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.     

Effect of polyethylene glycol on corrosion of fresh macroporous silicon in 1.0 M NaOH and application in determination of porosity and thickness by gravimetric measurement

Abstract

This work presents on improvement in gravimetric measurement for determining the porosity and thickness of microporous silicon. Herein, the corrosion of fresh macroporous silicon (f-MPSi) in 1.0?M NaOH with different concentrations of polyethylene glycol (PEG 200/400/600) was studied by weight loss measurement and scanning electron microscopy (SEM). The results showed that the corrosion rate decreased with increasing polyethylene glycol concentration, and increased with an increase in temperature. Polyethylene glycol can inhibit the corrosion of f-MPSi in NaOH solution. Moreover, 1.0?M NaOH/PEG 600 (10%) can be used as the optimized solution to remove f-MPSi for measuring its porosity and thickness by gravimetric measurement.     

基于连续量子级联激光器的1103.4cm–1处NH3混叠吸收光谱特性研究

由于NH3在大气气溶胶化学中具有重要作用,所以快速和精确反演NH3浓度对环境问题非常重要.本文以9.05μm的室温连续量子级联激光器(quantum cascade laser,QCL)作为光源,采用波长扫描直接吸收可调谐二极管激光吸收光谱(tunable diode laser absorption spectroscopy,TDLAS)技术,研究了QCL在1103.4 cm–1的光谱特性,获得了激光器控制的温度电流与波长的关系.设计了QCL二级温控的低压实验平台,测量氨气在1103.4 cm–1处的6条混叠吸收线,在降低压强的情况下谱线展宽变小,使混叠光谱分离,由此计算各条吸收线的线强,进一步对测量不确定度进行分析.针对混叠严重的光谱提出了低压分离单光谱精确反演气体浓度的方法,并进行了实验验证.通过与HITRAN数据库进行结果对比,得出氨气在1103.4 cm–1的实验测量线强值与数据库偏差为2.71%-4.71%,实验测量线强值的不确定度在2.42%-8.92%,极低压条件下反演浓度与实际值的偏差在1%-3%.