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Molecules (Basel, Switzerland) Sep 2022A new programed upper critical solution temperature-type thermoresponsive polymer was developed using water-soluble anionic polymer conjugates derived from...
A new programed upper critical solution temperature-type thermoresponsive polymer was developed using water-soluble anionic polymer conjugates derived from polyallylamine and phthalic acid with cleavage-induced phase transition property. Intrinsic charge inversion from anion to cation of the polymer side chain is induced through a side chain cleavage reaction in acidic aqueous media. With the progress of side chain cleavage under fixed external conditions, the polymer conjugates express a thermoresponsive property, followed by shifting a phase boundary due to the change in polymer composition. When the phase transition boundary eventually reached the examined temperature, phase transition occurs under fixed external conditions. Such new insight obtained in this study opens up the new concept of time-programed stimuli-responsive polymer possessing a cleavage-induced phase transition.
Topics: Anions; Phase Transition; Polymers; Stimuli Responsive Polymers; Temperature; Water
PubMed: 36144815
DOI: 10.3390/molecules27186082 -
Environmental Science & Technology Oct 2023The main driver of the potential toxicity of micro- and nanoplastics toward biota is often the release of compounds initially present in the plastic, i.e., polymer...
Effect of Polymer Aging on Uptake/Release Kinetics of Metal Ions and Organic Molecules by Micro- and Nanoplastics: Implications for the Bioavailability of the Associated Compounds.
The main driver of the potential toxicity of micro- and nanoplastics toward biota is often the release of compounds initially present in the plastic, i.e., polymer additives, as well as environmentally acquired metals and/or organic contaminants. Plastic particles degrade in the environment via various mechanisms and at different rates depending on the particle size/geometry, polymer type, and the prevailing physical and chemical conditions. The rate and extent of polymer degradation have obvious consequences for the uptake/release kinetics and, thus, the bioavailability of compounds associated with plastic particles. Herein, we develop a theoretical framework to describe the uptake and release kinetics of metal ions and organic compounds by plastic particles and apply it to the analysis of experimental data for pristine and aged micro- and nanoplastics. In particular, we elucidate the contribution of transient processes to the overall kinetics of plastic reactivity toward aquatic contaminants and demonstrate the paramount importance of intraparticulate contaminant diffusion.
Topics: Microplastics; Polymers; Biological Availability; Water Pollutants, Chemical; Metals; Plastics; Ions
PubMed: 37856883
DOI: 10.1021/acs.est.3c05148 -
Chemical Society Reviews Jan 2010Creating bioconjugates by combining polymers with peptides and proteins is an emerging multidisciplinary field of research that has enjoyed increased attention within... (Review)
Review
Creating bioconjugates by combining polymers with peptides and proteins is an emerging multidisciplinary field of research that has enjoyed increased attention within the scientific community. This critical review provides an overview of the strategies employed for the construction of these materials and will highlight the underlying synthetic methods used. This review is therefore relevant for chemists, material scientists and chemical biologists facing the challenge of constructing polypeptide-polymer bioconjugates in a controlled fashion (269 references).
Topics: Animals; Humans; Peptides; Polymers; Proteins
PubMed: 20023856
DOI: 10.1039/b807871h -
Advanced Healthcare Materials Mar 2019Block copolymers with unique architectures and those that can self-assemble into supramolecular structures are used in medicine as biomaterial scaffolds and delivery... (Review)
Review
Block copolymers with unique architectures and those that can self-assemble into supramolecular structures are used in medicine as biomaterial scaffolds and delivery vehicles for cells, therapeutics, and imaging agents. To date, much of the work relies on controlling polymer behavior by varying the monomer side chains to add functionality and tune hydrophobicity. Although varying the side chains is an efficient strategy to control polymer behavior, changing the polymer backbone can also be a powerful approach to modulate polymer self-assembly, rigidity, reactivity, and biodegradability for biomedical applications. There are many developments in the syntheses of polymers with segmented backbones, but these developments are not widely adopted as strategies to address the unique constraints and requirements of polymers for biomedical applications. This review highlights dual polymerization strategies for the synthesis of backbone-segmented block copolymers to facilitate their adoption for biomedical applications.
Topics: Biocompatible Materials; Free Radicals; Polymerization; Polymers
PubMed: 30369103
DOI: 10.1002/adhm.201800861 -
Journal of Controlled Release :... Dec 2015Sugar-based polymers have been extensively explored as a means to increase drug delivery systems' biocompatibility and biodegradation. Here,we review he use of... (Review)
Review
Sugar-based polymers have been extensively explored as a means to increase drug delivery systems' biocompatibility and biodegradation. Here,we review he use of sugar-based polymers for drug delivery applications, with a particular focus on the utility of the sugar component(s) to provide benefits for drug targeting and stimuli responsive systems. Specifically, numerous synthetic methods have been developed to reliably modify naturally-occurring polysaccharides, conjugate sugar moieties to synthetic polymer scaffolds to generate glycopolymers, and utilize sugars as a multifunctional building block to develop sugar-linked polymers. The design of sugar-based polymer systems has tremendous implications on both the physiological and biological properties imparted by the saccharide units and are unique from synthetic polymers. These features include the ability of glycopolymers to preferentially target various cell types and tissues through receptor interactions, exhibit bioadhesion for prolonged residence time, and be rapidly recognized and internalized by cancer cells. Also discussed are the distinct stimuli-sensitive properties of saccharide-modified polymers to mediate drug release under desired conditions. Saccharide-based systems with inherent pH- and temperature-sensitive properties, as well as enzyme-cleavable polysaccharides for targeted bioactive delivery, are covered. Overall, this work emphasizes inherent benefits of sugar-containing polymer systems for bioactive delivery.
Topics: Animals; Carbohydrates; Drug Delivery Systems; Humans; Polymers
PubMed: 26423239
DOI: 10.1016/j.jconrel.2015.09.053 -
Chemical & Pharmaceutical Bulletin 2017Smart design of polymeric materials may lead to intelligent materials exhibiting unique functional properties. Looking at nature, living systems use specific and... (Review)
Review
Smart design of polymeric materials may lead to intelligent materials exhibiting unique functional properties. Looking at nature, living systems use specific and reversible intermolecular interactions in realizing complex functions. Hence reversible bonds based on selective molecular recognition can impart artificial materials with unique functional properties. This review mainly focuses on supramolecular polymeric materials based on cyclodextrin-based host-guest interactions. Polymeric materials using molecular recognition at polymer main chain, side chain, and termini are described. Polymers carrying host and guest residues exhibit unique properties such as: 1) formation of macroscopic self-assembly of polymer gels carrying host and guest residues; 2) stimuli-responsive self-healing properties due to the reversible nature of host-guest interactions; and 3) macroscopic motion of artificial muscle cross-linked by host-guest interaction controlled by external stimuli. An overview of recent developments in this new frontier between materials science and life science is given.
Topics: Cyclodextrins; Macromolecular Substances; Polymers
PubMed: 28381672
DOI: 10.1248/cpb.c16-00778 -
The American Journal of Medicine Jul 2017
Topics: Embolism; Equipment Failure; Humans; Hydrophobic and Hydrophilic Interactions; Polymers
PubMed: 28216443
DOI: 10.1016/j.amjmed.2017.01.032 -
Molecules (Basel, Switzerland) Sep 2022The interaction of water with polymers is an intensively studied topic. Vibrational spectroscopy techniques, mid-infrared (MIR) and Raman, were often used to investigate...
The interaction of water with polymers is an intensively studied topic. Vibrational spectroscopy techniques, mid-infrared (MIR) and Raman, were often used to investigate the properties of water-polymer systems. On the other hand, relatively little attention has been given to the potential of using near-infrared (NIR) spectroscopy (12,500-4000 cm; 800-2500 nm) for exploring this problem. NIR spectroscopy delivers exclusive opportunities for the investigation of molecular structure and interactions. This technique derives information from overtones and combination bands, which provide unique insights into molecular interactions. It is also very well suited for the investigation of aqueous systems, as both the bands of water and the polymer can be reliably acquired in a range of concentrations in a more straightforward manner than it is possible with MIR spectroscopy. In this study, we applied NIR spectroscopy to investigate interactions of water with polymers of varying hydrophobicity: polytetrafluoroethylene (PTFE), polypropylene (PP), polystyrene (PS), polyvinylchloride (PVC), polyoxymethylene (POM), polyamide 6 (PA), lignin (Lig), chitin (Chi) and cellulose (Cell). Polymer-water mixtures in the concentration range of water between 1-10%(/) were investigated. Spectra analysis and interpretation were performed with the use of difference spectroscopy, Principal Component Analysis (PCA), Median Linkage Clustering (MLC), Partial Least Squares Regression (PLSR), Multivariate Curve Resolution Alternating Least Squares (MCR-ALS) and Two-Dimensional Correlation Spectroscopy (2D-COS). Additionally, from the obtained data, aquagrams were constructed and interpreted with aid of the conclusions drawn from the conventional approaches. We deepened insights into the problem of water bands obscuring compound-specific signals in the NIR spectrum, which is often a limiting factor in analytical applications. The study unveiled clearly visible trends in NIR spectra associated with the chemical nature of the polymer and its increasing hydrophilicity. We demonstrated that changes in the NIR spectrum of water are manifested even in the case of interaction with highly hydrophobic polymers (e.g., PTFE). Furthermore, the unveiled spectral patterns of water in the presence of different polymers were found to be dissimilar between the two major water bands in NIR spectrum ( + and + ).
Topics: Cellulose; Chitin; Lignin; Polymers; Polypropylenes; Polystyrenes; Polytetrafluoroethylene; Polyvinyl Chloride; Spectroscopy, Near-Infrared; Water
PubMed: 36144616
DOI: 10.3390/molecules27185882 -
Molecules (Basel, Switzerland) Feb 2023The increasing interest in stretchable conductive composite materials, that can be versatile and suitable for wide-ranging application, has sparked a growing demand for...
The increasing interest in stretchable conductive composite materials, that can be versatile and suitable for wide-ranging application, has sparked a growing demand for studies of scalable fabrication techniques and specifically tailored geometries. Thanks to the combination of the conductivity and robustness of carbon nanotube (CNT) materials with the viscoelastic properties of polymer films, in particular their stretchability, "surface composites" made of a CNT on polymeric films are a promising way to obtain a low-cost, conductive, elastic, moldable, and patternable material. The use of polymers selected for specific applications, however, requires targeted studies to deeply understand the interface interactions between a CNT and the surface of such polymer films, and in particular the stability and durability of a CNT grafting onto the polymer itself. Here, we present an investigation of the interface properties for a selected group of polymer film substrates with different viscoelastic properties by means of a series of different and complementary experimental techniques. Specifically, we studied the interaction of a single-wall carbon nanotube (SWCNT) deposited on two couples of different polymeric substrates, each one chosen as representative of thermoplastic polymers (i.e., low-density polyethylene (LDPE) and polypropylene (PP)) and thermosetting elastomers (i.e., polyisoprene (PI) and polydimethylsiloxane (PDMS)), respectively. Our results demonstrate that the characteristics of the interface significantly differ for the two classes of polymers with a deeper penetration (up to about 100 μm) into the polymer bulk for the thermosetting substrates. Consequently, the resistance per unit length varies in different ranges, from 1-10 kΩ/cm for typical thermoplastic composite devices (30 μm thick and 2 mm wide) to 0.5-3 MΩ/cm for typical thermosetting elastomer devices (150 μm thick and 2 mm wide). For these reasons, the composites show the different mechanical and electrical responses, therefore suggesting different areas of application of the devices based on such materials.
Topics: Polymers; Nanotubes, Carbon; Elastomers; Wearable Electronic Devices; Transducers
PubMed: 36838750
DOI: 10.3390/molecules28041764 -
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