Metal‐Free Reaction of ortho‐Carbonylated Alkynyl‐Substituted Arylaldehydes with Common Amines: Selective Access to Functionalized Isoindolinone and Indenamine Derivatives

Herein we describe a reaction of ortho‐carbonylated alkynyl‐substituted arylaldehydes with common primary amines that can provide functionalized isoindolinone and 3‐hydroxylindenamine products in high yields. Depending on the substituent size of primary amines, two distinct reaction pathways were exploited selectively, that are, an initial aza‐conjugate addition followed by hydrogen transfer to access isoindolinone framework and a unique oxa‐conjugate addition followed by Petasis–Ferrier rearrangement to afford indenamine derivatives. In the presence of Et₃N, the reaction property of small primary amines was changed, proceeding to afford 3‐hydroxylindenamine derivatives efficiently. These products contain interesting substructures that exist in many natural products and bioactive molecules. The reaction features contain the use of transition‐metal‐free catalysts, simple operation, broad substrate scope, and product diversity.     

Rational Design for Rotaxane Synthesis through Intramolecular Slippage: Control of Activation Energy by Rigid Axle Length

We describe a new concept for rotaxane synthesis through intramolecular slippage using π‐conjugated molecules as rigid axles linked with organic soluble and flexible permethylated α‐cyclodextrins (PM α‐CDs) as macrocycles. Through hydrophilic–hydrophobic interactions and flipping of PM α‐CDs, successful quantitative conversion into rotaxanes was achieved without covalent bond formation. The rotaxanes had high activation barrier for their de‐threading, so that they were kinetically isolated and derivatized even under conditions unfavorable for maintaining the rotaxane structures. ¹H NMR spectroscopy experiments clearly revealed that the restricted motion of the linked macrocycle with the rigid axle made it possible to control the kinetic stability by adjusting the length of the rigid axle in the precursor structure rather than the steric bulkiness of the stopper unit.     

Laws of Large Numbers for Cesàro alpha-integrable Random Variables under Dependence Condition AANA or AQSI

Both residual Cesàro alpha-integrability (RCI( α)) and strongly residual Cesàro alpha-integrability (SRCI(α)) are two special kinds of extensions to uniform integrability, and both asymp-totically almost negative association (AANA) and asymptotically quadrant sub-independence (AQSI) are two special kinds of dependence structures. By relating the RCI(α) property as well as the SRCI(α) property with dependence condition AANA or AQSI, we formulate some tail-integrability conditions under which for appropriate α the RCI(α) property yields L1-convergence results and the SRCI(α) property yields strong laws of large numbers, which is the continuation of the corresponding literature.     

Multi-stacked organic light-emitting diodes using zinc oxide nanoparticle interfacial layers

Stacked organic light-emitting diodes (SOLEDs) with 30-nm nanoparticle (NP) interfacial layers were investigated. Zinc oxide (ZnO) was used as an interfacial layer between two green polymer (GP) layers. SOLEDs with NP interfacial layers had higher device efficiency than did a single-unit device due to the high probability of exciton recombination that originated from the Auger electron-assisted energy up-conversion process. Although the current density and luminance of SOLEDs with ZnO NP interfacial layers were smaller than those of the reference device, the efficiency was doubled because of the big band alignment difference and the large band gap between GP and ZnO NP interfacial layers, which induced more radiative-exciton recombination.     

Synthesis and antitumor and antibacterial evaluation of fluoroquinolone derivatives(Ⅲ):Mono- and bis-Schiff-bases

To further explore an efficient modified route for the shift from an antibacterial fluoroquinolone to an antitumor one,mono-Schiff bases 6a-6h related to ciprofloxacin C3 carbonylhydrazone and bis-Schiff bases 4a-4h corresponding to C3/C7 carbonylhydrazone/hydrazone attached on a skeleton of ciprofloquinolone were designed and synthesized,and their in vitro antitumor activity against CHO,HL60,L1210 cells and antibacterial activity against Staphylococcus aureus and Escherichia coli were also reported.     

固态光聚合反应研究进展

光引发的固态聚合反应一直是令人感兴趣的研究领域.本文综述了固态光聚合的研究进展.着重介绍了双炔类体系,二烯类体系以及(甲基)丙烯酸酯体系的固态光聚合的研究工作以及应用前景.     

Development and validation of an LC/MS/MS method for simultaneous determination of shionone and epi‐friedelinol in rat plasma for pharmacokinetic study after oral administration of Aster tataricus extract

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method was developed and validated using spinasterol as the internal standard (IS) for the simultaneous determination of shionone and epi‐friedelinol in rat plasma. Plasma samples were pretreated using liquid–liquid extraction with ethyl ether. Chromatographic separation was achieved on a C₁₈ column (100 × 2.1 mm, 5 μm) with an isocratic elution consisting of acetonitrile–0.1% formic acid water (75:25, v/v) at a flow rate of 0.30 mL/min. Detection was performed under the selected reaction monitoring scan using an electrospray ionization in the positive ion mode. The mass transitions were as follows: m/z 427.4 → 95.1 for shionone, m/z 411.4 → 205.2 for epi‐friedelinol and m/z 395.3 → 105.2 for IS. All calibration curves exhibited good linearity (r > 0.995) over the concentration range for both components. The intra‐ and inter‐day precisions at three QC and lower limit of quantitation levels were both <10.21% in terms of relative standard deviation, and the accuracy ranged from ?7.13 to 8.02% in terms of relative error. The extraction recoveries of the compounds ranged from 82.07 to 89.81%. The developed method was successfully applied to the pharmacokinetic study of shionone and epi‐friedelinol after oral administration of Aster tataricus extract to rats. Copyright © 2015 John Wiley & Sons, Ltd.