Precise Synthesis of Ultra-High-Molecular-Weight Fluoropolymers Enabled by Chain-Transfer-Agent Differentiation under Visible-Light Irradiation

Ultra-high-molecular-weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible-deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain-transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible-light irradiation. In situ chain-end extensions from UHMW polymers facilitated the synthesis of well-defined block copolymers, revealing the excellent chain-end fidelity achieved by this method.     

氰基亚胺与亚甲基二氢苯并呋喃二酮类化合物的[3+2]环加成反应:螺吡唑类化合物的合成

采用具有环外双键的二氢苯并呋喃二酮类化合物和氰基亚胺的[3+2]环加成反应,在温和条件下,以高产率(78%~94%)和高非对映选择性(>20∶1dr)构建了一系列具有螺环结构的吡唑类化合物.     

An efficient synthesis of 9-anthrone lactone derivatives via the Knoevenagel condensation and intramolecular cyclization

One-step synthesis of 9-anthrone lactone derivatives from 1-acetyloxyanthraquinone with a variety of dicarbonyl substrates in the presence of K₂CO₃ by Knovenagel condensation and intramolecular cyclization is developed. Possible reaction mechanisms have been investigated using the density functional theory (DFT), which has been widely used in the study of reaction mechanism. The strategy could be useful for the synthesis of the core structure of marine natural product aspergiolide.     

基于Matlab GUI的微观化学反应过程可视化设计

Based on the quasi-classical trajectory (QCT) method and Matlab GUI technology, we developed a program code for visualizing the collision process of the elementary chemical reactions of the a + bc type. The general methodology of QCT, abstraction of dynamical properties of molecular collisions and the making of Graphical User Interface are introduced. The running results of an application to the reaction F + HCl→HF + Cl is also presented. The results showed that this program could vividly demonstrate the behavior and final state of the atom-diatom collision process in animated form. Students can interact with internal MATLAB code through graphical user interface, observe the reactive behavior and final results in real-time from multiple angles, which helps students to understand the complex reaction mechanism and deepen their perceptual impression of the chemical process at a microscopic atomic/molecular level.     

物理化学全线上教学的策略与实践

Remote teaching and learning have been adopted during the COVID-19 outbreak. In this particular period of time, a totally-online-teaching strategy was implemented by the teaching team of physical chemistry in Tianjin University. With the enrichment of learning resources, the optimization of the inspectors' teaching skills, as well as the elaborated managements of the whole learning process, the course has been given online successfully, though it is thought unsuitable for online teaching due to the abstruse theory and complex mathematical treatments involved in teaching. Both the central position of student and the leading role of teacher are greatly promoted in the newly developed totally-online-teaching process. The experiences obtained in this teaching process will lay great impact on teaching mode innovation in the future.     

Electron-donating methoxy group enhances the stability and efficiency of indole-based fluorescent probe for detecting Cu2+

Research on Chemical Intermediates - Two novel Schiff-base fluorescent probes bearing different substituents were synthesized by the reaction of indole derivatives with 4-aminoantipyrine. The...     

pH-Dependent Slipping and Exfoliation of Layered Covalent Organic Framework

Layered/two-dimensional covalent organic frameworks (2D COF) are crystalline porous materials composed of light elements linked by strong covalent bonds. Interlayer force is one of the main factors directing the formation of a stacked layer structure, which plays a vital role in the stability, crystallinity, and porosity of layered COFs. The as-developed new way to modulate the interlayer force of imine-linked 2D TAPB-PDA-COF (TAPB = 1,3,5-tris(4-aminophenyl)benzene, PDA = terephthaldehyde) by only adjusting the pH of the solution. At alkaline and neutral pH, the pore size of the COF decreases from 34 Å due to the turbostratic effect. Under highly acidic conditions (pH 1), TAPB-PDA-COF shows a faster and stronger turbostratic effect, thus causing the 2D structure to exfoliate. This yields bulk quantities of an exfoliated few/single-layer 2D COF, which was well dispersed and displayed a clear Tyndall effect (TE). Furthermore, nanopipette-based electrochemical testing also confirms the slipping of layers with increase towards acidic pH. A model of pH-dependent layer slipping of TAPB-PDA-COF was proposed. This controllable pH-dependent change in the layer structure may open a new door for potential applications in controlled gas adsorption/desorption and drug loading/releasing.     

A Mechanistic Study of the Multiple Roles of Oleic Acid in the Oil-Phase Synthesis of Pt Nanocrystals

Oleic acid (OAc) is commonly used as a surfactant and/or solvent for the oil-phase synthesis of metal nanocrystals but its explicit roles are yet to be resolved. Here, we report a systematic study of this problem by focusing on a synthesis that simply involves heating of Pt(acac)₂ in OAc for the generation of Pt nanocrystals. When heated at 80 °C, the ligand exchange between Pt(acac)₂ and OAc leads to the formation of a Pt^II–oleate complex that serves as the actual precursor to Pt atoms. Upon increasing the temperature to 120 °C, the decarbonylation of OAc produces CO, which can act as a reducing agent for the generation of Pt atoms and thus formation of nuclei. Afterwards, several catalytic reactions can take place on the surface of the Pt nuclei to produce more CO, which also serves as a capping agent for the formation of Pt nanocrystals enclosed by {100} facets. The emergence of Pt nanocrystals further promotes the autocatalytic surface reduction of Pt^II precursor to enable the continuation of growth. This work not only elucidates the critical roles of OAc at different stages in a synthesis of Pt nanocrystals, but also represents a pivotal step forward toward the rational synthesis of metal nanocrystals.