A photocleavable terpolymer hydrogel cross‐linked with o‐nitrobenzyl derivative cross‐linker is shown to be capable of self‐shaping without losing its physical integrity and robustness due to spontaneous asymmetric swelling of network caused by UV‐light‐induced gradient cleavage of chemical cross‐linkages. The continuum model and finite element method are used to elucidate the curling mechanism underlying. Remarkably, based on the self‐changing principle, the photosensitive hydrogels can be developed as photoprinting soft and wet platforms onto which specific 3D characters and images are faithfully duplicated in macro/microscale without contact by UV light irradiation under the cover of customized photomasks. Importantly, a quick response (QR) code is accurately printed on the photoactive hydrogel for the first time. Scanning QR code with a smartphone can quickly connect to a web page. This photoactive hydrogel is promising to be a new printing or recording material.
The chemical synthesis of a novel polyfuran, poly(2,3‐bis(hexylthio)‐[1,4]dithiino[2,3‐c]furan) ( PBDF ), substituted at the 2,3‐positions with an S‐alkylated dithiin unit, is reported. The new polymer has been characterized in terms of its electronic absorption, electrochemical, and thermal properties. Employment of the dithiin moiety provides intrinsic additional electroactivity, as well as a functional handle for substitution with alkyl groups, enhancing the processability of the polymer. The new polymer is compared with the closely related and well‐established literature compounds PEDOT and PEDTT as well‐studied, highly chalcogenated polythiophenes.
A novel one‐component type II polymeric photoinitiator, poly(vinyl alcohol)–thioxanthone (PVA–TX), is synthesized by a simple acetalization process and characterized. PVA–TX enables photopolymerization of methyl methacrylate and acrylamide in both organic and aqueous media. Photopolymerization proceeds even in the absence of a co‐initiator since PVA–TX possesses both chromophoric and hydrogen donating sites in the structure.
A series of optically active helical copolymers of phenylacetylenes are prepared by the rhodium‐catalyzed copolymerization of the imidazolidinone‐linked, catalytically active achiral phenylacetylenes and catalytically inactive chiral phenylacetylenes. The obtained chiral/achiral copolymers exhibit an induced circular dichroism in the UV–vis regions of the copolymer backbones resulting from a preferred‐handed helical conformation biased by the chiral imidazolidinone units incorporated in the copolymers. The copolymers are found to catalyze the asymmetric Diels–Alder reaction and produce the products with a moderate enantioselectivity in spite of the fact that the catalytically active units of the copolymers are achiral, indicating that the observed enantioselectivity totally originates from the helical chirality dynamically induced by the optically active, but catalytically inactive imidazolidinone units incorporated in the copolymers.
Here, a novel method is demonstrated for the preparation of three‐arm branched microporous organic nanotube networks (TAB‐MONNs) based on molecular templating of three‐arm branched core–shell bottlebrush copolymers and Friedel–Crafts alkylation reaction. The unique three‐arm branched bottlebrush copolymers are synthesized by a combination of atom transfer radical polymerization, reversible addition‐fragmentation chain transfer polymerization, and ring‐opening polymerization techniques. In this approach, the length and diameter of branched tube units can be well‐controlled by rational molecular design. Moreover, the as‐prepared TAB‐MONNs possess a high surface area and exhibit a superior adsorption capacity for Rhodamine 6G (R6G) and p‐cresol.
Diarylbutadiyne derivatives are ideal monomers for providing the π‐electron‐conjugated system of polydiacetylenes (PDAs). The geometrical parameters for diacetylene topochemical polymerization are known. However, control of the molecules under these parameters is yet to be addressed. This work shows that by simply tailoring diarylbutadiyne with amide side‐chain substituents, the arrangement of the substituents and the resulting hydrogen bond framework allows formation of π‐electron‐conjugated PDA.
Novel thermosensitive nanocomposite (NC) hydrogels consisting of organic/inorganic networks are prepared via in situ free radical polymerization of 2‐(2‐methoxyethoxy) ethyl methacrylate (MEO2MA) and oligo(ethylene glycol) methacrylate (OEGMA) in the presence of inorganic cross‐linker clay in aqueous solution. The obtained clay/P(MEO2MA‐co‐OEGMA) hydrogels exhibit double volume phase transition temperatures, an upper critical solution temperature (UCST), and a lower critical solution temperature (LCST), which can be controlled between 5 and 85 °C by varying the fraction of OEGMA units and the weight percentage of cross‐linker clay. These new types of NC hydrogels with excellent reversible thermosensitivity are promising for temperature‐sensitive applications such as smart optical switches.
Electrochemical impedance spectroscopy (EIS) is applied for investigating binding of lectins to multivalent glycopolymer brushes grafted from interdigital gold microelectrodes. By variation of the measuring frequency, EIS allows simultaneous analysis of binding at different subnanometer distances from the sensor surfaces. In this way, the binding dynamics along the brushes are quantified, giving an idea about the motion of the lectin through the brush layer. Two different brush lengths are investigated, revealing distinct dynamics of lectin binding due to changing topology of the brushes. Moreover, very low KD values in the nanomolar range are obtained. This unique platform may be used as sophisticated biosensor for detailed investigation of high‐affinity protein binding to polymer layers.
Molecular bottle‐brush functionalized single‐walled carbon nanotubes (SWCNTs) with superior dispersibility in water are prepared by a one‐pot synthetic methodology. Elongating the main‐chain and side‐chain length of molecular bottle‐brushes can further increase SWCNT dispersibility. They show significant enhancement of SWCNT dispersibility up to four times higher than those of linear molecular functionalized SWCNTs.
A range of amphiphilic polymers with diverse macromolecular architectures has been developed and incorporated into films and coatings with potential for marine antibiofouling applications, without resorting to addition of currently used biocidal, toxic agents. Novel “green” chemical technologies employ different building blocks to endow the polymer film with surface activity, functionality, structure, and reconstruction according to the outer environment as a result of a tailored amphiphilic character of the polymer platform. We emphasise how these features can interplay and add synergistically to affect antifouling and fouling‐release against common, widespread marine micro‐ and macro‐fouling organisms.
A triol‐functional crosslinker combining the thermoreversible properties of Diels–Alder (DA) adducts in one molecule is designed, synthesized, and used as an ideal substitute of a traditional crosslinker to prepare thermal recyclable cross‐linked polyurethanes with excellent mechanical properties and recyclability in a very simple and efficient way. The recycle property of these materials achieved by the DA/retro‐DA reaction at a suitable temperature is verified by differential scanning calorimetry and in situ variable temperature solid‐state NMR experiments during the cyclic heating and cooling processes. The thermal recyclability and remending ability of the bulk polyurethanes is demonstrated by three polymer processing methods, including hot‐press molding, injection molding, and solution casting. It is notable that all the recycled cross‐linked polymers display nearly invariable elongation/stress at break compared to the as‐synthesized samples. Further end‐group functionalization of this single molecular DA crosslinker provides the potential in preparing a wide range of recyclable cross‐linked polymers.
By anchoring alkynylplatinum(II) terpyridine molecular tweezer/pyrene recognition motif on the chain‐ends of telechelic polycaprolactone, high‐molecular‐weight supramolecular polymers have been successfully constructed via noncovalent chain extension, which demonstrate fascinating rheological and thermal properties. Moreover, the resulting assemblies exhibit interesting temperature‐ and solvent‐responsive behaviors, which are promising for the development of adaptive functional materials.
Understanding nanoscale structural hierarchy/complexity of hydrophilic flexible polymers is imperative because it can be viewed as an analogue to protein‐alike superstructures. However, current understanding is still in infancy. Herein the first demonstration of nanoscale structural hierarchy/complexity via copper chelation–induced self‐assembly (CCISA) is presented. Hierarchically‐ordered colloidal networks and disks can be achieved by deliberate control of spacer length and solution pH. Dynamic light scattering, transmission electron microscopy, and atomic force microscopy demonstrate that CCISA underwent supramolecular‐to‐supracolloidal stepwise‐growth mechanism, and underline amazing prospects to the hierarchically‐ordered superstructures of hydrophilic flexible polymers in water.
Hierarchical semicrystalline block copolymer nanoparticles are produced in a segmented gas‐liquid microfluidic reactor with top‐down control of multiscale structural features, including nanoparticle morphologies, sizes, and internal crystallinities. Control of multiscale structure on disparate length scales by a single control variable (flow rate) enables tailoring of drug delivery nanoparticle function including release rates.
Electrohydrodynamic cojetting has been employed to synthesize compartmentalized microfibers from thermally responsive hydrogels. The synthesis of the hydrogels as well as their transformation into compartmentalized microcylinders is discussed. After programmable shape‐shifting, snail‐like particles are obtained that undergo functional and structural reconfiguration in response to a change in temperature.
A linear supramolecular polymer based on the self‐assembly of an easily available copillar[5]arene monomer is efficiently prepared, which is evidenced by the NMR spectroscopy, viscosity measurement, and DOSY experiment. The single‐crystal X‐ray analysis reveals that the polymerization of the AB‐type monomer is driven by the quadruple CH•••π interactions and one CH•••O interaction.
In this study, a new type of functional, self‐assembled nanostructure formed from porphyrins and polyamidoamine dendrimers based on hydrogen bonding in an aqueous solution is presented. As the aggregates formed are promising candidates for solar‐energy conversion, their photocatalytic activity is tested using the model reaction of methyl viologen reduction. The self‐assembled structures show significantly increased activity as compared to unassociated porphyrins. Details of interaction forces driving the supramolecular structure formation and regulating catalytic efficiency are fundamentally discussed.
Well‐defined ABC triblock copolymers based on two hydrophilic blocks, A and C, and a hydrophobic block B are synthesized and their self‐assembly behavior is investigated. Interestingly, at the same solvent, concentration, pH, and temperature, different shape micelles are observed, spherical and worm‐like micelles, depending on the preparation method. Specifically, spherical micelles are observed with bulk rehydration while both spherical and worm‐like micelles are observed with film rehydration.
A facile and versatile method for the synthesis of Janus graphene oxide (GO) nanosheets with different structures is reported. Based on electrostatic assembly, Janus GO nanosheets can be easily functionalized with a template polymer or be defunctionalized by altering the ionic strength. By using this approach, Janus GO nanosheets are prepared successfully with hydrophobic polystyrene chains on one side and hydrophilic poly(2‐(dimethylamino)ethyl methacrylate) chains on the other side.
Pillararene‐containing thermoresponsive polymers are synthesized via reversible addition–fragmentation chain transfer polymerization using pillararene derivatives as the effective chain transfer agents for the first time. These polymers can self‐assemble into micelles and form vesicles after guest molecules are added. Furthermore, such functional polymers can be further applied to prepare hybrid gold nanoparticles, which integrate the thermoresponsivity of polymers and molecular recognition of pillararenes.
