Smart or stimuli-responsive polymers have garnered significant interest in the scientific community due to their response to different stimuli like pH, temperature, light, mechanical force, etc. Mechanophoric polymer is an intriguing class of smart polymers that respond to external mechanical force by producing fluorescent moieties and can be utilized for damage detection and stress-sensing assessment. In recent reports on mechanophoric polymers, different mechanophoric motifs such as spiropyran, rhodamine, coumarin, etc.
View Article and Find Full Text PDFIn the forefront of advanced materials, ultra-high molecular weight (UHMW) polymers, renowned for their outstanding mechanical properties, have found extensive applications across various domains. However, their production has encountered a significant challenge: the attainment of UHMW polymers with a low dispersity (Ɖ). Herein, we introduce the pioneering technique of ultrasound (US) initiated polymerization, which has garnered attention for its capability to successfully polymerize a multitude of monomers.
View Article and Find Full Text PDFMechanophoric polymers are an interesting class of smart polymers which contains a special force-sensitive molecular motif that can lead to a chemical change within the polymer network in response to mechanical force. This investigation reports the design of a mechanophoric polymer based on epoxy-functionalized rhodamine via a monomeric approach. In this case, rhodamine (Rh) is modified with glycidyl methacrylate (GMA) through an epoxy-amine reaction to design a vinyl-functionalized multi-armed macromonomer (Rh-GMA), which is reacted with butyl acrylate (BA) to prepare the crosslinked polymeric film.
View Article and Find Full Text PDFPolymers with furan functionality have been the subject of extensive research on developing sustainable materials applying a limited number of dynamic covalent approaches. Herein, we introduce a facile, dynamic non-covalent approach to make a furan polymer readily accessible for self-healing applications based on its electrophilic substitution (ES) with a commercially available 1,2,4-triazoline-3,5-dione (TAD) derivative, 4-phenyl-TAD (PTAD). A tailor-made furan polymer, poly(furfuryl methacrylate) (PFMA), considering it an initial illustrative example, was rapidly ES modified with PTAD to produce furfuryl-tagged triazolidine that subsequently associated via inter-molecular hydrogen (H-) bonding to produce a thermally reversible supramolecular polymer network under ambient conditions.
View Article and Find Full Text PDFThe effect of ionic liquids on the reversible addition-fragmentation chain transfer (RAFT) polymerization mediated by a visible-light-induced photoiniferter mechanism was investigated. ,-Dimethyl acrylamide was polymerized by photoiniferter polymerization in 1-ethyl-3-methylimidazolium ethylsulfate [EMIM][EtSO] ionic liquid. We observed a considerable increase in the polymerization rate constants in ionic liquids (ILs), as well as in the mixed solvent of water and the IL, compared to those observed with water alone as the solvent.
View Article and Find Full Text PDFIn recent times mucoadhesive drug delivery systems are gaining popularity in oral cancer. It is a malignancy with high global prevalence. Despite significant advances in cancer therapeutics, improving the prognosis of late-stage oral cancer remains challenging.
View Article and Find Full Text PDFIn this hi-tech world, the "smart coatings" have sparked significant attention among materials scientists because of their versatile applications. Various strategies have been developed to generate smart coatings in the past 2 decades. The layer-by-layer (LbL) technique is the most commonly employed strategy to produce a smart coating for suitable applications.
View Article and Find Full Text PDFDevelopment of fluorescent imaging probes is an important topic of research for the early diagnosis of cancer. Based on the difference between the cellular environment of tumor cells and normal cells, several "smart" fluorescent probes have been developed. In this work, a glycopolymer functionalized Förster resonance energy transfer (FRET) based fluorescent sensor is developed, which can monitor the pH change in cellular system.
View Article and Find Full Text PDFPhotodynamic therapy has emerged as a noninvasive treatment modality for several types of cancers. However, conventional hydrophobic photosensitizers (PS) suffer from low water solubility and poor tumor-targeting ability. Therefore, PS modified with glycopolymers can offer adequate water solubility, biocompatibility, and tumor-targeting ability due to the presence of multiple sugar units.
View Article and Find Full Text PDFAmphiphilic diblock copolymers containing dopamine and zwitterions are synthesized via the RAFT polymerization method, which undergo temperature-mediated micellization in aqueous media. The presence of catechol moiety in dopamine is exploited to form pH-responsive cross-links with ferric ions (Fe ) at different pH value. Herein, a comprehensive study of the effect of pH as well as temperature on the size and solution behavior of these cross-linked micelles is presented.
View Article and Find Full Text PDFEpoxy-based adhesives have gotten significant attention in the conservation of antiquities and repair or reconstruction of artifacts due to their excellent adhesion strength. However, it has become hard to detect repaired work in artifacts due to the transparent nature of epoxy-based adhesives. Hence, the making of fluorescent adhesives has become an exciting topic for art conservators.
View Article and Find Full Text PDFMacromol Rapid Commun
July 2021
Zwitterionic polymers by virtue of their unique chemical and physical attributes have attracted researchers in recent years. The simultaneous presence of positive and negative charges in the same repeat unit renders them of various interesting properties such as superhydrophilicity, which has significantly broadened their scope for being used in different applications. Among polyzwitterions of different architectures, micro- and/or nano-gels have started receiving attention only until recently.
View Article and Find Full Text PDFA unique, tailor-made, zwitterionic, dual thermoresponsive and fluorescent microgel probe was synthesized via Reversible Addition Fragmentation chain-Transfer (RAFT) polymerization. Microgels were prepared via oil in water (o/w) emulsion polymerization where poly(carboxybetaine) (PCB) acted as a macro-RAFT reagent as well as an emulsifier. The presence of poly(N-vinylcaprolactam) (PNVCL) in the microgel system imparts the thermoresponsiveness to the system and the presence of a rhodamine derivative as fluorophore makes it responsive to pH change of the system by showing a fluorescence emission at 580 nm (reddish orange color).
View Article and Find Full Text PDFConventional synthesis of polyurethane (PU) often involves the use of inherently toxic and overly moisture-sensitive isocyanates. Herein, we report the preparation of a self-healable hydrophobic polymer network having urethane linkages via a facile non-isocyanate route based on carbonylimidazole-amine reaction and dynamic Diels-Alder (DA) 'click' reaction based on furan-maleimide cycloaddition. This isocyanate-free DA 'clicked' polymer material showed excellent self-healing and hydrophobic characteristics.
View Article and Find Full Text PDFACS Appl Mater Interfaces
December 2020
Fouling on filtration membranes is induced by the nonspecific interactions between the membrane surface and the foulants, and effectively hinders their efficient use in various applications. Here, we established a facile method for the coating of membrane surface with a dual stimuli-responsive antifouling microgel system enriched with a high polyzwitterion content. Different poly(sulfobetaine) (PSB) zwitterionic polymers with defined molecular weights and narrow dispersities were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and integrated onto poly(-vinylcaprolactam) (PVCL) microgels via a controlled dosage of a cross-linker, adapting a precipitation polymerization technique to obtain a core-shell microstructure.
View Article and Find Full Text PDFMater Sci Eng C Mater Biol Appl
November 2020
In this study, a polyhedral oligomeric silsesquioxane-polycaprolactone (POSS-PCL)-cored octa-arm star-shaped glyco block copolymer (BCP), poly(ε-caprolactone)-b-poly(glucopyranose) (Star-POSS-PCL-b-PGlc) was successfully synthesized via the combination of ring opening polymerization (ROP) and MADIX (macromolecular design by interchange of xanthate) polymerization technique. Herein, initially octa(3-hydroxy-3-methylbutyl dimethylsiloxy) POSS (Star-POSS) was utilized to initiate the ROP of the ε-caprolactone to get octa-arm star-shaped Star-POSS-PCL. A successive bromination followed by xanthation of the synthesized Star-POSS-PCL polymer allowed us to further polymerize 3-O-acryloyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (AIpGlc) via MADIX polymerization.
View Article and Find Full Text PDFIn this work, we developed a synthetic strategy to synthesize dual-temperature-responsive low surface fouling zwitterionic microgels. Statistical poly(-vinylcaprolactam--glycidyl methacrylate) copolymers were synthesized by RAFT polymerization and post-modified by thiol-epoxy click reaction with thiol end-group-modified poly(sulfobetaine) macro-RAFT (PSB-SH) to obtain poly(-vinylcaprolactam--glycidyl methacrylate)--poly(sulfobetaine) (PVCL--PGMA--PSB) graft copolymers. Synthesized graft copolymers were cross-linked by diamine cross-linker in water-in-oil (w/o) inverse mini-emulsion to obtain zwitterionic microgels.
View Article and Find Full Text PDFIn this investigation, we report a non-covalent (ionic interlocking and hydrogen bonding) strategy of self-healing in a covalently crosslinked organic-inorganic hybrid nanocomposite hydrogel, with specific emphasis on tuning its properties fitting into a muscle mimetic material. The hydrogel was prepared via an in situ free radical polymerization of sodium acrylate (SA) and successive crosslinking in the presence of starch grafted with poly(2-(methacryloyloxy)ethyl trimethyl ammonium chloride) (PMTAC) and montmorillonite modified with cetyl ammonium bromide (OMMT). This hydrogel shows stimuli triggered self-healing following damage in both neutral and acidic solutions (pH = 7.
View Article and Find Full Text PDFHerein we have prepared an antifouling and self-healable poly(dimethyl siloxane) (PDMS) based hydrogel which consists of a mixture of curcumin loaded zwitterionic PDMS polymersomes and amine functionalized PDMS polymersomes prepared via Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization and a Schiff-base reaction. The curcumin loaded polymersome consists of a PDMS and poly([dimethyl-[3-(2-methyl-acryloylamino)-propyl]-(3-sulfopropyl)ammonium)] (poly(sulfobetaine)) based tri-block copolymer (BCP) and it was characterized by dynamic light scattering (DLS), high resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) analyses. To prepare the hydrogel, amine functionalized PDMS polymersomes were crosslinked with polyethylene glycol dialdehyde (PEG-DA) in pH 7.
View Article and Find Full Text PDFThe present investigation deals with the development of an acrylic-based polymeric emulsion that offers multifunctional properties such as superhydrophobic, antimicrobial, anti-icing, and self-cleaning. The said multifunctional waterborne emulsion was prepared via a surfactant-free reversible addition-fragmentation chain transfer (RAFT) polymerization technique. To accomplish this, a new class of ABC-type triblock copolymer (PMTAC--PBA--PIBA) based on 2-(methacryloyloxy) ethyl ammonium chloride (MTAC), -butyl acrylate, and isobornyl acrylate (IBA) was synthesized via a polymerization-induced self-assembly technique in a surfactant-free miniemulsion process.
View Article and Find Full Text PDFA well-defined glycopolymer based fluorescence active nanogel has been prepared via the combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and Diels-Alder (DA) "click" chemistry. To prepare the nanogel, initially, a functional AB block copolymer (BCP) poly(pentafluorophenyl acrylate)--poly(furfuryl methacrylate) (PPFPA--PFMA), having activated pentafluorophenyl ester group, was synthesized via RAFT polymerization. The activated pentafluorophenyl functionality was replaced by the amine functionality of glucosamine to introduce the amphiphilic BCP poly[2-(acrylamido) glucopyranose]--poly(furfuryl methacrylate) (PAG--PFMA).
View Article and Find Full Text PDFA self-healable antifouling hydrogel based on zwitterionic block copolymer was prepared via reversible addition-fragmentation chain transfer polymerization and Diels-Alder "click" chemistry. The hydrogel consists of a core-cross-linked zwitterionic block copolymer having poly(furfuryl methacrylate) as core and poly(dimethyl-[3-(2-methyl-acryloylamino)-propyl]-(3-sulfopropyl)ammonium) (poly(sulfobetaine)) as shell. The core was cross-linked with dithiobismaleimidoethane.
View Article and Find Full Text PDFAmphiphilic diblock copolymers of poly(furfuryl methacrylate) (PFMA) with cationic poly(2-(methacryloyloxy)ethyltrimethyl ammonium chloride) (PFMA-b-PMTAC) and anionic poly(sodium 4-vinylbenzenesulfonate) (PFMA-b-PSS) were prepared via reversible addition fragmentation chain-transfer (RAFT) polymerization by using PFMA as a macro-RAFT agent. The formation of the block copolymer was confirmed by FTIR and H NMR analyses. In water, the amphiphilic diblock copolymers, (PFMA-b-PMTAC) and (PFMA-b-PSS), formed micelles with PFMA in the core and the rest of the hydrophilic polymers like PMTAC and PSS in the corona.
View Article and Find Full Text PDFThis communication reports the preparation and characterization of a functional polymer bearing a pendant indole group via a reversible-addition fragmentation and chain transfer (RAFT) process followed by its modification via an Alder-ene 'click' reaction using a 1,2,4-triazoline-3,5-dione (TAD) derivative. The resultant functional polymer showed thermo-reversible as well as healing characteristics.
View Article and Find Full Text PDFThis investigation reports a one pot synthesis of silver nanoparticles (Ag Nps) using aqueous solution of chitosan-graft-poly(acrylamide) (Cts-g-PAAm) as a reducing agent and polyethylene glycol (PEG) as a stabilizing agent. The as synthesized Ag Nps was characterized by ultra violet-visible (UV-vis), Fourier transform infrared (FTIR) and X-ray diffraction (XRD) analysis. Field emission scanning electron microscopy (FESEM), dynamic light scattering (DLS) and transmission electron microscopy (TEM) showed that Ag Nps, which were stable upto more than 60 days, were spherical in shape and the particle size was in the range of 5-50 nm.
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