MRC专刊:高分子科学中的多组分反应

现代科技的快速发展给高分子结构和性能的多样性提出了迫切需求,对新型聚合反应和聚合物结构的追求是高分子化学持续不变的主题。

通过三种或以上原料在一锅反应中生成单一产物的多组分反应,享有原料简单、操作便捷、条件温和、环境友好、反应高效、产物结构多样等优势,近年来逐渐在高分子合成中崭露头角,被成功开发为多组分聚合,或用于聚合物后修饰,发展成为高效构筑多功能高分子库的有力手段。相比与其他聚合反应而言,多组分聚合享有一系列独特优势,包括聚合产物结构和性质的多样性、高分子主链和拓扑结构便捷可调、反应过程和条件可设计性强、可原位构筑新的功能基元等。

鉴于近年来高分子合成中多组分反应的广泛应用和快速发展,德国卡尔斯鲁厄理工学院Michael A. R. Meier教授、华南理工大学胡蓉蓉教授、香港科技大学/华南理工大学唐本忠院士等人为Macromolecular Rapid Communications期刊组织编撰了“高分子科学中的多组分反应”专刊。本专刊由11篇研究论文和8篇综述论文组成,内容覆盖了本领域大部分重要研究方向,包括基于经典的Passerini反应、Ugi反应、Hantzsch反应等的高分子合成;基于炔类单体的新型多组分聚合,用于构筑含第15-17族元素的杂链聚合物;采用天然小分子O2、H2O、CO2和S8等作为绿色单体构筑高分子产物的新型多组分聚合;通过多组分聚合制备具有不同化学元素组成、骨架共轭结构和拓扑结构的新型高分子;以及作为基因传递载体、聚集诱导发光材料、生物医用高分子和高分子吸附材料等的多组分聚合产物。

 多组分聚合和基于多组分反应的高分子后修饰可将简单单体高效便捷地转化为具有新颖结构和先进功能、丰富多样的高分子材料,推动高分子化学和高分子材料的快速发展,已成为高分子科学领域蓬勃发展的新兴方向。

专刊链接:https://onlinelibrary.wiley.com/toc/15213927/current

专刊文章如下:

Functional Heterochain Polymers Constructed by Alkyne Multicomponent Polymerizations

Functional heterochain polymers, such as DNA and proteins, are abundant and essential in nature, but are not ubiquitous among man‐made polymers due to the synthetic difficulties. The alkyne multicomponent polymerizations initiated in the early 2000s open a new door for the synthesis of conjugated heterochain polymers with diverse structures and unique properties.

文章链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000386

The Hantzsch Reaction in Polymer Chemistry: From Synthetic Methods to Applications

The Hantzsch reaction, one of the oldest and most famous multicomponent reactions, is used to develop polymers having 1,4‐dihydropyridine structures in the main and/or side chains. Preparation methods and applications (protein conjugation, formaldehyde detection, drug carrier, and anti‐bacterial adhesion) of these polymers are summarized.

文章链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000459

Multicomponent Reactions in Polymer Chemistry Utilizing Heavier Main Group Elements

The use of heavier elements is explored in multi‐component reactions and it is highlighted how—these to date less exploited—elements provide unique opportunities for a wide range of applications, specifically in sensing and materials science.

文章链接 https://onlinelibrary.wiley.com/doi/10.1002/marc.202000495

Ugi Reaction of Amino Acids: From Facile Synthesis of Polypeptoids to Sequence‐Defined Macromolecules

The Ugi reaction of amino acids has recently been introduced into polypeptoid chemistry as a new and powerful method to furnish polypeptoids. In this mini review, the recent progress on the application of the Ugi reaction of amino acids in polypeptoid science, including polypeptoid from sustainable furfural, sequence‐defined polypeptoids, and more, is summarized.

文章链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000515

Multicomponent Polymerizations Involving Green Monomers

The recent development of multicomponet polymerizations (MCPs) involving green monomers of oxygen (O2), water (H2O), and carbon dioxide (CO2) is reviewed from the aspects of the catalytic systems, polymerization conditions, molecular weights, yields, structures, and potential applications of resultant polymers. Furthermore, the existing challenges and the promising opportunities in this area are concisely discussed.

文章链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000547

Recent Advances on Fabrication of Polymeric Composites Based on Multicomponent Reactions for Bioimaging and Environmental Pollutant Removal

The recent advances in the fabrication of polymeric composites through multicomponent reactions, such as Mannich reaction, Debus–Radziszewski reaction, Biginelli reaction, mercaptoacetic acid locking imine reaction, Kabachnik–Fields reaction, and polycoupling reaction are summarized in this minireview. The potential applications of these functional polymeric composites in biomedical and environmental fields are highlighted and discussed in the following sections.

文章链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000563

One‐Step Multicomponent Polymerizations for the Synthesis of Multifunctional AIE Polymers

Functional polymers with aggregation‐induced emission (AIE) properties have attracted great attention due to their wide applications. Among various synthetic strategies, one‐step multicomponent polymerization is emerging as a powerful tool for constructing multifunctional AIE polymers. The commonly involved strategies include the use of AIEgen‐containing monomers and the in situ generation of AIE polymers.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000471

Multicomponent Polymerization for π‐Conjugated Polymers

This feature article outlines recent advancement of multicomponent polymerizations for the synthesis of π‐conjugated polymers, which are classified based upon the monomer alignment during polymerization. Challenges and outlook of this field are also provided.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000646

Elemental Sulfur Mediated Novel Multicomponent Redox Polycondensation for the Synthesis of Alternating Copolymers Based on 2,4‐Thiophene/Arene Repeating Units

A sulfur‐based multicomponent polycondensation is reported for the first time as an efficient tool for the synthesis of unprecedented alternating copolymers based on 2,4‐thiophene/arene repeating units starting from commercially available raw materials.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000695

CO2‐Strengthened Double‐Cross‐Linked Polymer Gels from Frustrated Lewis Pair Networks

A new double‐cross‐linking frustrated Lewis pair network is constructed through three‐component reaction of triarylborane, triarylphosphine, and CO2. CO2, as a kind of dynamic covalent crosslinking, can control and modulate the mechanical performance and healable ability of the polymer network system. This study will inspire a new way for the creation of gas‐based adaptive materials.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000699

Synthesis of Passerini‐3CR Polymers and Assembly into Cytocompatible Polymersomes

A facile, versatile and reproducible synthesis via the Passerini three component reaction (Passerini‐3CR) of amphiphilic copolymers, which self‐assemble into polymersomes is herein shown. These materials are rapidly internalized by breast cells, are cytocompatible and are well tolerated in healthy mice. This new route to polymersomes demonstrates the versatility of the Passerini‐3CR for new drug delivery systems which have properties advantageous for clinical translation.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000321

Catalyst‐Free Multicomponent Cyclopolymerizations of Diisocyanides, Activated Alkynes, and 1,4‐Dibromo‐2,3‐Butanedione: a Facile Strategy toward Functional Polyiminofurans Containing Bromomethyl Groups

A novel multicomponent cyclopolymerization of diisocyanides, activated alkynes, and 1,4‐dibromo‐2,3‐butanedione is developed to prepare polyiminofurans (PIFs) containing bromomethyl groups based on catalyst‐free one‐pot reactions under mild conditions. The polymers P1a2b3 and P1c2b3 exhibit unconventional emission with cluster‐triggered emission property. Thin films made from PIFs quickly degraded under UV irradiation, making them potentially useful as lithographic materials.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000463

Multicomponent Polymerization toward Cationic Polymers for Efficient Gene Delivery

A library of polycations containing tertiary amine, thioether, and hydroxyl groups are prepared via a multicomponent polymerization method. The polycations can condense DNA by tertiary amine groups and achieve efficient gene transfection efficiency. Thioether groups have the potency to scavenge reactive oxygen species spontaneously and reduced toxicity. Hydroxyl groups can shield the positive charges and improve the transfection efficiency in the serum.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000464

Synthesis and Encapsulation of Uniform Star‐Shaped Block‐Macromolecules

Three uniform star‐shaped block‐macromolecules (9.8–14.1 kDa) are synthesized in an iterative procedure via the arm‐first approach and carefully characterized with NMR, electrospray ionization mass spectrometry (ESI‐MS), and size exclusion chromatography (SEC) to confirm their purity. The obtained macromolecules are applied in solid–liquid phase transfer experiments to evaluate their abilities in encapsulating guest molecules.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000464

Shear‐Induced Adhesion of Alternating Peptides Prepared by Ugi Four‐Center Three‐Component Reaction

A facile strategy for preparing elastin‐mimetic alternating peptides for extraordinarily high strength and tough adhesion is demonstrated. Alternating peptides bearing elastin‐mimetic sequences are synthesized as a possible candidate of viscous adhesive. The polymers comprising glycine‐N‐Bn valine and glycine‐N‐MPM valine repeating units exhibit a unique shear‐induced adhesion capacity with high adhesion strength.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000480

Robust Fabrication of Fluorescent Cellulosic Materials via Hantzsch Reaction

Hantzsch reaction is employed for fabricating fluorescent cellulosic materials. A strong fluorescent emission around 460 nm can be achieved within 10 min at ambient temperature. The modification process hardly affects the intrinsic properties of cellulosic materials. This method is also shown to be generally applicable to various forms of cellulosic materials and different aldehydes.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000496

Hyperbranched Bisphosphonate‐Functional Polymers via Self‐Condensing Vinyl Polymerization and Postpolymerization Multicomponent Reactions

The synthesis of highly branched amino‐functional polymers via reversible addition‐fragmentation chain transfer (RAFT) self‐condensing vinyl polymerization is reported. The polymers are further functionalized via a multicomponent postpolymerization modification to introduce aminobisphophonate groups and to create stimuli‐responsive hydrogels. Analysis via dynamic light scattering (DLS) reveals interesting solution behavior influenced by the degree of branching of these polymers.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000578

Facile Multicomponent Polymerization and Postpolymerization Modification via an Effective Meldrum’s Acid‐Based Three‐Component Reaction

A Meldrum’s acid‐based multicomponent polymerization of Meldrum’s acid, dialdehyde, and diindole using proline as a catalyst can perform under mild conditions, resulting in complex polymers with well‐defined structures, high yields, and high molecular weights. Meanwhile, the multicomponent reaction is also demonstrated to be a powerful tool in the postpolymerization modification.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000578

Catalyst‐Free Four‐Component Polymerization of Propiolic Acids, Benzylamines, Organoboronic Acids, and Formaldehyde toward Functional Poly(propargylamine)s

A catalyst‐free, four‐component polymerization of propiolic acids, benzylamines, organoboronic acids, and formaldehyde is designed under mild condition, taking advantage of the high reactivity of carboxylic acid group‐activated alkyne monomers, to furnish poly(propargylamine)s with high molecular weights, high yields, good solubility and processibility, high thermal stability, high light refractivity, and unique photophysical property.

原文链接:https://onlinelibrary.wiley.com/doi/10.1002/marc.202000578