An Unusual Triphenylphosphine Oxide Catalyzed Stereoselective 1,3‐Dichlorination of Unsaturated Ketoesters

An unusual Ph₃PO‐catalyzed stereoselective 1,3‐dicholorination of an unsaturated ketoester has been developed. The novel activation mode involved in this cascade reaction can promote consecutively elusive transformations. The products were obtained with good yields and excellent stereoselectivities. This reaction makes important complementation to the limitations associated with the field of dichlorination.     

A Supercharged Fluorescent Protein as a Versatile Probe for Homogeneous DNA Detection and Methylation Analysis

Supercharged proteins are a new class of functional proteins with exceptional stability and potent ability to deliver bio‐macromolecules into cells. As a proof‐of‐principle, a novel application of supercharged proteins as a versatile biosensing platform for nucleic acid detection and epigenetics analysis is presented. Taking supercharged green fluorescent protein (ScGFP) as the signal reporter, a simple turn‐on homogenous method for DNA detection has been developed based on the polyionic nanoscale complex of ScGFP/DNA and toehold strand displacement. This assay shows high sensitivity and potent ability to detect single‐base mismatch. Furthermore, combined with bisulfite conversion, this ScGFP‐based assay was further applied to analyze site‐specific DNA methylation status of genomic DNA extracted from real human colon carcinoma tissue sample with ultrahigh sensitivity (4 amol methylated DNA).     

Turn-on fluorescence sensing of cyanide ions in aqueous solution简

A sensitive fluorescent probe, 2,2＇-bisbenzimidazole （L）, for CN has been developed. This structurally simple receptor displays great selectivity for the cyanide anion over other common inorganic anions in an aqueous environment. In addition, further study demonstrates the lower detection of the fluorescence response of the sensor to CN is in 10 9 mol/L range. Thus, the present probe should be applicable as a practical system for the monitoring of cyanide concentrations in aqueous samples.     

Accurate prediction of relative binding affinities of a series of HIV-1 protease inhibitors using semi-empirical quantum mechanical charge

A major challenge in computer-aided drug design is the accurate estimation of ligand binding affinity. Here, a new approach that combines the adaptive steered molecular dynamics (ASMD) and partial atomic charges calculated by semi-empirical quantum mechanics (SQMPC), namely ASMD-SQMPC, is suggested to predict the ligand binding affinities, with 24 HIV-1 protease inhibitors as testing examples. In the ASMD-SQMPC, the relative binding free energy (ΔG) is reflected by the average maximum potential of mean force (<PMF>_max) between bound and unbound states. The correlation coefficient (R²) between the <PMF>_max and experimentally determined ΔG is 0.86, showing a significant improvement compared with the conventional ASMD (R² = 0.52). Therefore, this study provides an efficient approach to predict the relative ΔG and reveals the significance of precise partial atomic charges in the theoretical simulations.     

Hierarchical self-assembly of 3D amphiphilic discrete organoplatinum(Ⅱ)metallacage in water

Here we described the design and synthesis of a discrete 3D amphiphilic metallacage 4,in which the tetragonal prismatic frameworks act as the hydrophobic cores and the poly(ethylene glycol)(PEG)chains as the hydrophilic tails.The structure of 4 was characterized by 1H NMR,31P NMR and electrospray ionization time-of-flight mass spectrometry(ESI-TOF-MS).Notably,4 with its Iong PEG tails was subsequently ordered into micelles at a low concentration(1.20×10^-6 mol/L)in water.As the concentration and cultivation time increased,the micelles can further self-assembly into nanofibers and nanoribbons.Considering the dynamic property of the coordination bond,these structures show reversible transformation under external stimuli.     

New cadinane sesquiterpenoids from Mikania micrantha

Abstract

Chemical investigation of the aerial parts of Mikania micrantha led to the isolation of eight sesquiterpenoids and ten diterpenoids, including five cadinane sesquiterpenoids (1?5), three bisabolene sesquiterpenoids (6???8), nine ent-kaurane diterpenoids (9–17), and an abietane diterpenoid (18). Among them, 1???3 are new and feature a rare lactone or furan ring derived from C-6 isopropyl group side chain. Compound 18 was isolated from genus Mikania for the first time, and was also the first example of abietane-type diterpenoids from this plant. Their structures were elucidated on the basis of extensive spectroscopic analyses (1D and 2D NMR, HRESIMS, and ECD). All compounds were examined for their inhibitory effects on lipopolysaccharide (LPS)-induced nitric oxide (NO) production in RAW 264.7 macrophage cells, and compound 18 exhibited pronounced inhibition on NO production (IC₅₀ = 11.04?µM), being comparable to the positive control, quercetin (IC₅₀ = 11.15?µM).     

A Single‐Atom Manipulation Approach for Synthesis of Atomically Mixed Nanoalloys as Efficient Catalysts

Synthesis of well‐defined atomically mixed alloy nanoparticles on desired substrates is an ultimate goal for their practical application. Herein we report a general approach for preparing atomically mixed AuPt, AuPd, PtPd, AuPtPd NAs(nanoalloys) through single‐atom level manipulation. By utilizing the ubiquitous tendency of aggregation of single atoms into nanoparticles at elevated temperatures, we have synthesized nanoalloys on a solid solvent with CeO₂ as a carrier and transition‐metal single atoms as an intermediate state. The supported nanoalloys/CeO₂ with ultra‐low noble metal content (containing 0.2 wt % Au and 0.2 wt % Pt) exhibit enhanced catalytic performance towards complete CO oxidation at room temperature and remarkable thermostability. This work provides a general strategy for facile and rapid synthesis of well‐defined atomically mixed nanoalloys that can be applied for a range of emerging techniques.     

Thermal decomposition behavior of naphthalene-labeled polyethylene

Pyrolysis–GC/mass spectrometry experiments reveal that naphthalene groups attached to maleated polyethylene as the 1-naphthylethyl ester are stable for relatively long periods of time at 170°C. Decomposition can be detected for samples heated for 2.0 min at 200°C, but even at that temperature, the extent of decomposition is very small. At higher temperatures, two of the decomposition products from the labeled polymer are readily understood: 1-vinylnaphthalene and 1-naphthylethanol can form by reactions that are well-precedented in the organic chemistry literature. At 200°C, only naphthalene is formed, which requires scission of the bond between the naphthyl ring and the C₁ carbon of the ethyl group. We suggest two possible pathways for this reaction. © 1996 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 34:2045–2049, 1996     

基于特征圆单目视觉的飞机舵面角位移标定技术

提出了一种基于特征圆单目视觉的非接触式飞机舵面角位移标定技术。用一台数码摄像机对固定在飞机舵面上的特征圆进行拍照,经数字图像处理后确定五个特征点的坐标,利用针孔成像和射影变换原理建立物像空间坐标解算模型,计算出特征圆的法线相对方向和圆心的相对位置,舵面角位移由该圆的法线方向确定。仿真结果表明,该方法具有标定过程简单、实时、快速和准确的特点,标定精度可达到0.1°。该技术也可用于航天器上实时测量交会对接时的相对位姿参数。     

多棱锥镜产生多光束干涉场的理论和实验研究

提出了一种使用多棱锥镜和多棱台镜产生多束相干光形成二维和三维光学格子的方法。理论分析和数值模拟了多束轴对称平面波干涉产生的二维及三维点阵结构的特性,得到了光场分布随光束数增加的关系,发现随着干涉光数目的增加,干涉场会复杂变化,当棱锥棱数足够多近似于一个圆锥时,干涉场会变为同心圆结构的贝塞尔光束的场分布。实验上使用多棱锥和多棱台镜进行了多光束干涉实验,得到了多束轴对称平面波干涉形成的光学格子,将数值模拟与实验结果进行了比较,二者完全吻合。