Layer‐by‐layer (LbL) assembly was conducted on CaCO3 microparticles pre‐doped with polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA) micelles, and resulted in micelles encapsulation in the microcapsules after core removal. Distribution of the micelles in the templates and capsules was characterized by transmission electron microscopy and confocal laser scanning microscopy. The micelles inside the capsules connected with each other to form a chain and network‐like structure with a higher density near the capsule walls. The hydrophobic PS cores were then able to load small uncharged hydrophobic drugs while the negatively charged PAA corona could induce spontaneous deposition of water‐soluble positively charged drugs such as doxorubicin.
Summary: We report a new method for the preparation of polyaniline nanoballs by using HAuCl4 as an oxidizing agent. During the reaction, aniline is oxidized and forms polyaniline whilst the hydrogen tetrachloroaurate is reduced and forms gold nanoparticles. These gold nanoparticles are found to decorate the nanoballs.
The resultant precipitate and corresponding TEM image of the gold‐nanoparticle covered polyaniline nanoball. 相似文献
PS‐b‐PAA spherical micelles with a liquid core and a PAA shell are prepared with the assistance of 1,2‐dichloroethane. During the process of adding a mixture of PNIPAM‐b‐P4VP and PEG‐b‐P4VP, multi‐layered micelles with a mixed corona that consists of both PNIPAM and PEG chains are constructed through the electrostatic interaction and hydrogen bonding between the PAA block and the P4VP block. When heating above the LCST, the PNIPAM chains collapse onto the PAA/P4VP complex layer while the PEG chains still stretch into the solution through the collapsed PNIPAM layer, which leads to the formation of hydrophilic channels around the PEG chains. The ibuprofen encapsulated in the hollow space can diffuse through the channels and its release rate can be controlled by changing the ratio of PEG chains to PNIPAM chains in the corona.
A dextran‐based dual‐sensitive polymer is employed to endow gold nanoparticles with stability and pH‐ and temperature‐sensitivity. The dual‐sensitive polymer is prepared by RAFT polymerization of N‐isopropylacrylamide from trithiocarbonate groups linked to dextran and succinoylation of dextran after polymerization. The functionalized nanoparticles show excellent stability under various conditions and can be stored in powder‐form. UV and DLS measurements confirm that the temperature‐induced optical changes and aggregation behaviors of the particles are strongly dependent on pH.
Summary: Polyelectrolyte multilayer films of poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) and PAH/poly(sodium 4‐styrenesulfonate) (PSS) based on electrostatic interactions as a driving force are patterned by room‐temperature nanoimprint lithography (RT‐NIL). Under an imprinting pressure of 40 bar for 8 min, well‐defined pattern structures with a line width of ≈330 nm and a separation of ≈413 nm are achieved. Meanwhile, hydrogen‐bonding‐directed multilayer films of poly(vinyl pyrrolidone) (PVPON)/poly(methyl acrylic acid) (PMAA) and poly(4‐vinylpyridine)/PAA can also be patterned in a similar way by RT‐NIL. The successful imprinting of these films originates from the high compressibility and fluidity of the layered polymeric films under high pressure.
SEM image of an imprinted (PAH/PAA)*20 film on silicon wafer. 相似文献
Summary: Polyaniline (PANI) nanowires and sub‐micro/nanostructured dendrites are synthesized and immobilized on PP‐g‐PAA film surfaces via routine oxidative polymerization of aniline under different conditions, where grafting poly(acrylic acid) (PAA) served as a template and dopant, and SDS as a surfactant. The immobilized PANI enhances the surface hydrophilicity of the poly(propylene) (PP) films, and a superhydrophilic surface is obtained in this way. The mechanism of forming different morphologies of PANI and of correspondingly obtaining a superhydrophilic surface are briefly discussed.
FESEM image shows the PANI sub‐micro/nanostructured dendrites immobilized on the surfaces of PP films. The modified surface is highly hydrophilic with a water contact angle of 3°. 相似文献
We report syntheses of phenylene‐, biphenylene‐, and terphenylene‐layered polymers with a xanthene scaffold by the modified Suzuki‐Miyaura coupling reaction. Their optical properties were studied in detail. The polymer end‐capped by nitrobenzene units, which act as fluorescence quenchers, exhibited the photo‐excited energy transfer from the layered oligophenylenes to the terminal units.
A polymer system based on polydiacetylene (PDA) supramolecules that emits red, green, and blue fluorescence has been constructed. The three‐color emitting system is comprised of red‐fluorescent PDA vesicles in which green‐fluorescent fluorescein molecules are encapsulated. Finally, the blue‐fluorescence component is introduced by reacting terminal amine groups on the PDA vesicle surfaces with fluorescamine. Thin PDA‐polymer‐containing poly(vinyl alcohol) films formed by using this strategy display red, green, and blue fluorescence upon excitation with light at specific wavelengths.
Gold nanoparticles (AuNP) with carboxyl groups on their surface were used in combination with PAH for the layer‐by‐layer coating of CaCO3 microparticles, followed by the dissolution of the CaCO3 core. SEM, TEM, and confocal microscopy are used to characterize the hybrid nanoparticles/polyelectrolyte capsules. As the AuNP have carboxyl groups on their surface, their charge density is pH dependent; therefore, the capsules exhibit a pH‐dependent swelling and can be deconstructed both at low and high pH. By covalent cross‐linking of the carboxyl groups of the AuNP and the amino groups of the PAH, it is possible to suppress the pH‐responsive behavior. AuNP are used as activation centers using IR light and this ability is used to release encapsulated material from the nanoparticles/polyelectrolyte capsules as well as for the enhancement of detection and imaging of such capsules by Raman microspectrosopy.
Enzyme‐loaded magnetic polyelectrolyte multilayer nanotubes prepared by layer‐by‐layer assembly combined with the porous template could be used as biomimetic nanoreactors. It is demonstrated that calcium carbonate can be biomimetically synthesized inside the cavities of the polyelectrolyte nanotubes by the catalysis of urease, and the size of the calcium carbonate precipitates was controlled by the cavity dimensions. The metastable structure of the calcium carbonate precipitates inside the nanotubes was protected by the outer shell of the polyelectrolyte multilayers. These features may allow polyelectrolyte nanotubes to be applied in the fields of nanomaterials synthesis, controlled release, and drug delivery.
The Michael reaction of chitosan with acrylic acid was carried out successfully, even in water alone as the reaction medium. As a consequence of its good solubility in water, the reaction product, N‐carboxyethylchitosan, showed excellent biodegradable properties with standard activated sludge.
Sixteen parallel polymerization reactions of 2‐ethyl‐2‐oxazoline have been performed at different temperatures in an automated synthesizer that allowed individual heating of each reactor. During the reactions samples were taken automatically, which were characterized by means of both online GPC and offline GC, in order to optimize the reaction temperature and to determine the activation energy of the polymerization.
Summary: The synthesis, morphology, and photophysical properties of PF‐b‐PAA with different coil lengths in dilute solutions of dichloromethane/methanol are reported. A tape‐like lamellar morphology is observed at a short coil length of PF‐b‐PAA. As the coil length increases, a large compound micelle, sphere, or vesicle is observed with different methanol contents because of the enhancement of the PAA swelling with methanol and the interfacial tension between the PF core and the PAA corona. Upon further increase of the coil length, an inverted morphology of a sphere or rod with a PF corona and PAA core is first observed but the core/corona is then reversed at a high methanol content as a result of the enhanced solubility of PAA. The morphological transformation leads to a significant variation in optical absorption or fluorescence characteristics because of the possible H‐aggregate formation.
Some of the various morphologies observed upon varying the coil length and the selective solvent content. 相似文献
Stable aqueous dispersions of nanoparticles were prepared by polyelectrolyte complex formation between well‐defined poly(ethylene glycol)‐block‐poly(2‐acrylamido‐2‐methyl‐1‐propane sodium sulfonate) and poly(ethylene glycol)‐block‐poly[2‐(dimethylamino)ethyl methacrylate] diblock copolymers. Controlled synthesis of the copolymers was achieved by water‐based atom transfer radical polymerization (ATRP). The nanoparticles were characterized by a quite narrow and monomodal size distribution as evidenced by dynamic light scattering (DLS) and confirmed by atomic force microscopy (AFM) after solution casting and freeze‐drying.
Annealing of PDADMAC/PSS multilayer microcapsules assembled on PSS‐doped CaCO3 particles at 80 °C for 30 min reduces their size dramatically from 6.9 ± 0.3 to 3.1 ± 0.5 µm. Methylene blue molecules are encapsulated by spontaneous deposition and post‐annealing with a concentration of 22 mg · mL?1, which is 1000 times higher than the feeding value. The unreleased MB molecules are retained stably for a long time, which are then protected by the capsules against reductive enzymes and keep their photodynamic activity. The viability of HeLa cells incubated with the MB‐loaded capsules decreases sharply from ≈75 (dark cytotoxicity) to ≈20% after irradiation with a laser at 671 nm and 60 J · cm?2 for 75 s.
We assess the elastic properties of PS‐b‐PAA vesicle membranes under different pH values by AFM force measurements. We find that based on the shell deformation theory, the values of the estimated apparent Young's modulus of the vesicle membranes decrease as the pH of the solution increases. The onset of the decrease of E coincides with the surface pKa determined from ζ‐potential measurements. This decrease of E at higher pH is attributed to electrostatic repulsion between the deprotonated PAA chains resulting in the thinning of the vesicle membrane.
Summary: Novel non‐covalently connected water‐soluble nanoparticles that contain poly(fluorene‐co‐phenylene) with hydroxy‐capped alkoxy side chains (PF3BOH) and poly(acrylic acid) (PAA) have been obtained and characterized. With different proportions of PF3BOH and PAA, the shape and size of the nanoparticles can be regulated. The nanoparticles are quite stable in water with no precipitate being observed after weeks. Transmission electron microscopy and dynamic laser light scattering are used to confirm the morphology of the PF3BOH/PAA nanoparticles. Their optical properties have been investigated and show similar optoelectronic properties to a PF3BOH solid film although they do not undergo aggregation.
TEM images of the nanoparticles obtained upon varying the PAA/PF3BOH content. 相似文献
Are hyperbranched polymers capable of forming entanglements? This is the central issue of this contribution. Hyperbranched polyglycerol (hbPG) samples with different molecular weights (600–106 000 g · mol−1), narrow polydispersities (1.2–1.8) and high degrees of branching (≈0.6) were prepared by anionic ring‐opening polymerization. The viscoelastic properties of these polymers with respect to molecular architecture and molar mass were investigated. At low molecular weights “classical” scaling behavior between zero shear viscosity and molecular weight can be observed, whereas between 3 000 and 10 000 g · mol−1 a plateau‐like area is found. The results indicate entanglement dynamics when exceeding a critical molar mass ( ≈ 20 000 g · mol−1) due to entangled hyperbranched polyglycerols.
Summary: High‐resolution FT‐IR spectroscopy has been used for the first time to characterize the variation of the unit cell dimensions of high‐density polyethylene (HDPE). In combination with the unit cell parameters of HDPE measured at different temperatures by Swan using wide‐angle X‐ray diffraction, the relationship between the rocking band shift (730 cm−1) and the change of the unit cell volume of HDPE has been established.
High‐resolution variable‐temperature FT‐IR spectra of HDPE rocking bands with decreasing temperature. 相似文献
