Generic applications of 13C‐detected NMR diffusion to formulated systems with suppression of thermal convection induced by proton decoupling

Fast and effective structural/compositional analysis on formulated systems represents one of the major challenges encountered in analytical science. ¹³C‐detected diffusion represents a promising tool to tackle the aforementioned challenges, particularly in industry. Toward exploring the generic applications of ¹³C‐detected diffusion, thermal convection induced by ¹H decoupling has been identified as a key factor that resulted in significantly reduced resolution in the diffusion dimension. Optimization of experimental parameters and utilization of double‐stimulated echo‐based pulse sequence both can effectively suppress the thermal convection caused by the ¹H decoupling, the success of which allows robust and generic applications of ¹³C‐detected diffusion to systems from mixtures of small molecules, polymer blends, and copolymers to actual complex formulated systems. The method is particularly powerful in differentiating small molecules from polymers, polymer blends from copolymers, and end‐group analysis. Copyright © 2016 John Wiley & Sons, Ltd.     

Fabrication and luminescent properties of Eu(BMPPA)3BPy complex and its functionalized silica nanocomposites

Luminescent silica nanocomposites functionalized with a Eu-complex have been prepared and characterized.The europium complex is composed of 2,2'-bipyridyl(BPy) and 2-(4-bromomethyI)-phenylpropionic acid(BMPPA),which contains highly active benzyl bromide substituents and can covalently bind with poly(4-vinylpyridine)(P4VP)-modified silica nanoparticles(nanoSiO_2P4VP) to form nanoSiO_2P4VPEuBPy composites.Microscopic images revealed that the nanoSiO_2P4VPEuBPy composites easily formed aggregates,due to an inter-particle binding caused by the benzyl bromide among the composites.The as-prepared nanocomposites showed the typical emissions of Eu(III) ions at the wavelengths from 580 nm to 750 nm designated to the ~5D_0→~7F_n transitions.Time-resolved fluorescence decay measurements revealed that the emission lifetime was approximately 0.204 ms and 0.576 ms for the nanoSiO_2EuBPy composites,a little shorter than that in the Eu(BMPPA)_3BPy complex.     

Mono‐ and Dinuclear Phosphorescent Rhenium(I) Complexes: Impact of Subcellular Localization on Anticancer Mechanisms

Elucidation of relationship among chemical structure, cellular uptake, localization, and biological activity of anticancer metal complexes is important for the understanding of their mechanisms of action. Organometallic rhenium(I) tricarbonyl compounds have emerged as potential multifunctional anticancer drug candidates that can integrate therapeutic and imaging capabilities in a single molecule. Herein, two mononuclear phosphorescent rhenium(I) complexes ( Re1 and Re2 ), along with their corresponding dinuclear complexes ( Re3 and Re4 ), were designed and synthesized as potent anticancer agents. The subcellular accumulation of Re1–Re4 was conveniently analyzed by confocal microscopy in situ in live cells by utilizing their intrinsic phosphorescence. We found that increased lipophilicity of the bidentate ligands could enhance their cellular uptake, leading to improved anticancer efficacy. The dinuclear complexes were more potent than the mononuclear counterparts. The molecular anticancer mechanisms of action evoked by Re3 and Re4 were explored in detail. Re3 with a lower lipophilicity localizes to lysosomes and induces caspase‐independent apoptosis, whereas Re4 with higher lipophilicity specially accumulates in mitochondria and induces caspase‐independent paraptosis in cancer cells. Our study demonstrates that subcellular localization is crucial for the anticancer mechanisms of these phosphorescent rhenium(I) complexes.     

Copper‐Catalyzed Difunctionalization of Activated Alkynes by Radical Oxidation–Tandem Cyclization/Dearomatization to Synthesize 3‐Trifluoromethyl Spiro[4.5]trienones

A copper‐catalyzed difunctionalizing trifluoromethylation of activated alkynes with the cheap reagent sodium trifluoromethanesulfinate (NaSO₂CF₃ or Langlois’ reagent) has been developed incorporating a tandem cyclization/dearomatization process. This strategy affords a straightforward route to synthesis of 3‐(trifluoromethyl)‐spiro[4.5]trienones, and presents an example of difunctionalization of alkynes for simultaneous formation of two carbon–carbon single bonds and one carbon–oxygen double bond.     

In-situ SiN combined with etch-stop barrier structure for high-frequency AlGaN/GaN HEMT

The etch-stop structure including the in-situ SiN and AlGaN/GaN barrier is proposed for high frequency applications.The etch-stop process is realized by placing an in-situ SiN layer on the top of the thin AlGaN barrier.F-based etching can be self-terminated after removing SiN,leaving the AlGaN barrier in the gate region.With this in-situ SiN and thin barrier etch-stop structure,the short channel effect can be suppressed,meanwhile achieving highly precisely controlled and low damage etching process.The device shows a maximum drain current of 1022 mA/mm,a peak transconductance of 459 mS/mm,and a maximum oscillation frequency(fmax)of 248 GHz.     

The regularity of the multiple higher-order poles solitons of the NLS equation

Based on the inverse scattering method, the formulae of one higher-order pole solitons and multiple higher-order poles solitons of the nonlinear Schrödinger equation (NLS) equation are obtained. Their denominators are expressed as , where is a matrix frequently constructed for solving the Riemann-Hilbert problem, and the asterisk denotes complex conjugate. We take two methods for proving is invertible. The first one shows matrix is equivalent to a self-adjoint Hankel matrix , proving . The second one considers the block-matrix form of , proving . In addition, we prove that the dimension of is equivalent to the sum of the orders of pole points of the transmission coefficient and its diagonal entries compose a set of basis.