Controllable fabrication and characterization of biocompatible core-shell particles and hollow capsules as drug carrier

SiO₂@CdSe core-shell particles were fabricated by controllable deposition CdSe nanoparticles on silica colloidal spheres. Step-wise coating process was tracked by the TEM and XRD measurements. In addition, SiO₂@CdSe/polypyrrole(PPy) multi-composite particles were synthesized based on the as-prepared SiO₂@CdSe particles by cationic polymerization. The direct electrochemistry of myoglobin (Mb) could be performed by immobilizing Mb on the surface of SiO₂@CdSe particles. Immobilized with Mb, SiO₂@CdSe/PPy-Mb also displayed good bioelectrochemical activity. It confirmed the good biocompatible property of the materials with protein. CdSe hollow capsules were further obtained as the removal of the cores of SiO₂@CdSe spheres. Hollow and porous character of CdSe sub-meter size capsules made them becoming hopeful candidates as drug carriers. Doxorubicin, a typical an antineoplastic drug, was introduced into the capsules. A good sustained drug release behavior of the loading capsules was discovered via performing a release test in the PBS buffer (pH 7.4) solution at 310 k. Furthermore, SiO₂@CdSe/PPy could be converted to various smart hollow capsules via selectively removal of their relevant components.     

Novel synthesis and electrophoretic response of low density TiO-TiO2-carbon black composite

Novel low density TiO-TiO₂-carbon black composite was synthesized, which involved the deposition of inorganic coating on the surface of core-shell latex particles and subsequent removal of latex particles by calcination in high-purity nitrogen. The morphology and interior structure were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The images exhibited the composite had spherical shape and smooth surface, and the interior structure was hollow or porous. X-ray diffraction peaks (XRD) were mostly in agreement with the standard diffraction patterns of rutile TiO₂. In addition, the observed peaks at 2θ of 43.5°, 50.6° and 74.4° can be indexed to (1 1 1), (2 0 0) and (2 2 0) planes of cubic phase TiO. The X-ray photoelectron spectroscopy (XPS) results indicated that composite consisted of carbon black, TiO and TiO₂. The apparent density of the composite was suitable to 1.62 g cm⁻³, due to density matching with suspending media. Glutin-arabic gum microcapsules containing TiO-TiO₂-carbon black composite electrophoretic liquid were prepared via complex coacervation. The particles in the microcapsules showed excellent electrophoretic mobility under a DC field.     

Preparation and Characterization of Poly(Methyl Methacrylate) Coated TiO2 Nanoparticles

Titanium dioxide (TiO₂) nanoparticles were modified with poly(methyl methacrylate) (PMMA) to improve the dispersion stability of the nanoparticles in a dielectric medium and to reduce the density mismatch between TiO₂ and a dielectric medium for a microcapsule‐type electrophoretic display application. Nanoparticles were coated with PMMA by in situ dispersion polymerization. The PMMA‐coated TiO₂ nanoparticles were characterized by fourier transform‐infrared spectrometrey (FT‐IR), electrophoretic light scattering (ELS), and scanning electron microscopy (SEM). Density of PMMA‐coated TiO₂ nanoparticles was found to be dependent on the thickness of the PMMA coating on the nanoparticles. An increase of thermal stability of the PMMA layer and the contents of PMMA on the surface of the nanoparticles were measured via thermogravimetric analysis (TGA).     

Fabrication of diarylide yellow pigments/modified SiO2 core-shell hybrid composite particles for electrophoretic displays

Diarylide yellow pigments/modified SiO₂ core-shell hybrid composite particles were fabricated via a newly developed two-step procedure. The surface of diarylide yellow pigments was coated with SiO₂ by the hydrolysis of Na₂SiO₃. The obtained particles were then modified with in situ generated 3-aminopropylsilanetriol or succinic acid to form composite particles containing amino or carboxyl groups. The FT-IR spectra, TGA and TEM showed that the particles had a core-shell structure, the SEM suggested that the surface morphology of the composite particles was smooth, and the XPS and zeta potential measurement indicated that the composite particles had a high charge load. The obtained composite particles have been applied as electrophoretic particles in the electronic paper, which demonstrated that the newly developed procedure is an effective way to produce various organic/inorganic composite particles used for electrophoretic displays.     

乳化剂组成与压力对中空聚合物微球的影响

 在高温高压下,以单分散的P(St-MAA)为种子微球,采用碱/冷却法制备了P(St-MAA)中空聚合物微球。研究了乳化剂 (Tween-80和Span-80) 组成对P(St-MAA)种子微球的影响和压力对其形成中空结构的影响。扫描电子显微镜、透射电子显微镜等测试分析表明,乳化剂组成对种子微球的分散性影响明显：P（St-MAA)粒子的单分散性随着Tween-80含量的增加而逐渐变好。当单体St与MAA质量比一定时,乳化剂Tween-80与Span-80的质量比为3∶1时,可得到制备中空微球必需的单分散P(St-MAA)种子微球;种子微球经高温高压处理后,可形成平均壁厚为50 nm的单分散中空聚合物微球。     

Investigations of Pulse‐Plasma‐Polymer Coating on TiO2 Nanoparticles and Their Dispersion

An amorphous acrylic acid (AA) polymer coating was generated on TiO₂ nanoparticles through pulse radio frequency (RF) plasma polymerization. The AA plasma synthesis mechanism was studied by its optical emission spectrum. The chemical structures of AA–plasma‐polymer were carefully investigated by Fourier transform infrared spectroscopy (FTIR). The dispersion behaviors of AA‐coated and uncoated TiO₂ nanoparticles in glycol solution were characterized by ultraviolet absorbency and particle size distribution measurements. The results showed that the aggregation of TiO₂ nanoparticles in glycol solution was effectively lowered and the dispersion was improved a lot after AA–plasma‐polymer coating. The pulse plasma coating parameters played an important role in the dispersion enhancement of TiO₂ nanoparticles. By properly regulating the pulse discharge parameters, the system could gain the highest radical–monomer reactions rate, the most compatible functional groups on the nanoparticles, and the best dispersion in the background media.     

Preparation of monodisperse polystyrene/silica core-shell nano-composite abrasive with controllable size and its chemical mechanical polishing performance on copper

Monodisperse silica-coated polystyrene (PS) nano-composite abrasives with controllable size were prepared via a two-step process. Monodisperse positively charged PS colloids were synthesized via polymerization of styrene by using a cationic initiator. In the subsequent coating process, silica formed shell on the surfaces of core PS particles via the ammonia-catalyzed hydrolysis and condensation of tetraethoxysilane. Neither centrifugation/water wash/redispersion cycle process nor surface modification or addition surfactant was needed in the whole process. The morphology of the abrasives was characterized by scanning electron microscope. Transmission electron microscope and energy dispersive X-ray analysis results indicated that silica layer was successfully coated onto the surfaces of PS particles. Composite abrasive has a core-shell structure and smooth surface. The chemical mechanical polishing performances of the composite abrasive and conventional colloidal silica abrasive on blanket copper wafers were investigated. The root mean square roughness decreases from 4.27 nm to 0.56 nm using composite abrasive. The PS/SiO₂ core-shell composite abrasives exhibited little higher material removal rate than silica abrasives.     

Preparation and electrophoretic response of poly(methyl methacrylate-co-methacrylic acid) coated TiO2 nanoparticles for electronic paper application

Titanium dioxide (TiO₂) nanoparticles were encapsulated with poly(methyl methacrylate-co-methacrylic acid) (PMMA-co-MAA) via simple method of coacervation, in order to improve the dispersion stability of the nanoparticles in a dielectric medium and to reduce the density mismatch between TiO₂ and a dielectric medium for a electrophoretic display application. The morphology of PMMA-co-MAA coated TiO₂ nanoparticles were observed via SEM and electrophoretic light scattering (ELS). It was found that density of PMMA coated TiO₂ nanoparticles were reduced by coating process via gas pycnometer. Electrophoretic mobility of the fabricated nanoparticles in a low dielectric medium with charge control agent was measured via electrophoretic light scattering spectrophotometer for potential application in electronic paper technology.     

Facile preparation and characterization of hollow poly(St-co-MMA-co-BA-co-MAA) core–double shell latex nanoparticles for electrophoretic displays

Novel core–double shell particles with poly(methyl methacrylate-co-butyl acrylate) (PMMA-co-BA) as the cores, poly(methyl methacrylate-co-butyl acrylate-co-methacrylic acid) (PMMA-co-BA-co-MAA) as the inner shells, poly(styrene-co-methyl methacrylate) (PS-co-MMA) as the outer shells were prepared by soap-free emulsion polymerization. The acid–alkali osmotic swelling processes were made before the outer shells wrapped for bigger aperture. The optimal experiment conditions were summarized. The morphology and size of the hollow latex particles were observed by transmission electron microscopy. The results showed that the uniform sizes of the hollow latex particles were about 230 nm. The electrophoretic mobility of them in tetrachloroethylene was 0.91 × 10⁻¹⁰ m² V⁻¹ s⁻¹, and the Zeta-potential was 5.87 mV. The results showed that the hollow polymer particles can used as background particles.     

Study on Dispersion of TiO2 Particles During Polymerization of PET

An important factor influencing the stability of colloidal suspension is zeta potential (ζ-potential) on the surface of particles. In this work, ζ-potential of TiO₂ particles in ethylene glycol (EG) with various additives for poly(ethyleneterephthalate) (PET) polymerization, such as metallic salts, phosphoric acid and alkyl phosphates, were investigated by electrophoretic mobility method. The dispersion stability of TiO₂/EG suspension was influenced by decrease in the absolute value of the ζ-potential by the addition of metal acetates as well as phosphates. The addition of triethylamine (TEA) in the TiO₂/EG suspension restrained the change of ζ-potential from negative to positive, which resulted from phosphoric acid. The molar ratio of phosphoric acid to an acetate was found to have an influence on the dispersion ability of TEA in TiO₂/EG suspension. Effect of metallic salts, phosphoric acid and TEA on the stability of TiO₂/EG suspension was studied in the actual polymerization of PET. It was proved that the addition of TEA is highly effective for the dispersion of TiO₂ particles in PET, even in the presence of metallic salts, phosphoric acid and its alkyl phosphates.     

Effect of surface treatment of magnetic particles on the preparation of magnetic polymer microspheres by miniemulsion polymerization

Surface treated magnetic particles were used to prepare well encapsulated submicron polystyrene/magnetic (PS/Fe₃O₄) composite microspheres via miniemulsion polymerization. The effects of the different surface treatment agents Disperbyk-106, Disperbyk-111, KH550, sodium dodecyl sulfate (SDS) and oleic acid were investigated on the encapsulation of polymer via miniemulsion polymerization. The interface interactions between magnetic particles, dispersants and coupling agents were analyzed from their IR spectra. It was found that Disperbyk-106 was the best dispersant in terms of preparing magnetic polymer microspheres with high encapsulation efficiency. The effect of wet or dry magnetic particles on encapsulation was also discussed.     

Synthesis, characterization and antibacterial action of hollow titania spheres

Hollow titania spheres were synthesized using the cationic polystyrene lattices which were prepared by polymerization in suspension of styrene using 2,2′-azobis (2-methylpropionamidine) dihydrochloride (AMPA) as an initiator. These cationic colloidal particles were dispersed in absolute ethanol in the presence of poly(vinylpyrrolidone) (PVP), solution of sodium chloride (NaCl) and mixed with ethanolic solutions of titanium tetraisopropoxide (TTIP). Subsequently, hollow spheres of titania compounds were obtained by calcinations of the so-coated polystyrene lattices at elevated temperature in air. The hollow titania spheres were characterized with scanning electron microscopy (SEM), FT-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). Moreover, antibacterial action of illuminated hollow titania spheres on pure culture of Escherichia coli (E. coli) was studied. A decrease of E. coli concentration was observed after illumination of bacteria in the presence of hollow titania spheres.     

Fabrication of nano-structured polythiophene nanoparticles in aqueous dispersion

The synthetic route of unsubstituted polythiophene (PT) nanoparticles was investigated in aqueous dispersion via Fe³⁺-catalyzed oxidative polymerization. With this new synthetic method, high conversion of thiophene monomers was obtained with only a trace of FeCl₃. The dispersion state showed that the PT nanoparticles were well dispersed in many polar solvents, compared to non-polar solvents, such as acetone, chloroform, hexane, and ethyl acetate. To compare the photoluminescence properties between PT nanoparticle dispersion and PT bulk polymers, the PL intensities were measured in the same measuring conditions. Further, core–shell poly(styrene/thiophene) (poly(St/Th)) latex particles were successfully prepared by Fe³⁺-catalyzed oxidative polymerization during emulsifier-free emulsion polymerization. The different polymerization rates of each monomer resulted in core–shell structure of the poly(St/Th) latex particles. The PL data of the only crumpled shells gave evidence that the shell component of core–shell poly(St/Th) latex particles is indeed PT, which was corroborated by SEM data. PL intensity of the core–shell poly(St/Th) nanoparticle dispersion was much higher than that of the PT nanoparticle dispersion, due to its thin shell layer morphology, which was explained by the self-absorption effect.     

Synthesis of Core-Shell Latex Particles Through One-Step Emulsion Polymerization

Polystyrene/polyacrylate acid (PSt/PAA) core-shell latex particles were obtained through a one-step emulsion polymerization by making use of controlled distribution of the reaction monomer at different temperatures. The polymerization conversion and stability were characterized to find appropriate synthetic conditions. The results show that the mixed solution of certain proportions of St, AA, and distilled water were inhomogeneous at lower temperature, e.g. 25°C, but the mixed solution would become more and more homogeneous with increasing temperature. The mixed solution became completely homogeneous at 75°C. After this, according to the results of uniformity degree change, the pre-emulsion temperature was set at 75°C, and the polymerization temperature was 65°C. α,α-Azobisisobutyronitrile was used as initiator. Stable latex and latex particles, with obvious core-shell structure, were obtained. The composition of the mixed solution was characterized by UV-vis spectrophotometry. The morphology of latex particles was observed using transmission electron microscopy and scanning electron microscopy. The research provides a new method to obtain polymer particles with a core-shell structure.     

NMR relaxivity of coated and non-coated size-sorted maghemite nanoparticles

ABSTRACT

The effect of polymer coating on MNR relaxometry of maghemite nanoparticles has been studied. The samples were carefully sorted by size in order to reach narrow size distribution (<0.2) with size ranging from 4.5 to 12.5?nm. Relaxation dispersion profile as well as studies at a fixed Larmor frequency, were recorded for numerous either uncoated or polymer coated samples. The NMR relaxivities r₁ and r₂ increase with nanoparticle diameter. We have analysed the role of polydispersity for nanoparticles with the same mean size on the dispersion curves. We have compared the role of coating on nanoparticles NMR relaxivity between bare and poly(sodium acrylate-co-maleate) coated nanoparticles. We have investigated the influence of nanoparticle size on the T₁ and T₂ activation energy Ea. While Ea decreases with nanoparticle diameter when determined from T₁, it increases from T₂ determination. The influence is more important for small particles (<9?nm) than for big particles (>9?nm). Moreover, the PAAMA coating changes the energy Ea obtained from T₂: Ea becomes independent of the nanoparticle diameter. These results highlight the need of a complete characterisation of the role of the coating on the relaxation of magnetic particles.     

基于动态溶胀法制备中空聚合物微球

以表面带正电荷的m级聚苯乙烯微球为种子,经过甲苯、二乙烯基苯溶胀,聚合与包覆等过程制备了直径约5 m的中空聚合物微球。研究了溶剂类型、溶剂用量对动态溶胀法制备的中空聚合物微球粒径、分布和结构的影响,讨论了中空聚合物微球的形成机理。结果表明:添加一定量甲苯、二甲苯等挥发性溶剂是动态溶胀法形成中空聚合物微球的前提;甲苯用量越多,溶胀后形成的中空结构越明显,孔径越大;选择低溶解性的二甲苯溶剂更有利于中空结构的形成。     

Preparation of magnetic latexes functionalized with chloromethyl groups via emulsifier-free miniemulsion polymerization

Functionalized crosslinked polystyrene-co-divinylbenzene-co-chloromethylstyrene magnetic latex particles were prepared via emulsifier-free miniemulsion polymerization using 2, 2′ azobis (2-amidinopropane) dihydrochloride (V-50) as an initiator and in the presence of magnetite nanoparticles in the monomers. Transmission electron microscopy (TEM) proved the presence of magnetite nanoparticles in polymer particles. Differential scanning calorimetery (DSC) analysis of the product showed an exothermic signal due to crosslinking of chains through electrophilic aromatic substitution of phenyl groups with chloromethyl groups in the presence of the dispersed Fe₃O₄ as Lewis acid. This was proven by thermogravimetric analysis (TGA) via the loss of gaseous HCl. The results were also compared with those of magnetite-free miniemulsion polymerization using V-50.     

Characteristics of Photonic Bandgap Fibres with Hollow Core＇s Inner Surface Coated by a Layer Material

Hollow core＇s inner surface coating in a photonic bandgap fibre （PBCF） is investigated by means of finite element method. The coat material and thickness-dependence dispersion curve and group velocity dispersion are numerically studied. The coating with materials of low index or small thickness will rise up the dispersion curve but will not induce surface modes. However, coating with materials of high index or big coat thickness will induce surface modes and avoided-crossings. By varying coat material＇s refractive index and thickness, the appearances of surface modes and avoided-crossings can be changed. It is found that the avoided-crossing can enormously enlarge the negative dispersion which can find applications in dispersion compensation. We numerically achieve a negative dispersion as large as -21416.15ps/nm/km. The results give a physical insight into the propagation properties of PBGFs with the hollow core coated by a layer of material and are of crucial significance in the applications of PBGF coating.     

Preparation of low density TiO2/poly (methyl methacrylate) composite particles by emulsifier-free emulsion polymerization

Based on the 3-(trimethoxysilyl) propylmethacrylate (MPS) modified TiO₂ particles, the TiO₂/poly (methyl methacrylate) (PMMA) composite particles have been prepared successfully via emulsifier-free emulsion polymerization in water. A facile floating-sinking method is proposed to roughly evaluate the composite particles’ density. Chemical component of obtained composite particles was identified by Fourier transform infrared spectra (FTIR). The morphology and grain size of the composite particles were investigated by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Thermal analysis of the composite particles was measured by differential thermal analysis-thermo gravimetric analysis (DTA-TGA). The zeta potential and electrophoretic mobility of composite particles with suitable density in water was measured by dynamic light scattering (DLS).     

Graphene-based hollow TiO2 composites with enhanced photocatalytic activity for removal of pollutants

Catalytically active graphene-based hollow TiO₂ composites(TiO₂/RGO) were successfully synthesized via the solvothermal method. Hollow TiO₂ microspheres are uniformly dispersed on RGO. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) were used for the characterization of prepared photocatalysts. The mass of GO was optimized in the photocatalytic removal of rhodamine B (RhB) as a model dye pollutants. The results showed that graphene-based hollow TiO₂ composites exhibit a significantly enhanced photocatalytic activity in degradation of RhB under either UV or visible light irradiation. The formation of the graphene-based hollow TiO₂ composites and the photocatalytic mechanisms under UV and visible light were also discussed.