Poly(n‐butylacrylate)@polystyrene nanoparticles behaving as a capsule‐based sealing nanoadditive are synthesized through an optimized semicontinuous emulsion polymerization protocol. Solid state time‐domain 1H‐NMR and 13C magic angle spinning (MAS) NMR analysis suggest strong phase separation. Line width of 13C resonances in cross polarization and single pulse experiment MAS‐NMR spectra indicates that the peculiar mobility of each phase is preserved at the nanoscale. Atomic force spectroscopy (AFM) shows the permanence of spherical shape in absence of solvent (i.e., subsequent to strong capillary and surface forces) up to moderate external load, as well as the possibility of plastically deforming the polystyrene shell and ultimately triggering the nanoparticle flow at higher force loads. The breakdown characteristic of the nanoparticle shows for the first time baroplastic behavior on a single particle with precise biphasic core@shell morphology.
Cyclic polymers with alternating monomer sequence are synthesized for the first time based on the ring‐closure strategy. Well‐defined telechelic alternating polymers are synthesized by reversible addition–fragmentation chain transfer polymerization by copolymerizing the electron acceptor monomer of N‐benzylmaleimide and donor monomer of styrene with a feed ratio of 1 between them. The corresponding cyclic alternating polymers are then produced by the UV‐induced Diels–Alder click reaction to ring‐close the linear alternating polymer precursors under highly diluted reaction solution.
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.
Nine different perylene derivatives are prepared and their ability to initiate, when combined with an iodonium salt (and optionally N‐vinylcarbazole), a ring‐opening cationic photopolymerization of epoxides under very soft halogen lamp irradiation is investigated. One of them is particularly efficient under a red laser diode exposure at 635 nm and belongs now to the very few systems available at this wavelength. The photochemical mechanisms are studied by steady‐state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry, and laser flash photolysis techniques.
Effectively detecting pH changes plays a critical role in exploring cellular functions and determining physiological and pathological processes. A novel ratiometric pH probe based on a glycopolymer, armored with properties of serum‐stability, tumor‐targeting, and pH monitoring, is designed. Random copolymers of 2‐(methacrylamido) glucopyranose and fluorescein O‐methacrylate are first synthesized by reversible addition fragmentation chain transfer polymerization. Acryloxyethyl thiocarbamoyl rhodamine B is then attached to the polymer chain to prepare ratiometric fluorescent pH probes via a thiol‐ene reaction. The synthesized polymeric probes are characterized by NMR, gel permeation chromatography, UV–vis spectroscopy, and transmission electron microscopy, and the fluorescence responses are examined in phosphate buffer at different pHs. The cytotoxicity and confocal imaging experiments of the probes are detected using HeLa cells, demonstrating a low toxicity and superior biocompatibility for detecting pH changes in bioapplications.
The synthesis of propargyl‐functional poly(carbonate)s with different content of glycidyl propargyl ether (GPE) units is achieved via the copolymerization of propargyl glycidyl ether and carbon dioxide. A new type of functional poly(carbonate) synthesized directly from CO2 and the glycidyl ether is obtained. The resulting polymers show moderate polydispersities in the range of 1.6–2.5 and molecular weights in the range of 7000–10 500 g mol−1. The synthesized copolymers with varying number of alkyne functionalities and benzyl azide are used for the copper‐catalyzed Huisgen‐1,3‐dipolar addition. Moreover, the presence of vicinal alkyne groups opens a general pathway to produce functional aliphatic poly(carbonate)s from a single polymer scaffold.
Described herein is a new printing method—direct writing of conducting polymers (CPs)—based on pipette‐tip localized continuous electrochemical growth. A single barrel micropipette containing a metal wire (Pt) is filled with a mixture of monomer, supporting electrolyte, and an appropriate solvent. A droplet at the tip of the pipette contacts the substrate, which becomes the working electrode of a micro‐electrochemical cell confined to the tip droplet and the pipette. The metallic wire in the pipette acts as both counter and reference electrode. Electropolymerization forms the CP on the working electrode in a pattern controlled by the movement of the pipette. In this study, various width poly(pyrrole) 2D and 3D structures are extruded and characterized in terms of microcyclic voltammetry, Raman spectroscopy, and scanning electron microscopy.
Pure quaternary tetraalkylammonium chlorides with one long alkyl chain dissolved in various organic solvents constitute a new class of cellulose solvents. The electrolytes are prepared in high yields and purity by Menshutkin quaternization, an inexpensive and easy synthesis route. The pure molten tetraalkylammonium chlorides dissolve up to 15 wt% of cellulose. Cosolvents, including N,N‐dimethylacetamide (DMA), may be added in large excess, leading to a system of decreased viscosity. Contrary to the well‐established solvent DMA/LiCl, cellulose dissolves in DMA/quaternary ammonium chlorides without any pretreatment. Thus, the use of the new solvent avoids some disadvantages of DMA/LiCl and ionic liquids, the most extensively employed solvents for homogeneous cellulose chemistry.
Synthesis of a cyclodextrin (CD) polyrotaxane is achieved for the first time by simultaneous free radical polymerization of isoprene, threading by CD, and stoppering by copolymerization of styrene. This reaction is performed in an eco‐friendly manner in an aqueous medium similar to classical emulsion polymerization. Threaded CD rings of the polyrotaxane are cross‐linked by hexamethylene diisocyanate, leading to highly elastic slide‐ring gels.
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.
Copolymers of 2‐(methacrylamido)glucopyranose (MAG) and methacrylic acid (MAA) are synthesized by RAFT polymerization and then used as templates to prepare glycopolymer‐functionalized Ag nanoclusters (Gly‐Ag NCs) through microwave irradiation. Polymers and the resulting nanoclusters are characterized by NMR, GPC, UV‐Vis, SEM, TEM, AAS and fluorescence spectroscopy. The bio‐activity of the fluorescent Gly‐Ag NCs are further examined using GLUT‐1 over‐expressing cancer cells K562. Gly‐Ag NCs show efficient binding ability toward K562 cells and inhibit the cell viability in a dose dependent manner (IC50 = 0.65 μg mL–1), indicating their potential biological applications for both cancer imaging and targeted cancer therapy.
1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene (TBD)‐catalyzed polycondensation reactions of fatty acid derived dimethyl dicarbamates and diols are introduced as a versatile, non‐isocyanate route to renewable polyurethanes. The key step for the synthesis of dimethyl carbamate monomers from plant‐oil‐derived dicarboxylic acids is based on a sustainable base‐catalyzed Lossen rearrangement. The formed polyurethanes with molecular weights up to 25 kDa are characterized by SEC, DSC, and NMR analysis.
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 new molecular recognition motif between a water soluble pillar[10]arene ( WP10 ) and 1,10‐phenanthrolinium guest ( G ) in water is established. Mainly driven by the cooperativity of multiple electrostatic interactions, hydrophobic interactions, and π–π stacking interactions between WP10 and G , this host–guest complex exhibits a high association constant in water, which is about 17 times higher than that between WP10 and paraquat ( PQ ). Furthermore, this size selective host–guest complexation is employed to tune the lower critical solution temperature behavior of a random copolymer with PQ derivative pendants.
Endowing unimolecular soft nanoobjects with biomimetic functions is attracting significant interest in the emerging field of single‐chain technology. Inspired by the compartmentalized structure and polymerase activity of metalloenzymes, copper‐containing compact nanoglobules have been designed, synthesized, and characterized endowed with metalloenzyme mimicking characteristics toward controlled synthesis of water‐soluble polymers and thermoresponsive hydrogels. When compared to metalloenzymes, artificial nanoobjects endowed with metalloenzyme mimicking characteristics offer increased stability against thermal changes and reduced degradability by hydrolytic enzymes.
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.
Porous conjugated polymers are synthesized by metal‐catalyzed coupling reactions. The progress for porous polymers when planar or tetrahedral building blocks are connected by alkyne units into novel materials is highlighted. The most prominent reaction for the buildup of the microporous alkyne‐bridged polymers is the Sonogashira reaction, connecting alkynes to aromatic iodides or bromides. The availability of the building blocks and the potency of the Sonogashira reaction allow preparing a large variety of intrinsically porous polymeric materials, in which rigid struts connect multipronged centers. The microporous polymers are used as catalysts and as storage materials for gases and sensors. Postfunctionalization schemes, understanding of structure‐property relationships, and the quest for high porosity are pertinent.
Sulfonated poly(ether ether ketone) (SPEEK) thin film performs reversible thermochromic property by developing the color to be yellowish at the temperature above 190 °C. The detailed analyses based on temperature‐dependent techniques suggest the thermal treatment inducing the shifting of the hydrogen bond network between the sulfonated group and the hydrated water molecules to the π–π stacking among aromatic rings in SPEEK chains. Although it is general that the polymer chain packing is unfavorable at high temperature, the present work shows a good example that when the polymer chains can form specific molecular interaction, such as π–π stacking, even in harsh thermal treatment, a rearrangement will effectively occur, which leads to an external stimuli‐responsive property.
Rewritable optical storage has been obtained in a spiropyran doped liquid crystal polymer films. Pictures can be recorded on films upon irradiation with UV light passing through a grayscale mask and they can be rapidly erased using visible light. Films present improved photosensitivity and optical contrast, good resistance to photofatigue, and high spatial resolution. These photochromic films work as a multifunctional, dynamic photosensitive material with a real‐time image recording feature.
