Thermoresponsive poly(ionic liquid): Controllable RAFT synthesis,thermoresponse, and application in dispersion RAFT polymerization

The thermoresponsive poly(ionic liquid) of poly[1‐(4‐vinylbenzyl)‐3‐methylimidozolium tetrafluoroborate] trithiocarbonate (P[VBMI][BF₄]‐TTC) showing the soluble‐to‐insoluble phase transition in the methanol/water mixture at the upper critical solution temperature (UCST) was synthesized by solution RAFT polymerization and the synthesized P[VBMI][BF₄]‐TTC was employed as macro‐RAFT agent to mediate the RAFT polymerization under dispersion condition to afford the thermoresponsive diblock copolymer nanoparticles of poly[1‐(4‐vinylbenzyl)‐3‐methylimidozolium tetrafluoroborate]‐b‐polystyrene (P[VBMI][BF₄]‐b‐PS). The controllable solution RAFT polymerization was achieved as indicated by the linearly increasing polymer molecular weight with the monomer conversion and the narrow molecular weight distribution. The P[VBMI][BF₄]‐TTC macro‐RAFT agent mediated dispersion polymerization afforded the P[VBMI][BF₄]‐b‐PS nanoparticles, the size of which was uncorrelated with the polymerization degree of the P[VBMI][BF₄] block. Several parameters including the polymerization degree, the polymer concentration and the water content in the solvent of the methanol/water mixture were found to be correlated with the UCST of the poly(ionic liquid). The synthesized poly(ionic liquid) is believed to be a new thermos‐responsive polymer and will be useful in material science. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 945–954     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

A New Eremophilane Sesquiterpenoid from Ligularia przewalskii

Chemistry of Natural Compounds - A new eremophilane sesquiterpenoid, 3β-acetoxy-6α-angeloyloxy-eremophil-1(10),7(11),8(9)-trien-12,8-olide (1), was isolated from Ligularia przewalskii....     

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.