Site-selective Csp3-H aryloxylation of natural product Tanshinone IIA and its analogues

A novel catalyst-free Csp³-H aryloxylation approach allowing for rapid installation of a wide range of aryloxyl groups regioselectively at the C-4 position of Tanshinone IIA under simple and mild conditions was developed. This unique protocol exhibited atom-/step-economy, low cost, high efficiency and robust functional-group tolerance, which will greatly facilitate to diversify the A-ring of the bioactive natural product.     

Electrochemical Determination of Uric Acid Using a Multiwalled Carbon Nanotube Platinum–Nickel Alloy Glassy Carbon Electrode

Platinum–nickel nanoparticles were synthesized by a reduction procedure. The Pt–Ni/C composite was characterized by X-ray diffraction, infrared spectroscopy, transmission electron microscopy, and electrochemical analysis. The measurements show that the Pt–Ni/multiwalled carbon nanotubes provided higher electrocatalytic activity for the oxidation of uric acid than Pt–Ni/carbon black. The sensor prepared from the characterized material provided a long linear dynamic range from 0.1 to 240.4?µM with a detection limit of 0.03?µM and a sensitivity of 41.21?µA?mM^?1?cm^?2. The reported modified electrode also provided excellent selectivity, good stability, and satisfactory reproducibility for the determination of uric acid.     

An isothermal strand displacement amplification strategy for nucleic acids using junction forming probes and colorimetric detection

The authors describe a method for DNA target recognition and signal amplification that is based on the target-induced formation of a three way junction. The subsequent assembly of two DNA probes releases the inhibitory strand and triggers a downstream strand displacement amplification. This causes the formation of a G-rich single sequence that binds to a hemin monomer with its peroxidase-mimicking properties. The resulting peroxidase (POx) activity is quantified by using H₂O₂ and TMB as the substrate. In the presence of an inhibitor, in contrast, the POx-like activity is strongly reduced. This forms the basis for a highly sensitive DNA assay. It has a 0.8 pM detection limit when operated at a wavelength of 450 nm and was applied to the isothermal determination of target DNA with high selectivity.

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Graphical abstract Schematic of the assay: Introduction of target results in the formation of a three way junction. The subsequent assembly of two probes releases the inhibitory strand and triggers a downstream strand displacement amplification, generating amount of G-rich single sequence which causes peroxidase-mimicking activity on binding to a hemin monomer.

     

Metal-Chelate Affinity Precipitation with Thermo-Responsive Polymer for Purification of <Emphasis Type="Italic">ε</Emphasis>-Poly-<Emphasis Type="SmallCaps">l</Emphasis>-Lysine

ε-Poly-l-lysine (ε-PL) is a natural preservative for food processing industry. A thermo-responsive polymer, attached with Cu²⁺ or Ni²⁺, was prepared for metal-chelate affinity precipitation for purification of ε-PL. The low critical solution temperatures (LCSTs) of these polymers were close to the room temperature (31.0–35.0 °C). The optimal adsorption conditions were as follows: pH 4.0, 0 mol/L NaCl, ligand density 75.00 μmol/g, and 120 min. The ligand Cu²⁺ showed a stronger affinity interaction with ε-PL and the highest adsorption amount reached 251.93 mg/g polymer. The elution recovery of ε-PL could be 98.42% with 0.50 mol/L imidazole (pH = 8.0) as the eluent. The method could purify ε-PL from fermentation broth and the final product was proved as electrophoretic pure by SDS-PAGE. Moreover, these affinity polymers could be recycled after the purification of ε-PL and the recoveries were above 95.00%.

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Graphical Abstract Scheme for affinity precipitation of ε-PL

     

Broadband reflective liquid crystal films induced by facile temperature-dependent coexistence of chiral nematic and TGB phase

A wide pitch gradient covering the near infrared region (750.0–2500.0 nm) were facilely obtained by simple controlling temperature difference to LC mixtures with a twist grain boundary (TGB)–N* phase transition. After the pitch gradient formed, the structure of broad reflective bandwidth was fixed through polymerisation of monomers in mixtures by UV irradiation. It was found that the temperature difference between the up and down side of the samples was critical to form wide-pitch gradient distribution. Additionally, the reflection wavelength and bandwidth of films could be adjusted by the applied temperature difference with the widest bandwidth up to 1750 nm. This simple method for the preparation of broad reflective films was expected to be used in the fields like architectural energy conservation or infrared shield.     

SOME DYNAMICAL PROPERTIES OF THE UNIVERSAL UNFOLDING OF PITCHFORK

From the point of view of dynamics,the phenomenon of mode jumpingin the imperfect pitchfork problem is discussed.The dynamical mechanism of modeljumping of structures,such as plate and shell,that is brought about by the extremurninstability,is explained.Finally,we give numerical simulation to show the validity ofour results.     

煤在瓦斯一维渗流作用下的初次破坏

作者观察了煤在瓦斯一维渗流作用下的初次破坏,发现破坏煤体呈球冠状;临界破坏瓦斯超压取决于卸载条件,煤型的强度、半径和长度,以及煤型所受的侧压,但与瓦斯吸附特性无关。对实验例进行了数值分析,结果表明煤体的破坏属于拉伸破坏;卸载速率的增高,侧向围压的减小与煤型几何半径的增大将使得煤体在瓦斯渗流作用下更易于破坏。     

汽车碰撞砼护拦过程的数值模拟

将汽车与砼护拦简化为刚体，给出了描述碰撞过程中车辆三维空间运动的Ｅｕｌｅｒ－Ｌａｇｒａｎｇｅ方程－微分代数方程组，采用半显式外插方法求解上述方程组。数值计算得出的车辆各方向上的最大平均加速度、最大侧倾角、最大俯仰角、车轮沿护拦面的最大爬升值及车辆脱离护拦时的弹出角等结果是从乘员风险和车辆轨迹等多角全面评估砼护拦的安全性能的重要依据。针对美国ＮｅｗＪｅｒｃｙ型砼护拦的实际算例与文献结果吻合较好。     

弯曲狭窄管内血液流的分析

与血管狭窄有关的异常血液动力学特征在血管疾病的发生和发展过程中起着重要的作用,由于血管狭窄和弯曲的综合影响,将会出现一系列有趣的流体力学现象,本文研究具有对称狭窄的弯曲小动脉内定常血液流动,在一定的假设条件下,直接从支配血液流动的Navier-Stokes方程求出问题的摄动解,由此求得弯曲狭窄管內血液流动的轴向速度、二次流速度及压力梯度等分析表达式,并进一步求得轴向和周向血管壁切应力。本文的结果是先前有关狭窄直管和弯曲均匀管流动研究的拓广。     

Convenient synthesis of chiral H4-BINOL via direct hydrogenation of BINOL

<正>A simple,highly effective hydrogenation of chiral BINOL to provide H_4-BINOL in multigram scale with good yield(up to 78% yield) was developed.A series of heterogeneous catalysts was tested in the hydrogenation;;the best result was obtained with 5%Pd/ C in EtOH under the H_2 pressure of 50 bar for 2 h.This method is a more useful method for practical synthesis of optically pure H_4- BINOL than other available methods.