High pressure-promoted cycloadditions of ketene acetals and α,β-unsaturated aldehydes and ketones

Cycloadditions of ketene acetals with α,β-unsaturated carbonyl compounds are strongly promoted by high pressure. The influence of the solvent and the substitution pattern on the product distribution at 12 kBar has been investigated. In the polar solvent, acetonitrile, α,β-unsaturated aldehydes not having large β-substituents, yield mainly cyclobutane aldehydes, which are minor products at normal pressure. The products can be transformed under basic conditions without ring opening.     

PtRuAgCoNi高熵合金纳米颗粒高效电催化氧化5-羟甲基糠醛

5-羟甲基糠醛(HMF)的电催化氧化被认为是合成2,5-呋喃二甲酸(FDCA)最环保、经济和有效的方法之一,它可作为聚呋喃二甲酸乙二醇酯(PEF)的生物基前体。在这项工作中,我们通过低温溶剂热法合成了PtRuAgCoNi高熵合金纳米颗粒,并在不改变颗粒结构和组成的情况下进行了简易的处理以去除表面活性剂。负载在碳载体上的合金纳米催化剂无论是否含有表面活性剂在HMF电催化氧化为FDCA的过程中都表现出比商业Pt/C更好的催化性能。且表面活性剂的去除可以进一步提高其电催化性能,表明高熵合金纳米粒子在电催化和绿色化学中具有广阔的应用前景。     

软机器人的运动行为研究进展

软机器人的出现不仅弥补了传统机器人的缺点,并逐渐成为机器人领域的热点和前沿之一,近年来该领域研究进展十分迅速。本文总结了典型软机器人的运动行为的研究进展,介绍了软机器人按材质类型的分类(包括液晶软机器人、生物分子软机器人、PDMS软机器人、液体软机器人和自振荡凝胶软机器人)及其功能和潜在应用,讨论了当前不同类别软机器人运动的特点和存在的问题,在此基础上展望了软机器人领域面临的机遇、挑战和未来发展方向。     

Flow-induced shear stress and deformation of a core–shell-structured microcapsule in a microchannel

A numerical model was developed and validated to investigate the fluid–structure interactions between fully developed pipe flow and core–shell-structured microcapsule in a microchannel. Different flow rates and microcapsule shell thicknesses were considered. A sixth-order rotational symmetric distribution of von Mises stress over the microcapsule shell can be observed on the microcapsule with a thinner shell configuration, especially at higher flow rate conditions. It is also observed that when being carried along in a fully developed pipe flow, the microcapsule with a thinner shell tends to accumulate stress at a higher rate compared to that with a thicker shell. In general, for the same microcapsule configuration, higher flow velocity would induce a higher stress level over the microcapsule shell. The deformation gradient was used to capture the microcapsule's deformation in the present study. The effect of Young's modulus on the microcapsule shell on the microcapsule deformation was investigated as well. Our findings will shed light on the understanding of the stability of core–shell-structured microcapsule when subjected to flow-induced shear stress in a microfluidic system, enabling a more exquisite control over the breakup dynamics of drug-loaded microcapsule for biomedical applications.     

A sensitive and selective HPLC–MS3 method for therapeutic drug monitoring of meropenem and its validation by comparison with HPLC–MS2 methods

Meropenem, a representative β-lactam antibiotic, is widely used to treat complicated and serious infections. Therefore, it is of great significance to monitor the plasma drug concentration for individualized antimicrobial therapy. This study first describes the development and validation of high-performance liquid chromatography–tandem mass spectrometry cubed method for monitoring meropenem in human plasma. Protein precipitation with methanol and a chromatographic analysis time of 7 min make this method simple and of high throughput. Meropenem was extracted from human plasma with recoveries >94.1%. Calibration curves were linear (R² > 0.995) in the concentration range of 0.5–50 μg/mL. Overall accuracy and precision did not exceed 8.0% as well as no significant matrix effect was observed. The novelty of this method is that the triple-stage mass spectrometry technology improves the selectivity and sensitivity. A comparison of the presented method and traditional liquid chromatography–tandem mass spectrometry method was assessed in 44 patients treated with meropenem and Passing–Bablok regression coefficients and Bland–Altman plots showed that no significant difference between the two methods. So the triple-stage mass spectrometry method developed in this study is appropriate and practical for the monitor of meropenem in the daily clinical laboratory practice.     

d-Orbital Reconstructions Forced by Double Bow-Shaped Deformations and Second Coordination Sphere Effects of Cu(II) Heme Analogs in HER**

Both geometric architecture and electronic configurations of heme proteins contribute to its activity. In this work we designed and synthesized a series of four copper(II) porphyrin complexes ( 4 -, 3 -, 2 - and 1 -Cu) where the molecular conformations are modulated by a pair of stepwise shortened straps on the same porphyrin side (cis-ortho) to give double bow-shaped skeletons. Single crystal structures demonstrate that the straps gradually increase the saddle deformation and the deviation of the metal centers, which is in accordance with two, unusual d-orbital reconstructions of two different ground states, as revealed by 4 K EPR and DFT calculations. In the study of the electrocatalytic hydrogen evolution reaction (HER), 1 -Cu, with the shortest straps, showed the most apparent improvement of activity. Second coordination sphere (SCS) effects created by the double bow-shaped architecture and the strong saddle porphyrin core in 1 -Cu are found to play key roles in proton trapping during the catalytic process. The work contributes a novel strategy to improve the catalytic performance of heme analogs through ligand geometric modulation.     

Reactions of a Four-Membered Borete with Carbon,Silicon, and Gallium Donor Ligands: Fused and Spiro-Type Boracycles

Donor-acceptor cyclopropanes or cyclobutanes are dipolar reagents, which are widely used in the synthesis of complex organic (hetero)cycles in ring expansion reactions. Applying this concept to boron containing heterocycles, the four-membered borete cyclo-iPr₂N-BC₁₀H₆ reacted with the carbon donor ligands 2,6-xylylisonitrile and the carbene IMes :C(NMesCH)₂ with ring expansion and ring fusion, respectively. In particular, the tetracyclic structure formed with IMes displays zwitterionic character and absorption in the visible region. In contrast to the carbene IMes, the heavier carbenoids :Si(NDippCH)₂ and :Ga(AmIm) with a two-coordinate donor atom afford spiro-type bicyclic compounds, which display four-coordinate geometry at silicon or gallium. (TD-)DFT calculations provide deeper insight into the mechanism of formation and the absorption properties of these new compounds.     

Direct Synthesis of Adipic Esters and Adiponitrile via Photoassisted Cobalt-Catalyzed Alkene Hydrodimerization

The direct hydrodimerization of acrylates and acrylonitrile offers a general streamlined access to industrially important intermediates to nylon 6,6. However, a practical catalytic method for this process has thus far underdeveloped owing to the challenges in regioselectivity and environmental compatibility of applied reagents. Here, we report a cobalt-catalyzed tail-to-tail hydrodimerization of activated alkenes driven by a visible-light photoredox catalysis at ambient temperature, which is applicable to both adipates and adiponitrile synthesis from potentially renewable feedstocks. This protocol utilizes half equivalent of hantzsch ester as a recyclable two-electron and two-proton donor with the assistance of catalytic amount of base as a proton shuttle, and has been shown to be highly regioselective and efficient for hydrodimerizing various activated alkenes to 1,4-difunctionalized butane derivatives.     

非富勒烯受体DA'D型稠环单元的结构修饰及电池性能研究

近年来,设计和合成高性能非富勒烯受体(NFAs)材料已经成为太阳能电池研究领域的前沿课题。基于DA'D型稠环结构的NFAs由于具有吸光系数高、能级和带隙可调、结构易于修饰、分子可高效合成、光电学性能优异等优点而受到了越来越广泛的关注。在短短7年的时间里,能量转换效率(PCE)从3%~4%提高到18%。2019年初邹应萍等报道了一个优秀的受体分子Y6,与PM6共混制备单结电池,获得了15.7%的能量转换效率。Y6类受体材料的中心给电子单元为DA'D型稠环结构,缺电子单元(A')通过氮原子与两个给电子单元(D)并联形成稠环结构,这有助于降低前线分子轨道能级并增强吸收,同时与氮相连的两个烷基链和位于噻吩并噻吩β位的两个侧链则有助于提高溶解度及调节结晶性。自Y6问世以来,人们对分子的结构剪裁进行了深入的研究,并报道了数十种新的结构。在这些新的受体中,DA'D部分的结构裁剪对提高器件效率和太阳能电池的性能起着至关重要的作用。本文对A'、D单元和侧链结构修饰的研究进展进行了综述。通过选择几组受体,对最近报道的分子进行分类,并将它们的光学、电化学、电学和光电性质与精确的结构修饰相关联,从而对结构-性能关系进行全面概述。     

基于生物炭的高级氧化技术降解水中有机污染物

碳基材料催化剂因具有良好的催化性能,同时可避免金属催化剂的重金属沥出造成的二次污染问题,常被应用于高级氧化领域。其中,以废弃生物质为原材料热解产生的生物炭,不仅具有催化潜力,还具有低成本和绿色环保等优势,被广泛用于活化过氧化氢、过一硫酸氢盐和过二硫酸盐等过氧化物降解水中有机污染物。本文介绍了生物炭的前体种类和制备方法、阐述了二者对生物炭活化能力的影响,总结了生物炭活化过氧化物的机理,分析了水质对降解污染物的影响,综述了生物炭的改性、循环使用及再生,指出了这一技术存在的问题并对后续研究进行了展望。