Fabrication of CdSe composite by using the amphiphilic block copolymer as template

CdSe nanoparticles of improved stability against aggregation were synthesized by using amphiphilic block copolymer polyacrylonitrile-block-poly(ethylene glycol)-block-polyacrylonitrile (PAN-b-PEG-b-PAN, PEA). The products were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopic (HRTEM). The optical properties were characterized by UV-vis spectrophotometer and the room temperature photoluminescence (PL). The results revealed that the CdSe nanoparticles have been uniformly distributed throughout the copolymer with diameters of 6-7 nm and the produced novel hybrid nanocomposites displayed obviously quantum size effects and interesting fluorescence features. FTIR results provided the information on the interaction between the copolymer and the nanoparticles. The TGA revealed that the thermal property of the copolymer enhanced due to the interaction of the nanoparticles and the groups of the copolymer.     

Gold nanoparticles grown on star-shaped block copolymer monolayers

We report on the growth of gold nanoparticles in polystyrene/poly(2-vinyl pyridine) (PS/P2VP) star-shaped block copolymer monolayers. These amphiphilic PS(n)P2VP(n) heteroarm star copolymers differ in molecular weight (149,000 and 529,000 Da) and the number of arms (9 and 28). Langmuir-Blodgett (LB) deposition was utilized to control the spatial arrangement of P2VP arms and their ability to reduce gold nanoparticles. The PS(n)P2VP(n) monolayer acted as a template for gold nanoparticle growth because of the monolayer's high micellar stability at the liquid-solid interface, uniform domain morphology, and ability to adsorb Au ions from the water subphase. UV-vis spectra and AFM and TEM images confirmed the formation of individual gold nanoparticles with an average size of 6 ± 1 nm in the P2VP-rich outer phase. This facile strategy is critical to the formation of ultrathin polymer-gold nanocomposite layers over large surface areas with confined, one-sided positioning of gold nanoparticles in an outer P2VP phase at polymer-silicon interfaces.     

Fabrication of self-organized chemically and topologically heterogeneous patterns on the surface of polystyrene-b-oligothiophene block copolymer films

A novel fabrication of the chemically and topologically heterogeneous patterns on the surface of polymeric films over an area of more than 1 square centimeter in a single step was demonstrated by using the self-organizing character of polystyrene-b-oligothiophene block copolymers. Hexagonally arranged open pores of a size of approximately 2 mum are spontaneously formed by casting the polymer solution under a moist air flow. The amphiphilic character of the polystyrene-b-oligothiophene block copolymers played the crucial role as a surfactant to stabilize the inverse emulsion of water droplets in the organic solvent, and subsequently the structure of the arranged hydrophilic oligothiophene segments remained on the interiors of the micropores. The chemical composition of the surface of the microporous films was characterized by time-of-flight secondary ion mass spectrometry (ToF-SIMS) to prove the chemical heterogeneity. The ToF-SIMS imaging clearly indicated that the oligothiophene forms the aggregated structure on the interior of the open micropores on the surface while the flat area on the surface was covered with the polystyrene.     

功能型聚合物光子晶体的制备及应用

光子晶体因其特殊的光调控性能,在各类高性能光学器件方面具有重要的应用前景.本文主要阐述了功能型聚合物光子晶体的制备方法及其在防护涂层、高效发光、高灵敏检测和高性能光信息存储等方面的应用.     

Stimuli-responsive 2D polyelectrolyte photonic crystals for optically encoded pH sensing

A versatile photonic crystal sensing motif based on a two-dimensional (2D) inverse opal monolayer of stimuli-responsive polyelectrolyte gel with tunable optical properties is reported. The photonic membrane shows prompt response to pH and can be readily read out from either its optical spectra or interference colours.     

Fabrication and characterization of core-shell photonic crystals via a dipping process

High-quality polystyrene (PS) colloidal photonic crystals in large area were fabricated in 24 h via a capillary-enhanced process. Then, the photonic crystals with core-shell structure were obtained by incorporating silica nanoparticles into the interstitial space of opal template via a dipping process. The filling ratio (V_silica) of interstitial space could be manipulated by dipping colloidal crystals into suspensions with different concentrations of silica nanoparticles, which in turn renders the obtained core-shell photonic crystals. The absorptive peak of opal without dipping process is at 445 nm as measured by UV–vis spectrometry. The filling ratios of 0.130, 0.167 and 0.253 can be calculated according to the modified Bragg's Law, which corresponds to the absorptive peaks for core-shell opals at 453, 463 and 469 nm obtained from suspensions with silica nanoparticles of 0.017, 0.122, and 0.244 wt%, respectively. Therefore, by using this dipping process, the characteristic absorption wavelength for photonic crystal will be varied easily, efficiently and cost effectively than that by traditional methods for constructing opal from monodispersed colloids of different diameters.     

Fabrication of photonic crystals with nigrosine-doped poly(MMA-co-DVB-co-MAA) particles

A convenient approach was developed to fabricate monodisperse nigrosine-doped poly(methyl methacrylate-co-divinylbenzene-co-methacrylic acid) nanoparticles with different cross-linkage by soap-free emulsion polymerization at boiling status and swelling process. The dye-doped nanoparticles were used for the fabrication of colloidal crystal films and beads. It was found that nigrosine dye in the nanoparticles can efficiently depress the light scattering inside the colloidal crystal films and eliminate the iridescent effect in the photonic beads. These results make the colloidal crystals useful in photonic paper, bioassay, and so on.     

Hydrostatic pressure effect on the phase transitions of a closed-loop type block copolymer by using 2D FTIR correlation spectroscopy

The effect of hydrostatic pressure (P) on the phase transitions of polystyrene-block-poly(n-pentyl methacrylate) copolymer [PS-b-PnPMA] was investigated with FTIR spectroscopy at various temperatures. The experiments were performed by using a specially designed pressure cell optimized for low-pressure regime (<100 bar) with a higher resolution ( approximately 1 bar). The size of the closed loop consisting of both the lower disorder-to-order transition (LDOT) and the upper order-to-disorder transition (UODT) measured by FTIR spectroscopy becomes smaller with increasing P, consistent with results obtained from birefringence measurement. At lower temperatures with increasing P, the PS main chains are found to move before the PnPMA main chains. This is because the mobility of the PnPMA main chains is restricted due to the cluster formation of the alkyl side chain. At higher temperatures, the PnPMA block chains are more mobile than the PS block chains due to their larger specific volumes. The results indicate that the LDOT is mainly affected by a favorable directional interaction between PS and PnPMA blocks due to the cluster formation of the alkyl side chain, whereas the UODT depends on the combinatorial entropy.     

Fabrication of SiO2 hollow microsphere with urchin-like structure based on template from directed assembly of block copolymer

We report here a novel strategy for fabrication of SiO₂ hollow microspheres with urchin-like structure based on templates from directed assembly of block copolymer, poly(2-cinnamoyloxyethyl acrylate)-block-poly(acrylic acid-co-styrene) (PCEA-b-P(AA-co-Sty)). The structures of template from directed assembly of copolymers as well as that of as-obtained hollow SiO₂ microspheres were observed by a combination technique of optical microscope, scanning electron microscope, and transmission electron microscopy. It is shown that the hollow microspheres consist of aligned SiO₂ “spines” radially growing from the core which are induced a favorable growth by the structures of the template from directed assembly of PCEA-b-P(AA-co-Sty). The “spine” density of the hollow SiO₂ sphere can be tuned by controlling the structure of the copolymer with different hydrolysis degree of poly(tert-butyl-acrylate) to PAA, and the ultimate size of the resultant SiO₂ hollow sphere can be adjusted by solvent and temperature in the sol–gel process, etc.     

Fabrication of spherical colloidal crystals using electrospray

We demonstrated the use of electrohydrodynamic atomization to prepare uniform-sized emulsion droplets in which equal spheres of silica or polystyrene were dispersed. The size of the emulsion droplets was easily controlled by the electric field strength and the flow rate, independently of the diameter of the nozzles. During the evaporation of solvent in the droplets, spherical colloidal crystals were formed by self-assembly of the monodisperse colloidal spheres. The diameter of the spherical colloidal crystals was in the range of 10-40 microm. Depending on the stability of colloidal particles, the morphology of the self-assembled structure was varied. In particular, silica spheres in ethanol droplets were self-assembled into compactly packed silica colloidal crystals in spherical shapes, whereas polystyrene latex spheres in toluene droplets self-assembled into spherical colloidal crystal shells with hollow cores. The silica colloidal assemblies reflected diffraction colors according to the three-dimensionally ordered arrangement of silica spheres.     

Fabrication of block copolymer brushes on hollow sphere surface via reverse iodine transfer polymerization

The block copolymer brushes grafted from hollow sphere surface via reverse iodine transfer polymerization (RITP) were investigated in this work. A sufficient amount of azo initiator was introduced onto hollow sphere surface firstly. Then the monomer methyl methacrylate (MMA) was polymerized via surface-initiated reverse iodine transfer polymerization (RITP) using azo group modified hollow sphere as initiator. The microstructure of the samples was characterized by FT-IR, (1)H NMR, respectively. Results indicated that the poly(methyl methacrylate) (PMMA) with end functionality of alkyl iodine group had grafted from hollow sphere surface. TEM observations showed that the average diameter of hollow core was central at 1.3-1.4 μm and the average wall thickness increased from 103 nm to 138 nm and 172 nm after grafting polymerization of MMA and Tb complex, respectively. The closely linear plots of molecular weight (M(n)) versus conversion, linear kinetic plots for the free polymer formed in solution and the ability to extend the chains by sequential addition of monomer indicated that the RITP was a controlled process with a "living" characteristic.     

Fabrication of 3D polymeric photonic arrays and related applications

This review article describes the state-of-art methodologies, mainly self-assembly routes, which are in practice to fabricate photonic crystals (PCs) for advanced applications. The self-assembly of colloidal building blocks is an effective, affordable, and tunable approach to fabricate varieties of photonic materials of desired shapes and surface areas. Because of easy fabrication and controlled performance factors, PCs emerged as a potential platform for designing and developing optical devices with desired features such as photonic bandgap, high reflectance/transmittance, low loss, and lasing in the visible range of wavelengths. To develop next-generation optoelectronics and optical system, significant efforts are being made to explore novel and cost-effective fabrication methods to design and develop 3D-PCs platform, which is covered in this mini-review. The challenges, potential alternatives, and prospects of self-assembled 3D PCs are also discussed in this review.     

Fabrication and characterization of glutathione-responsive nanoparticles from the disulfide bond-bridged block copolymer

The purpose of this paper is to fabricate novel nanoparticles (NPs) from a single disulfide bond-bridged block copolymer poly(hydroxyethyl methacrylate)-S-S-polycaprolactone (PHEMA-S-S-PCL). The novel biomaterial was synthesized by ring-opening polymerization and reversible addition–fragmentation chain transfer polymerization. The cargo-free NPs were fabricated with the solvent evaporation method, and studies on NPs' characterizations were carried out. The hydrogen nuclear magnetic resonance (¹H NMR) and Fourier transform infrared spectroscopy spectra confirmed the synthesis of PHEMA-S-S-PCL copolymer. Thermo-gravimetric analysis curves indicated that the obtained PHEMA-S-S-PCL copolymer had good thermostability. Transmission electron microscopy and dynamic light scatter results suggested that the cargo-free NPs were in round shapes with an average diameter of 103.6 ± 0.12 nm. The low critical micelle concentration of cargo-free NPs (7.9 × 10^?4 mg/ml) indicated that these NPs would keep their spherical shapes after being attenuated by abundant liquid (e.g., blood or body fluid). Furthermore, these NPs showed high stability at the presence of bovine serum albumin. Therefore, it could be speculated that these NPs would not be absorbed by proteins in blood, and they could be used as a candidate carrier for drug delivery.     

Fabrication of nanoaggregates of a triple hydrophilic block copolymer by cetyltrimethylammonium chloride binding

A triple hydrophilic block copolymer composed of poly(ethylene oxide), poly(sodium 2-acrylamido-2-methylpropanesulfonate), and poly(methacrylic acid) (PEO-PAMPS-PMAA) does not form a micelle by itself when it is dissolved in water. However, if the anionic PAMPS and/or PMAA blocks are electrically neutralized with a cationic surfactant, such as cetyltrimethylammonium chloride (CTAC), micelle-like nanoaggregates are obtained, where the core is formed by the insolubilized PAMPS and/or PMAA blocks. Formation of the nanoaggregates was confirmed by dynamic light scattering (DLS) measurements and scanning electron microscopy (SEM), while the binding of CTAC to PEO-PAMPS-PMAA was monitored by electrophoresis measurements. The aggregates were characterized by fluorescence spectroscopy as well as DLS and SEM. It was found that the nanoaggregates have a spherical structure, and the hydrodynamic diameter ranges from 125 to 193 nm depending on the concentrations of the PEO-PAMPS-PMAA and CTAC. The critical aggregate concentration is on the order of 10-4 g L-1 when the ionic blocks of PEO-PAMPS-PMAA are fully neutralized with CTAC.     

Fabrication of Hydrophilic and Sponge-like PVDF/Brush-like Copolymer Blend Membranes Using Triethylphosphate as Solvent简

Porous PVDF blend membranes with good hydrophilicity and a symmetric structure were prepared by the phase inversion method using amphiphilic brush-like copolymers, P（MMA-r-PEGMA）, as hydrophilic additive and triethylphosphate （TEP） as solvent. P（MMA-r-PEGMA） was synthesized by radical polymerization in TEP. Then the obtained amphiphilic copolymer solution was mixed with PVDF and TEP to prepare the dope solution. The effects of P（MMA-r-PEGMA） content and coagulation composition on membrane morphologies were investigated using scanning electron microscopy （SEM）. The results demonstrated that, even blended with amphiphilic copolymers, a symmetric structure can be formed. Hollow fiber membranes with a mainly symmetric structure were also fabricated. The dry hollow fiber membranes showed good hydrophilicity, high flux and good rejection performance because of their hydrophilic surface and pores wall.     

One-step synthesis of silver nanoparticles by sonication or heating using amphiphilic block copolymer as templates

Block copolymer-supported Ag Nps (nanoparticles) have either a "cherry"-like or "raspberry"-like morphology [Antonietti, et al., Adv. Mater. 7 (1995) 1000-1005] depending on the amount of silver nitrate loading and the external conditions. Sonication favors silver nitrate and polyethyleneimine diffusion; the nucleation sites are well distributed in the micellar cores, so it is easy to form the cherry-like Ag NP colloids. However, when the amount of silver nitrate is decreased, it is heating that induces the formation of raspberry-like Ag NP colloids. The Ag NP colloids were investigated by transmission electron microscopy to demonstrate the nanosize dimensions and the location of the Ag NPs in the micelles. X-ray diffraction was employed to determine the crystal structure of the Ag NPs. UV-vis spectroscopy was employed for further qualitative characterization of the optical properties of Ag NPs.     

Synthesis of isocyanate-based brush block copolymers and their rapid self-assembly to infrared-reflecting photonic crystals

The synthesis of rigid-rod, helical isocyanate-based macromonomers was achieved through the polymerization of hexyl isocyanate and 4-phenylbutyl isocyanate, initiated by an exo-norbornene functionalized half-titanocene complex. Sequential ruthenium-mediated ring-opening metathesis polymerization of these macromonomers readily afforded well-defined brush block copolymers, with precisely tunable molecular weights ranging from high (1512 kDa) to ultrahigh (7119 kDa), while maintaining narrow molecular weight distributions (PDI = 1.08-1.39). The self-assembly of these brush block copolymers to solid thin-films and their photonic properties were investigated. Due to the rigid architecture of these novel polymeric materials, they rapidly self-assemble through simple controlled evaporation to photonic crystal materials that reflect light from the ultra-violet, through the visible, to the near-infrared. The wavelength of reflectance is linearly related to the brush block copolymer molecular weight, allowing for predictable tuning of the band gap through synthetic control of the polymer molecular weight. A combination of scanning electron microscopy and optical modeling was employed to explain the origin of reflectivity.     

Fabrication of an open Au/nanoporous film by water-in-oil emulsion-induced block copolymer micelles

Water-in-oil (W/O) emulsion-induced micelles with narrow size distributions of approximately 140 nm were prepared by sonicating the polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer in the toluene/water (50:1 vol %). The ordered nanoporous block copolymer films with the hydrophilic P2VP interior and the PS matrix were distinctly fabricated by casting the resultant solution on substrates, followed by evaporating the organic solvent and water. The porous diameter was estimated to be about 70 nm. Here, we successfully prepared the open nanoporous nanocomposites, the P2VP domain decorated by Au (5+/-0.4 nm) nanoparticles based on the methodology mentioned. We anticipate that this novelty enhances the specific function of nanoporous films.     

Near-infrared light-triggered dissociation of block copolymer micelles using upconverting nanoparticles

We demonstrate a novel strategy enabling the use of a continuous-wave diode near-infrared (NIR) laser to disrupt block copolymer (BCP) micelles and trigger the release of their "payloads". By encapsulating NaYF(4):TmYb upconverting nanoparticles (UCNPs) inside micelles of poly(ethylene oxide)-block-poly(4,5-dimethoxy-2-nitrobenzyl methacrylate) and exposing the micellar solution to 980 nm light, photons in the UV region are emitted by the UCNPs, which in turn are absorbed by o-nitrobenzyl groups on the micelle core-forming block, activating the photocleavage reaction and leading to the dissociation of BCP micelles and release of co-loaded hydrophobic species. Our strategy of using UCNPs as an internal UV or visible light source upon NIR light excitation represents a general and efficient method to circumvent the need for UV or visible light excitation that is a common drawback for light-responsive polymeric systems developed for potential biomedical applications.