Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition. 相似文献
As an effective separation tool, free-flow electrophoresis has not been used for purification of low-abundance protein in complex sample matrix. Herein, lysozyme in complex egg white matrix was chosen as the model protein for demonstrating the purification of low-content peptide via an FFE coupled with gel fitration chromatography (GFC). The crude lysozyme in egg while was first separated via free-flow zone electrophoresis (FFZE). After that, the fractions with lysozyme activity were condensed via lyophilization. Thereafter, the condensed fractions were further purified via a GFC of Sephadex G50. In all of the experiments, a special poly(acrylamide- co-acrylic acid) (P(AM-co-AA)) gel electrophoresis and a mass spectrometry were used for identification of lysozyme. The conditions of FFZE were optimized as follows: 130 μL/min sample flow rate, 4.9 mL/min background buffer of 20 mM pH 5.5 Tris-Acetic acid, 350 V, and 14 °C as well as 2 mg/mL protein content of crude sample. It was found that the purified lysozyme had the purity of 80% and high activity as compared with its crude sample with only 1.4% content and undetectable activity. The recoveries in the first and second separative steps were 65% and 82%, respectively, and the total recovery was about 53.3%. The reasons of low recovery might be induced by diffusion of lysozyme out off P(AM-co-AA) gel and co-removing of high-abundance egg ovalbumin. All these results indicated FFE could be used as alternative tool for purification of target solute with low abundance. 相似文献
Tuning the coordination environments of metal single atoms (M1) in single-atom catalysts has shown large impacts on catalytic activity and stability but often barely on selectivity in thermocatalysis. Here, we report that simultaneously regulating both Rh1 atoms and ZrO2 support with alkali ions (e.g., Na) enables efficient switching of the reaction products from nearly 100 % CH4 to above 99 % CO in CO2 hydrogenation in a wide temperature range (240–440 °C) along with a record high activity of 9.4 molCO gRh−1 h−1 at 300 °C and long-term stability. In situ spectroscopic characterization and theoretical calculations unveil that alkali ions on ZrO2 change the surface intermediate from formate to carboxy species during CO2 activation, thus leading to exclusive CO formation. Meanwhile, alkali ions also reinforce the electronic Rh1-support interactions, endowing the Rh1 atoms more electron deficient, which improves the stability against sintering and inhibits deep hydrogenation of CO to CH4. 相似文献
The selective oxygenation of ubiquitous C(sp3)−H bonds remains a highly sought-after method in both academia and the chemical industry for constructing functionalized organic molecules. However, it is extremely challenging to selectively oxidize a certain C(sp3)−H bond to afford alcohols due to the presence of multiple C(sp3)−H bonds with similar strength and steric environment in organic molecules, and the alcohol products being prone to further oxidation. Herein, we present a practical and cost-efficient electrochemical method for the highly selective monooxygenation of benzylic C(sp3)−H bonds using continuous flow reactors. The electrochemical reactions produce trifluoroacetate esters that are resistant to further oxidation but undergo facile hydrolysis during aqueous workup to form benzylic alcohols. The method exhibits a broad scope and exceptional site selectivity and requires no catalysts or chemical oxidants. Furthermore, the electrochemical method demonstrates excellent scalability by producing 115 g of one of the alcohol products. The high site selectivity of the electrochemical method originates from its unique mechanism to cleave benzylic C(sp3)−H bonds through sequential electron/proton transfer, rather than the commonly employed hydrogen atom transfer (HAT). 相似文献
Journal of Thermal Analysis and Calorimetry - As high heat dissipation has increasingly become the primary factor restricting the capability of electronic elements, and the high temperature of the... 相似文献
Branched polyolefin microstructures resulting from so‐called “chain walking” are a fascinating feature of late transition metal catalysts; however, to date it has not been demonstrated how desirable branched polyolefin microstructures can be generated thereby. We demonstrate how highly branched polyethylenes with methyl branches (220 Me/1000 C) exclusively and very high molecular weights (ca. 106 g mol?1), reaching the branch density and microstructure of commercial ethylene–propylene elastomers, can be generated from ethylene alone. At the same time, polar groups on the main chain can be generated by in‐chain incorporation of methyl acrylate. Key to this strategy is a novel rigid environment in an α‐diimine PdII catalyst with a steric constraint that allows for excessive chain walking and branching, but restricts branch formation to methyl branches, hinders chain transfer to afford a living polymerization, and inverts the regioselectivity of acrylate insertion to a 1,2‐mode. 相似文献
To demonstrate the effect of axial ligands on the structure–activity relationship, a series of axially substituted silicon phthalocyanines (SiPcs) have been synthesized with changes to the axial ligands. The reactivity of the axial ligand upon shielding by the phthalocyanine ring current, along with their stability, photophysical, and photodynamic therapy (PDT) activities were compared and evaluated for the first time. As revealed by single‐crystal XRD analysis, rotation of the axial ? OMe ligands was observed in SiPc 3 , which resulted in two molecular configurations coexisting synchronously in both the solid and solution states and causing a split of the phthalocyanine α protons in the 1H NMR spectra that is significantly different from all SiPcs reported so far. The remarkable photostability, good singlet oxygen quantum yield, and efficient in vitro photodynamic activity synergistically show that compound 3 is one of the most promising photosensitizers for PDT. 相似文献
In this study, the wave propagation properties of piezoelectric sandwich nanoplates deposited on an orthotropic viscoelastic foundation are analyzed by considering the surface effects (SEs). The nanoplates are composed of a composite layer reinforced by graphene and two piezoelectric surface layers. Utilizing the modified Halpin-Tsai model, the material parameters of composite layers are obtained. The displacement field is determined by the sinusoidal shear deformation theory (SSDT). The Euler-Lagrange equation is derived by employing Hamilton’s principle and the constitutive equations of piezoelectric layers considering the SEs. Subsequently, the nonlocal strain gradient theory (NSGT) is used to obtain the equations of motion. Next, the effects of scale parameters, graphene distribution, orthotropic viscoelastic foundation, and SEs on the propagation behavior are numerically examined. The results reveal that the wave frequency is a periodic function of the orthotropic angle. Furthermore, the wave frequency increases with the increase in the SEs.