Mechanochemical Synthesis of Aryl Fluorides by Using Ball Milling and a Piezoelectric Material as the Redox Catalyst

Aryl fluorides are important structural motifs in many pharmaceuticals. Although the Balz–Schiemann reaction provides an entry to aryl fluorides from aryldiazonium tetrafluoroborates, it suffers from drawbacks such as long reaction time, high temperature, toxic solvent, toxic gas release, and low functional group tolerance. Here, we describe a general method for the synthesis of aryl fluorides from aryldiazonium tetrafluoroborates using a piezoelectric material as redox catalyst under ball milling conditions in the presence of Selectfluor. This approach effectively addresses the aforementioned limitations. Furthermore, the piezoelectric material can be recycled multiple times. Mechanistic investigations indicate that this fluorination reaction may proceed via a radical pathway, and Selectfluor plays a dual role as both a source of fluorine and a terminal reductant.     

Piezoelectrically Mediated Reactions: From Catalytic Reactions to Organic Transformations

Recently, piezocatalysis has attracted considerable attention as a new type of renewable mechanical energy conversion technology, which relies on the strain induced polarization of the piezoelectric material. This new technology has been extensively applied in the applications of water splitting, water remediation, gas purification and tumor therapy. Despite the rapid development in the piezocatalysis, the utilization of piezoelectric materials for synthetic purpose is still under exploration. Piezoelectric means to promote organic reactions expand the scope of piezoelectrically mediated reactions and show successes in both organic and polymer synthesis. Herein, we provide a comprehensive review on recent progress of piezoelectrically mediated reactions, catalytic mechanisms and applications in the last few years. The limitations and future directions of this area are also discussed. We believe this review will provide new insights into the underlying mechanism of piezoelectric mediated electron transfer process and guide the design of new chemistry.      

基于弯扭组合梁元的多段折叠翼离散突风响应

基于弯扭组合梁元对大展弦比多段折叠翼的离散突风响应特性进行了研究。首先，将平面一般梁元叠加扭转自由度得到一种新的弯扭组合梁元，建立包含折叠角参数的缩减有限元模型。其次，对片条理论进行修正以得到不同折叠角度下弯扭组合梁元上的气动力，构建多段折叠翼在离散突风作用下的动力学方程。最后，引入Laplace变换处理动力学方程中的积分微分项，得到折叠角对翼尖加速度、翼根弯/扭矩等响应的影响。一个近地面无人机三段式折叠翼的算例结果表明，机翼固有频率会随着折叠角的变化呈现非线性性态，相比舒展状态，折叠角的存在虽不能明显减小翼尖加速度，但能够有效减小翼根弯/扭矩响应。     

Mechanoredox Catalysis Enables a Sustainable and Versatile Reversible Addition-Fragmentation Chain Transfer Polymerization Process

The sustainable synthesis of macromolecules with control over sequence and molar mass remains a challenge in polymer chemistry. By coupling mechanochemistry and electron-transfer processes (i.e., mechanoredox catalysis), an energy-conscious controlled radical polymerization methodology is realized. This work explores an efficient mechanoredox reversible addition-fragmentation chain transfer (RAFT) polymerization process using mechanical stimuli by implementing piezoelectric barium titanate and a diaryliodonium initiator with minimal solvent usage. This mechanoredox RAFT process demonstrates exquisite control over poly(meth)acrylate dispersity and chain length while also showcasing an alternative to the solution-state synthesis of semifluorinated polymers that typically utilize exotic solvents and/or reagents. This chemistry will find utility in the sustainable development of materials across the energy, biomedical, and engineering communities.     

Piezoelectric atomization of liquids with dynamic viscosities up to 175 cP at room temperature

Piezoelectric atomization has been applied in the field of respiratory medicine delivery and chemistry. However, the wider application of this technique is limited by the viscosity of the liquid. High-viscosity liquid atomization has great potential for applications in aerospace, medicine, solid-state batteries and engines, but the actual development of atomization is behind expectations. In this study, instead of the traditional model of single-dimensional vibration as a power supply, we propose a novel atomization mechanism that uses two coupled vibrations to induce micro-amplitude elliptical motion of the particles on the surface of the liquid carrier, which produces a similar effect as localized traveling waves to push the liquid forward and induce cavitation to achieve atomization. To achieve this, a flow tube internal cavitation atomizer (FTICA) consisting of a vibration source, a connecting block and a liquid carrier is designed. The prototype can atomize liquids with dynamic viscosities up to 175 cP at room temperature with a driving frequency of 507 kHz and a voltage of 85 V. The maximum atomization rate in the experiment is 56.35 mg/min, and the average atomized particle diameter is 10 µm. Vibration models for the three parts of the proposed FTICA are established, and the vibration characteristics and atomization mechanism of the prototype were verified using the vibration displacement measurement experiment and the spectroscopic experiment. This study offers new possibilities for transpulmonary inhalation therapy, engine fuel supply, solid-state battery processing and other areas where high-viscosity microparticle atomization is needed.     

压电基因传感器研究进展

压电基因传感器是一种新型的生物传感器，它将压电传感器的灵敏性和DNA杂交反应结合在一起。与传统的基因检测技术相比，压电基因传感器具有结构简单、不需要标记、检测时间短等特点。本对压电基因传感器的研究现状作了综述，包括压电基因传感器的原理、测量技术、固定方法、以及压电基因传感器在各个领域的应用。