By simply blending two diblock copolymers with the same chemistry but with different compositions one is able to create well‐defined larger soft nanoparticles as well as bimodal soft nanoparticles. Specifically, blending two diblock copolymers in a solvent good for both blocks followed by a gradual introduction of a non‐solvent results in a mixed micelle, larger than their pure block‐copolymer‐forming micelles. The formation of well‐defined larger micelle is due to the balance between the ability of the mixed micelles to assemble or merge in comparison to their pure diblock copolymer micelles. Evidently, the blending ratio, the mixing protocol, and non‐solvent addition rate are crucial to achieving well‐defined larger or bimodal micelles.
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 rapid access to 2,2′‐bithiazole‐based copolymers has been developed on the basis of the sequential palladium‐catalyzed C H/C X and C H/C H coupling reactions. To assemble a “copolymer” through homopolymerization, a type of symmetric A‐B‐A‐type building block is designed as the monomer and prepared via the regioselective C5 H arylation of thiazole. A PdCl2/CuCl‐cocatalyzed oxidative C H/C H homopolymerization has been established to afford the 2,2′‐bithiazole‐based copolymers with high Mn (up to 69400). The current protocol features atom‐ and step‐economy and exhibits a potential in the highly efficient construction of conjugated copolymers.
Hierarchical self‐assembly of transient composite hydrogels is demonstrated through a two‐step, orthogonal strategy using nanoparticle tectons interconnected through metal–ligand coordination complexes. The resulting materials are highly tunable with moduli and viscosities spanning many orders of magnitude, and show promising self‐healing properties, while maintaining complete optical transparency.
A simple strategy is provided to construct a novel pH‐ and sugar‐induced shape memory hydrogel based on dynamic phenylboronic acid (PBA)–diol interactions formed by PBA‐modified sodium alginate (Alg‐PBA) and poly(vinyl alcohol) (PVA). The dynamic PBA–diol ester bonds serve as temporary cross‐links and stabilize the deformed shape of the hydrogel. The disassociation of the PBA–diol ester bonds is explored in acidic conditions and aqueous solutions of glucose and fructose, which endow the hydrogel with shape memory performances.
Vinyl acetate is polymerized in the living way under the irradiation of blue light‐emitting diodes (LEDs) or sunlight without photocatalyst at ambient temperature. 2‐(Ethoxycarbonothioyl)sulfanyl propanoate is exclusively added and acts as initiator and chain transfer agent simultaneously in the current system. Poly(vinyl acetate) with well‐regulated molecular weight and narrow molecular weight distribution (Đ < 1.30) is synthesized. Near quantitative end group fidelity of polymer is demonstrated by nuclear magnetic resonance (NMR) and matrix‐assisteed laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS).
The chemical control of cell division has attracted much attention in the areas of single cell‐based biology and high‐throughput screening platforms. A mussel‐inspired cytocompatible encapsulation method for achieving a “cell‐division control” with cross‐linked layer‐by‐layer (LbL) shells is developed. Catechol‐grafted polyethyleneimine and hyaluronic acid are chosen as polyelectrolytes for the LbL process, and the cross‐linking of polyelectrolytes is performed at pH 8.5. Cell division is controlled by the number of the LbL nanolayers and cross‐linking reaction. We also suggest a new measuring unit, , for quantifying “cell‐division timing” based on microbial growth kinetics.
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.
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.
The preparation of multifunctional polymers and block copolymers by a straightforward one‐pot reaction process that combines enzymatic transacylation with light‐controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light‐controlled polymerization, leading to multifunctional methacrylate‐based polymers with well‐defined microstructure.
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.
In the last decades, metallopolymers have received great attention due to their various applications in the fields of materials and chemistry. In this article, a neutral 18‐electron exo‐substituted η4‐cyclopentadiene CpCo(I) unit‐containing polymer is prepared in a controlled/“living” fashion by combining facile click chemistry and ring‐opening metathesis polymerization (ROMP). This Co(I)‐containing polymer is further used as a heterogeneous macromolecular catalyst for atom transfer radical polymerization (ATRP) of methyl methacrylate and styrene.
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.
Using the third‐generation Grubbs catalyst, the living ring‐opening metathesis polymerization of ferrocene/cobalticenium copolymers is conducted with theoretical numbers of 25 monomer units for each block, and their redox and electrochemical properties allow using the Bard–Anson electrochemical method to determine the number of metallocenyl units in each block.
The electrical memory characteristics of the n‐channel organic field‐effect transistors (OFETs) employing diverse polyimide (PI) electrets are reported. The synthesized PIs comprise identical electron donor and three different building blocks with gradually increasing electron‐accepting ability. The distinct charge‐transfer capabilities of these PIs result in varied type of memory behaviors from the write‐one‐read‐many (WORM) to flash type. Finally, a prominent flexible WORM‐type transistor memory is demonstrated and shows not only promising write‐many‐read‐many (WMRM) multilevel data storage but also excellent mechanical and retention stability.
Polydopamine‐based coatings are fabricated via an electric field‐accelerating and ‐directing codeposition process of polydopamine with charged polymers such as polycations, polyanions, and polyzwitterions. The coatings are uniform and smooth on various substrates, especially on those adhesion‐resistant materials including poly(vinylidene fluoride) and poly(tetrafluoroethylene) membranes. Moreover, this electric field‐directed deposition method can be applied to facilely prepare Janus membranes with asymmetric chemistry and wettability.
The formation of a poly(2,6‐carbazole) derivative during an electrochemical polymerization process is shown. Comparison of 3,5‐bis(9‐octyl‐9H‐carbazol‐2‐yl)pyridine and 3,5‐bis(9‐octyl‐9H‐carbazol‐3‐yl)pyridine by electrochemical and UV–Vis‐NIR spectroelectrochemical measurements and DFT (density functional theory) calculation prove the formation of a poly(2,6‐carbazole) derivative. Both of the compounds form stable and electroactive conjugated polymers.
Two‐dimensional (2D) palladium nanocube array is achieved on plasma‐etched block copolymer templates, while the well‐aligned nanocubes remain active. Anisotropic nanocubes are site‐selectively assembled on various nanopatterns by capillary force. The nanocube array is proved to be easily tunable, and the dimensional commensurability plays a key role in the configurations of the nanocube assemblies. Not only catalytic nanocube array under confinement but also template for the growth of nanoscale zinc oxide (ZnO) nanorods is exemplified as the potential application of the nanoarray.
Herein, for rate‐tunable controlled release, the authors report a new facile method to prepare multiresponsive amphiphilic supramolecular diblock copolymers via the cooperative complexation between a water‐soluble pillar[10]arene and paraquat‐containing polymers in water. This supramolecular diblock copolymer can self‐assemble into multiresponsive polymeric micelles at room temperature in water. The resultant micelles can be further used in the controlled release of small molecules with tunable release rates depending on the type of single stimulus and the combination of various stimuli.
In this work, the synthesis of various halogenated thiophenol derivatives is presented. These thiophenols are used as monomers in light‐initiated SRN1‐type radical polymerization reactions. The method provides easy access to industrially relevant poly(paraphenylene sulfide) and poly(metaphenylene sulfide). The influence of the halide leaving group and of other substituents in the thiophenol monomer on the polymerization process is investigated.
