Stimuli-Responsive Polymers

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Smart and Functional Polymers".

Deadline for manuscript submissions: closed (31 October 2023) | Viewed by 11879

Special Issue Editor


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Guest Editor
The Michael M. Szwarc Polymer Research Institute, State University of New York – ESF, Syracuse, NY 13210, USA
Interests: synthesis and characterization of polymers with novel macromolecular architectures: Linear, dendritic, linear-dendritic, star-dendritic, cyclo-dendritic, dendronized, hyperbranched and linear-hyperbranched; biocompatible and biodegradable polymers, novel polymeric systems for drug delivery and diagnosis (theranostics materials); “living” polymerization methods; macromolecular self-assembly and interfacial transport; polymer-supported biocatalysis and “green” chemistry, semi-artificial enzymes
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Special Issue Information

Dear Colleagues,

Polymer materials that are able to undergo macro-, micro- or nano-phase size and shape changes under external stimuli are attracting increasing interest in advanced research and technology. The aim of this Special Issue is to discuss recent progress in this dynamically expanding area. We are inviting manuscripts, which report novel developments on stimuli-responsive polymers (natural, synthetic and their hybrids), reacting to specific changes in their environment (polarity, pH, temperature, magnetic fields) and/or signals of artificial or natural (biological) origin. A special emphasis will be placed on experimental and theoretical investigations, tracing potential applications of those responsive polymers in areas, including, but not limited to, smart materials, sustained drug delivery, “green” chemistry (synthesis and catalysis), sensing, synthetic biopolymer interactions, antifouling surfaces and coatings, and theranostics, to name a few.

Prof. Dr. Ivan Gitsov
Guest Editor

Manuscript Submission Information

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Keywords

  • stimuli-responsive polymers
  • polymer self-assembly
  • amphiphilic polymers
  • block copolymers
  • supramolecular polymers
  • conjugated polymers
  • peptide self-assembly
  • co-networks
  • polymer liquid crystals

Published Papers (7 papers)

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14 pages, 4222 KiB  
Article
The Domain and Structural Characteristics of Ferroelectric Copolymers Based on Vinylidene Fluoride Copolymer with Tetrafluoroethylene Composition (94/6)
by Valentin V. Kochervinskii, Evgeniya L. Buryanskaya, Alexey S. Osipkov, Dmitriy S. Ryzhenko, Dmitry A. Kiselev, Boris V. Lokshin, Aleksandra I. Zvyagina and Gayane A. Kirakosyan
Polymers 2024, 16(2), 233; https://doi.org/10.3390/polym16020233 - 15 Jan 2024
Cited by 1 | Viewed by 709
Abstract
This paper presents data on the macroscopic polarization of copolymer films of vinylidene fluoride with tetrafluoroethylene obtained with a modified apparatus assembled according to the Sawyer–Tower Circuit. The kinetics of the polarization process were analyzed taking into consideration the contributions of both bound [...] Read more.
This paper presents data on the macroscopic polarization of copolymer films of vinylidene fluoride with tetrafluoroethylene obtained with a modified apparatus assembled according to the Sawyer–Tower Circuit. The kinetics of the polarization process were analyzed taking into consideration the contributions of both bound and quasi-free (impurity) charges. It was shown that an “abnormal” decrease in conductivity was observed in fields near the coercive fields. This could be associated with the appearance of deep traps of the impurity charge carriers formed by the polar planes of β-phase crystals. The conductivity data obtained from the charge and current responses differed. It was concluded that chain segments contributing to polarization with sufficiently low fields were present in the amorphous phase. A comparison showed that the average size of β-phase crystals (crystals of X-ray diffraction reflection width) was almost one order of magnitude lower than the domain size obtained using piezoresponse force microscopy (PFM). The analysis of the fast-stage dielectric response before and after polarization indicated that as the external polarizing field increased in the ferroelectric polymer chains, conformational transitions occurred according to the T3GT3G → (-TT-)n и TGTG → (-TT-)n types. This was accompanied by an increase in the effective dipole moment in the amorphous phase chains. The analysis of the IR spectroscopy data obtained in transmission and ATR modes revealed a difference in the conformational states of the chains in the core and surface parts of the film. Full article
(This article belongs to the Special Issue Stimuli-Responsive Polymers)
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14 pages, 3311 KiB  
Article
Surface Functionalization of 4D Printed Substrates Using Polymeric and Metallic Wrinkles
by Johnson N. Agyapong, Bo Van Durme, Sandra Van Vlierberghe and James H. Henderson
Polymers 2023, 15(9), 2117; https://doi.org/10.3390/polym15092117 - 28 Apr 2023
Viewed by 1559
Abstract
Wrinkle topographies have been studied as simple, versatile, and in some cases biomimetic surface functionalization strategies. To fabricate surface wrinkles, one material phenomenon employed is the mechanical-instability-driven wrinkling of thin films, which occurs when a deforming substrate produces sufficient compressive strain to buckle [...] Read more.
Wrinkle topographies have been studied as simple, versatile, and in some cases biomimetic surface functionalization strategies. To fabricate surface wrinkles, one material phenomenon employed is the mechanical-instability-driven wrinkling of thin films, which occurs when a deforming substrate produces sufficient compressive strain to buckle a surface thin film. Although thin-film wrinkling has been studied on shape-changing functional materials, including shape-memory polymers (SMPs), work to date has been primarily limited to simple geometries, such as flat, uniaxially-contracting substrates. Thus, there is a need for a strategy that would allow deformation of complex substrates or 3D parts to generate wrinkles on surfaces throughout that complex substrate or part. Here, 4D printing of SMPs is combined with polymeric and metallic thin films to develop and study an approach for fiber-level topographic functionalization suitable for use in printing of arbitrarily complex shape-changing substrates or parts. The effect of nozzle temperature, substrate architecture, and film thickness on wrinkles has been characterized, as well as wrinkle topography on nuclear alignment using scanning electron microscopy, atomic force microscopy, and fluorescent imaging. As nozzle temperature increased, wrinkle wavelength increased while strain trapping and nuclear alignment decreased. Moreover, with increasing film thickness, the wavelength increased as well. Full article
(This article belongs to the Special Issue Stimuli-Responsive Polymers)
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15 pages, 3191 KiB  
Article
Formation of pH-Responsive Cotton by the Adsorption of Methyl Orange Dye
by Mateja Kert and Jasna Skoko
Polymers 2023, 15(7), 1783; https://doi.org/10.3390/polym15071783 - 03 Apr 2023
Cited by 1 | Viewed by 1941
Abstract
The interest in pH-sensitive textile sensors is growing in the global market. Due to their low-cost production, mechanical stability, flexibility, air-permeability, washability, and reusability, they are more suitable than electronic sensor systems. The research tailored the pH-sensitive textile by applying the pH indicator [...] Read more.
The interest in pH-sensitive textile sensors is growing in the global market. Due to their low-cost production, mechanical stability, flexibility, air-permeability, washability, and reusability, they are more suitable than electronic sensor systems. The research tailored the pH-sensitive textile by applying the pH indicator methyl orange to the cotton fabric during conventional dyeing. Adsorption of methyl orange dye to cotton fabric is hindered due to electrostatic repulsive forces between dye anions and negatively charged cotton fibre. To overcome this problem, chemical modification of cotton fabric using a commercial product was performed. The pH sensitivity of the dyed fabric was spectrophotometrically evaluated. In addition, the colour fastness of dyed cotton fabric to washing, light, hot pressing and rubbing was investigated according to valid SIST EN ISO standards. The research results show that the pH-responsive cotton fabric was successfully developed. The chemical modification of cotton fabric is crucial for the increased adsorption of methyl orange dye. The halochromic effect was not only perceived spectrophotometrically but also with the naked eye. The developed halochromic cotton fabric showed poor colour fastness to light and good colour fastness to hot pressing and rubbing, while no significant improvement in colour fastness to washing was observed, even though the fabric was after-treated with a cationic fixing agent. Higher adsorption of the methyl orange dye to the cotton fabric during the dyeing process leads to less wastewater pollution after dyeing with unfixed dye and, thus, a reduction in wastewater treatment costs. Full article
(This article belongs to the Special Issue Stimuli-Responsive Polymers)
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14 pages, 4502 KiB  
Article
Supramolecular Linear-Dendritic Nanoreactors: Synthesis and Catalytic Activity in “Green” Suzuki-Miyaura Reactions
by Xin Liu, F. Max Yavitt and Ivan Gitsov
Polymers 2023, 15(7), 1671; https://doi.org/10.3390/polym15071671 - 28 Mar 2023
Cited by 1 | Viewed by 1425
Abstract
This study describes the synthesis of novel amphiphilic linear-dendritic block copolymers and their self-assembly in water to form supramolecular nanoreactors capable of catalyzing Suzuki-Miyaura coupling reactions under “green” conditions. The block copolymers were formed through copper(I)-catalyzed alkyne-azide cycloaddition between azide functionalized poly(benzyl ether) [...] Read more.
This study describes the synthesis of novel amphiphilic linear-dendritic block copolymers and their self-assembly in water to form supramolecular nanoreactors capable of catalyzing Suzuki-Miyaura coupling reactions under “green” conditions. The block copolymers were formed through copper(I)-catalyzed alkyne-azide cycloaddition between azide functionalized poly(benzyl ether) dendrons as the perfectly branched blocks, as well as bis-alkyne modified poly(ethylene glycol), PEG, as the linear block. A first-generation poly(benzyl ether) dendron (G1) was coupled to a bis-alkyne modified PEG with molecular mass of 5 kDa, forming an ABA copolymer (G1)2-PEG5k-(G1)2 (yield 62%), while a second-generation dendron (G2) was coupled to a 11 kDa bis-alkyne modified PEG to produce (G2)2-PEG11k-(G2)2 (yield 49%). The structural purity and low dispersity of the linear-dendritic copolymers were verified by size-exclusion chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Their self-assembly was studied by dynamic light scattering, showing that (G1)2-PEG5k-(G1)2 and (G2)2-PEG11k-(G2)2 formed single populations of micelles (17 nm and 37 nm in diameter, respectively). The triazole rings located at the boundaries between the core and the corona are efficient chelating groups for transition metals. The ability of the micelles to complex Pd was confirmed by 1H NMR, transmission electron microscopy, and inductively coupled plasma. The catalytic activity of the supramolecular linear-dendritic/Pd complexes was tested in water by model Suzuki-Miyaura reactions in which quantitative yields were achieved within 3 h at 40 °C, while, at 17 °C, a yield of more than 70% was attained after 17 h. Full article
(This article belongs to the Special Issue Stimuli-Responsive Polymers)
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22 pages, 3213 KiB  
Article
Stimuli-Responsive Self-Assembly of Poly(2-(Dimethylamino)ethyl Methacrylate-co-(oligo ethylene glycol)methacrylate) Random Copolymers and Their Modified Derivatives
by Antiopi Vardaxi and Stergios Pispas
Polymers 2023, 15(6), 1519; https://doi.org/10.3390/polym15061519 - 19 Mar 2023
Cited by 5 | Viewed by 1949
Abstract
In this work, the synthesis and the stimuli-responsive self-assembly behavior of novel double-hydrophilic poly(2-(dimethylamino)ethyl methacrylate-co-(oligo ethylene glycol)methacrylate) random copolymers and their chemically modified derivatives are presented. The synthesis of P(DMAEMA-co-OEGMA) copolymers of different DMAEMA mass compositions was successfully conducted through RAFT polymerization, further [...] Read more.
In this work, the synthesis and the stimuli-responsive self-assembly behavior of novel double-hydrophilic poly(2-(dimethylamino)ethyl methacrylate-co-(oligo ethylene glycol)methacrylate) random copolymers and their chemically modified derivatives are presented. The synthesis of P(DMAEMA-co-OEGMA) copolymers of different DMAEMA mass compositions was successfully conducted through RAFT polymerization, further followed by the hydrophilic/hydrophobic quaternization with methyl iodide (CH3I), 1-iodohexane (C6H13I), and 1-iodododecane (C12H25I). The tertiary and quaternary amines are randomly arranged within the DMAEMA segment, responding thus to pH, temperature, and salt alterations in aqueous solutions. Light scattering techniques elucidated the intramolecular self-folding and intermolecular self-assembly of polymer chains of P(DMAEMA-co-OEGMA) copolymers upon exposure to different pHs and temperatures. Q(P(DMAEMA-co-OEGMA)) cationic polyelectrolytes demonstrated moderate response to pH, temperature, and ionic strength as a result of the permanent hydrophilic/hydrophobic profile, closely connected with the attached alkyl chains and the quaternization degree. Moreover, fluorescence spectroscopy measurements confirmed the internal micropolarity and the picture of the aggregate inner structure. Full article
(This article belongs to the Special Issue Stimuli-Responsive Polymers)
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14 pages, 3204 KiB  
Communication
Facile Synthesis of Light-Switchable Polymers with Diazocine Units in the Main Chain
by Shuo Li, Katrin Bamberg, Yuzhou Lu, Frank D. Sönnichsen and Anne Staubitz
Polymers 2023, 15(5), 1306; https://doi.org/10.3390/polym15051306 - 05 Mar 2023
Cited by 3 | Viewed by 1764
Abstract
Unlike azobenzene, the photoisomerization behavior of its ethylene-bridged derivative, diazocine, has hardly been explored in synthetic polymers. In this communication, linear photoresponsive poly(thioether)s containing diazocine moieties in the polymer backbone with different spacer lengths are reported. They were synthesized in thiol-ene polyadditions between [...] Read more.
Unlike azobenzene, the photoisomerization behavior of its ethylene-bridged derivative, diazocine, has hardly been explored in synthetic polymers. In this communication, linear photoresponsive poly(thioether)s containing diazocine moieties in the polymer backbone with different spacer lengths are reported. They were synthesized in thiol-ene polyadditions between a diazocine diacrylate and 1,6-hexanedithiol. The diazocine units could be reversibly photoswitched between the (Z)- and (E)-configurations with light at 405 nm and 525 nm, respectively. Based on the chemical structure of the diazocine diacrylates, the resulting polymer chains differed in their thermal relaxation kinetics and molecular weights (7.4 vs. 43 kDa) but maintained a clearly visible photoswitchability in the solid state. Gel permeation chromatography (GPC) measurements indicated a hydrodynamic size expansion of the individual polymer coils as a result of the ZE pincer-like diazocine switching motion on a molecular scale. Our work establishes diazocine as an elongating actuator that can be used in macromolecular systems and smart materials. Full article
(This article belongs to the Special Issue Stimuli-Responsive Polymers)
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46 pages, 21337 KiB  
Perspective
Stimuli-Responsive Principles of Supramolecular Organizations Emerging from Self-Assembling and Self-Organizable Dendrons, Dendrimers, and Dendronized Polymers
by Virgil Percec, Dipankar Sahoo and Jasper Adamson
Polymers 2023, 15(8), 1832; https://doi.org/10.3390/polym15081832 - 09 Apr 2023
Cited by 7 | Viewed by 1840
Abstract
All activities of our daily life, of the nature surrounding us and of the entire society and its complex economic and political systems are affected by stimuli. Therefore, understanding stimuli-responsive principles in nature, biology, society, and in complex synthetic systems is fundamental to [...] Read more.
All activities of our daily life, of the nature surrounding us and of the entire society and its complex economic and political systems are affected by stimuli. Therefore, understanding stimuli-responsive principles in nature, biology, society, and in complex synthetic systems is fundamental to natural and life sciences. This invited Perspective attempts to organize, to the best of our knowledge, for the first time the stimuli-responsive principles of supramolecular organizations emerging from self-assembling and self-organizable dendrons, dendrimers, and dendronized polymers. Definitions of stimulus and stimuli from different fields of science are first discussed. Subsequently, we decided that supramolecular organizations of self-assembling and self-organizable dendrons, dendrimers, and dendronized polymers may fit best in the definition of stimuli from biology. After a brief historical introduction to the discovery and development of conventional and self-assembling and self-organizable dendrons, dendrimers, and dendronized polymers, a classification of stimuli-responsible principles as internal- and external-stimuli was made. Due to the enormous amount of literature on conventional dendrons, dendrimers, and dendronized polymers as well as on their self-assembling and self-organizable systems we decided to discuss stimuli-responsive principles only with examples from our laboratory. We apologize to all contributors to dendrimers and to the readers of this Perspective for this space-limited decision. Even after this decision, restrictions to a limited number of examples were required. In spite of this, we expect that this Perspective will provide a new way of thinking about stimuli in all fields of self-organized complex soft matter. Full article
(This article belongs to the Special Issue Stimuli-Responsive Polymers)
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