Fabrication of polymeric replicas of cell surfaces with nanoscale resolution

We report an approach for fabricating biomimetic surface replicas of cells with nanoscale resolution. Fixed cells serve as a template for a two-stage replica molding process. Cast from the template, the impression replica contains a reproduction of cellular topographical features indented into its surface, and cast from the impression replica, the relief replica contains a copy of these features protruding from its surface. Various polymers and cells can be utilized, and scanning electron microscopy, atomic force microscopy, and white light interferometry analyses confirm the replication of nanoscale features. These replicas are useful for investigating cellular function and for biomimetic tissue engineering.     

Recent advances in fabrication of monolayer colloidal crystals and their inverse replicas

Monolayer colloidal crystals(MCCs)are two-dimensional(2D)colloidal crystals consisting of a monolayer of monodisperse colloidal particles arrayed with a 2D periodic order.In recent years,MCCs have attracted intensive interest because they can act as 2D photonic crystals and be used as versatile templates for fabrication of various 2D nanostructure arrays.In this review,we provide an overview of the recent progress in the controllable fabrication of MCCs and their inverse replicas.First,some newly-developed methods for the self-assembly of MCCs based on different strategies including interfacial assembly and convective assembly are introduced.Second,some representative novel methods regarding the fabrication of various functional2D inverse replicas of MCCs,such as 2D arrays of nanobowls,nanocaps,and hollow spheres,as well as 2D monolayer inverse opals(MIOs),are described.In addition,the potential applications of MCCs and their inverse replicas are discussed.     

Fabrication of functional hollow carbon spheres with large hollow interior as active colloidal catalysts

In this study,we have established a facile method to synthesize functional hollow carbon spheres with large hollow interior,which can act as active colloidal catalysts.The method includes the following steps:first,hollow polymer spheres with large hollow interior were prepared using sodium oleate as the hollow core generator,and 2,4-dihydroxybenzoic acid and hexamethylene tetramine(HMT) as the polymer precursors under hydrothermal conditions;Fe 3+ or Ag + cations were then introduced into the as-prepared hollow polymer spheres through the carboxyl groups;finally,the hollow polymer spheres can be pseudomorphically converted to hollow carbon spheres during pyrolysis process,meanwhile iron or silver nanoparticles can also be formed in the carbon shell simultaneously.The structures of the obtained functional hollow carbon spheres were characterized by TEM,XRD,and TG.As an example,Ag-doped hollow carbon spheres were used as colloid catalysts which showed high catalytic activity in 4-nitrophenol reduction reaction.     

Fabrication of anisotropic silica hollow microspheres using polymeric protrusion particles as templates

Anisotropic polystyrene/poly(styrene-co-divinylbenzene) (PS/P(S-DVB)) protrusion particles with various morphologies such as eyeball-like, snowman-like, and raspberry-like were synthesized using a modified seeded polymerization method by dynamically controlling and stabilizing the phase separation. The effects of swelling agent, crosslinker, and monomer concentrations on the particle morphologies were studied. Using the PS/P(S-DVB) protrusion particles as templates, anisotropic silica (SiO₂) hollow microspheres were fabricated facilely. The obtained anisotropic silica hollow spheres had a potential application in rapid waste removal and detoxification extraction with a very simple procedure.     

Fabrication of gradient colloidal topography

A rather simple but yet effective way to self-assemble polystyrene (PS) beads in gradient colloidal crystal topography is proposed. The PS bead concentration, solvent, and substrate have a big effect on the colloidal crystal topography. Whether the gradient-shaped crystals can form or not depends on the Bond number [Bo; the ratio of gravitational potential energy (G) to adhesive energy (E(a)), or gravitational to capillary forces]. When Bo < 1, that is, the capillary force dominates over the gravitational force, the liquid meniscus is stable. The gradient-shaped crystals can form. Otherwise, PS beads form a uniform multilayer structure.     

Fabrication of large scale two-dimensional colloidal crystal of polystyrene particles by an interfacial self-ordering process

Monolayer films of hexagonal close-packed polystyrene (PS) spheres were formed at the air-water interface through a self-ordering process without using Langmuir trough. The contact angle of PS particles on the surface of water was determined by an interfacial swelling method. It was found that the concentration and the nature of surfactant had an obvious influence on the arrangement of PS particles. PS suspension containing Triton X 100 (TX 100) of an appropriate concentration self-assembled into a closely packed monolayer on the surface of water. Sodium dodecyl sulfonate, an anionic surfactant, had a relative weak influence on the arrangement of pre-dried PS particles, in contrast, had an obvious effect on newly synthesized PS particles. Quantitative ultraviolet-visible (UV-vis) absorption spectrometry indicated that about 3% of the added TX 100 was adsorbed on the PS particle surface. Laser diffraction patterns on the monolayer film were used to investigate the lattice orientation. Ultraviolet-visible-near infrared (UV-vis-NIR) spectra of monolayer films of different sized PS particles displayed that the method presented here was universal for preparation of two-dimensional (2D) colloidal crystals.     

Peptide-modified inverted colloidal crystal scaffolds with bone marrow stromal cells in the treatment for spinal cord injury

Carboxyl groups of surface-tethered poly(acrylic acid) (PAA) brushes should be able to serve as versatile moieties for a wide range of chemical modifications, including an attachment of bioactive species that can act as sensing probes for biosensors. In this research, poly(tert-butyl acrylate) (Pt-BA) brushes were prepared by surface-initiated atom transfer radical polymerization of tert-butyl acrylate. PAA brushes were then obtained after removal of the tert-butyl groups from the Pt-BA brushes by acid hydrolysis. The carboxyl group density of the PAA brushes can be varied as a function of chain length or molecular weight. The reactivity of the carboxyl groups of PAA brushes towards the immobilization of biotin, a frequently used model bioactive probe in biosensing applications, was evaluated. Qualitative determination of streptavidin (SA) binding to the biotin-attached PAA brushes was verified by fluorescence microscopy. The efficiency of the PAA brushes to act as a three dimensional (3D) precursor layer for biosensing applications was further demonstrated using surface plasmon resonance (SPR), where the biotin-attached PAA brushes showed an enhanced signal for the biospecific binding of SA in comparison with a self-assembled monolayer (SAM) of a carboxyl-terminated alkanethiol, used as a model two-dimensional (2D) conventional precursor layer. The PAA brushes showed very low non-specific interactions with two other tested proteins of a similar pI but different sizes. This desirable feature should be highly beneficial for the development of biosensors.     

Dye/gelled colloidal photonic crystal composites and their reversible pH-responsive optical behaviors

We introduced dyes, the colors of which are variable by changing the pH of their medium solutions, into gelled colloidal photonic crystals (GCPCs) and investigated their reversible pH-responsive optical behaviors. When the extinction position of the dye overlaps with the Bragg peak of the GCPC, the Bragg-diffracted light can be trapped in the GCPC; when the extinction position of the dye is shifted out of the Bragg peak of the GCPC, the Bragg diffracted light is free and can escape out of the GCPC. The optical behaviors of dye/gelled colloidal photonic crystal composites are reversible to the pH changes of their surrounding medium.     

Template synthesis of hydrogel composite hollow spheres against polymeric hollow latex

Hierarchically structured hydrogel hollow spheres with functional hydrogels located at desired sites are expected to have new properties. We have developed a facile swelling polymerization route using a polymer hollow sphere as template to synthesize hierarchically structured hydrogel hollow spheres. It is significant to pre-swell the template shell with good solvents, such as chloroform containing oil-soluble initiators to control interaction, thus, polymerization locus of different water-soluble functional monomers. Some representative hydrogel composite hollow spheres such as poly(N-isopropylarylamide) and poly(acrylic acid) with different morphologies have been synthesized. Hydrogels with functional groups can favorably complex with desired materials; hierarchically structured inorganic or polymer composite hollow spheres are synthesized by a sol–gel process of the inorganic precursor by using different hydrogel composite hollow spheres as templates.     

Fabrication and application of inorganic hollow spheres

Inorganic hollow spheres have attracted considerable interest due to their singular properties and wide range of potential applications. In this critical review, we provide a comprehensive overview of the preparation and applications of inorganic hollow spheres. We first discuss the syntheses of inorganic hollow spheres by use of polymers, inorganic nonmetals, metal-based hard templates, small-molecule emulsion, surfactant micelle-based soft-templates, and the template-free approach. For each method, a critical comment is given based on our knowledge and related research experience. We go on to discuss some important applications of inorganic hollow spheres in 0D, 2D, and 3D arrays. We conclude this review with some perspectives on the future research and development of inorganic hollow spheres (235 references).     

Fabrication of liquid crystal Fe3O4 composites and their magnetorheological properties

Some supramolecular polyacrylate-based liquid crystal polymers (PLCPs) were prepared by polyacrylic acid, a liquid crystal monomer and 3,5-pyridinedicarboxylic acid. Series of magnetic liquid crystal particles (Fe₃O₄@PLCPs) with core-shell structure were prepared by modifying surface of magnetic nanoparticles Fe₃O₄ by the PLCPs. The Fe₃O₄@PLCPs showed a saturation magnetization strength above 51.17 emu/g, which is similar to pure magnetic Fe₃O₄, indicating good magnetism and magnetic field dependence. Series of magnetorheological fluids were fabricated by Fe₃O₄@PLCPs (using as dispersed phase) and silicone oil (using as carrier liquid). The effects of mesogen, magnetic particle, and the polymer matrix on magnetorheological performance and settling stability were investigated. The magnetorheological fluid based on 10% Fe₃O₄@PLCP-1 showed the best performance at an applied magnetic field of 100 mT in this study. Furthermore, the magnetorheological fluids showed excellent settling stability because the density of Fe₃O₄@PLCPs was lower than that of Fe₃O₄. The Fe₃O₄@PLCPs-based fluids presented certain application potential in the field of magnetic fluid due to the excellent magnetorheological effect and settling stability.     

Formation of colloidal CuO nanocrystallites and their spherical aggregation and reductive transformation to hollow Cu2O nanospheres

In this work, we demonstrate that cuprous oxide Cu(2)O nanospheres with hollow interiors can be fabricated from a reductive conversion of aggregated CuO nanocrystallites without using templates. A detailed process mechanism has been revealed: (i) formation of CuO nanocrystallites; (ii) spherical aggregation of primary CuO crystallites; (iii) reductive conversion of CuO to Cu(2)O; and (iv) crystal aging and hollowing of Cu(2)O nanospheres. In this template-free process, Ostwald ripening is operative in (iv) for controlling crystallite size in shell structures and thus for precisely tuning the optical band gap energy (E(g)) of resultant semiconductor nanostructures. For the first time, a wealth of colorful Cu(2)O hollow nanospheres (outer diameters in 100-200 nm), with variable E(g) in the range of 2.405-2.170 eV, has been fabricated via this novel chemical route. Considering their unique hollow structure and facile tuning in band gap energy, the prepared Cu(2)O hollow spheres can be potentially useful for harvesting solar energy in the visible range. Possibility of fabrication of Cu-Cu(2)O nanocomposites has also been discussed.     

Dry etching of colloidal crystal films

Two types of non-close-packed colloidal crystal films were prepared by etching the films made of polystyrene nanospheres using a hyperthermal neutral beam of oxygen gas. Etching without sintering above glass transition temperature of the polymer particles resulted in the non-close-packed structure of the nanospheres, in which polystyrene nanospheres in different lattice planes touched each other due to the reduction in the size of the nanospheres that occurred during the etching process. In contrast, a different non-close-packed structure with inter-connecting networks between etched nanospheres was generated by annealing of the colloidal crystal and a subsequent etching process. The photonic bandgap could be tuned during this dry etching of colloidal photonic crystals. This connected open structure could be used as a template for a silica inverse opal by chemical vapor deposition. An alternative dry etching process, reactive ion etching, mainly affected the morphology of particles near the top surface, and only a slight change in the stop band position of the colloidal crystal film was observed.     

Fabrication of colloidal crystals with tubular-like packings

Methods are reported for the fabrication of colloidal crystal wires with tubular packings. Both free and silica-encased wires have been prepared. Porous silicon membranes are infiltrated with silica spheres, treated with silane, and annealed. After removal of the silicon template, short annealing times were found to result in colloidal crystal wires with varied packing geometries, while repeated annealing cycles produced a thin translucent silica sheath around the wires. Packing in the wires varies with the channel diameter of the Si membrane. The channels used in this study typically produce colloidal crystal wires with six strands, though wires with four to seven strands have been observed. Both chiral and achiral packings are also possible.     

Shell cross-linked cylinders of polyisoprene-b-ferrocenyldimethylsilane: formation of magnetic ceramic replicas and microfluidic channel alignment and patterning

Stable organometallic cylindrical nanostructures have been prepared by shell cross-linking of PI320-b-PFS53 wormlike micelles in hexane through metal-catalyzed hydrosilylation at 23 degrees C. The cross-linked structures permit the formation of cylindrical ceramic replicas containing size- and separation-tunable arrays of Fe nanoclusters. In addition, microfluidic alignment of the cross-linked cylinders was possible.     

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.     

pH-Responsive hollow polymeric microspheres and concentric hollow silica microspheres from silica-polymer core-shell microspheres

Nearly monodispersed silica-poly(methacrylic acid) (SiO 2-PMAA) core-shell microspheres were synthesized by distillation-precipitation polymerization from 3-(trimethoxysilyl)propylmethacrylate-silica (SiO 2-MPS) particle templates. SiO 2-PMAA-SiO 2 trilayer hybrid microspheres were subsequently prepared by coating of an outer layer of SiO 2 on the SiO 2-PMAA core-shell microspheres in a sol-gel process. pH-Responsive PMAA hollow microspheres with flexible (deformable) shells were obtained after selective removal of the inorganic SiO 2 core from the SiO 2-PMAA core-shell microspheres by HF etching. The pH-responsive properties of the PMAA hollow microspheres were investigated by dynamic laser scattering (DLS). On the other hand, concentric and rigid hollow silica microspheres were prepared by selective removal of the PMAA interlayer from the SiO 2-PMAA-SiO 2 trilayer hybrid microspheres during calcination. The hybrid composite microspheres, pH-sensitive hollow microspheres, and concentric hollow silica microspheres were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray (EDX) analysis.     

Fabrication and biocompatible characterization of magnetic hollow capsules

Monodispersed Fe3O4/polypyrrole （PPy） hollow particles were synthesized via controllable in-situ deposition and polymerization techniques using poly（styrene-co-acrylic） （PSA） latex as template. Field-dependent magnetization plot illustrates that the capsules are superparamagnetic at 300 K. FTIR spectrum confirms that the myoglobin （Mb） molecule adsorbed on the surface of Fe3O4/PPy hollow particle essentially retains its native structure. Furthermore, direct electrochemistry of Mb can be realized on Fe3O4/PPy capsules modified pyrolytic graphite disk electrode, which indicates that the magnetic conductive polymer capsules can promote the electron transfer of protein.     

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.