Exploring the Condensation Reaction between Aromatic Nitriles and Amino Thiols To Optimize In Situ Nanoparticle Formation for the Imaging of Proteases and Glycosidases in Cells

The condensation reaction between 6-hydroxy-2-cyanobenzothiazole (CBT) and cysteine has been shown for various applications such as site-specific protein labelling and in vivo cancer imaging. This report further expands the substrate scope of this reaction by varying the substituents on aromatic nitriles and amino thiols and testing their reactivity and ability to form nanoparticles for cell imaging. The structure–activity relationship study leads to the identification of the minimum structural requirement for the macrocyclization and assembly process in forming nanoparticles. One of the scaffolds made of 2-pyrimidinecarbonitrile and cysteine joined by a benzyl linker was applied to design fluorescent probes for imaging caspase-3/7 and β-galactosidase activity in live cells. These results demonstrate the generality of this system for imaging hydrolytic enzymes.     

介质材料二次电子发射特性对微波击穿的影响

以介质填充的平行板放电结构为例,本文主要研究了介质填充后微波低气压放电和微放电的物理过程.为了探究介质材料特性对微波低气压放电和微放电阈值的影响,本文采用自主研发的二次电子发射特性测量装置,测量了7种常见介质材料的二次电子发射系数和二次电子能谱.依据二次电子发射过程中介质表面正带电的稳定条件,计算了介质材料稳态表面电位与二次电子发射系数以及能谱参数的关系.在放电结构中引入与表面电位相应的等效直流电场后,依据电子扩散模型和微放电中电子谐振条件,分别探讨了介质表面稳态表面电位的大小对微波低气压放电和微放电阈值的影响.结果表明,介质材料的二次电子发射系数以及能谱参数越大,介质材料的稳态表面电位也越大,对应的微波低气压放电和微放电阈值也越大.所得结论对于填充介质的选择有一定的理论指导价值.     

Design and experimental validation of a nonlinear controller for underactuated surface vessels

Nonlinear Dynamics - This paper addresses the problem of trajectory tracking control of an underactuated surface vessel moving in a two-dimensional space in the presence of unknown disturbances. In...     

Establishment and validation of an SIL-IS LC–MS/MS method for the determination of ibuprofen in human plasma and its pharmacokinetic study

In this work, we developed and validated a highly sensitive, rapid and stable LC–MS/MS method for the determination of ibuprofen in human plasma with ibuprofen-d3 as a stable isotopically labeled internal standard (SIL-IS). Human plasma samples were prepared by one-step protein precipitation. The chromatographic separation was achieved on a Poroshell 120 EC-C₁₈ (2.1 × 50 mm, 2.7 μm). Aqueous solution (containing 0.05% acetic acid and 5 mm NH₄Ac) and methanol were selected as the mobile phase with gradient elution. An electrospray ionization source was applied and operated in negative ion mode. Multiple reaction monitoring mode was used for quantification using target fragment ions m/z 205.0 → 161.1 for ibuprofen and m/z 208.0 → 164.0 for SIL-IS, respectively. This method exhibited a linear range of 0.05–36 μg/ml for ibuprofen with correlation coefficient >0.99. Mean recoveries of ibuprofen in human plasma ranged from 78.4 to 80.9%. The RSD of intra- and inter-day precision were both < 5%. The accuracy was between 88.2 and 103.67%. The matrix effect was negligible in human plasma, including lipidemia and hemolytic plasma. A simple, efficient and accurate LC–MS/MS method was successfully established and applied to a pharmacokinetic study in healthy Chinese volunteers after a single oral administration of ibuprofen granules.     

黏弹性接触界面端附近的奇异应力场

研究蠕变加载条件下线黏弹性材料接触界面端附近的奇异应力场问题.考虑接触界面的摩擦,假设界面端的滑移方向不改变,相对滑移量微小,且其与位移同量级,由此线性化局部边界条件,根据对应原理得到Laplace变换域中的界面端应力场,导出时域中奇异应力场的卷积积分表达式.对卷积积分核函数进行数值反演,考虑接触材料的两类组合,一是持久模量具有量级上的差异,另一是持久模量接近相同.算例结果证实核函数可以用准弹性法求得的解析式较准确地近似.在此基础上,利用积分中值定理,并引入各应力分量的修正系数,得到黏弹性奇异应力场的简化式.结合核函数的数值反演结果分析修正系数表达式的取值范围,得到如下结论,若两相接触材料的持久模量相差很大,可以采用准弹性解的解析式较准确地描述界面端的奇异应力场;一般情况下,应力场不存在统一的奇异值和应力强度系数,当采用类似于准弹性解的表达式近似给出黏弹性应力场时,可以估计此近似描述的误差限.文中最后采用有限元分析黏弹性板端部嵌入部位的应力场,算例包括了黏弹性板与弹性金属支承、黏弹性板与黏弹性垫层所形成的滑移接触界面端,利用黏弹性有限元的数值结果验证理论分析所得结论的有效性.      

Miktoarm star‐shaped poly(lactic acid) copolymer: Synthesis and stereocomplex crystallization behavior

The miktoarm star‐shaped poly(lactic acid) (PLA) copolymer, (PLLA)₂‐core‐(PDLA)₂, was synthesized via stepwise ring‐opening polymerization of lactide with dibromoneopentyl glycol as the starting material. ¹H NMR and FTIR spectroscopy proved the feasibility of synthetic route and the successful preparation of star‐shaped PLA copolymers. The results of FTIR spectroscopy and XRD showed that the stereocomplex structure of the copolymer could be more perfect after solvent dissolution treatment. Effect of chain architectures on crystallization was investigated by studying the nonisothermal and isothermal crystallization of the miktoarm star‐shaped PLA copolymer and other stereocomplexes. Nonisothermal differential scanning calorimetry and polarizing optical microscopy tests indicated that (PLLA)₂‐core‐(PDLA)₂ exhibited the fastest formation of a stereocomplex in a dynamic test due to its special structure. In isothermal crystallization tests, the copolymer exhibited the fast crystal growth rate and the most perfect crystal morphology. The results reveal that the unique molecular structure has an important influence on the crystallization of the miktoarm star‐shaped PLA copolymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 814–826     

Synthesis of a highly active amino‐functionalized Fe3O4@SiO2/APTS/Ru magnetic nanocomposite catalyst for hydrogenation reactions

An amino‐functionalized silica‐coated Fe₃O₄ nanocomposite (Fe₃O₄@SiO₂/APTS) was synthesized. The Fe₃O₄@SiO₂ microspheres possessed a well‐defined core–shell structure, uniform sizes and high magnetization. An immobilized ruthenium nanoparticle catalyst (Fe₃O₄@SiO₂/APTS/Ru) was obtained after coordination and reduction of Ru³⁺ on the Fe₃O₄@SiO₂/APTS nanocomposite. The Ru nanoparticles were not only ultra‐small with nearly monodisperse sizes but also had strong affinity with the surface of Fe₃O₄@SiO₂/APTS. The obtained catalyst exhibited excellent catalytic performance for the hydrogenation of a variety of aromatic nitro compounds, even at room temperature. Moreover, Fe₃O₄@SiO₂/APTS/Ru was easily recovered using a magnetic field and directly reused for at least five cycles without significant loss of its activity.     

High efficiency of Mn–Ce‐modified TiO2 catalysts for the low‐temperature oxidation of Hg0 under a reducing atmosphere

Manganese‐ and cerium oxide‐modified titania catalysts were prepared by the deposition precipitation for the removal of elemental mercury (Hg⁰) from simulated yellow phosphorus off‐gas at low temperature. In addition, these catalysts were characterized by X‐ray diffraction, Brunauer–Emmett–Teller measurements, X‐ray photoelectron spectroscopy and field‐emission scanning electron microscope to determine the surface morphology of the obtained compounds and explore their formation mechanism. The results revealed that a Mn–Ce loading and reaction temperature of 10% and 150 °C, respectively, as well as a Mn/Ce molar ratio of 2:1, led to an optimal efficiency for the oxidation of elemental mercury. Furthermore, the effects of flue gas components were investigated. The presence of O₂ clearly promoted the oxidation of Hg⁰. A CO atmosphere did not affect the Hg⁰ oxidation, when compared with N₂, whereas the presence of H₂S and water vapor inhibited the oxidation process. Furthermore, the X‐ray photoelectron spectroscopy spectra of Hg 4f revealed that the elemental mercury adsorbed by the catalyst is present as HgO. Finally, the Hg⁰ catalytic oxidation mechanism was discussed on the basis of the experimental results and characterization analysis.     

Generation and Reactivity of a One-Electron-Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand

The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [Mn^V(TAML)(N-Mes)]⁻ ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC₆H₄)₃N ]^+.[SbCl₆]⁻ and the resulting Mn^VI species readily undergoes H-atom transfer and nitrene transfer reactions.