A membrane separation technique for optimizing sample preparation of MALDI-TOF MS detection

Here, we report a new method based on the combination of membrane separation technology and nanomaterial to rapid detection of peptides and protein with MALDI-TOF MS. This method shows advantages as it can inhibit the heterogeneous of sample spot and enhance the target molecular signal intensity.     

Electronic Communication between S=1/2 Spins in Negatively‐charged Double‐caged Fullerene C60 Derivative Bonded by Two Single Bonds and Pyrrolizidine Bridge

Radical anion salt {cryptand[2.2.2] (K⁺)}₂(bispheroid)^2??3.5C₆H₄Cl₂ ( 1 ) of the double‐caged fullerene C₆₀ derivative, in which fullerene cages are linked by a cyclobutane bridging cycle and additionally by a pyrrolizidine moiety, was obtained. Each fullerene cage in this derivative accepts one electron on reduction, thus forming the (bispheroid)^2? dianions with two interacting S=1/2 spins on the neighboring cages. Low‐temperature magnetic measurements reveal a singlet ground state of the bispheroid dianions whereas triplet contributions prevail at increased temperature. An estimated exchange interaction between two spins J/k_B=?78 K in 1 indicates strong magnetic coupling between them, nearly two times higher than that (J/k_B=?44.7 K) in previously studied (C₆₀^?)₂ dimers linked via a cyclobutane bridge only. The enhancement of magnetic coupling in 1 can be explained by a shorter distance between the fullerene cages and, possibly, an additional channel for the magnetic exchange provided by a pyrrolizidine bridge. Quantum‐chemical calculations of the lowest electronic state of the dianions by means of multi‐configuration quasi‐degenerate perturbation theory support the experimental findings.     

Nickel-catalyzed intramolecular C–H arylation using aryl pivalates as electrophiles

This paper describes a method for nickel catalyzed intramolecular C–H arylation using aryl pivalates as electrophiles. The transformation is efficient for the synthesis of diverse electronically and sterically differentiated dibenzofurans. Additionally, the method could be expanded toward the synthesis of carbazoles. Preliminary mechanistic studies of the transformation are also described.     

Palladium-catalyzed cross-coupling: a historical contextual perspective to the 2010 Nobel Prize

In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki joined the prestigious circle of Nobel Laureate chemists for their roles in discovering and developing highly practical methodologies for C-C bond construction. From their original contributions in the early 1970s the landscape of the strategies and methods of organic synthesis irreversibly changed for the modern chemist, both in academia and in industry. In this Review, we attempt to trace the historical origin of these powerful reactions, and outline the developments from the seminal discoveries leading to their eminent position as appreciated and applied today.     

相容的聚甲基丙烯酸甲酯/[C12 MIM][PF6]离子液体体系在超临界CO2中的发泡性能

通过快速卸压法, 以超临界CO2为物理发泡剂, 研究了相容的聚甲基丙烯酸甲酯(PMMA)/1-n-十二烷基-3-甲基咪唑六氟磷酸盐([C12 MIM][PF6])离子液体(IL)复合体系的发泡性能. 加入IL后, PMMA对CO2的吸收量增加; 复合体系的玻璃化转变温度(Tg)随IL含量的增加而降低. IL对PMMA发泡行为的影响取决于发泡条件. 在较低温度和压力下, 纯PMMA无法发泡, IL的加入可促进泡孔形成; 提高温度和压力, 纯PMMA可以发泡, IL的加入在提高泡孔尺寸的同时使泡孔仍然保持尺寸分布均匀的微米级结构.     

Tuning the metal-adsorbate chemical bond through the ligand effect on platinum subsurface alloys

Scratching beneath the surface: Pt-M(3d)-Pt(111) (M(3d) = Co, Ni) bimetallic subsurface alloys have been designed to show the ligand effect tunes reactivity in oxygen and hydrogen adsorption systems. The platinum-oxygen bond order was investigated by oxygen atom projection in the occupied and unoccupied space using X-ray emission spectroscopy (XES) and X-ray absorption spectroscopy (XAS).     

固体酸SO42-/ZrO2-CeO2催化小桐子油脂肪酸制备生物柴油的实验研究

用沉淀浸渍法制备了固体酸催化剂SO₄^2-/ZrO₂-CeO₂,用于催化小桐籽油脂肪酸与甲醇酯化制备生物柴油。考察了焙烧温度和CeO₂负载量对催化剂活性的影响,并进行了单因素实验和动力学研究。研究表明,SO₄^2-/ZrO₂-CeO₂有较高的催化活性,当甲醇与脂肪酸体积比 2∶1,反应温度150 ℃,催化剂用量为脂肪酸质量的8%,反应60 min时,脂肪酸转化率可达0.9403。动力学计算表明,该酯化反应的表观活化能为45.31 kJ/mol,动力学模型为-dc_A/dt=38371e^-45310/RTc_A^1.44。     

极性金属间化合物MgIn2的合成、晶体结构及能带特征

在惰性气氛氩气保护下,通过高温固相反应合成得到了一个二元极性金属间化合物MgIn2。经X-射线单晶衍射与元素分析等方法确定了其晶体结构。MgIn2属立方体系,空间群为Fd3m(No.227),晶体学参数a=0.956 13(16)nm,V=0.874 1(3)nm3,Z=8,R1=0.035 3,wR2=0.082 8。MgIn2属于CaAl2结构类型,其结构特征为[In4]四面体通过共用顶点In原子链接而成的三维框架结构,Mg原子填充在三维框架的空隙中。能带结构计算表明MgIn2属于金属性的化合物。     

Crystallization of Ammonium Nitrate Under Organised Monolayers at Air-Aqueous Interface

The crystallization of NH₄NO₃ under compressed Langmuir monolayers of carboxybe-taine(C₂₂N₃COO^-),C₂₂H₁₅N(CH₂)₃(CH₂)₃COO^--[C₂₂N₃COO^-] and dioleoyl-L-a-lecithin(DOPC) was studied by means of π-A. ΔV-A and fluorescence microscopy (FM). The surface pressure, surface potential and molecular area of C₂₂N₃COO^- were decreased on the NH₄NO₃ solution subphase. The surface pressure and molecular area of DOPC was increased. The surface potential of DOPC was decreased. We can directly observe the surface crystallization of NH₄NO₃ by FM. The results revaled that C₂₂N₃COO^- monolayer was the promoter of NH₄NO₃ surface crystallization. In contrast,DOPC monolayer was the inhibitor of the surface crystallization of NH₄NO₃.     

介孔C/SiO2粉体的制备及对阳离子型染料的吸附

采用吸附法处理染料废水需要合适的吸附剂。利用溶剂蒸发自组装法,以甲阶酚醛树脂为碳源、介孔SiO2粉体为载体制备介孔C/SiO2粉体,表征所制C/SiO2粉体的结构,研究C/SiO2粉体对阳离子型染料亚甲基蓝和阳离子红X-GRL的吸附性能,并与相同条件下制备的非负载的多孔C粉体以及介孔SiO2载体进行比较。结果表明,介孔C/SiO2粉体的孔窗口为11~18 nm,比表面积为303 m2.g-1,比孔容为1.11 cm3.g-1;C/SiO2粉体对这两种染料吸附量均高于C粉体和SiO2载体;在pH≤10的范围内,吸附量随pH值增大而显著提高。