Strong P=P pi Bonds: The First Synthesis of a Stable Phosphanyl Phosphenium Ion

A 35-fold excess of methyl triflate (2) is required to quantitively prepare 3, the first phosphanyl phosphenium ion, from diphosphene 1. Experimental data and calculations indicate that the P=P bond becomes stronger upon alkylation.     

Reactions of a Ga/P‐Based Frustrated Lewis Pair with HX (X = F – I), Heterocumulenes R–NCY (Y = O,S) and Chalcogens–Adduct Formation and Surprising Stability towards Protolysis

Treatment of the geminal Ga/P‐based frustrated Lewis pair (FLP) Mes₂P–C(GatBu₂)=C(H)–Ph ( 1 ) with HX (X = F, Cl, Br, I) afforded the corresponding adducts 2 with the protons bound to the P and the halide anions coordinated to the Ga atoms. Short intramolecular contacts may indicate P–H ··· X hydrogen bonding interactions. The Br and I compounds ( 2c , 2d ) were accessible in moderate yields even when aqueous solutions of the acids were employed. These unexpected reactions confirm the surprising stability of FLP 1 towards protolysis. Heterocumulenes R–N=C=Y (Y = O, S) and 1 yielded adducts with two different structural motifs. The N=C=Y groups were coordinated to the FLP either via the C=Y (Y = S; Ph–N=C=O) or the C=N bonds (Ph–N=C=O, Et–N=C=O). For phenyl isocyanate the C=O bonded isomer was observed in the solid state, while both isomeric forms were detected in solution. Steric shielding and the hardness of the atoms may influence the formation of the respective isomer. Cleavage of the C=S bonds of isothiocyanates was observed for the first time and afforded a sulfur adduct 9a , in which an S atom (electron sextet) was bound to the lone pair of electrons at phosphorus and to the Lewis acidic Ga atom. Four‐membered PCGaY heterocycles resulted, which were also synthesized in high yields by the direct reaction of 1 with propylene sulfide or selenium.     

Valence Isomerization of a 1,3-Diphosphacyclobutane-2,4-diyl: Photochemical Ring Closure to 2,4-diphosphabicyclo[1.1.0]butane and Its Thermal Ring Opening to gauche-1,4-Diphosphabutadiene

The bond stretch isomer 1,3-diphosphacyclobutane-2,4-diyl 1 was transformed photochemically to give the previously unknown 2,4-diphosphabicyclo[1.1.0]butane 2 , which itself can be converted thermally into gauche-1,4-diphosphabutadiene 3 . The crystal structures of these three energy-rich valence isomers of 1,2-diphosphete have been determined. R=SiMe₃; Mes*=2,4,6-tBu₃C₆H₂.     

通过交联抑制高温下氢键的解离提高聚酰亚胺的耐热性和尺寸稳定性

将炔基结构引入该聚酰亚胺主链中,通过热引发化学交联反应构建化学限域位点,抑制高温下氢键的减弱和解离,进而通过交联和高温下更加稳定的氢键协同性提升了该PI薄膜在高温下的尺寸稳定性.结果表明,相对于线性PI,交联后PI在400℃的强氢键含量达到26.1%,与未交联PI相比提高了近50%,从而将300~400℃范围的的热膨胀系数(CTE)从33.8×10?6/K降低至5.1×10^?6/K.最终制备的PI膜的Tg高达452℃,40~400℃范围内的CTE仅为2.1×10^?6/K,拉伸强度高达231 MPa,有望用于AMOLED的基底材料.     

Dynamic Oxime-Urethane Bonds,a Versatile Unit of High Performance Self-healing Polymers for Diverse Applications

Oxime-urethane bond featuring with high reversibility even at room temperature and multiple reactivity is an emerging dynamic covalent bond, and has shown great potential for self-healing polymers, which are one of the most attractive development directions for next generation of polymeric materials. In this review, recent progresses on the oxime-urethane-based self-healing polymers, including their designs and applications in diverse fields such as biomedicine, flexible electronics, soft robots...     

小型高分辨电子轰击离子源反射式飞行时间质谱仪的研制

常用的气体分析质谱仪使用四极杆质谱作为分析器,分辨率一般低于300,无法解决同质量数离子带来的干扰问题.本实验自行研制了一种小型高分辨气体分析质谱仪,它采用电子轰击离子源反射式飞行时间质量分析器.仪器腔体总长45 cm,在m/z 28的位置,质量分辨率达到3000(Full width at half maximum,FWHM),实现了CO和N2的半峰谷分离;在m/z 69的位置,仪器分辨率达到5000(FWHM).在直接大气压进样条件下,可以检测到空气中136Xe(含量7.8 μ g/m3)和80Kr(含量2.8 μg/m3).使用ADC采集时,仪器的动态范围为1 06.该仪器将作为高端气体质谱仪,应用于过程监测在线分析、环境有机挥发物研究、热分析质谱及催化反应监测等领域.     

一个高度灵敏和高选择性铝离子比率探针的合成及应用

本文构建了一种基于3-苯丙噻唑基-2-羟基-5-甲基苯甲醛的荧光探针用于检测铝离子。该荧光探针能够灵敏、高选择性地检测铝离子,并显示出颜色和强烈的荧光变化双重响应。研究结果表明,该探针对铝离子表现出非常好的荧光增强效果,检测过程中其它金属离子不会对检测结果产生明显的干扰。其比率荧光强度(I490/I567)与铝离子的浓度(0~20μmol/L)之间具有良好的线性关系,检测限低至0.5μmol/L。由于具有高效的选择性,该探针可以用于检测污染河水中的铝离子含量。     

Correlating Glycoforms of DC-SIGN with Stability Using a Combination of Enzymatic Digestion and Ion Mobility Mass Spectrometry

The immune scavenger protein DC-SIGN interacts with glycosylated proteins and has a putative role in facilitating viral infection. How these recognition events take place with different viruses is not clear and the effects of glycosylation on the folding and stability of DC-SIGN have not been reported. Herein, we report the development and application of a mass-spectrometry-based approach to both uncover and characterise the effects of O-glycans on the stability of DC-SIGN. We first quantify the Core 1 and 2 O-glycan structures on the carbohydrate recognition and extracellular domains of the protein using sequential exoglycosidase sequencing. Using ion mobility mass spectrometry, we show how specific O-glycans, and/or single monosaccharide substitutions, alter both the overall collision cross section and the gas-phase stability of the DC-SIGN isoforms. We find that rather than the mass or length of glycoprotein modifications, the stability of DC-SIGN is better correlated with the number of glycosylation sites.     

Correlating Glycoforms of DC‐SIGN with Stability Using a Combination of Enzymatic Digestion and Ion Mobility Mass Spectrometry

The immune scavenger protein DC‐SIGN interacts with glycosylated proteins and has a putative role in facilitating viral infection. How these recognition events take place with different viruses is not clear and the effects of glycosylation on the folding and stability of DC‐SIGN have not been reported. Herein, we report the development and application of a mass‐spectrometry‐based approach to both uncover and characterise the effects of O‐glycans on the stability of DC‐SIGN. We first quantify the Core 1 and 2 O‐glycan structures on the carbohydrate recognition and extracellular domains of the protein using sequential exoglycosidase sequencing. Using ion mobility mass spectrometry, we show how specific O‐glycans, and/or single monosaccharide substitutions, alter both the overall collision cross section and the gas‐phase stability of the DC‐SIGN isoforms. We find that rather than the mass or length of glycoprotein modifications, the stability of DC‐SIGN is better correlated with the number of glycosylation sites.     

还原氧化石墨烯改性少层剥离石墨增强石墨基钾离子电池负极稳定性

钾在石墨中嵌入电位较低,因此石墨负极可使钾离子电池具有较高的能量密度,是一种理想的钾离子电池负极材料。然而,石墨嵌钾后的体积膨胀率高达60%,导致钾离子电池的循环稳定性较差。此外,钾嵌入石墨层间的动力学过程缓慢,制约了钾离子电池倍率性能的提升。在本工作中,我们用还原氧化石墨烯(rGO)包覆剥离石墨(EG),得到一种具有协同效应的层状复合材料。一方面,以少层的EG代替石墨可以减少由于钾的嵌入/脱嵌所引起的体积膨胀和内部应力;另一方面,外层rGO可以避免EG的堆叠,这有利于加速动力学过程并在钾化/去钾化过程中稳定结构。当复合材料所用EG和GO的质量比为1 : 1时,其性能达到最优,在50 mA·g^-1的电流密度下能够提供443 mAh·g^-1的比容量;在电流密度为800 mA·g^-1时,比容量为190 mAh·g^-1,保持率为42.9%。相同测试条件下,纯EG和rGO的容量保持率仅为14.2%和27.2%。测试结果说明EG-1/rGO-1复合材料在比容量和倍率性能两个方面得到了提升。     

高效液相色谱非多孔型阴离子交换柱分析DNA片段

建立了高效液相色谱非多孔型阴离子交换柱分离ＤＮＡ片段的方法,用ＴＳＫｇｅｌＤＥＡＥ－ＮＰＲ柱、Ｔｒｉｓ－ＨＣｌ缓冲液（ｐＨ９．０）、１．０ｍｏｌ／ＬＮａＣｌ多阶式线性梯度洗脱,分析了核酸分子量参照物ｐＢＲ３２２ＤＮＡ－ＨａｅⅢ,ＬａｍｂｄａＤＮＡ－ＨｉｎｄⅢ及乙肝病毒基因ＰＣＲ产物,探讨了梯度、流速对分离的影响,方法简便、快速、分辨率高     

Synthesis of Di‐ and Trixanthones that Display High Stability and a Visual Fluorescence Response to Strong Acid

Three dixanthones ( 1 – 3 ) and an unprecedented C_3h‐symmetric trixanthone ( 4 ) were synthesized through a three‐step approach in overall yields above 63 %. These compounds possessed a planar π‐conjugated system and formed tight face‐to‐face columnar stacks, as confirmed by single‐crystal structural analysis. In comparison with xanthone, the fluorescence emissions of compounds 1 – 4 showed significant red‐shifts, with improved quantum yields. Moreover, the fluorescence emissions of compounds 1 – 4 could be modulated in a strongly acidic environment without decomposition, which led to a further red‐shift of the emissions, as well as enhancement of the emission intensities. These compounds have potential applications as optoelectronic materials and/or chemosensors.     

高效锂离子筛吸附剂MnO2·0.5H2O的软化学合成及吸附性能研究

以MnCl2·4H2O,LiOH·H2O等试剂为初始原料,采用溶胶-凝胶、水热处理、固化等软化学合成步骤制备了锂离子筛前驱体Li1.6Mn1.6O4,并经稀盐酸抽锂后得到了高选择性锂离子筛吸附剂MnO2·0.5H2O.着重对合成过程中锂锰比,氧化剂用量等因素影响进行了探讨,并对所制备吸附剂的吸附性能进行了研究.结果表明,经软化学合成步骤制备的锂离子筛对Li 有良好的吸附量和选择性,在未来从海水、卤水等液态锂资源富集或提取锂的应用中具有很大的潜力.     

High Uptake and Fast Transportation of LiPF6 in a Porous Aromatic Framework for Solid‐State Li‐Ion Batteries

Solid‐state Li‐ion batteries (SSLIBs) have recently attracted substantial attention from scientists for the advantages of better safety performance. However, there are still several key challenges in SSLIBs that need to be addressed, such as low energy density, poor thermal stability or cycle stability, and large interface resistance. This contribution introduces a novel SSLIB with a porous aromatic framework (PAF‐1) accommodating LiPF₆ that was used as the solid‐state electrolyte (SSE) replacing the liquid electrolyte and diaphragm of traditional Li‐ion batteries. The charge, discharge capacity, rate performance and cycle stability of the SSLIB were remarkably enhanced.     

The RING Domain of the Scaffold Protein Ste5 Adopts a Molten Globular Character with High Thermal and Chemical Stability

Ste5 is a scaffold protein that controls the pheromone response of the MAP‐kinase cascade in yeast cells. Upon pheromone stimulation, Ste5 (through its RING‐H2 domain) interacts with the β and γ subunits of an activated heterodimeric G protein and promotes activation of the MAP‐kinase cascade. With structural and biophysical studies, we show that the Ste5 RING‐H2 domain exists as a molten globule under native buffer conditions, in yeast extracts, and even in denaturing conditions containing urea (7 M ). Furthermore, it exhibits high thermal stability in native conditions. Binding of the Ste5 RING‐H2 domain to the physiological Gβ/γ (Ste4/Ste18) ligand is accompanied by a conformational transition into a better folded, more globular structure. This study reveals novel insights into the folding mechanism and recruitment of binding partners by the Ste5 RING‐H2 domain. We speculate that many RING domains may share a similar mechanism of substrate recognition and molten‐globule‐like character.     

Thermal‐Induced Formation of a Three‐Dimensional Nanoplasmonic Sensor from Ag Nanocubes with High Stability and Reusability

Nanoplasmonic sensors based on the localized surface plasmon resonance (LSPR) of noble metal nanoparticles have many advantages, such as real‐time detection, no need for reagent labelling, and no use of complicated equipment. However, the nanoplasmonic sensors with two dimensional structures usually suffer from a low LSPR signal and thus low sensitivity due to the low density of the nanoparticles. In addition, complicated surface functionalization is always required to suppress the non‐specific binding of the analyst to the substrate of the sensor, because the two types of surface, that is, metal and substrate surfaces, are simultaneously exposed to the reaction medium. To overcome these problems, an innovative thermal‐induced method has been proposed in the present work, to construct three dimensional (3D) nanostructure of Ag nanocubes on both surfaces of the substrate by using the unique amphiphilic property of 2‐diethylaminoethanethiol. The prepared nanoplasmonic sensor is highly sensitive due to the high density of 3D structure of the nanoparticles and the low non‐specific binding since only one type of surface is exposed. To enhance the stability of the sensor, a thin SiO₂ overlayer was formed on the surface without using an additional coupling agent. Furthermore, the Ni^II‐nitriloacetic acid (Ni^II‐NTA) complex was covalently bound on the surface, so that the regeneration and reuse of the sensor becomes easy. Therefore, the easy fabrication, high stability, and good reusability of this 3D LSPR sensor makes our method competitive for the development of nanoplasmonic sensors.