Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

Highly diastereoselective multicomponent synthesis of polysubstituted 2-hydroxy-2-trifluoromethylpiperidineswith four and five stereogenic centers

The Michael–Mannich cascade cyclization of cyano olefins, ethyl 4,4,4-trifluoro-3-oxobutanoate, aromatic aldehydes and ammonium acetate provides convenient stereoselective formation of ethyl 5,5-dicyano-4,6-diaryl-2-hydroxy-2-(trifluoromethyl)piperidine-3-carboxylates with fourstereogenic centers and dialkyl 4,6-diaryl-5-cyano-2-hydroxy-2-(trifluoromethyl)piperidine-3,5-dicarboxylates with five stereogenic centers. Ammonium acetate plays dual role, acting as a base and as a nitrogen source.     

Calcium-based coordination polymers from a solvothermal synthesis of HKUST-1 in 3D printed autoclaves

A mixed-metal 1D coordination polymer [CaCu(HBTC)₂(H2O)₈]_n (where H₃BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu₃(BTC)₂(H₂O)₃]_n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H₂BTC)₂(H₂O)₅]_n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave.     

基于XPS对硫铁矿去除SeO2-3的机理研究

硒是动植物及人体生长必需的十五种微量元素之一，具有清除体内自由基、抗氧化、增强免疫力等功能，但其安全剂量的范围却很窄。利用扫描电子显微镜（SEM）和X射线衍射仪（XRD）对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体，粒径范围在17～200 nm之间，平均粒径138 nm。XRD衍射图谱中的特征峰与FeS₂衍射图谱中各峰位置基本一致，因此判定硫铁矿中主要化学组分为FeS₂，且图谱中基本没有杂峰，表明制备过程中并未混入杂质，样品纯度较高。实验结果表明，该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪（XPS）对硫铁矿去除水体中SeO2-₃的机理进行了研究。研究结果表明, （1）在较为广泛的实验pH范围（pH 2.2～11.5），硫铁矿均能有效去除水体中SeO2-₃，去除效率（除pH值7.8以外）均达到90%以上；（2）硫铁矿与SeO2-₃发生反应后，其主要组成元素的XPS特征峰结合能有所减小，表明硫铁矿表面发生了一定化学变化；（3）酸碱环境下硫铁矿去除SeO2-₃的机理不完全相同，酸性环境下，硫铁矿对SeO2-₃的去除是单纯的氧化还原过程，即硫铁矿中被酸活化的S2-₂将SeO2-₃还原为单质Se(0)，并且酸性越强，SeO2-₃去除效果越好；碱性环境下，SeO2-₃的去除过程中氧化还原与络合反应并存，硫铁矿表面有络合态Fe(OH)SeO₃和单质Se(0)两种存在形态，且碱性越强，络合态Fe(OH)SeO₃含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-₃为代表的可变价金属阴离子提供重要理论依据和应用基础。     

Rh(III)-Catalyzed One-Step Synthesis of ortho-Alkynylated Perylene Imide Dyes: Optical and Electrochemical Properties of New Derivatives

A one-step Rh-catalyzed site-selective ortho-C−H alkynylation of perylene as well as naphthalene mono- and diimides is reported. A single step regioselective access to ortho-C−H alkynylated derivatives of these ryleneimides not only increases the step economy of the ortho-functionalization on these dyes but also provides a quick access route towards highly functionalized dyes that have potential optoelectronic applications. Increased solubility of tetra(triisopropylsilyl)acetylenyl PDIs in organic solvents greatly enhances their utility for further derivatization.     

Enhanced Power Density of Alcohol Biofuel Cell by Polymer-assisted Crosslinks of 3D Graphene on Carbon Paper as the Bioanode

Herein, we successfully construct the 3D biocompatible graphene through crosslinking 2D graphene nanosheet onto carbon fiber paper with poly(diallyldimethylammonium chloride) (PDDA) as anode of the alcohol biofuel cell. Compared with the bioanode without 3D graphene, the current density and output power of PDDA-graphene-ADH bioanode is increased by 23 % and 41 % at a high concentration of ethanol at pH 8.9, suggesting the stabilization role of graphene in enzyme loading. The study provides us a deep analysis on structures and performances of the bioanode incl. electrochemistry, X-ray photoelectron spectra, and atomic force microscopy images, which is significant to develop the new methods to construct 3D porous electrodes in energy conversion device.     

Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.