolate frameworks (ZIFs). Preferential access to the ZIF-8 and ZIF-8-90 frameworks by ethane compared to ethylene is directly visualized from two-dimensional ¹H-¹H spin diffusion MAS NMR spectroscopy and further verified by computational density distributions. The ¹H MAS NMR spectroscopy provides an alternative for straightforwardly extracting the adsorption selectivity of ethane/ethylene mixture at 1.1∼9.6 bar in ZIFs, which is consistent with the IAST predictions.     

Hydrochlorination of acetylene using expanded multilayered vermiculite (EML-VMT)-supported catalysts

Catalyst supports have very important effects on catalyst performance.A novel expanded multilayered vermiculite(EML-VMT) is successfully used as the catalyst support for the acetylene hydrochlorination.By mixing carbon on the surface of EML-VMT[i.e.,EML-VMT-C),the HgCl_2/EML-VMT-C achieved a high acetylene conversion of 97.3%,a vinyl chloride selectivity of 100%and a turn over frequency(TOF) value of 8.83 × 10~(-3)s~(-1) at a temperature of 140 C,an acetylene gas hourly space velocity(GHSV) of 108 h~(-1)',and a feed volume ratio V(HC1)/V(C_2H_2) of 1.15.Moreover,the HgCl_2/EML-VMT-C shows good stability.The EML-VMT also shows potential in the preparation of other EML-VMT-supported catalysts.     

Impact of the Spatial Organization of Bifunctional Metal–Zeolite Catalysts on the Hydroisomerization of Light Alkanes

Improving product selectivity by controlling the spatial organization of functional sites at the nanoscale is a critical challenge in bifunctional catalysis. We present a series of composite bifunctional catalysts consisting of one‐dimensional zeolites (ZSM‐22 and mordenite) and a γ‐alumina binder, with platinum particles controllably deposited either on the alumina binder or inside the zeolite crystals. The hydroisomerization of n‐heptane demonstrates that the catalysts with platinum particles on the binder, which separates platinum and acid sites at the nanoscale, leads to a higher yield of desired isomers than catalysts with platinum particles inside the zeolite crystals. Platinum particles within the zeolite crystals impose pronounced diffusion limitations on reaction intermediates, which leads to secondary cracking reactions, especially for catalysts with narrow micropores or large zeolite crystals. These findings extend the understanding of the “intimacy criterion” for the rational design of bifunctional catalysts for the conversion of low‐molecular‐weight reactants.     

Anomalous Pore‐Density Dependence in Nanofluidic Osmotic Power Generation

Osmotic power generation in biomimetic nanofluidic systems has attracted considerable research interest owing to the enhanced performance and long‐term stability. Towards practical applications, when extrapolating the materials from single‐nanopore to multi‐pore membranes, conventional viewpoint suggests that, to gain high electric power density, the porosity should be as high as possible. However, recent experimental observations show that the commonly‐used linear amplification method largely overestimates the actual performance, particularly at high pore density. Herein, we provide a theoretical investigation to understand the reason. We find a counterintuitive pore‐density dependence in high porosity nanofluidic systems that, once the pore density approaches more than 1×10⁹ pores/cm², the overall output electric power goes down with the increasing pore density. The excessively high pore density impairs the charge selectivity and induces strong ion concentration polarization, which undermines the osmotic power generation process. By optimizing the geometric size of the nanopores, the performance degradation can be effectively relieved. These findings clarify the origin of the unsatisfactory performance of the current osmotic nanofluidic power sources, and provide insights to further optimize the device.