A Porphyrin-Based Covalent Organic Framework for Metal-Free Photocatalytic Aerobic Oxidative Coupling of Amines

Imines are important intermediates in drug synthesis. Photocatalytic aerobic oxidative coupling of amines has been considered as a clean and promising way to produce imines and has attracted great attention. Herein, we designed and synthesized a novel two-dimensional porphyrin-based covalent organic framework (Por-BC-COF) which adopts an AA stacking mode with excellent crystallinity, high Brunauer–Emmett–Teller surface areas (1200 m² g⁻¹), wide light absorption range (200–1300 nm) and good stability in a variety of organic solvents. Por-BC-COF can be used as a metal-free heterogeneous photocatalyst for the photocatalytic oxidation of amines to imines under visible light and red light with a high yield (97 %). This work presents a novel and efficient COF photocatalyst in the application of light-driven organic synthesis.     

Quantitative study of cellular heterogeneity in doxorubicin uptake and its pharmacological effect on cancer cells

Cellular heterogeneity in doxorubicin (DOX) uptake and its relationship with pharmacological effect on cancer cells were quantitatively investigated for the first time. An in vitro experimental model was established by treating human leukemia K562 and breast cancer MCF‐7 cells with different schedules of DOX with or without surface P‐glycoprotein (P‐gp) inhibitor verapamil (VER). The cellular heterogeneity in DOX uptake was quantitatively examined by single‐cell analysis using capillary electrophoresis coupled with laser‐induced fluorescence detection. The corresponding cytotoxic effect was tested by cellular morphology, 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐tetrazolium and flow cytometry assays. The expression of cellular membrane surface P‐gp was determined by flow cytometry. Results showed that the cellular heterogeneity exists in DOX uptake. The single‐high DOX schedule leads to lower uptake heterogeneity and higher mean drug uptake. The cellular heterogeneity in DOX uptake was found to be negatively correlated with drug cytotoxicity and surface P‐gp expression, with r = ?0.7680 to ~ ?0.9587. VER reduces the cellular variation in DOX uptake, suggesting that surface P‐gp may be one of the causes of the cellular heterogeneity in DOX uptake. This research demonstrates the importance of quantitative study of cellular heterogeneity in drug uptake and its potential application in drug schedule design, response prediction and therapy modulation. Copyright © 2014 John Wiley & Sons, Ltd.     

Stereoselective Synthesis of Alkenyl Alcohols Using Dissolving Metal (Ca,Na) Reduction

Use of the calcium-ethylenediamine and sodium-liquid ammonia reduction systems for the ring opening of dihydropyran derivatives was studied. (Z)-Alkenyl alcohols and (E)-alkenyl alcohols were stereoselectively synthesized respectively.     

Reductive Cleavage of S-S Bond by Samarium Diiodide: A Novel Method for the Synthesis of Disulfides

Samarium diiodide reductively cleaves the S-S bond of sodium alkyl thiosulfates to give the corresponding disulfides in moderate to good yields under mild and neutral conditions.     

Dual template method to prepare hierarchical porous carbon nanofibers for high-power supercapacitors

Hierarchical porous carbon nanofibers serving as electrode materials are prepared through carbonization and hydrofluoric acid treatment of polyacrylonitrile-based electrospinning involving dual templates. The hierarchical porous structures are synergistically tailored by varying template contents in the spinning solution. The carbon nanofibers prepared from the electrospinning of polyacrylonitrile containing 15/15 wt.% polymethylmethacrylate/tetraethyl orthosilicate exhibit the largest specific surface area (699 m² g^?1) and microporous volume (0.196 cm³ g^?1). In 6 M KOH electrolyte, a symmetrical supercapacitor equipped with the hierarchical porous carbon nanofibers demonstrates its high-end specific capacitance of 170 F g^?1, superior rate capability, and high-power density output up to 14.7 kW kg^?1. Cycling evolution indicates capacitance fading is only 5.8 % of initial capacitance at a current density of 1 A g^?1 even after 8,000 cycles. The excellent electrochemical performances of the carbon nanofiber are mainly ascribed to the optimized pore size distributions of both micropores and mesopores and the unique hierarchical pore structures possessed by abundant micropores.     

Novel Synthetic Approach Toward C‐Substituted Piperazine Derivatives via C‐N Bonds Formation of α‐Bromoarylethanones and Ethanolamine

A new method for the synthesis of novel C‐substituted piperazine derivatives bearing aryl substituents on 2,6‐C positions has been developed by one‐pot three‐component sequential reaction of α‐bromoarylethanones with ethanolamine in the presence of formic acid. The structure of the novel compounds was established by nuclear magnetic resonance (NMR), mass spectrometry (MS), and elemental analysis. In addition, the crystal structure of 4e was determined by single X‐ray crystallography and a possible reaction mechanism was proposed.