A polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) micellar structure with a P2VP core containing 5 nm CdS nanoparticles (NPs) and a PS shell formed in toluene that is a good solvent for PS block undergoes the core‐shell inversion by excess addition of methanol that is a good solvent for P2VP block. It leads to the formation of micellar shell‐embedded CdS NPs in the methanol major phase. The spontaneous crystalline growth of Au NPs on the CdS surfaces positioned at micellar shells without a further reduction process is newly demonstrated. The nanostructure of Au/CdS/PS‐b‐P2VP hybrid NPs is confirmed by transmission electron microscopy, energy‐dispersive X‐ray, and UV‐Vis absorption.
Water‐dispersible PEGylated nanoparticles (NPs) presenting amine‐reactive conjugation sites at their surfaces were synthesized and their ability to react with amines was demonstrated. An amphiphilic block copolymer bearing an N‐succinimidyl ester at its water‐soluble end was synthesized by the consecutive controlled radical polymerization of poly(ethylene glycol) methacrylate and styrene from a functional halide initiator. After purification of the copolymer, NPs of approximately 40 nm were obtained by a self‐assembly process in water. The reactivity of the NPs was evidenced by reacting them with primary amines, including a fluorescent dye. The activated ester remained stable throughout all synthetic steps and a nearly quantitative coupling efficiency was obtained.
Summary: Polystyrene (PS) micro‐ and nanospheres with uniform dimensions and smooth surfaces have been produced by electrospray. The effect of PS molecular weight on beads morphology and the fundamental role of concentration have been investigated. Moreover, a new apparatus was designed to collect the polymer spheres during the process and to prevent the coalescence among the spheres.
PS micro‐ and nanospheres produced by electrospray 相似文献
This work reports on thermally tunable surface wettability of electrospun fiber mats of: polystyrene (PS)/poly(N‐isopropylacrylamide) (PNIPA) blended (bl‐PS/PNIPA) and crosslinked poly[(N‐isopropylacrylamide)‐co‐[methacrylic acid)] (PNIPAMAA) (xl‐NIPAMAA). Both the bl‐PS/PNIPA and xl‐PNIPAMAA fiber mats demonstrate reversibly switchable surface wettability, with the bl‐PS/PNIPA fiber mats approaching superhydrophobic ≥150° and superhydrophilic contact angle (CA) values at extreme temperatures. Weight loss studies carried out at 10 °C indicate that the crosslinked PNIPAMAA fiber mats had better structural integrity than the bl‐PS/PNIPA fiber mats. PNIPA surface chemistry and the Cassie–Baxter model were used to explain the mechanism behind the observed extreme wettability.
Summary: A unique and simple method to prepare films with various ordered nanoscopic cylindrical patterns on the surface is reported. Various solutions of gemini surfactants with different spacers were used as a nanotemplate, on which thick polymer films were fabricated by the supramolecular assembly of a native or chemically modified polystyrene‐block‐poly(ethylene/butylene)‐block‐polystyrene (SEBS) triblock copolymer. At the air/polymer surface, normal oriented cylindrical nanodomains formed by poly(ethylene/butylene) (PEB) block associates surrounded by polystyrene (PS) blocks are exhibited. While at the polymer/surfactant solution interface, parallel cylindrical nanodomains formed by PEB block stripes alternating with PS block stripes are observed. The ordered structure of the surface can be adjusted by changing the surfactant and the chemical nature of the polymer. In a special case using Gemini 16‐1‐Ph‐1‐16 and SEBS chemically modified with 2 wt.‐% maleic anhydride, a nearly perfect hexagonal ordered structure is obtained.
The AFM micrograph and associated FFT (inset) of the morphology of a SEBS thick film formed on a 16‐1‐Ph‐1‐16 solution to give a nearly perfect hexagonal ordered structure. 相似文献
CdSe nanoparticles stabilized with the amphiphilic diblock copolymer polystyrene‐block‐poly(4‐vinylpyridine) were spread from toluene dispersion on the water surface. Monolayers could be transferred onto solid substrates using the Langmuir‐Blodgett technique. By means of atomic force and scanning electron microscopy highly symmetric ring and disk‐like structures with diameters ranging between 150 nm and 1200 nm were observed.
AFM image of a mixed monolayer of copolymer 12 and CdSe nanoparticles stabilized with polystyrene‐block‐poly(4‐vinylpyridine). 相似文献
Direct observation of the miscibility improving effect of ultra‐small polymeric nanoparticles (radius ≈4 nm) in model systems of soft nanocomposites is reported. We have found thermodynamically arrested phase separation in classical poly(styrene) (PS)/poly(vinyl methyl ether) blends when PS linear chains were totally replaced by ultra‐small, single chain PS nanoparticles, as determined by thermo‐optical microscopy measurements. Partial arrested phase splitting on heating was observed when only some of the PS chains were replaced by unimolecular PS nanoparticles, leading to a significant increase of the lower critical solution temperature (LCST) of the system (up to 40 °C at 15 vol.‐% nanoparticle content). Atomic force microscopy and rheological experiments supported these findings. Thermodynamic arrest of the phase separation process induced by replacement of linear polymer chains by unimolecular polymer nanoparticles could have significant implications for industrial applications requiring soft nanocomposite materials with excellent nanoparticle dispersion in a broad temperature range.
A novel approach is employed to produce core–corona nanospheres, which introduces a stereoregular hydrophilic part to an amphiphilic block copolymer. The resultant morphology is reported using isotactic‐poly(methacrylic acid)‐block‐poly(butyl acrylate). Infrared spectroscopy revealed a supramolecular interaction, and X ray diffraction revealed the crystallization of the outer isotactic‐poly(methacrylic acid) part. The nanostructure, which looks like a nanosized ‘grape’, was formed when nanospheres and nanofibers coexisted simultaneously and partially fused.
A simple scheme to fabricate 2‐D arrays of Au/titania hybrid nanopatterns is presented, using polystyrene‐block‐poly(ethylene oxide) diblock copolymer (PS‐b‐PEO) as templates coupled with sol–gel chemistry. Both the functionalized Au nanoparticles (NPs) and titania precursors are selectively incorporated into the PEO domain. A series of morphologies ranging from nanodot to nanowire arrays is formed and the mechanism of morphological evolution is discussed. Such hybrid films exhibit characteristic localized surface plasmon resonance bands originating from the coupling between neighboring Au NPs spatially located in a controlled manner.
This paper studies a kind of hollow nanospheres prepared by self‐assembly β‐cyclodextrins (β‐CDs) and poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) (pluronic F127) for gene delivery. It was found that this kind of hollow nanospheres enable load PEI10K/DNA and the resulting F127 NH2 βCD/(PEI10K/DNA) with 0.08 µg/well DNA display equal or higher gene delivery capability compared to PEI10K/DNA with 1 µg/well DNA in the absence or presence of serum. The cytotoxicity of the nanospheres was over 100 times lower than that of PEI10K.
A versatile approach to fabricate monodisperse poly[styrene‐co‐(divinyl benzene)] (PS‐co‐DVB) microcapsules that contain a single gold nanoparticle (AuNP) has been demonstrated. Using the PS‐co‐DVB microcapsule as a microreactor, aqueous HAuCl4 and NaBH4 solutions are subsequently infiltrated. The size of the resulting AuNP inside of the PS‐co‐DVB microcapsules is easily tunable by controlling the repeated infiltration cycles of aqueous HAuCl4 and NaBH4. PS‐co‐DVB microcapsules that contain a single silver and palladium nanoparticle are also obtained by following a similar protocol.
We report that the nanostructures of poly(styrene‐block‐4‐vinylpyridine) block copolymer (PS‐b‐P4VP) thin film on a wafer substrate can be re‐assembled by sequential vapor treatment using selected solvents. Metal or other inorganic nanoparticles that were randomly pre‐loaded inside or on the surface of PS‐b‐P4VP thin film could be pulled to the rim of PS and P4VP along with the movements of PS and P4VP blocks during the treatment. As a result, the patterned polymeric or inorganic/polymer composite nanoisland and nanoring arrays were fabricated.
Summary: A novel non‐aqueous emulsion system, consisting of cyclohexane as the continuous and acetonitrile as the dispersed phase, is described. Stabilization of the system can be achieved by using polyisoprene‐block‐poly(methyl methacrylate) copolymers as emulsifiers. The suitability of this system for performing water‐sensitive, catalytic, and oxidative polymerizations and polycondensations is demonstrated by the synthesis of poly(3,4‐ethylenedioxythiophene), poly(thiophene‐3‐yl‐acetic acid), and polyacetylene. In all cases spherical nanoparticles with diameters as small as 23 nm can be obtained.
This contribution presents a new strategy for preparing nanocapsules with a shell made of a supramolecular polymer which repeating units are held together by reversible interactions rather than covalent bonds. These nanocapsules were prepared in classical miniemulsion through interfacial addition reaction of a diisocyanate (IPDI) and a monoamine (iBA), forming low‐molecular weight bis‐ureas moieties which are strong self‐complementary interacting molecules through hydrogen‐bonding. The nanocapsules present a diameter around 100 nm, and MALDI‐TOF MS and 1H NMR analyses confirm the expected molecular characteristics for the shell. This strategy opens the scope of a new type of nanomaterials exhibiting stimuli‐responsiveness due to the reversible interaction linking the repeating units.
The morphology of a thin film was studied for a binary mixture of asymmetric PS‐b‐PMMA block copolymers on a flat silicon wafer coated with 50 nm thick silicon oxide. AFM and TEM reveal that the PMMA cylinders orient perpendicular to the substrate by tuning the film thickness. Furthermore, grating substrates with different width and depth are used to guide the alignment of the perpendicular cylinders. As a result, an array of highly ordered, hexagonally packed PMMA cylinders in the PS matrix with a domain spacing of less than 25 nm has been produced.
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.
Gold nanoparticles‐coated polystyrene (AuNPs‐coated PS) composite particles with raspberry‐like morphology are successfully prepared with the aid of a unique thermodynamically driving effect. It is of considerable interest that the AuNPs generate and self‐assemble with raw, ordinary PS microspheres that preexist in the oxidation–reduction systems. The synthesized AuNPs‐coated PS composite particles have been extensively characterized using scanning electron microscope, transmission electron microscope, and UV–Vis‐NIR spectroscopy. The results indicate that the morphology of the resultant composite particles is governed by simply changing the amount and type of reductants and the concentration of PS microspheres. The AuNPs‐coated PS composite particles also exhibit the good surface‐enhanced Raman scattering and catalytic performances.
Summary: Polymer nanospheres are synthesized by free‐radical dispersion copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) with a methacryloyl‐terminated polystyrene (PS‐MC) macromonomer in cyclohexane. Such polymer nanospheres are stabilized sterically with polystyrene (PS)‐grafted chains in cyclohexane at temperatures greater than 34 °C (the Θ temperature for PS). Ordered microporous surface films are constructed by casting these core‐shell‐type nanospheres from hot cyclohexane solution at 20 °C. The results indicate the possibility of fixation or encapsulation of functional materials after microporous patterning of the core‐shell‐type nanospheres.
SEM photograph of a vertical section of a hexagonal micropore film obtained here. 相似文献
Summary: We demonstrate in this communication that large‐scale coaxial nanocables of polypyrrole (PPy)/TiO2 can be obtained via three steps: (1) synthesis of TiO2 nanofibers by electrospinning; (2) physical adsorption Fe3+ oxidant on the surface of TiO2 nanofibers; (3) followed by polymerization of pyrrole (from vapor) on the surface of TiO2 nanofibers. During the synthesis, the PPy formed on TiO2 nanofibers as a template and formed PPy/TiO2 coaxial nanocables. TEM image proved that PPy (20 nm thickness) covered the surface of TiO2 nanofibers. Fourier‐transform infrared (FTIR), X‐ray photoelectron spectra (XPS), and X‐ray diffraction patterns (XRD) characterized the chemical structure of the coaxial nanocables. Surface photovoltage spectroscopy (SPS) revealed the surface properties of the PPy/TiO2 coaxial nanocables.
TEM image of individual PPy/TiO2 coaxial nanocable. 相似文献
Summary: The cationic polymerization of poly(tert‐butyl vinyl ether) using N‐methyleneamine equivalents derived from a Lewis acid/1,3,5‐trimethylhexahydro‐1,3,5‐triazine (TMTA) co‐initiating system is reported. The resulting polymers possessed secondary amine functionality at the chain terminus, verified by derivatization with 4‐chloro‐7‐nitrobenzo‐2‐oxa‐1,3‐diazole (NBD‐Cl) and subsequent analysis with GPC‐UV (470 nm) and 1H NMR.
Use of N‐methyleneamine equivalents lacking aryl substituents to afford amine‐terminated poly(tert‐butyl vinyl ether). 相似文献
