Chemistry Organic Chemistry

Advanced Polymer Synthesis and Characterization

Description

This cluster of papers focuses on the advances in living radical polymerization techniques, including atom transfer radical polymerization (ATRP), reversible addition–fragmentation chain transfer (RAFT), and nitroxide-mediated polymerization. It also explores the application of click chemistry, self-assembly of block copolymers, and the synthesis of functional polymers such as vesicles and micelles.

Keywords

Living Radical Polymerization; Click Chemistry; Block Copolymers; Self-Assembly; Thiol-Ene Chemistry; Vesicles; RAFT Process; Controlled Polymerization; Micelles; Functional Polymers

Block copolymer micelles are water-soluble biocompatible nanocontainers with great potential for delivering hydrophobic drugs. An understanding of their cellular distribution is essential to achieving selective delivery of drugs at the … Block copolymer micelles are water-soluble biocompatible nanocontainers with great potential for delivering hydrophobic drugs. An understanding of their cellular distribution is essential to achieving selective delivery of drugs at the subcellular level. Triple-labeling confocal microscopy in live cells revealed the localization of micelles in several cytoplasmic organelles, including mitochondria, but not in the nucleus. Moreover, micelles change the cellular distribution of and increase the amount of the agent delivered to the cells. These micelles may thus be worth exploring for their potential to selectively deliver drugs to specified subcellular targets.
This Perspective presents recent advances in macromolecular engineering enabled by ATRP. They include the fundamental mechanistic and synthetic features of ATRP with emphasis on various catalytic/initiation systems that use parts-per-million … This Perspective presents recent advances in macromolecular engineering enabled by ATRP. They include the fundamental mechanistic and synthetic features of ATRP with emphasis on various catalytic/initiation systems that use parts-per-million concentrations of Cu catalysts and can be run in environmentally friendly media, e.g., water. The roles of the major components of ATRP—monomers, initiators, catalysts, and various additives—are explained, and their reactivity and structure are correlated. The effects of media and external stimuli on polymerization rates and control are presented. Some examples of precisely controlled elements of macromolecular architecture, such as chain uniformity, composition, topology, and functionality, are discussed. Syntheses of polymers with complex architecture, various hybrids, and bioconjugates are illustrated. Examples of current and forthcoming applications of ATRP are covered. Future challenges and perspectives for macromolecular engineering by ATRP are discussed.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMetal-Catalyzed Living Radical PolymerizationMasami Kamigaito, Tsuyoshi Ando, and Mitsuo SawamotoView Author Information Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 606-8501, Japan Cite this: … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMetal-Catalyzed Living Radical PolymerizationMasami Kamigaito, Tsuyoshi Ando, and Mitsuo SawamotoView Author Information Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 606-8501, Japan Cite this: Chem. Rev. 2001, 101, 12, 3689–3746Publication Date (Web):December 12, 2001Publication History Received14 July 2001Published online12 December 2001Published inissue 1 December 2001https://pubs.acs.org/doi/10.1021/cr9901182https://doi.org/10.1021/cr9901182research-articleACS PublicationsCopyright © 2001 American Chemical SocietyRequest reuse permissionsArticle Views16747Altmetric-Citations3103LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Copolymers,Living polymerization,Organic compounds,Radical polymerization,Styrenes Get e-Alerts
Amphiphilic block copolymers (ABCs) are important in interface and particle stabilization. Following consideration of the various methods of synthesis of ABCs, mesophases and micelles of block copolymers and the solubilization … Amphiphilic block copolymers (ABCs) are important in interface and particle stabilization. Following consideration of the various methods of synthesis of ABCs, mesophases and micelles of block copolymers and the solubilization and adhesion of ABCs are considered. The Figure shows micelles formed by a polystyrene-poly(vinylpyridine) copolymer. Nanoparticles and ABC/nanoparticle hybrid systems are also reviewed.
Crew-cut micelle-like aggregates of various morphologies prepared from polystyrene-b-poly(acrylic acid), PS-b-PAA, diblock copolymers under near-equilibrium conditions, were studied by transmission electron microscopy (TEM). The insoluble block (PS) contents in the … Crew-cut micelle-like aggregates of various morphologies prepared from polystyrene-b-poly(acrylic acid), PS-b-PAA, diblock copolymers under near-equilibrium conditions, were studied by transmission electron microscopy (TEM). The insoluble block (PS) contents in the copolymers ranged from 80 to 98 wt %. In spherical micelles, the micelle cores, formed by aggregation of the PS blocks, were generally monodisperse. A comparison between star and crew-cut micelles showed that the latter are distinguished by a low density of corona chains on the core surface and a low degree of stretching of the PS blocks in the cores. As the PAA content in block copolymer decreased, the morphology of the aggregates changed progressively from spheres to cylinders, to bilayers (both vesicles and lamellae), and eventually to compound micelles consisting of an assembly of inverted micelles surrounded by a hydrophilic surface. The compound micelles are believed to be a new morphology for block copolymers. The addition of homopolystyrene to the diblocks changed the morphologies from bilayers or cylinders to spheres. The present system provides the first instance in which all these multiple aggregate morphologies have been observed directly in block copolymers in a low molecular weight solvent with changing copolymer composition. It is believed that this is the only way so far to prepare stable nanosize glassy vesicles of block copolymers which form spontaneously and can be isolated in water and studied directly by electron microscopy.
For three types of linear polycondensing systems, equilibrium molecular size distributions, including rings as allowable species, are derived. Average molecular weights and amounts of ring and chain fractions are calculated … For three types of linear polycondensing systems, equilibrium molecular size distributions, including rings as allowable species, are derived. Average molecular weights and amounts of ring and chain fractions are calculated therefrom. The fractions of rings are shown to increase with dilution, and with molecular weight. It is shown that beyond a critical dilution it is sometimes possible to obtain 100 percent yield of rings by driving the condensation to completion. Detailed calculations are made for two important cases corresponding to condensations of the decamethylene glycol-adipic acid type: (1) for equimolar amounts of the two monomers, and (2) unequal amounts, with one monomer type completely reacted.
As a basis for understanding emulsion polymerization, the kinetics of free radical reactions in isolated loci is discussed subject to the condition that the free radicals are supplied to the … As a basis for understanding emulsion polymerization, the kinetics of free radical reactions in isolated loci is discussed subject to the condition that the free radicals are supplied to the loci from an external source. Three cases of interest are considered: that in which the average number of free radicals per locus is small compared with unity, that in which this number approximates one-half, and that in which the number is large. Of these three possibilities, the second, in which the free radicals per locus approximate one-half, is by far the most interesting as it explains in a satisfactory manner the characteristic features of styrene emulsion polymerization. For this case the average rate of reaction per locus is independent of the size of the locus, since this rate is simply one-half the rate of polymerization of a single free radical. Thus the rate of emulsion polymerization, the concentration of monomer in the loci, and the number of loci present provide the information needed for calculating the chain propagation constant for the monomer. A simplified treatment is given for approximating the number of reaction loci (polymer particles) produced in emulsion polymerization when the rate of polymerization per locus is constant (see case 2 above). The law obtained indicates that the number of particles should increase with the soap concentration (3/5ths power) and with the rate of formation of free radicals (2/5ths power), but should decrease with increasing rate of growth of the free radicals (−2/5ths power).
ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTTransition Metal-Catalyzed Living Radical Polymerization: Toward Perfection in Catalysis and Precision Polymer SynthesisMakoto Ouchi, Takaya Terashima, and Mitsuo Sawamoto*View Author Information Department of Polymer Chemistry, Graduate School … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTTransition Metal-Catalyzed Living Radical Polymerization: Toward Perfection in Catalysis and Precision Polymer SynthesisMakoto Ouchi, Takaya Terashima, and Mitsuo Sawamoto*View Author Information Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan* To whom correspondence should be addressed. Phone: +81-75-383-2600. Fax: +81-75-383-2601. E-mail: [email protected]Cite this: Chem. Rev. 2009, 109, 11, 4963–5050Publication Date (Web):September 29, 2009Publication History Received1 July 2009Published online29 September 2009Published inissue 11 November 2009https://pubs.acs.org/doi/10.1021/cr900234bhttps://doi.org/10.1021/cr900234breview-articleACS PublicationsCopyright © 2009 American Chemical SocietyRequest reuse permissionsArticle Views19677Altmetric-Citations1159LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Copolymers,Living polymerization,Monomers,Polymers Get e-Alerts
ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorNEXTFunctional Polymers from Novel Carboxyl-Terminated Trithiocarbonates as Highly Efficient RAFT AgentsJohn T. Lai, Debby Filla, and Ronald SheaView Author Information Noveon, Inc., … ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorNEXTFunctional Polymers from Novel Carboxyl-Terminated Trithiocarbonates as Highly Efficient RAFT AgentsJohn T. Lai, Debby Filla, and Ronald SheaView Author Information Noveon, Inc., 9911 Brecksville Rd, Brecksville, Ohio 44141 Cite this: Macromolecules 2002, 35, 18, 6754–6756Publication Date (Web):August 2, 2002Publication History Received8 March 2002Revised12 July 2002Published online2 August 2002Published inissue 1 August 2002https://pubs.acs.org/doi/10.1021/ma020362mhttps://doi.org/10.1021/ma020362mrapid-communicationACS PublicationsCopyright © 2002 American Chemical SocietyRequest reuse permissionsArticle Views26091Altmetric-Citations1327LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Monomers,Organic compounds,Polymers,Radical polymerization,RAFT polymerization Get e-Alerts
In the past decade, polymersomes (also referred to as polymeric vesicles) have attracted rapidly growing interest based on their intriguing aggregation phenomena, cell and virus-mimicking dimensions and functions, as well … In the past decade, polymersomes (also referred to as polymeric vesicles) have attracted rapidly growing interest based on their intriguing aggregation phenomena, cell and virus-mimicking dimensions and functions, as well as tremendous potential applications in medicine, pharmacy, and biotechnology. Unlike liposomes self-assembled from low molecular weight lipids, polymersomes are in general prepared from macromolecular amphiphiles of various architectures including amphiphilic diblock, triblock, graft and dendritic copolymers. Polymersomes exhibit very unique features highlighted with high stability, tunable membrane properties, versatility, and capacity of transporting hydrophilic as well as hydrophobic species such as anticancer drugs, genes, proteins, and diagnostic probes. Recently, much effort has been directed to the development of intelligent polymersomes that respond to internal or external stimuli, in particular, pH, temperature, redox potential, light, magnetic field, and ultrasound, either reversibly or nonreversibly. Stimuli-sensitive polymersomes have emerged as novel programmable delivery systems in which the release of the encapsulated contents can be readily modulated by the stimulus. The stimuli-responsive release may result in significantly enhanced therapeutic efficacy and minimized possible side effects. It is also feasible to form and disassemble polymersomes in water simply by applying an appropriate stimulus. In this article, recent advances in stimuli-sensitive polymersomes have been reviewed, and perspectives on future developments have been discussed.
The present Communication compares the thermosensitivity in dilute aqueous solutions of well-defined copolymers composed of 95% of 2-(2-methoxyethoxy)ethyl methacrylate (MEO2MA) and 5% of oligo(ethylene glycol) methacrylate (OEGMA, Mn = 475 … The present Communication compares the thermosensitivity in dilute aqueous solutions of well-defined copolymers composed of 95% of 2-(2-methoxyethoxy)ethyl methacrylate (MEO2MA) and 5% of oligo(ethylene glycol) methacrylate (OEGMA, Mn = 475 g·mol-1) and poly(N-isopropylacrylamide) (PNIPAM) samples having similar degrees of polymerization and chain-ends. The thermoresponsive behavior of P(MEO2MA-co-OEGMA) was found to be overall comparable, and in some cases, superior to PNIPAM. Hence, P(MEO2MA-co-OEGMA) copolymers can be considered as ideal structures, which combine both the properties of poly(ethylene glycol) and PNIPAM in a single macromolecule.
This review traces the development of addition–fragmentation chain transfer agents and related ring-opening monomers highlighting recent innovation in these areas. The major part of this review deals with reagents that … This review traces the development of addition–fragmentation chain transfer agents and related ring-opening monomers highlighting recent innovation in these areas. The major part of this review deals with reagents that give reversible addition–fragmentation chain transfer (RAFT). These reagents include dithioesters, trithiocarbonates, dithiocarbamates and xanthates. The RAFT process is a versatile method for conferring living characteristics on radical polymerizations providing unprecedented control over molecular weight, molecular weight distribution, composition and architecture. It is suitable for most monomers polymerizable by radical polymerization and is robust under a wide range of reaction conditions. It provides a route to functional polymers, cyclopolymers, gradient copolymers, block polymers and star polymers.
Abstract Among the living radical polymerization techniques, reversible addition–fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in … Abstract Among the living radical polymerization techniques, reversible addition–fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl‐thio compounds used as chain‐transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:5347–5393, 2005
Conventional metal-catalyzed organic radical reactions and living radical polymerizations (LRP) performed in nonpolar solvents, including atom-transfer radical polymerization (ATRP), proceed by an inner-sphere electron-transfer mechanism. One catalytic system frequently used … Conventional metal-catalyzed organic radical reactions and living radical polymerizations (LRP) performed in nonpolar solvents, including atom-transfer radical polymerization (ATRP), proceed by an inner-sphere electron-transfer mechanism. One catalytic system frequently used in these polymerizations is based on Cu(I)X species and N-containing ligands. Here, it is reported that polar solvents such as H(2)O, alcohols, dipolar aprotic solvents, ethylene and propylene carbonate, and ionic liquids instantaneously disproportionate Cu(I)X into Cu(0) and Cu(II)X(2) species in the presence of a diversity of N-containing ligands. This disproportionation facilitates an ultrafast LRP in which the free radicals are generated by the nascent and extremely reactive Cu(0) atomic species, while their deactivation is mediated by the nascent Cu(II)X(2) species. Both steps proceed by a low activation energy outer-sphere single-electron-transfer (SET) mechanism. The resulting SET-LRP process is activated by a catalytic amount of the electron-donor Cu(0), Cu(2)Se, Cu(2)Te, Cu(2)S, or Cu(2)O species, not by Cu(I)X. This process provides, at room temperature and below, an ultrafast synthesis of ultrahigh molecular weight polymers from functional monomers containing electron-withdrawing groups such as acrylates, methacrylates, and vinyl chloride, initiated with alkyl halides, sulfonyl halides, and N-halides.
The ability of amphiphilic block copolymers to self-assemble in selective solvents has been widely studied in academia and utilized for various commercial products. The self-assembled polymer vesicle is at the … The ability of amphiphilic block copolymers to self-assemble in selective solvents has been widely studied in academia and utilized for various commercial products. The self-assembled polymer vesicle is at the forefront of this nanotechnological revolution with seemingly endless possible uses, ranging from biomedical to nanometer-scale enzymatic reactors. This review is focused on the inherent advantages in using polymer vesicles over their small molecule lipid counterparts and the potential applications in biology for both drug delivery and synthetic cellular reactors.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAtom Transfer Radical PolymerizationKrzysztof Matyjaszewski and Jianhui XiaView Author Information Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213 Cite this: Chem. Rev. 2001, 101, 9, 2921–2990Publication … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAtom Transfer Radical PolymerizationKrzysztof Matyjaszewski and Jianhui XiaView Author Information Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213 Cite this: Chem. Rev. 2001, 101, 9, 2921–2990Publication Date (Web):September 12, 2001Publication History Received15 February 2001Published online12 September 2001Published inissue 1 September 2001https://pubs.acs.org/doi/10.1021/cr940534ghttps://doi.org/10.1021/cr940534gresearch-articleACS PublicationsCopyright © 2001 American Chemical SocietyRequest reuse permissionsArticle Views62803Altmetric-Citations6994LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Copolymers,Monomers,Organic compounds,Polymerization,Radical polymerization Get e-Alerts
Abstract A new graphically-evaluable linear method is suggested for the determination of the reactivity ratios of copolymerization. The proposed new equation is very well adaptable for visual determination of the … Abstract A new graphically-evaluable linear method is suggested for the determination of the reactivity ratios of copolymerization. The proposed new equation is very well adaptable for visual determination of the applicability of the copolymer composition equation. If the experimental data are adequate to the composition equation, the procedure offers a simple and reliable method for the graphical determination of copolymerization constants.
Block copolymer (BCP) self-assembly has attracted considerable attention for many decades because it can yield ordered structures in a wide range of morphologies, including spheres, cylinders, bicontinuous structures, lamellae, vesicles, … Block copolymer (BCP) self-assembly has attracted considerable attention for many decades because it can yield ordered structures in a wide range of morphologies, including spheres, cylinders, bicontinuous structures, lamellae, vesicles, and many other complex or hierarchical assemblies. These aggregates provide potential or practical applications in many fields. The present tutorial review introduces the primary principles of BCP self-assembly in bulk and in solution, by describing experiments, theories, accessible morphologies and morphological transitions, factors affecting the morphology, thermodynamics and kinetics, among others. As one specific example at a more advanced level, BCP vesicles (polymersomes) and their potential applications are discussed in some detail.
Importance of the field: The advancement in material design and engineering has led to the rapid development of new materials with increasing complexity and functions. Both non-degradable and degradable polymers … Importance of the field: The advancement in material design and engineering has led to the rapid development of new materials with increasing complexity and functions. Both non-degradable and degradable polymers have found wide applications in the controlled delivery field. Studies on drug release kinetics provide important information into the function of material systems. To elucidate the detailed transport mechanism and the structure-function relationship of a material system, it is critical to bridge the gap between the macroscopic data and the transport behavior at the molecular level.Areas covered in this review: The structure and function information of selected non-degradable and degradable polymers have been collected and summarized from literature published after the 1990s. The release kinetics of selected drug compounds from various material systems is discussed in case studies. Recent progress in the mathematical models based on different transport mechanisms is highlighted.What the reader will gain: This article aims to provide an overview of structure-function relationships of selected non-degradable and degradable polymers as drug delivery matrices.Take home message: Understanding the structure-function relationship of the material system is key to the successful design of a delivery system for a particular application. Moreover, developing complex polymeric matrices requires more robust mathematical models to elucidate the solute transport mechanisms.
Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled … Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on organic/inorganic systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.
Block copolymers consist of two or more chemically different polymers connected by covalent linkages. In solution, repulsion between the blocks leads to a variety of morphologies, which are thermodynamically driven. … Block copolymers consist of two or more chemically different polymers connected by covalent linkages. In solution, repulsion between the blocks leads to a variety of morphologies, which are thermodynamically driven. Polyferrocenyldimethylsilane block copolymers show an unusual propensity to forming cylindrical micelles in solution. We found that the micelle structure grows epitaxially through the addition of more polymer, producing micelles with a narrow size dispersity, in a process analogous to the growth of living polymer. By adding a different block copolymer, we could form co-micelles. We were also able to selectively functionalize different parts of the micelle. Potential applications for these materials include their use in lithographic etch resists, in redox-active templates, and as catalytically active metal nanoparticle precursors.
This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in … This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.
Units of 2-ureido-4-pyrimidone that dimerize strongly in a self-complementary array of four cooperative hydrogen bonds were used as the associating end group in reversible self-assembling polymer systems. The unidirectional design … Units of 2-ureido-4-pyrimidone that dimerize strongly in a self-complementary array of four cooperative hydrogen bonds were used as the associating end group in reversible self-assembling polymer systems. The unidirectional design of the binding sites prevents uncontrolled multidirectional association or gelation. Linear polymers and reversible networks were formed from monomers with two and three binding sites, respectively. The thermal and environmental control over lifetime and bond strength makes many properties, such as viscosity, chain length, and composition, tunable in a way not accessible to traditional polymers. Hence, polymer networks with thermodynamically controlled architectures can be formed, for use in, for example, coatings and hot melts, where a reversible, strongly temperature-dependent rheology is highly advantageous.
Abstract Monomers composed of a (meth)acrylate moiety connected to a short poly(ethylene)glycol (PEG) chain are versatile building‐blocks for the preparation of “smart” biorelevant materials. Many of these monomers are commercial … Abstract Monomers composed of a (meth)acrylate moiety connected to a short poly(ethylene)glycol (PEG) chain are versatile building‐blocks for the preparation of “smart” biorelevant materials. Many of these monomers are commercial and can be easily polymerized by either anionic, free‐radical, or controlled radical polymerization. The latter approach allows synthesis of well‐defined PEG‐based macromolecular architectures such as amphiphilic block copolymers, dense polymer brushes, or biohybrids. Furthermore, the resulting polymers exhibit fascinating solution properties in aqueous medium. Depending on the molecular structure of their monomer units, non linear PEG analogues can be either insoluble in water, readily soluble up to 100 °C, or thermoresponsive. Thus, these polymers can be used for building a wide variety of modern materials such as biosensors, artificial tissues, smart gels for chromatography, and drug carriers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3459–3470, 2008
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXT"Green" Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric MaterialsNicolay V. Tsarevsky and Krzysztof MatyjaszewskiView Author Information Department of Chemistry, Carnegie … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXT"Green" Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric MaterialsNicolay V. Tsarevsky and Krzysztof MatyjaszewskiView Author Information Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213 Cite this: Chem. Rev. 2007, 107, 6, 2270–2299Publication Date (Web):May 27, 2007Publication History Received10 August 2006Published online27 May 2007Published inissue 1 June 2007https://pubs.acs.org/doi/10.1021/cr050947phttps://doi.org/10.1021/cr050947presearch-articleACS PublicationsCopyright © 2007 American Chemical SocietyRequest reuse permissionsArticle Views13565Altmetric-Citations1189LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Ligands,Monomers,Polymers,Radical polymerization Get e-Alerts
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNew Polymer Synthesis by Nitroxide Mediated Living Radical PolymerizationsCraig J. Hawker, Anton W. Bosman, and Eva HarthView Author Information IBM Almaden Research Center, 650 Harry Road, San … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNew Polymer Synthesis by Nitroxide Mediated Living Radical PolymerizationsCraig J. Hawker, Anton W. Bosman, and Eva HarthView Author Information IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099 Cite this: Chem. Rev. 2001, 101, 12, 3661–3688Publication Date (Web):October 25, 2001Publication History Received9 April 2001Published online25 October 2001Published inissue 1 December 2001https://pubs.acs.org/doi/10.1021/cr990119uhttps://doi.org/10.1021/cr990119uresearch-articleACS PublicationsCopyright © 2001 American Chemical SocietyRequest reuse permissionsArticle Views20992Altmetric-Citations3592LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Copolymerization,Copolymers,Free radicals,Living polymerization,Radical polymerization Get e-Alerts
This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that … This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 62, 1402). This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.
ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorLiving Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer: The RAFT ProcessJohn Chiefari, Y. K. (Bill) Chong, Frances Ercole, Julia Krstina, Justine Jeffery, … ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorLiving Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer: The RAFT ProcessJohn Chiefari, Y. K. (Bill) Chong, Frances Ercole, Julia Krstina, Justine Jeffery, Tam P. T. Le, Roshan T. A. Mayadunne, Gordon F. Meijs, Catherine L. Moad, Graeme Moad, Ezio Rizzardo, and San H. ThangView Author Information CSIRO Molecular Science, Bag 10, Clayton South, Clayton, Victoria 3169, Australia Cite this: Macromolecules 1998, 31, 16, 5559–5562Publication Date (Web):July 22, 1998Publication History Received27 March 1998Revised10 June 1998Published online22 July 1998Published inissue 1 August 1998https://pubs.acs.org/doi/10.1021/ma9804951https://doi.org/10.1021/ma9804951rapid-communicationACS PublicationsCopyright © 1998 American Chemical SocietyRequest reuse permissionsArticle Views47371Altmetric-Citations4564LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Living polymerization,Monomers,Physical and chemical properties,Polymers,RAFT polymerization Get e-Alerts
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCopolymerization. I. A Basis for Comparing the Behavior of Monomers in Copolymerization; The Copolymerization of Styrene and Methyl MethacrylateFrank R. Mayo and Frederick M. LewisCite this: J. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCopolymerization. I. A Basis for Comparing the Behavior of Monomers in Copolymerization; The Copolymerization of Styrene and Methyl MethacrylateFrank R. Mayo and Frederick M. LewisCite this: J. Am. Chem. Soc. 1944, 66, 9, 1594–1601Publication Date (Print):September 1, 1944Publication History Published online1 May 2002Published inissue 1 September 1944https://pubs.acs.org/doi/10.1021/ja01237a052https://doi.org/10.1021/ja01237a052research-articleACS PublicationsRequest reuse permissionsArticle Views6189Altmetric-Citations1780LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
This Perspective summarizes the features and limitations of reversible addition–fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and … This Perspective summarizes the features and limitations of reversible addition–fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and an application point of view, has matured over the past 20 years. It is aimed at both experts in the field and newcomers, including undergraduate and postgraduate students, as well as nonexperts in polymerization who are interested in developing their own polymeric structures by exploiting the simple setup of a RAFT polymerization.
Vesicles are microscopic sacs that enclose a volume with a molecularly thin membrane. The membranes are generally self-directed assemblies of amphiphilic molecules with a dual hydrophilic-hydrophobic character. Biological amphiphiles form … Vesicles are microscopic sacs that enclose a volume with a molecularly thin membrane. The membranes are generally self-directed assemblies of amphiphilic molecules with a dual hydrophilic-hydrophobic character. Biological amphiphiles form vesicles central to cell function and are principally lipids of molecular weight less than 1 kilodalton. Block copolymers that mimic lipid amphiphilicity can also self-assemble into vesicles in dilute solution, but polymer molecular weights can be orders of magnitude greater than those of lipids. Structural features of vesicles, as well as properties including stability, fluidity, and intermembrane dynamics, are greatly influenced by characteristics of the polymers. Future applications of polymer vesicles will rely on exploiting unique property-performance relations, but results to date already underscore the fact that biologically derived vesicles are but a small subset of what is physically and chemically possible.
Abstract This is a polymer physics textbook for upper level undergraduates and first year graduate students. Any student with a working knowledge of calculus, physics and chemistry should be able … Abstract This is a polymer physics textbook for upper level undergraduates and first year graduate students. Any student with a working knowledge of calculus, physics and chemistry should be able to read this book. The essential tools of the polymer physical chemist or engineer are derived in this book without skipping any steps. The book is a self-contained treatise that could also serve as a useful reference for scientists and engineers working with polymers. While no prior knowledge of polymers is assumed, the book goes far beyond introductory polymer texts in the scope of what is covered. The fundamental concepts required to fully understand polymer melts, solutions and gels in terms of both static structure and dynamics are explained in detail. Problems at the end of each Chapter provide the reader with the opportunity to apply what has been learned to practice. The book is divided into four parts. After an introduction in Chapter 1, where the necessary concepts from a first course on polymers are summarized, the conformations of single polymer chains are treated in Part 1. Part 2 deals with the thermodynamics of polymer solutions and melts, including the conformations of chains in those states. Part 3 applies the concepts of Part 2 to the formation and properties of polymer networks. Finally, Part 4 explains the essential aspects of how polymers move in both melt and solution states. In all cases, attention is restricted to concepts that are firmly entrenched in the field.
Introduction (Krzysztof Matyjaszewski and Thomas P. Davis). Contributors. 1. Theory of Radical Reactions (Johan P. A. Heuts). 2. Small Radical Chemistry (Martin Newcomb). 3. General Chemistry of Radical Polymerization (Bunichiro … Introduction (Krzysztof Matyjaszewski and Thomas P. Davis). Contributors. 1. Theory of Radical Reactions (Johan P. A. Heuts). 2. Small Radical Chemistry (Martin Newcomb). 3. General Chemistry of Radical Polymerization (Bunichiro Yamada and Per B. Zetterlund). 4. The Kinetics of Free Radical Polymerization (Christopher Barner-Kowollik, Philipp Vana, and Thomas P. Davis). 5. Copolymerization Kinetics (Michelle L. Coote and Thomas P. Davis). 6. Heterogeneous Systems (Alex M. van Herk and Michael Monteiro). 7. Industrial Applications and Processes (Michael Cunningham and Robin Hutchinson). 8. General Concepts and History of Living Radical Polymerization (Krzysztof Matyjaszewski). 9. Kinetics of Living Radical Polymerization (Takeshi Fukuda, Atsushi Goto, and Yoshinobu Tsujii). 10. Nitroxide Mediated Living Radical Polymerization (Craig J. Hawker). 11. Fundamentals of Atom Transfer Radical Polymerization (Krzysztof Matyjaszewski and Jianhui Xia). 12. Control of Free Radical Polymerization by Chain Transfer Methods (John Chiefari and Ezio Rizzardo). 13. Control of Stereochemistry of Polymers in Radical Polymerization (Akikazu Matsumoto). 14. Macromolecular Engineering by Controlled Radical Polymerization (Yves Gnanou and Daniel Taton). 15. Experimental Procedures and Techniques for Radical Polymerization (Stefan A. F. Bon and David M. Haddleton). 16. Future Outlook and Perspectives (Krzysztof Matyjaszewski and Thomas P. Davis). Index.
Star polymers—macromolecules featuring multiple arms radiating from a central core—offer unique potential for biomedical applications due to their tunable architecture, multifunctionality and ability to incorporate stimuli-responsive and biocompatible components. In … Star polymers—macromolecules featuring multiple arms radiating from a central core—offer unique potential for biomedical applications due to their tunable architecture, multifunctionality and ability to incorporate stimuli-responsive and biocompatible components. In this study, functional star polymers with oligo (ethylene glycol) methyl ether methacrylate (OEOMA) arms and 2-(dimethylamino)ethyl methacrylate (DMAEMA) core units were synthesized via atom transfer radical polymerization (ATRP) using the “arm-first” strategy. The star polymers were used as nanoreactors for the in situ reduction of silver nitrate to form silver nanoparticles (AgNPs) without additional reducing agents. UV–Vis spectroscopy confirmed the formation of spherical AgNPs with absorption maxima around 430 nm, and transmission electron microscopy revealed uniform particle morphology. These hybrid nanomaterials (STR-AgNPs) were incorporated into polymethyl methacrylate (PMMA)-based bone cement to impart antibacterial properties. Mechanical testing showed that the compressive strength remained within acceptable limits, while antibacterial assays against E. coli demonstrated a significant inhibition of bacterial growth. These findings suggest that STR-AgNPs serve as promising candidates for infection-resistant bone implants, providing localized antibacterial effects while maintaining mechanical integrity and biocompatibility.
Many acrylic‐methacrylic block copolymer sequences remain inaccessible due to synthetic limitations. Herein, photoinduced electron/energy transfer (PET) catalysis is leveraged to reverse blocking order limitations in trithiocarbonate (TTC)‐mediated reversible addition‐fragmentation chain … Many acrylic‐methacrylic block copolymer sequences remain inaccessible due to synthetic limitations. Herein, photoinduced electron/energy transfer (PET) catalysis is leveraged to reverse blocking order limitations in trithiocarbonate (TTC)‐mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization. We synthesized poly(methyl acrylate‐b‐methyl methacrylate) by PET‐RAFT using fac‐Ir(ppy)3, achieving predictable, linear increases in molecular weight with conversion. Kinetics studies showed that adding a tertiary amine (triethanolamine) introduced a reversible redox reaction to stabilize the TTC radical during chain extensions, leading to more uniform block copolymers (Ð < 1.47) compared to block copolymers synthesized without amine (Ð < 1.56). To highlight the utility of this method, previously inaccessible triblock copolymers of poly(methyl acrylate) and poly(methyl methacrylate) blocks were investigated. The order of acrylic and methacrylic blocks impacted the physical properties of compositionally similar polymeric materials. For example, a high molecular weight triblock copolymer (P(MMA‐b‐MA‐b‐MMA), Mn = 564 kg/mol) thermoplastic elastomer showed exceptional strain (> 1600%) with full shape recovery. Overall, we report (i) a new methodology to unlock synthetic access to acrylic‐methacrylic block copolymers using TTCs and photocatalysis, (ii) insight into photocatalyst‐mediated radical polymerization, and (iii) synthesis of new high‐performance materials.
Many acrylic‐methacrylic block copolymer sequences remain inaccessible due to synthetic limitations. Herein, photoinduced electron/energy transfer (PET) catalysis is leveraged to reverse blocking order limitations in trithiocarbonate (TTC)‐mediated reversible addition‐fragmentation chain … Many acrylic‐methacrylic block copolymer sequences remain inaccessible due to synthetic limitations. Herein, photoinduced electron/energy transfer (PET) catalysis is leveraged to reverse blocking order limitations in trithiocarbonate (TTC)‐mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization. We synthesized poly(methyl acrylate‐b‐methyl methacrylate) by PET‐RAFT using fac‐Ir(ppy)3, achieving predictable, linear increases in molecular weight with conversion. Kinetics studies showed that adding a tertiary amine (triethanolamine) introduced a reversible redox reaction to stabilize the TTC radical during chain extensions, leading to more uniform block copolymers (Ð < 1.47) compared to block copolymers synthesized without amine (Ð < 1.56). To highlight the utility of this method, previously inaccessible triblock copolymers of poly(methyl acrylate) and poly(methyl methacrylate) blocks were investigated. The order of acrylic and methacrylic blocks impacted the physical properties of compositionally similar polymeric materials. For example, a high molecular weight triblock copolymer (P(MMA‐b‐MA‐b‐MMA), Mn = 564 kg/mol) thermoplastic elastomer showed exceptional strain (> 1600%) with full shape recovery. Overall, we report (i) a new methodology to unlock synthetic access to acrylic‐methacrylic block copolymers using TTCs and photocatalysis, (ii) insight into photocatalyst‐mediated radical polymerization, and (iii) synthesis of new high‐performance materials.
In this paper, different poly((ethylene glycol)-(propylene glycol)) methacrylate (P(EGPG)MA) hydrogels were synthesized by gamma-radiation-induced polymerization and crosslinking from a monomer–bisolvent mixture using the following monomers: (ethylene glycol)6 methacrylate (EG6MA), ((ethylene … In this paper, different poly((ethylene glycol)-(propylene glycol)) methacrylate (P(EGPG)MA) hydrogels were synthesized by gamma-radiation-induced polymerization and crosslinking from a monomer–bisolvent mixture using the following monomers: (ethylene glycol)6 methacrylate (EG6MA), ((ethylene glycol)6-(propylene glycol)3) methacrylate (EG6PG3MA), ((propylene glycol)6-(ethylene glycol)3) methacrylate (PG6EG3MA), and (propylene glycol)5 methacrylate (PG5MA), along with different water/ethanol compositions as the solvent. The monomer–bisolvent mixture was exposed to various radiation doses (5, 10, 15, 25, and 50 kGy). Considerable emphasis was placed on optimizing and tuning the reaction conditions necessary for the fabrication of methacrylic networks with pendant EGPG terminals. A further investigation was conducted on the effects of monomer composition, different preparation conditions, and radiation processing on thermal properties, microstructure, swelling behavior, and volume phase transition. Special attention was dedicated to PPG6EG3MA hydrogel, whose volume phase transition temperature is near physiological temperatures. This study identifies an optimal radiation dose and a water/ethanol solvent ratio for the synthesis of the radiation-induced hydrogels. Employing ionizing radiation within the sterilization dose range enables the simultaneous fabrication and sterilization of these hydrogels, offering an efficient production process. The findings provide new insights into the role of bisolvent composition on hydrogel formation and properties, and they present practical guidelines for optimizing hydrogel synthesis across a wide range of applications.
We report herein a self‐adaptive surface‐initiated bimetal‐mediated controlled radical polymerization (SI‐BMCRP) for fabricating various polymer brushes using microliter volumes under ambient conditions. The introduction of bimetal CuZn alloy can self‐adaptively … We report herein a self‐adaptive surface‐initiated bimetal‐mediated controlled radical polymerization (SI‐BMCRP) for fabricating various polymer brushes using microliter volumes under ambient conditions. The introduction of bimetal CuZn alloy can self‐adaptively control the dissociation of copper species while still realizing the controllability of polymer brush growth with high oxygen tolerance at a wide range of distances between the bimetal alloy and the initiator‐modified substrate. The successful fabrication of multiscale and multifunctional polymer brushes with high‐end group fidelity and patterned architectures further demonstrates the robust nature of SI‐BMCRP. The resultant polymer brushes show great potential for new applications in moisture‐enabled electricity generation, breath monitoring and speech recognition.
Reversible adhesives are crucial for enabling high-strength, eco-friendly bonding with on-demand detachment, yet achieving fully sustainable adhesives with high-strength and reliable detachment remains a challenge. Here, we present a supramolecular … Reversible adhesives are crucial for enabling high-strength, eco-friendly bonding with on-demand detachment, yet achieving fully sustainable adhesives with high-strength and reliable detachment remains a challenge. Here, we present a supramolecular adhesive derived from natural materials, namely supramolecular adhesive tailored by organic solvents (SATO), comprising tannic acid, β-cyclodextrin, and organic solvents (DMSO, ethylene glycol, or glycerol) integrated through dynamic hydrogen-bond networks. The optimized SATO achieves robust interfacial adhesion strength up to 4.1 MPa, with retained adhesion (~0.8 MPa) even after 30 repeated bonding-debonding cycles. The adhesive demonstrates humidity-sensitive adhesion and exceptional freeze resistance, retaining ~96% of its initial adhesion strength after 7 days storage at -50 °C. When used to fabricate sand columns, SATO achieves compressive strengths of >11 MPa while enabling rapid on-demand disintegration within 2 s via water exposure. By synergizing eco-friendliness, high mechanical performance, and reversible adhesion, SATO holds promise for applications in arid environment and temporary structural engineering.
We report herein a self‐adaptive surface‐initiated bimetal‐mediated controlled radical polymerization (SI‐BMCRP) for fabricating various polymer brushes using microliter volumes under ambient conditions. The introduction of bimetal CuZn alloy can self‐adaptively … We report herein a self‐adaptive surface‐initiated bimetal‐mediated controlled radical polymerization (SI‐BMCRP) for fabricating various polymer brushes using microliter volumes under ambient conditions. The introduction of bimetal CuZn alloy can self‐adaptively control the dissociation of copper species while still realizing the controllability of polymer brush growth with high oxygen tolerance at a wide range of distances between the bimetal alloy and the initiator‐modified substrate. The successful fabrication of multiscale and multifunctional polymer brushes with high‐end group fidelity and patterned architectures further demonstrates the robust nature of SI‐BMCRP. The resultant polymer brushes show great potential for new applications in moisture‐enabled electricity generation, breath monitoring and speech recognition.
ABSTRACT This study aims to synthesize and evaluate the physicochemical and biological properties of poly(acrylic acid) (PAA) and its block copolymer with N‐acryloyl‐L‐tryptophan (PNALT), specifically focusing on their suitability for … ABSTRACT This study aims to synthesize and evaluate the physicochemical and biological properties of poly(acrylic acid) (PAA) and its block copolymer with N‐acryloyl‐L‐tryptophan (PNALT), specifically focusing on their suitability for biomedical applications. PAA and PAA‐b‐PNALT were synthesized via RAFT polymerization using benzyl dodecyl trithiocarbonate (BDTTC) as the chain transfer agent (CTA). Kinetic studies were performed using 1 H NMR to monitor acrylic acid (AA) conversion. Molecular weight evolution and polymer dispersity were analysed by GPC. Thermal behaviour was evaluated by TGA and DSC, while micelle formation was assessed using DLS and TEM. Cytotoxicity was evaluated on RAW 264.7 and MCF‐7 cell lines via MTT assay. The polymerization followed pseudo‐first‐order kinetics with a linear increase in molar mass and narrow PDI. PAA‐b‐PNALT exhibited enhanced thermal stability compared to PAA, as shown by TGA. No distinct Tg was observed in DSC, suggesting stability between 25–130°C. DLS and TEM confirmed self‐assembly of PAA‐b‐PNALT into spherical micelles (80–220 nm). MTT assays demonstrated good cytocompatibility of both polymers, with PAA‐b‐PNALT showing improved biocompatibility, particularly at 50 µM on MCF‐7 cells. PAA‐b‐PNALT exhibits desirable features such as controlled molar mass, thermal stability, self‐assembly into micelles, and enhanced cytocompatibility. These properties position it as a promising candidate for applications in drug delivery, tissue engineering, and related biomedical technologies.
Polymeric nanoparticles based on poly(ethyl cyanoacrylate) (PECA) and poly(ε-caprolactone) (PCL) were synthesized via semicontinuous microemulsion polymerization for potential biomedical applications. A systematic evaluation of four surfactants (Tween 80, Alkonat L70, … Polymeric nanoparticles based on poly(ethyl cyanoacrylate) (PECA) and poly(ε-caprolactone) (PCL) were synthesized via semicontinuous microemulsion polymerization for potential biomedical applications. A systematic evaluation of four surfactants (Tween 80, Alkonat L70, Genapol LRO, and Brij-20) was carried out to determine their effects on micelle formation and particle size. Brij-20 enabled the formation of nanoparticles under 100 nm, with optimal conditions identified at 4% surfactant concentration and pH 1.75. The polymerization process included acid-catalyzed ring-opening of ε-caprolactone, followed by the semicontinuous addition of ethyl-2-cyanoacrylate under an inert atmosphere. Copolymerization was confirmed through FT-IR spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and differential scanning calorimetry, revealing a glass transition temperature (Tg) of 110.9 °C, indicating PECA as the dominant phase. Thermogravimetric analysis showed two decomposition events corresponding to each polymer. Transmission electron microscope analysis revealed nanoparticles averaging 51.74 nm in diameter. These findings demonstrate the feasibility of producing PECA-PCL nanoparticles with controlled size and composition, suitable for drug delivery and other biomedical uses.
Enzymatic PET depolymerization represents a promising approach for establishing a circular economy for PET plastics. Nonetheless, limitations in enzyme activity persist as significant challenges to its industrial application. In this … Enzymatic PET depolymerization represents a promising approach for establishing a circular economy for PET plastics. Nonetheless, limitations in enzyme activity persist as significant challenges to its industrial application. In this research, the backbone structure of the β6-β7 loop for PET hydrolase Bhr-PETase derived from the thermophilic bacterium HR29 was reconstructed by introducing double mutations (H218N/F222M), resulting in variant Bhr-NMT with high thermal stability (Tm = 92.9 °C) and 87% increase in activity. Moreover, the loop reconstruction mutations are transplanted into the engineered PET hydrolases LCC-ICCG and Kubu-PM12, resulting variants LCC-ICCG-NM (Tm = 92.4 °C) and Kubu-PM12-NM (Tm = 92.9 °C). Under high substrate concentration (165 g kg-1) and an enzyme loading of 0.5 mgenzyme gPET-1, the designed variants Bhr-NMT, LCC-ICCG-NM, and Kubu-PM12-NM achieve an overall conversion of 93%, 90%, and 94%, respectively, outperforming the benchmark LCC-ICCG (85%). Notably, under reduced enzyme loading (0.3 mgenzyme gPET-1), Kubu-PM12-NM still reaches an overall conversion of 91%, which is significantly superior to benchmarks Kubu-PM12 (83%) and LCC-ICCG (71%). Overall, the engineered PET hydrolases demonstrate significant potential for industrial PET waste recycling.
Abstract Shape‐changeable inorganic/organic hybrid particles in response to light stimulus have received great interest due to their potential applications in sensors and catalysis. However, the light‐induced precise shape transition of … Abstract Shape‐changeable inorganic/organic hybrid particles in response to light stimulus have received great interest due to their potential applications in sensors and catalysis. However, the light‐induced precise shape transition of hybrid block copolymer/inorganic nanoparticles (BCP/NPs) particles remains a considerable challenge. Herein, the light‐responsive hybrid BCP/NPs vesicles are fabricated by introducing PS tethered gold nanoparticles (AuNPs@PS) into polystyrene‐o‐nitrobenzyl ester‐polyethylene oxide (PS‐ o‐NBE ‐PEO) scaffolds. Upon UV irradiation, the hybrid PS‐ o‐NBE ‐PEO /NPs vesicles incorporated with smaller AuNPs can transform into hybrid porous spherical particles due to the photocleavage of the o‐NBE bond in PS‐ o‐NBE ‐PEO scaffolds. Besides, attributed to the difference in conformational entropy loss of the BCP/AuNPs co‐assembly system, the eventual distribution of AuNPs and the correspondingly shape‐converted degree of BCP/NPs assemblies depends on the size of NPs. Furthermore, hybrid BCP/AuNPs and BCP/PtNPs assemblies can be prepared by the in situ reduction of metal precursors in BCP templates. Thus, light‐responsive hybrid BCP/NPs particles with various internal structures are generated and the adjustable shape transformation of hybrid BCP/NPs particles is realized by UV stimulus, the obtained results open a unique and promising route to fabricate smart materials.
Abstract Self‐assembly of block copolymers in solution provides access to different nanostructures depending on block composition and processing conditions. However, more complex hierarchical nanostructures as found in nature remain challenging … Abstract Self‐assembly of block copolymers in solution provides access to different nanostructures depending on block composition and processing conditions. However, more complex hierarchical nanostructures as found in nature remain challenging to achieve. In this study, the influence of a β‐sheet forming tetrapeptide sequence (GFFG) is investigated at the interface of an amphiphilic block copolymer based on poly(butyl acrylate) (PBA) and poly(ethylene oxide) (PEO). Using atomic force microscopy (AFM) and tip‐enhanced Raman spectroscopy (TERS), nanoscale insights are provided into the structural organisation and mechanical properties of these hybrid materials. Both the tetrapeptide‐containing block copolymer and a control block copolymer without the peptide linker form wormlike micelles in water. However, the incorporation of the peptide linker alters the micelle morphology by increasing the contour length sixfold compared to the control polymer and by altering the mechanical properties of the wormlike micelles. TERS analysis confirms the presence of ordered β ‐sheet structures at the hydrophilic/hydrophobic interface, which increase the bending stiffness of the micelles. The introduction of additional secondary interactions, such as those induced by the peptide linker, therefore appears as an interesting lever to manipulate the structure formation and mechanical properties block copolymer micelles, opening up interesting design strategies for tailor‐made hierarchically structured nanomaterials.
ABSTRACT Cholesterol‐terminated poly(acrylic acid) was prepared through a simple two‐step method, consisting of the reversible‐deactivation radical polymerization of tert ‐butyl acrylate with a cholesterol‐based initiator and acidic hydrolysis of the … ABSTRACT Cholesterol‐terminated poly(acrylic acid) was prepared through a simple two‐step method, consisting of the reversible‐deactivation radical polymerization of tert ‐butyl acrylate with a cholesterol‐based initiator and acidic hydrolysis of the tert ‐butyl group. The Cu(0)/Cu(II) catalytic system allowed the controlled polymerization of tert ‐butyl acrylate with narrow dispersity in less than an hour. Kinetic studies revealed that the initial catalyst ratio influences the polymerization time by means of an induction period that increases with the [Cu(II)] 0 /[Cu(0)] 0 ratio. The effect of nitrogen purge and freeze‐pump‐thaw cycles was assessed, and both were found to be equally effective in the system deoxygenation. The synthesized polymers exhibited a high degree of chain‐end fidelity, as evidenced by the results of chain extension experiments. This makes the system interesting for the formation of block copolymers with cholesterol‐termination, broadening its range of applicability.
ABSTRACT An envisioned circular economy of commonly used polymers, high‐density polyethylene (HDPE) and isotactic polypropylene ( i PP), is challenging due to their immiscibility with almost all other plastics. Therefore, … ABSTRACT An envisioned circular economy of commonly used polymers, high‐density polyethylene (HDPE) and isotactic polypropylene ( i PP), is challenging due to their immiscibility with almost all other plastics. Therefore, highly effective compatibilizers and synthetic protocols permitting their large‐scale production are highly desirable. Herein, we report the efficient one‐pot synthesis of strictly linear HDPE‐ b ‐ i PP diblock copolymers achieved by coordinative chain transfer polymerization (CCTP). Various diblock copolymers with short and very narrow distributed HDPE ( M n = 1400–2400 g × mol −1 ; Ð = 1.4) and long i PP segments were synthesized and used to compatibilize HDPE/ i PP blends. The synthesized block copolymers differ in their overall molecular weights ( M n = 10,600–60,600 g × mol −1 ) by varying the i PP segment, whereas the HDPE block was kept in a narrow range. Block copolymers with a molecular weight from M n = 23,000–39,000 g × mol −1 are competitive or outperform commercial compatibilizers, INFUSE TM and INTUNE TM , with the highest efficiency in compatibilizing 30/70 (wt./wt.) HDPE/ i PP blends by a 5 wt.‐% copolymer addition. SEM studies revealed that after adding the diblock copolymer, HDPE core shell structures were formed, and the HDPE particle size decreases compared to the neat blend, avoiding HDPE particles from debonding during tensile deformation tests.
Many chemical, physical, and biological methods have been applied for plastic pollution as a global environmental problem. Polyethylene terephthalate (PET) is a commonly used polymer for many human life-related applications … Many chemical, physical, and biological methods have been applied for plastic pollution as a global environmental problem. Polyethylene terephthalate (PET) is a commonly used polymer for many human life-related applications (food and water containers). In this paper, PET was hydrolyzed in a alcoholic NaOH medium at 110°C to obtain sodium terephthalate (Na-Terephthalate) that refluxed with glycerine and polyvinyl alcohol (PVA). PVA-terephthalate polymeric composite formed a flexible thin film. Other composites were prepared using PVA, Na-Terephthalate, and glycerine and NiCl2.6H2O, ZnSO4.7H2O, Sr(NO3)2, or FeCl3. All PVA-terephthalate composites were characterized using FTIR, XRD, SEM, and DTA. Additionally, all prepared composites were screened for their microbial activity against E. coli, S. aureus, P. aeruginosa, and Candida albicans. The PVA-terephthalate composite showed a good to moderate inhibition zone towards S. aureus, P. aeruginosa, and Candida albicans. All metallic composites showed a negative response against P. aeruginosa and Candida albicans. The Zinc composite exhibited a noticeable inhibition zone against E. coli and S. aureus. These newly prepared composites (PVA-terephthalate, Nickel, and Iron composites) were evaluated for endo- and/or exothermic DTA peaks. The exothermic temperature of the Nickel composite was higher than the Iron composite, while PVA-terephthalate did not show any exothermic reaction. The obtained characteristics suggest promising materials for industrial applications such as seedling planting bags, food coating, and packaging materials, starting with minimizing PET quantity in the environment. The addition of metal salt to the blend composition may be a good suggestion in other research fields such as optical or electric applications.
The glass transition temperature (Tg) is undoubtedly one of the most important characteristics of polymers, and investigating its dependence on their structure and composition is crucial from both fundamental and … The glass transition temperature (Tg) is undoubtedly one of the most important characteristics of polymers, and investigating its dependence on their structure and composition is crucial from both fundamental and application points of view. This study deals with the unexpected relationship between Tg and the average molecular weight between crosslinking points (Mc) in nanophase-separated polystyrene-l-poly(dimethylsiloxane) (PSt-l-PDMS) and polystyrene-l-poly(dimethylsiloxane)/divinylbenzene (PSt-l-PDMS/DVB) polymer conetworks. In order to reveal the correlation between the Tg and Mc, a library of PSt-l-PDMS and PSt-l-PDMS/DVB conetworks was synthesized, and their compositions and Tgs were determined. Instead of the expected increase of Tg with decreasing Mc, a reverse correlation was found. Namely, the Tg decreases with decreasing Mc in these conetworks. Correlation analyses showed that the Tg linearly depends on 1/Mc, similar to the Fox-Flory relationship for homopolymers with their Mn, that is, Tg = Tg,ꝏ -K/Mc for the investigated conetworks, independent of the absence or presence of relatively low amounts of DVB as an additional small molecular weight crosslinker. This means that the PDMS macrocrosslinker acts like scissors by interrupting the mobility of the crosslinked PSt chains in the conetworks, and the Tg of the PSt segments will be close to that of PSt homopolymers with the same Mn as Mc, as found by comparison. Consistent with previous findings with other conetworks, the presence of the scissors effect of the macromolecular crosslinker in the PSt-l-PDMS and PSt-l-PDMS/DVB conetworks indicates that the scissors effect is a general phenomenon for polymer conetworks formed by crosslinking with a macromolecular crosslinker. The observed unusual Tg versus Mc relationship in the conetworks can be utilized in designing such novel materials with predetermined Tgs required for targeted applications.
The growing demand for biodegradable polymers capable of stimuli-responsive drug release is challenged by limitations in facile synthetic methods. In this study, two biotin-functionalized amphiphilic polyesters (P1 and P2) were … The growing demand for biodegradable polymers capable of stimuli-responsive drug release is challenged by limitations in facile synthetic methods. In this study, two biotin-functionalized amphiphilic polyesters (P1 and P2) were synthesized through step-growth polymerization, aiming to achieve biotin receptor-mediated cancer cell selective uptake. In addition to polar biotin, P2 incorporates a hydrophobic fluorescent dye, which enabled intracellular fluorescence tracking. P2 self-assembled into highly biocompatible spherical nanoaggregates (∼120 nm) in water, which showed effective encapsulation of the hydrophobic anticancer drug doxorubicin (DOX). It displayed ∼85-90% internalization in biotin-overexpressed cancer cells (HeLa and MCF7) contrary to only ∼5-10% uptake in noncancerous cells (NIH 3T3), as determined by flow cytometry and fluorescence microscopy. Cell-selective DOX release was likely induced by the polyester degradation in the acidic cancer microenvironment and via endogenous esterases, evident from size exclusion chromatography (SEC) and dynamic light scattering (DLS) experiments. These findings highlight the potential of stimuli-responsive degradable polyester nanocarriers for targeted cancer treatment.
<title>Abstract</title> Poly(methyl methacrylate-ra-<italic>N</italic>-[tris(hydroxymethyl)methyl]acrylamide-g-ε-caprorolactone) random-graft copolymer was obtained by simultaneous reaction in a single step using free-radical polymerization and ring-opening polymerization techniques. In the presence of 2,2'-azobisisobutyronitrile, <italic>N</italic>-[tris(hydroxymethyl)methyl]acrylamide and four different … <title>Abstract</title> Poly(methyl methacrylate-ra-<italic>N</italic>-[tris(hydroxymethyl)methyl]acrylamide-g-ε-caprorolactone) random-graft copolymer was obtained by simultaneous reaction in a single step using free-radical polymerization and ring-opening polymerization techniques. In the presence of 2,2'-azobisisobutyronitrile, <italic>N</italic>-[tris(hydroxymethyl)methyl]acrylamide and four different vinyl monomers (acrylamide, butyl methacrylate, methyl methacrylate, and styrene) were separately incorporated, and ε-caprolactone (or β-butyrolactone) was simultaneously grafted to the hydroxyl groups of the copolymer. The dependence of eight different graft copolymers on the monomer type was investigated by applying identical experimental parameters. The effects of the monomer type on the molecular weights and dispersity values were examined. The spectroscopic properties of the obtained products were determined using Fourier-transform infrared and proton-nuclear magnetic resonance spectroscopies, and their thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry techniques. The average molecular weights were defined using gel permeation chromatography. The morphological properties were examined with scanning electron microscope.