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Chemical Communications (Cambridge,... Jun 2023Reversible Addition-Fragmentation Chain Transfer (RAFT) step-growth polymerization is an emerging method that synergistically combines the benefits of RAFT... (Review)
Review
Reversible Addition-Fragmentation Chain Transfer (RAFT) step-growth polymerization is an emerging method that synergistically combines the benefits of RAFT polymerization (functional group and user-friendly nature) and step-growth polymerization (versatility of the polymer backbone). This new polymerization method is generally achieved by using bifunctional reagents of monomer and Chain Transfer Agent (CTA), that efficiently yield Single Monomer Unit Insertion (SUMI) adducts under stoichiometrically balanced conditions. This review covers a brief history of the RAFT-SUMI process and its transformation into RAFT step-growth polymerization, followed by a comprehensive discussion of various RAFT step-growth systems. Furthermore, characterizing the molecular weight evolution of step-growth polymerization is elaborated based on the Flory model. Finally, a formula is introduced to describe the efficiency of the RAFT-SUMI process, assuming rapid chain transfer equilibrium. Examples of reported RAFT step-growth and SUMI systems are then categorized based on the driving force.
Topics: Polymerization; Polymers; Molecular Weight
PubMed: 37287313
DOI: 10.1039/d3cc01087b -
Macromolecular Rapid Communications Mar 2021Structurally complex π-conjugated polymers hold great promise as key components in sensor and electronic devices; however, their syntheses have not been a trivial task.... (Review)
Review
Structurally complex π-conjugated polymers hold great promise as key components in sensor and electronic devices; however, their syntheses have not been a trivial task. From a synthetic efficiency perspective, it would be more attractive to access these materials using convenient and efficient methods from simple building blocks. One such synthetic tool, multicomponent polymerization, can accommodate modularity and provide highly efficient syntheses. This feature article outlines several multicomponent polymerization strategies for the synthesis of various π-conjugated polymers, which are classified based upon how the monomers are aligned during polymerization. Additionally, the challenges and outlooks of this field are highlighted and discussed.
Topics: Polymerization; Polymers
PubMed: 33325573
DOI: 10.1002/marc.202000646 -
Chemistry, An Asian Journal Dec 2022The reliance of both our life and industry on fossil resource and the alarming accumulation of polymeric materials in the environment have presented huge challenges to... (Review)
Review
The reliance of both our life and industry on fossil resource and the alarming accumulation of polymeric materials in the environment have presented huge challenges to sustainable society. Nowadays, utilization of renewable monomers as building blocks for polymeric materials has emerged as a hot topic and increasingly gained attention from chemists. As a class of biomass with abundance and low cost, terpenes are typical hydrocarbon-rich natural compounds, and some of them, such as myrcene and farnesene, are inherently suitable for coordination polymerization. In this review, we focus on the rare-earth metal catalyzed highly regio- and stereoselective polymerization of bio-based conjugated dienes, especially the ones from terpene-derived compounds with or without modifications. This review also discusses the future direction on the modification of these bio-based conjugated dienes.
Topics: Polymerization; Coordination Complexes; Metals, Rare Earth; Polyenes; Biomass; Polymers; Terpenes
PubMed: 36165273
DOI: 10.1002/asia.202200892 -
Biomacromolecules Nov 2020Vesicle-templated polymerization has developed into a mature research area over the last 35 years. The main purpose of this approach was to produce hollow polymeric... (Review)
Review
Vesicle-templated polymerization has developed into a mature research area over the last 35 years. The main purpose of this approach was to produce hollow polymeric nanocapsules from low-cost chemicals, utilizing a simple emulsion-polymerization-like process. Over the years, understanding of the different varieties of the approach has grown. In retrospect, the characterization methods utilized to determine the morphologies are essential to draw the right conclusions. In this Review, first, an overview of the earlier attempts to produce nanocapsules with uniformous wall thickness will be given, looking at the results with the current understandings, greatly enhanced by quantification of the different morphologies through cryo-TEM images. The latest approach, reactive oligomer assisted transcriptive synthesis, seems to be able to fulfill the initial purpose and almost 100% of nanocapsule morphologies can be formed under the right conditions.
Topics: Emulsions; Nanocapsules; Polymerization; Polymers
PubMed: 32510945
DOI: 10.1021/acs.biomac.0c00558 -
Chemical Society Reviews Apr 2022The modulation of protein surface physicochemistry through single point mutations can trigger polymerization, which is facilitated by subunit repetition within a... (Review)
Review
The modulation of protein surface physicochemistry through single point mutations can trigger polymerization, which is facilitated by subunit repetition within a homomeric complex. Furthermore, monogenic disorders may result from aberrant supramolecular assemblies caused by missense mutations that modify the protein surface. Noteworthy from a therapeutic perspective, small molecules have been shown to not only mediate and enhance polymerization, analogous to a surface residue perturbation, but also bind and stabilize the repeating unit to inhibit the self-assembly event. We exemplify pharmacological manipulation of polymeric protein assemblies using some recently reported studies. The aim of this Viewpoint is to highlight opportunities to rationally control protein polymerization for therapeutic benefit.
Topics: Polymerization; Polymers
PubMed: 35266488
DOI: 10.1039/d2cs00070a -
Journal of the American Chemical Society Aug 2022Since its inception, atom transfer radical polymerization (ATRP) has seen continuous evolution in terms of the design of the catalyst and reaction conditions; today, it... (Review)
Review
Since its inception, atom transfer radical polymerization (ATRP) has seen continuous evolution in terms of the design of the catalyst and reaction conditions; today, it is one of the most useful techniques to prepare well-defined polymers as well as one of the most notable examples of catalysis in polymer chemistry. This Perspective highlights fundamental advances in the design of ATRP reactions and catalysts, focusing on the crucial role that mechanistic studies play in understanding, rationalizing, and predicting polymerization outcomes. A critical summary of traditional ATRP systems is provided first; we then focus on the most recent developments to improve catalyst selectivity, control polymerizations via external stimuli, and employ new photochemical or dual catalytic systems with an outlook to future research directions and open challenges.
Topics: Catalysis; Polymerization; Polymers
PubMed: 35882005
DOI: 10.1021/jacs.2c05364 -
ChemPlusChem Jan 2022The growing environmental pollution and the expected depleting of fossil resources have sparked interest in recent years for polymers obtained from monomers originating... (Review)
Review
The growing environmental pollution and the expected depleting of fossil resources have sparked interest in recent years for polymers obtained from monomers originating from renewable sources. Furthermore, nature can provide a variety of building blocks with special structural features (e. g. side groups or stereo-elements) that cannot be obtained so easily via fossil-based pathways. In this context, terpenes are widespread natural compounds coming from non-food crops, present in a large variety of structures, and ready to use as monomers with or without further modifications. The present review aims to provide an overview of how chemists can stereospecifically polymerize terpenes, particularly the acyclic ones like myrcene, ocimene, and farnesene, using different metal catalyst systems in coordination-insertion polymerization. Attention is also paid to their copolymers, which have recently been disclosed, and to the possible applications of these bio-based materials in various industrial sectors such as in the field of elastomers. © 2021 The Authors. ChemPlusChem published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
Topics: Catalysis; Metals; Polymerization; Polymers; Terpenes
PubMed: 34674387
DOI: 10.1002/cplu.202100366 -
Small (Weinheim An Der Bergstrasse,... May 2023The combination of biomolecules and synthetic polymers provides an easy access to utilize advantages from both the synthetic world and nature. This is not only important... (Review)
Review
The combination of biomolecules and synthetic polymers provides an easy access to utilize advantages from both the synthetic world and nature. This is not only important for the development of novel innovative materials, but also promotes the application of biomolecules in various fields including medicine, catalysis, and water treatment, etc. Due to the rapid progress in synthesis strategies for polymer nanomaterials and deepened understanding of biomolecules' structures and functions, the construction of advanced polymer-based biohybrid nanostructures (PBBNs) becomes prospective and attainable. Polymerization-induced self-assembly (PISA), as an efficient and versatile technique in obtaining polymeric nano-objects at high concentrations, has demonstrated to be an attractive alternative to existing self-assembly procedures. Those advantages induce the focus on the fabrication of PBBNs via the PISA technique. In this review, current preparation strategies are illustrated based on the PISA technique for achieving various PBBNs, including grafting-from and grafting-through methods, as well as encapsulation of biomolecules during and subsequent to the PISA process. Finally, advantages and drawbacks are discussed in the fabrication of PBBNs via the PISA technique and obstacles are identified that need to be overcome to enable commercial application.
Topics: Polymerization; Polymers; Prospective Studies; Nanostructures; Catalysis
PubMed: 36737834
DOI: 10.1002/smll.202207457 -
Biomacromolecules Nov 2020A comprehensive overview of the fundamentals of emulsion polymerization and related processes is presented with the object of providing theoretical and practical... (Review)
Review
A comprehensive overview of the fundamentals of emulsion polymerization and related processes is presented with the object of providing theoretical and practical understanding to researchers considering use of these methods for synthesis of polymer colloids across a wide range of applications. Hence, the overview has been written for a general scientific audience with no prior knowledge assumed. Succinct introductions are given to key topics of background science to assist the reader. Importance is placed on ensuring mechanistic understanding of these complex polymerizations and how the processes can be used to create polymer colloids that have particles with well-defined properties and morphology. Mathematical equations and associated theory are given where they enhance understanding and learning and where they are particularly useful for practical application. Practical guidance also is given for new researchers so that they can begin using the various processes effectively and in ways that avoid common mistakes.
Topics: Colloids; Emulsions; Polymerization; Polymers
PubMed: 32543173
DOI: 10.1021/acs.biomac.0c00769 -
Macromolecular Rapid Communications Oct 2023Over the past decade, polymerization-induced self-assembly (PISA) has fully proved its versatility for scale-up production of block copolymer nanoparticles with tunable... (Review)
Review
Over the past decade, polymerization-induced self-assembly (PISA) has fully proved its versatility for scale-up production of block copolymer nanoparticles with tunable sizes and morphologies; yet, there are still some limitations. Recently, seeded PISA approaches combing PISA with heterogeneous seeded polymerizations have been greatly explored and are expected to overcome the limitations of traditional PISA. In this review, recent advances in seeded PISA that have expanded new horizons for PISA are highlighted including i) general considerations for seeded PISA (e.g., kinetics, the preparation of seeds, the selection of monomers), ii) morphological evolution induced by seeded PISA (e.g., from corona-shell-core nanoparticles to vesicles, vesicles-to-toroid, disassembly of vesicles into nanospheres), and iii) various well-defined nanoparticles with hierarchical and sophisticated morphologies (e.g., multicompartment micelles, porous vesicles, framboidal vesicles, AX -type colloidal molecules). Finally, new insights into seeded PISA and future perspectives are proposed.
Topics: Polymerization; Micelles; Nanospheres; Polymers; Kinetics
PubMed: 37615609
DOI: 10.1002/marc.202300334