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Nature Communications Jan 2023Polymers with low ceiling temperatures (T) are highly desirable as they can depolymerize under mild conditions, but they typically suffer from demanding synthetic...
Polymers with low ceiling temperatures (T) are highly desirable as they can depolymerize under mild conditions, but they typically suffer from demanding synthetic conditions and poor stability. We envision that this challenge can be addressed by developing high-T polymers that can be converted into low-T polymers on demand. Here, we demonstrate the mechanochemical generation of a low-T polymer, poly(2,5-dihydrofuran) (PDHF), from an unsaturated polyether that contains cyclobutane-fused THF in each repeat unit. Upon mechanically induced cycloreversion of cyclobutane, each repeat unit generates three repeat units of PDHF. The resulting PDHF completely depolymerizes into 2,5-dihydrofuran in the presence of a ruthenium catalyst. The mechanochemical generation of the otherwise difficult-to-synthesize PDHF highlights the power of polymer mechanochemistry in accessing elusive structures. The concept of mechanochemically regulating the T of polymers can be applied to develop next-generation sustainable plastics.
Topics: Polymers; Cyclobutanes; Plastics; Catalysis
PubMed: 36641481
DOI: 10.1038/s41467-023-35925-2 -
Macromolecular Rapid Communications Jan 2019Direct (hetero)arylation polymerization exploits the palladium-catalyzed activation of aromatic CH bonds for the atom-economical synthesis of conjugated polymers for... (Review)
Review
Direct (hetero)arylation polymerization exploits the palladium-catalyzed activation of aromatic CH bonds for the atom-economical synthesis of conjugated polymers for a wide range of applications. This account outlines how direct arylation methodologies overcome many of the limitations of contemporary polymerization techniques at both the research and production scale, and explains how monomer design and reaction conditions must be tailored to ensure high polymer molecular weight, yield, and structural integrity. Current research aims to improve further this reaction's profile as a sustainable methodology while at the same time making it competitive with the Migita-Stille and Miyaura-Suzuki polymerizations both in scope of accessible structures and synthetic efficiency. This feature article charts the recent developments and future directions of CH activation research as it moves toward becoming at once an industrially feasible, environmentally friendly, and synthetically powerful polymerization technique.
Topics: Catalysis; Molecular Structure; Palladium; Polymerization; Polymers
PubMed: 30199142
DOI: 10.1002/marc.201800512 -
Chemical Society Reviews Dec 2009The control over comonomer sequences is barely studied in macromolecular science nowadays. This is an astonishing situation, taking into account that sequence-defined... (Review)
Review
The control over comonomer sequences is barely studied in macromolecular science nowadays. This is an astonishing situation, taking into account that sequence-defined polymers such as nucleic acids and proteins are key components of the living world. In fact, fascinating biological machines such as enzymes, transport proteins, cytochromes or sensory receptors would certainly not exist if evolution had not favored chemical pathways for controlling chirality and sequences. Thus, it seems obvious that synthetic polymers with controlled monomer sequences have an enormous role to play in the materials science of the next centuries. The goal of this tutorial review is to shed light on this highly important but embryonic field of research. Both biological and synthetic mechanisms for controlling sequences in polymerization processes are critically discussed herein. This state-of-the-art overview may serve as a source of inspiration for the development of new generations of synthetic macromolecules.
Topics: Biopolymers; Chemistry; Polymers
PubMed: 20449057
DOI: 10.1039/b806413j -
Chemical Society Reviews Jan 2004Polymer brushes produced by controlled surface-initiated polymerization provide a route to surfaces coated with well-defined thin polymer films that are covalently bound... (Review)
Review
Polymer brushes produced by controlled surface-initiated polymerization provide a route to surfaces coated with well-defined thin polymer films that are covalently bound to the substrate. All of the major controlled polymerization techniques have been applied to the synthesis of polymer brushes and examples of each are presented here. Many examples of brush synthesis in the literature have used the living atom transfer radical polymerization (ATRP) system, and in this tutorial review a particular focus is given to examples of this technique.
Topics: Models, Chemical; Nanotechnology; Particle Size; Polymers; Surface Properties; Surface-Active Agents
PubMed: 14737505
DOI: 10.1039/b210143m -
Nature Nov 2023
Topics: Polymers; Biocompatible Materials
PubMed: 37953305
DOI: 10.1038/d41586-023-03497-2 -
Chemical Society Reviews Sep 2013Stimuli-responsive polymer films undergo interesting structural and property changes upon external stimuli. Their applications have extended from smart coatings to...
Stimuli-responsive polymer films undergo interesting structural and property changes upon external stimuli. Their applications have extended from smart coatings to controlled drug release, smart windows, self-repair and other fields. This tutorial review summarizes non-covalent bonding, reversible reactions and responsive molecules that have played important roles in creating stimuli-responsive systems, and presents the recent development of three types of responsive polymer systems: layer-by-layer polymer multilayer films, polymer brushes, and self-repairing polymer films, with a discussion of their response mechanism. Future research efforts include comprehensive understanding of the response mechanism, producing polymer systems with controlled response properties regarding single or multiple external signals, combining polymer film fabrication with nanotechnology, improving the stability of polymer films on substrates, and evaluating the toxicity of the degradation products.
Topics: Cycloaddition Reaction; Electricity; Hydrogen-Ion Concentration; Polymers; Surface Properties; Temperature
PubMed: 23749141
DOI: 10.1039/c3cs60023h -
Journal of Colloid and Interface Science Jan 2010Nowadays, functionalized conducting polymer nanomaterials have been received great attention in nanoscience and nanotechnology because of their large surface area. This... (Review)
Review
Nowadays, functionalized conducting polymer nanomaterials have been received great attention in nanoscience and nanotechnology because of their large surface area. This article reviews various methods for synthesis of conducting polymer nanostructures and their applications in sensing materials, focusing on hard-template, soft-template and other methods and the formation mechanism of conducting polymer nanostructures by these methods. Conducting polymer nanostructures, such as nanotubes, nanowires, and nanoparticles, as sensing platforms for various applications are also summarized.
Topics: Biosensing Techniques; Electric Conductivity; Nanostructures; Polymers; Surface Properties
PubMed: 19837415
DOI: 10.1016/j.jcis.2009.09.029 -
Analytica Chimica Acta Jan 2014Mass spectrometry (MS) is the most versatile and comprehensive method in "OMICS" sciences (i.e. in proteomics, genomics, metabolomics and lipidomics). The applications... (Review)
Review
Mass spectrometry (MS) is the most versatile and comprehensive method in "OMICS" sciences (i.e. in proteomics, genomics, metabolomics and lipidomics). The applications of MS and tandem MS (MS/MS or MS(n)) provide sequence information of the full complement of biological samples in order to understand the importance of the sequences on their precise and specific functions. Nowadays, the control of polymer sequences and their accurate characterization is one of the significant challenges of current polymer science. Therefore, a similar approach can be very beneficial for characterizing and understanding the complex structures of synthetic macromolecules. MS-based strategies allow a relatively precise examination of polymeric structures (e.g. their molar mass distributions, monomer units, side chain substituents, end-group functionalities, and copolymer compositions). Moreover, tandem MS offer accurate structural information from intricate macromolecular structures; however, it produces vast amount of data to interpret. In "OMICS" sciences, the software application to interpret the obtained data has developed satisfyingly (e.g. in proteomics), because it is not possible to handle the amount of data acquired via (tandem) MS studies on the biological samples manually. It can be expected that special software tools will improve the interpretation of (tandem) MS output from the investigations of synthetic polymers as well. Eventually, the MS/MS field will also open up for polymer scientists who are not MS-specialists. In this review, we dissect the overall framework of the MS and MS/MS analysis of synthetic polymers into its key components. We discuss the fundamentals of polymer analyses as well as recent advances in the areas of tandem mass spectrometry, software developments, and the overall future perspectives on the way to polymer sequencing, one of the last Holy Grail in polymer science.
Topics: Chromatography, High Pressure Liquid; Mass Spectrometry; Polymers; Software; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; Tandem Mass Spectrometry
PubMed: 24370093
DOI: 10.1016/j.aca.2013.10.027 -
Bioconjugate Chemistry Mar 2017As potent and selective therapeutic agents, peptides and proteins are an important class of drugs, but they typically have suboptimal pharmacokinetic profiles. One... (Review)
Review
As potent and selective therapeutic agents, peptides and proteins are an important class of drugs, but they typically have suboptimal pharmacokinetic profiles. One approach to solve this problem is their conjugation with "stealth" polymers. Conventional methods for conjugation of this class of polymers to peptides and proteins are typically carried out by reactions that have poor yield and provide limited control over the site of conjugation and the stoichiometry of the conjugate. To address these limitations, new chemical and biological approaches have been developed that provide new molecular tools in the bioconjugation toolbox to create stealth polymer conjugates of peptides and proteins with exquisite control over their properties. This review article highlights these recent advances in the synthesis of therapeutic peptide- and protein-stealth polymer conjugates.
Topics: Animals; Chemistry Techniques, Synthetic; Humans; Models, Molecular; Peptides; Polymers; Proteins
PubMed: 27998056
DOI: 10.1021/acs.bioconjchem.6b00652 -
Physical Chemistry Chemical Physics :... Mar 2011In recent years, interfacial properties have been tailored with nanostructured polymer assemblies to generate materials with specific properties and functions for... (Review)
Review
In recent years, interfacial properties have been tailored with nanostructured polymer assemblies to generate materials with specific properties and functions for application in diverse fields, including biomaterials, drug delivery, catalysis, sensing, optics and corrosion. This perspective begins with a brief introduction of the assembly techniques that are commonly employed for the synthesis of nanostructured polymer materials, followed by discussions on how the interfaces influence the properties and thus the functionalities of the polymer materials prepared. Applications of the interfacial polymer nanostructures, particularly for the immobilization and encapsulation of cargo, are then reviewed, focusing on stimuli-responsive cargo release from the polymer nanostructured assemblies for controlled delivery applications. Finally, future research directions in these areas are briefly discussed.
Topics: Capsules; Enzymes; Nanostructures; Polymers
PubMed: 21331404
DOI: 10.1039/c0cp02287j