Chitosan is a functional polymer with diverse applications in biomedicine, agriculture, water treatment, and beyond. Via derivatization of pristine chitosan, its functionality can be tailored to desired applications, e.g.
View Article and Find Full Text PDFNitroxide-mediated polymerization (NMP) and nitroxide exchange reaction (NER) are very efficient methodologies that require only suitable alkoxyamine derivatives and create different polymeric architectures in a controlled manner. Herein, the synthesis of star polymers containing TEMPO-substituted symmetric zinc phthalocyanine (ZnPc) is presented via NMP and NER. Moreover, linear polymer formation is conducted in a single arm on TEMPO-substituted asymmetric ZnPc to elucidate the properties of star polymers.
View Article and Find Full Text PDFArtificial photomodulated channels represent a significant advancement toward practical photogated systems because of their remote noncontact stimulation. Ion transport behaviors in artificial photomodulated channels, however, still require further investigation, especially in multiple nanochannels that closely resemble biological structures. Herein, we present the design and development of photoswitchable ion nanochannels inspired by natural channelrhodopsins (ChRs), utilizing photoresponsive polymers grafted anodic aluminum oxide (AAO) membranes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Responsive photonic crystals (RPCs) exhibit dynamic chromism upon trigger by various solvents, showing potential applications in qualitative identification and quantitative analysis of multicomponent solvents. However, distinguishing similar solvents, especially traces of cosolvents, remains challenging due to the limited sensitivity of RPCs. To address this, we herein introduce brush-like polymeric gels inside photonic crystals, forming a brush-like polymeric photonic gel (BPPG) that can trace tiny component changes.
View Article and Find Full Text PDFMacromol Rapid Commun
October 2024
Synthesis of polyurethane-type poly[3]rotaxanes is achieved by polyaddition between a cyclodextrin (CD)-based [3]rotaxane diol and various diisocyanate species, which provide a more defined structure compared to conventional polyrotaxane syntheses. In this study, hydroxyl groups on CDs of [3]rotaxane diol are initially acetylated, and deprotected after the polyaddition to introduce polyurethane backbone structure into polyrotaxane framework. Despite a relatively complicated chemical structure, [3]rotaxane diol monomer is successfully synthesized in a high yield (overall 67%) without any taxing purification process, which is beneficial for practical applications.
View Article and Find Full Text PDFElemental sulfur has shown to be a promising alternative feedstock for development of novel polymeric materials with high sulfur content. However, the utilization of inverse vulcanized polymers is restricted by the limitation of functional comonomers suitable for an inverse vulcanization. Control over properties and structure of inverse vulcanized polymers still poses a challenge to current research due to the dynamic nature of sulfur-sulfur bonds and high temperature of inverse vulcanization reactions.
View Article and Find Full Text PDFThe decryption and verification of encrypted information a simple and efficient method is always difficult and challenging in the field of information security. Herein, a series of water-sensitive fluorescent microgels are fabricated for highly secured anti-counterfeiting with authenticity identification. The initial negatively charged microgels (MG) are made up of -isopropylacrylamide (NIPAM), acrylic acid (AAc) and anthracen-9-yl acrylate (9-ANA, blue fluorescent monomer).
View Article and Find Full Text PDFMain-chain stimuli-responsive polymers synthesized via polymerization techniques that do not rely on metal-based catalysis are highly desirable for economic reasons and to avoid metal-polymer interactions. Herein, we introduce a metal-free head-to-tail organobase-catalyzed hydroxyl-yne click polymerization of an AB-type monomer to realize photoswitchable polymers featuring α-bismines as main-chain repeating units. The prepared main-chain α-bisimine-based polymers show excellent photoswitching in solution.
View Article and Find Full Text PDFDeveloping effective amyloidosis inhibitors poses a significant challenge due to the dynamic nature of the protein structures, the complex interplay of interfaces in protein-protein interactions, and the irreversible nature of amyloid assembly. The interactions of amyloidogenic polypeptides with other peptides play a pivotal role in modulating amyloidosis and fibril formation. This study presents a novel approach for designing and synthesizing amyloid interaction surfaces using segments derived from the amyloid-promoting sequence of amyloid β-peptide [VF(Aβ(18-19)/FF(Aβ(19-20)/LVF(Aβ(17-19)/LVFF(Aβ(17-20)], where VF, FF, LVF and LVFF stands for valine phenylalanine dipeptide, phenylalanine phenylalanine dipeptide, leucine valine phenylalanine tripeptide and leucine valine phenylalanine phenylalanine tetrapeptide, respectively.
View Article and Find Full Text PDFPurely organic room-temperature phosphorescence (RTP) materials have received intense attention due to their fascinating optical properties and advanced optoelectronic applications. The promotion of intersystem crossing (ISC) and minimalization of nonradiative dissipation under ambient conditions are key prerequisites for realizing high-performance organic RTP; However, the ISC process is generally inefficient for organic fluorogens and the populated triplet excitons are always too susceptible to be well stabilized by conventional means. Particularly, organizing organic fluorophores into compact and ordered entities by supramolecular dynamic interactions has proven to be a newly-emerged strategy to boost the ISC process greatly and suppress the non-radiative relaxations immensely, facilitating the population and stabilization of triplet excitons to access high-performance organic RTP.
View Article and Find Full Text PDFThe search for new redox-active organic materials (ROMs) is essential for the development of sustainable energy-storage solutions. In this study, we present a new class of cyclobuta[]quinoxaline-1,2-diones or squaric acid quinoxalines (SQXs) as highly promising candidates for ROMs featuring exceptional stability and high redox potentials. While simple 1,2- and 1,3-squaric acid amides (SQAs), initially reported by Hünig and coworkers decades ago, turned out to exhibit low stability in their radical cation oxidation states, we demonstrate that embedding the nitrogen atoms into a quinoxaline heterocycle leads to robust two-electron SQX redox systems.
View Article and Find Full Text PDFAlthough various research efforts have been made to produce a vascular-like network structure as scaffolds for tissue engineering, there are still several limitations. Meanwhile, no articles have been published on the direct embedding of cells within a glucose sensitive sacrificial hydrogel followed by three-dimensional (3D) bioprinting to fabricate vascular structures. In this study, the hydrogel composed of reversibly crosslinked poly(ethylene glycol) diacrylate and dithiothreitol with borax and branched polyethylenimine was used as the sacrificial hydrogel to fabricate vascular-like network structure.
View Article and Find Full Text PDFWe report a novel method for the fabrication of polymeric Janus nanorods sequential polymerization from anodic aluminum oxide (AAO) templates. Dual compositions can be incorporated into individual nanorods and endow versatile potential applications. This fabrication strategy paves the way for constructing multifunctional nanostructures and brings together different materials in a single entity.
View Article and Find Full Text PDFMagnesium electrolytes based on a polycarbonate with either magnesium tetrakis(hexafluoroisopropyloxy) borate (Mg(B(HFIP))) or magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)) for magnesium batteries were prepared and characterized. The side-chain-containing polycarbonate, poly(2-butyl-2-ethyltrimethylene carbonate) (P(BEC)), was synthesized by ring opening polymerization (ROP) of 5-ethyl-5-butylpropane oxirane ether carbonate (BEC) and mixed with Mg(B(HFIP)) or Mg(TFSI) to form low- and high-salt-concentration polymer electrolytes (PEs). The PEs were characterized by impedance spectroscopy, differential scanning calorimetry (DSC), rheology, linear sweep voltammetry, cyclic voltammetry, and Raman spectroscopy.
View Article and Find Full Text PDFMacromol Rapid Commun
October 2023
Herein, novel photoresponsive spiropyran (SP)-based P(DEGMA-co-SpMA) copolymers with variable percentages of SP fractions are synthesized. The SP group present in these polymers exhibited the abilities of reversible photoisomerism. Their photoresponsive, structural, and thermal properties have been investigated and compared using various characterization techniques.
View Article and Find Full Text PDFThe aggregation of a cyclodextrin (CD)-based [3]rotaxane has been observed and analyzed in detail for the first time in this work. Although the hexagonal packing aggregation of CD-based polyrotaxane is a well known phenomenon, corresponding studies in terms of rotaxanes without any polymer structure have not been conducted so far, probably owing to the difficulty of the molecular design. We synthesized a series of [3]rotaxane species by using a urea-end-capping method and evaluated their aggregation behavior by XRD and SEM measurements.
View Article and Find Full Text PDFBranched sulfonated polymers present considerable potential for application as proton exchange membranes, yet investigation of branched polymers containing sulfonated branched centers remains to be advanced. Herein, we report a series of polymers with ultradensely sulfonated branched centers, namely, B--SPAEKS, where represents the degree of branching. In comparison with the analogous polymers bearing sulfonated branched arms, B--SPAEKS showed a reduced water affinity, resulting in less swelling and lower proton conductivity.
View Article and Find Full Text PDFPoly(ethylene oxide) block copolymers (PEO BCP) have been demonstrated to exhibit remarkably high lithium ion (Li) conductivity for Li batteries applications. For linear poly(isoprene)--poly(styrene)--poly(ethylene oxide) triblock copolymers (PIPSPEO), a pronounced maximum ion conductivity was reported for short PEO molecular weights around 2 kg mol. To later enable a systematic exploration of the influence of the PI and PS block lengths and related morphologies on the ion conductivity, a synthetic method is needed where the short PEO block length can be kept constant, while the PI and PS block lengths could be systematically and independently varied.
View Article and Find Full Text PDFACS Macro Lett
February 2022
Herein, the synthesis of polyethylene via an innovative post-polymerization modification (PPM) approach is reported. For this, a block copolymer of poly[-(acryloyloxy)phthalimide] (PAP) is synthesized by straightforward reversible addition-fragmentation chain-transfer (RAFT) polymerization using a dedicated macroRAFT transfer agent. Upon decarboxylation of the PAP block, followed by efficient block copolymer cleavage, a polyethylene homopolymer with a predictable degree of polymerization is obtained.
View Article and Find Full Text PDFHerein the decarboxylation of poly[N-(acryloyloxy)phthalimide] (PAP) for the synthesis of functionalized polymers is reported. PAP homopolymer and block copolymers are used as precursor polymers for the straightforward functionalization via decarboxylation and subsequent Michael-type addition or nitroxide radical coupling (NRC).
View Article and Find Full Text PDFThe inverse vulcanization produces high sulfur content polymers from alkenes and elemental sulfur. Control over properties such as the molar mass or the solubility of polymers is not well established, and existing strategies lack predictability or require large variations of the composition. Systematic design principles are sought to allow for a targeted design of materials.
View Article and Find Full Text PDFResearchers have dedicated their efforts for the creation of a wide choice of complex and precise macromolecular architectures over the past 100 years. Among them, cyclic polymers benefit from their absence of terminal chains and from their singular topology to minimize their hydrodynamic volume in solution, increase their chemical stability, limit their number of possible conformations as well as a reduce their propensity to crystallize or to form entanglements in comparison to their acyclic counterparts. While monocyclic structures have already been widely investigated and reviewed, reports on more complex polycyclic structures are rare.
View Article and Find Full Text PDFIn this work, a facile preparation method was proposed to reduce natural organics fouling of hydrophobic membrane via UV grafting polymerization with methacrylic acid (MAAc) and methyl acrylamide (MAAm) as hydrophilic monomers, followed by multihydrogen bond self-assembly. The resulting poly(vinylidene fluoride)-membranes were characterized with respect to monomer ratio, chemical structure and morphology, surface potential, and water contact angle, as well as water flux and organic foulants ultrafiltration property. The results indicated that the optimal membrane modified with a poly(MAAc-co-MAAm) polymer gel layer derived from a 1:1 monomer ratio exhibited superior hydrophilicity and excellent gel layer stability, even after ultrasonic treatment or soaking in acid or alkaline aqueous solution.
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