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.
Electrospun polymer fibers are gaining importance because of their unique properties and applications in areas such as drug delivery, catalysis, or tissue engineering. Most studies to control the morphology and properties of electrospun polymer fibers focus on changing the electrospinning conditions. The effects of post‐treatment processes on the morphology and properties of electrospun polymer fibers, however, are little studied. Here, the effect of thermal annealing on the surface properties of electrospun polymer fibers is investigated. Poly(methyl methacrylate) and polystyrene fibers are fist prepared by electrospinning, followed by thermal annealing processes. Upon thermal annealing, the surface roughness of the electrospun polymer fibers decreases. The driving force of the smoothing process is the minimization of the interfacial energy between polymer fibers and air. The water contact angles of the annealed polymer fibers also decrease with the annealing time.
Anion recognition between the triurea receptor and phosphate anion is demonstrated as the cross‐linkage to build supramolecular polymer gels for the first time. A novel multi‐block copolymer ( 3) is designed to have functional triurea groups as cross‐linking units along the polymer main chain. By virtue of anion coordination between the triurea receptor and phosphate anion with a binding mode of 2:1, supramolecular polymer gels are then prepared based on anion recognition using 3 as the building block.
Ferrocene‐based polymers have drawn much attention in the past decades due to their unique properties and promising applications. However, the synthesis of hyperbranched polymers is still a great challenge. Here, two ferrocene‐based hyperbranched polytriazoles with high molecular weights are facilely prepared by the click polymerization reactions of ferrocene‐containing diazides ( 1 ) and tris(4‐ethynylphenyl)amine ( 2 ) using Cu(PPh3)3Br as catalyst in dimethylformamide at 60 °C for 5 and 9 h in satisfactory yields of 54.0% and 52.3%. The resulting polytriazoles are soluble in common organic solvents and thermally stable, with 5% weight loss temperatures up to 307 °C. They can be used as precursors to produce nanostructured ceramics with good magnetizability by pyrolysis at elevated temperature.
This communication describes a simple and effective method for welding electrospun nanofibers at the cross points to enhance the mechanical properties of their nonwoven mats. The welding is achieved by placing a nonwoven mat of the nanofibers in a capped vial with the vapor of a proper solvent. For polycaprolactone (PCL) nanofibers, the solvent is dichloromethane (DCM). The welding can be managed in a controllable fashion by simply varying the partial pressure of DCM and/or the exposure time. Relative to the pristine nanofiber mat, the mechanical strength of the welded PCL nanofiber mat can be increased by as much as 200%. Meanwhile, such a treatment does not cause any major structural changes, including morphology, fiber diameter, and pore size. This study provides a generic method for improving the mechanical properties of nonwoven nanofiber mats, holding great potential in various applications.
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 thermally stable 2D array of spheres and their morphology control become important for the fabrication of novel nanostructures. Here, a simple method is presented for fabrication of large‐area and well‐ordered arrays of carbonized polystyrene (PS) hollow spheres with a controlled (close‐packed or non‐close‐packed hexagonal) morphology, prepared by combining the self‐assembly of PS‐grafted silica nanoparticles, etching, electron irradiation, and subsequent thermal annealing. Fine control in the 2D or 3D nanostructure of carbon materials can open up new opportunities for high‐performance nanoscale applications that require an efficient fabrication method for preparation of the porous carbon array.
A triptycene‐based microporous organic polymer (MOP) in which 2,6‐bis(benzimidazol‐2‐yl)pyridine (bbp) is incorporated as linkage and coordination site is designed and synthesized. Pd(II) ions are further immobilized in this MOP through the coordination interactions between Pd(II) ion and nitrogen atoms of bbp. The resulting material shows high stability and exhibits excellent heterogeneously catalytic activity for the Suzuki–Miyaura cross‐coupling reaction. Its high efficiency can be maintained after being reused for a number of cycles.
A new and easy method of stimuli‐triggered growth and removal of a bioreducible nanoshell on nanoparticles is reported. The results show that pH or temperature could induce the aggregation of disulfide‐contained branched polymers at the surface of nanoparticles; subsequently, the aggregated polymers could undergo intermolecular disulfide exchange to cross‐link the aggregated polymers, forming a bioreducible polymer shell around nanoparticles. When these nanoparticles with a polymer shell are treated with glutathione (GSH) or d,l ‐dithiothreitol (DTT), the polymer shell could be easily removed from the nanoparticles. The potential application of this method is demonstrated by easily growing and removing a bioreducible shell from liposomes, and improvement of in vivo gene transfection activity of liposomes with a bioreducible PEG shell.
The nanostructures of thin films spin‐coated from binary blends of compositionally symmetric polystyrene‐b‐polybutadiene (PS‐b‐PB) diblock copolymer having different molar masses are investigated by means of atomic force microscopy (AFM) and grazing‐incidence small‐angle X‐ray scattering (GISAXS) after spin‐coating and after subsequent solvent vapor annealing (SVA). In thin films of the pure diblock copolymers having high or low molar mass, the lamellae are perpendicular or parallel to the substrate, respectively. The as‐prepared binary blend thin films feature mainly perpendicular lamellae in a one‐phase state, indicating that the higher molar mass diblock copolymer dominates the lamellar orientation. The lamellar thickness decreases linearly with increasing volume fraction of the low molar mass diblock copolymer. After SVA, well‐defined macrophase‐separated nanostructures appear, which feature parallel lamellae near the film surface and perpendicular ones in the bulk.
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.
Polyurethane (PU) monomer mixtures containing commercially available o‐nitrobenzyl‐based photocleavable monomers have been formulated and tested as low‐cost positive tone photoresists. The photolysis reaction is studied by UV spectroscopy. Well‐defined micropatterns on 2 μm thick photodegradable PU films are obtained using 365 nm light exposure. This strategy is also extended to improved formulations based on synthesized o‐nitrobiphenylpropyl derivatives with enhanced photochemical properties for single photon excitation and high two‐photon absorption cross‐sections. Improved pattern resolution in 2D and the capability of 3D resolution using a scanning laser at 780 nm is demonstrated. This work demonstrates the potential of PUs as readily available, versatile, and easy‐to‐use photoresist materials for low‐cost lithography applications.
This work demonstrates a new halogenation reaction through sequential radical and halogen transfer reactions, named as “radical and atom transfer halogenation” (RATH). Both benzoxazine compounds and poly(2,6‐dimethyl‐1,4‐phenylene oxide) have been demonstrated as active species for RATH. Consequently, the halogenated compound becomes an active initiator of atom transfer radical polymerization. Combination of RATH and sequential ATRP provides an convenient and effective approach to prepare reactive and crosslinkable polymers. The RATH reaction opens a new window both to chemical synthesis and molecular design and preparation of polymeric materials.
Enzymes are attractive, “green” alternatives to chemical catalysts within the industrial sector, but their robustness to environmental conditions needs optimizing. Here, an enzyme is tagged chemically and recombinantly with a self‐assembling peptide that allows the conjugate to spontaneously assemble with pure peptide to form β‐sheet‐rich nanofibers decorated with tethered enzyme. Above a critical concentration, these fibers entangle and form a 3D hydrogel. The immobilized enzyme catalyzes chemical transformations and critically its stability is increased significantly where it retains activity after exposure to high temperatures (90 °C) and long storage times (up to 12 months).
A novel strategy for the incorporation of carbon dioxide into polymers is introduced. For this purpose, the Ugi five‐component condensation (Ugi‐5CC) of an alcohol, CO2, an amine, an aldehyde, and an isocyanide is used to obtain step‐growth monomers. Polymerization via thiol‐ene reaction or polycondensation with diphenyl carbonate gives diversely substituted polyurethanes or alternating polyurethane‐polycarbonates, respectively. Furthermore, the application of 1,12‐diaminododecane and 1,6‐diisocyanohexane as bifunctional components in the Ugi‐5CC directly results in the corresponding polyamide bearing methyl carbamate side chains ( = 19 850 g mol−1). The latter polymer is further converted into the corresponding polyhydantoin in a highly straightforward fashion.
For a singlet–triplet coupled molecular system, the efficiency of forward and reverse intersystem crossing processes can be enhanced by reducing the energy gap between the singlet and triplet excited states (ΔEST), thus prolonging the exciton lifetimes. This has been proven beneficial for many emerging applications such as molecular luminescence, optoelectronics, and photonics. Here, a strategy is proposed to create small ΔEST by polymerizing fluorescent dye molecules, the efficacy of which is justified by density functional theory calculations and ultrafast spectroscopy. Thus, singlet–triplet exciton communication through polymerization‐enhanced intersystem crossing is also proposed.
A double‐layer hollow fiber is fabricated where an isoporous surface of polystyrene‐block‐poly(4‐vinylpyridine) is fixed on a support layer by co‐extrusion. Due to the sulfonation of the support layer material, delamination of the two layers is suppressed without increasing the number of subsequent processing steps for isoporous composite membrane formation. Electron microscope‐energy‐dispersive X‐ray spectroscopy images unveil the existence of a high sulfur concentration in the interfacial region by which in‐process H‐bond formation between the layers is evidenced. For the very first time, our study reports a facile method to fabricate a sturdy isoporous double‐layer hollow fiber.
A novel route for the synthesis of poly(ethylene glycol)‐b‐polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one‐pot procedure under near‐visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mo1−1 and a polydispersity index of 1.20.
Polymer brushes have a large potential for controlling properties such as surface lubrication or wetting through facile functionalization. Polymer chemistry, chain density, and length impact on the wetting properties of brushes. This study explores the use of diblock copolymer brushes with different block length and spatial arrangement of the blocks to tune surface wettability. Block copolymer brushes of the polyelectrolyte [2‐(methacryloyloxy)ethyl] trimethylammonium chloride (PMETAC) with a contact angle of 17° and a hydrophobic block of 1H, 1H, 2H, 2H‐perfluorodecyl Acrylate (PPFDA) with a contact angle of 130° are synthesized by RAFT polymerization. By changing the sequence of polymerization either block is synthesized as top or bottom block. By varying the concentration of initiator the length of the blocks is varied. Contact angle values with intermediate values between 17° and 130° are measured. In addition, by changing solvent pH and in presence of a different salt the contact angle of the copolymer brushes can be fine tuned. Brushes are characterized by atomic force microscopy, Raman confocal microscopy, and X‐ray photoelectron spectroscopy.
Thin, phenylboronic acid‐containing polymer coatings are potentially attractive sensory layers for a range of glucose monitoring systems. This contribution presents the synthesis and properties of glucose‐sensitive polymer brushes obtained via surface RAFT polymerization of 3‐methacrylamido phenylboronic acid (MAPBA). This synthetic strategy is attractive since it allows the controlled growth of PMAPBA brushes with film thicknesses of up to 20 nm via direct polymerization of MAPBA without the need for additional post‐polymerization modification or deprotection steps. QCM‐D sensor chips modified with a PMAPBA layer respond with a linear change in the shift of the fundamental resonance frequency over a range of physiologically relevant glucose concentrations and are insensitive toward the presence of fructose, thus validating the potential of these polymer brush films as glucose sensory thin coatings.
