Microfluidization-assisted synthesis of hollow mesoporous silica nanoparticles

Hollow mesoporous silica nanoparticles (HMSNs) with the diameter in range of 100–500 nm and the wall thickness of about 50 nm were synthesized by templates of cetyltrimethylammonium bromide under the assistant of microfluidization technique. These HMSNs were demonstrated effective drug loading and a pH-responsive drug release.     

Synthesis of double mesoporous core-shell silica spheres with tunable core porosity and their drug release and cancer cell apoptosis properties

In this work, we demonstrate a simple two-pot approach to double mesoporous core–shell silica spheres (DMCSSs) with uniform size of 245–790 nm, shell thickness of 41–80 nm and surface area and total pore volume of 141–618 m² g^?1 and 0.14–0.585 cc g^?1, respectively. First, solid silica spherical particles were synthesized by the Stöber method and used as a core. Second, a mesoporous shell could be formed around the silica cores by using an anionic surfactant and a co-structure directing agent. It was found that mesopores can be anchored within dense silica cores during mesoporous silica shell formation, synchronously the base group with surfactant assistant can etch the dense silica cores to re-organize new mesostructure, so that double mesoporous core–shell silica sphere (DMCSS) structure can be obtained by a single surfactant-templating step. The spherical size and porosity of the silica cores of DMCSS together with shell thickness can be tuned by controlling Stöber parameters, including the concentrations of ammonia, solvent and tetraethoxysilane and the reaction time. DMCSS were loaded with ketoprofen and thymoquinone, which are an anti-inflammatory and a potential novel anti-cancer drug, respectively. Both drugs showed controlled release behavior from the pores of DMCSS. Drug uptakes within DMCSS were ～27 and 81 wt.% for ketoprofen and thymoquinone, respectively. Furthermore, DMCSS loaded with thymoquinone was more effective in inducing cancer cell apoptosis than uncontained thymoquinone, because of the slow release of the drug from the mesoporous structure.     

Fabrication of sub-micrometer-sized jingle bell-shaped hollow spheres from multilayered core-shell particles

Jingle bell-shaped hollow spheres were fabricated starting from multilayered particles composed of a silica core, a polystyrene inner shell, and a titania outer shell. Composite particles of silica core-polystyrene shell, synthesized by coating a 339-nm-sized silica core with a polystyrene shell of thickness 238 nm in emulsion polymerization, were used as core particles for a succeeding titania-coating. A sol-gel method was employed to form the titania outer shell with a thickness of 37 nm. The inner polystyrene shell in the multilayered particles was removed by immersing them in tetrahydrofuran. These successive procedures could produce jingle bell-shaped hollow spheres that contained a silica core in the titania shell.     

Superparamagnetic Fe3O4SiO2 nanocomposites: enabling the tuning of both the iron oxide load and the size of the nanoparticles

Using a water-in-oil microemulsion system, silica nanoparticles containing superparamagnetic iron oxide (SPIO) crystals have been prepared and characterized. With this method, the loading of iron oxide crystals, the thickness of the silica shells, and the overall particle sizes are tunable. Moving from low to high water concentration, within the microemulsion region, resulted in a gradual shift from larger particles, ca. 100 nm and fully loaded with SPIOs, to smaller particles, ca. 30 nm containing only one or a few SPIOs. By varying the amount of silica precursor, the thickness of the silica shell was altered. Field dependent magnetization measurements showed the magnetic properties of the SPIOs were preserved after the synthesis.     

Effect of pore size on the performance of composite adsorbent

Three kinds of commercial silica gels with pore size of 2–3, 4–7 and 8–10 nm respectively are used for preparing composite adsorbents by soaking them into the aqueous solution of calcium chloride. The test result indicates that both the water uptake and adsorption rate of composite adsorbents prepared from 4–7 and 8–10 nm silica gels improve greatly compared to pure silica gels, but they do not for 2–3 nm silica gels. The silica gel with pore size of 2–3 nm is not suitable for preparing the composite adsorbent by impregnation method due to the pore blockage because of the small pore size. The SCP and COP of the adsorption chiller with sample SA50 are 128.3 Wkg^?1 and 0.27 respectively at the hot source temperature of 90 °C, which are largely superior to that of SA0. Hence using the composite adsorbent instead of the pure silica gel can reduce the size of the adsorption chiller.     

Strong cellulose nanofibre–nanosilica composites with controllable pore structure

Flexible nanocellulose composites with silica nanoparticle loading from 5 to 77 wt% and tunable pore size were made and characterised. The pore structure of the new composites can be controlled (100–1000 nm to 10–60 nm) by adjusting the silica nanoparticle content. Composites were prepared by first complexing nanoparticles with a cationic dimethylaminoethyl methacrylate polyacrylamide, followed by retaining this complex in a nanocellulose fibre network. High retention of nanoparticles resulted. The structural changes and pore size distribution of the composites were characterised through scanning electron microscopy (SEM) and mercury porosimetry analysis, respectively. The heavily loaded composites formed packed bed structures of nanoparticles. Film thickness was approximately constant for composites with low loading, indicating that nanoparticles filled gaps created by nanocellulose fibres without altering their structure. Film thickness increased drastically for high loading because of the new packed bed structure. Unexpectedly, within the investigated loading range, the level of the tensile index on nanocellulose mass basis remained constant, showing that the silica nanoparticles did not significantly interfere with the bonding between the cellulose nanofibres. This hierarchically engineered material remains flexible at all loadings, and its unique packing enables use in applications requiring nanocellulose composites with controlled pore structure and high surface area.     

Ultrathin silica films immobilized on gold supports: fabrication, characterization, and modification

A novel method for covalent attachment of ultrathin silica films (thickness <10 nm) to gold substrates is reported. Silica layers were prepared using spin-coating of sol-gel precursor solutions onto gold substrates that were cleaned and oxidized using UV photo-oxidation in an ozone atmosphere. The gold oxide layer resulting from this process acts as a wetting control and adhesive agent for the ultrathin silica layer. Control of silica layer thickness between approximately 6 and 60 nm through modification of precursor solution composition or by repetitive deposition is demonstrated. Films were characterized using infrared spectroscopy, ellipsometry, atomic force microscopy, and cyclic voltammetry. For the standard deposition parameters developed here, films were determined to be 5.5 +/- 0.75 nm thick, and were stable in aqueous solutions ranging in pH from 2 to 10 for at least 30 min. Films contained nanoscopic defects with radii of 相似文献   

Synthesis of hierarchical hollow silica microspheres containing surface nanoparticles employing the quasi-hard template of poly(4-vinylpyridine) microspheres

A facile method of preparing hierarchical hollow silica microspheres containing surface silica nanoparticles (HHSMs) through the sol-gel process of tetraethylorthosilicate employing a quasi-hard template of non-cross-linking poly(4-vinylpyridine) microspheres is proposed. The quasi-hard template contains the inherent catalyst of the basic pyridine group, and a few of the polymer chains can escape from the template matrix into the aqueous phase, which initiates the sol-gel process spontaneously both on the surface of the template used to prepare the hollow silica shell and in the aqueous phase to produce the surface silica nanoparticles. By tuning the weight ratio of the silica precursor to the quasi-hard template, HHSMs with a size of about 180 nm and a shell thickness ranging from 14 to 32 nm and surface silica nanoparticles ranging from 17 to 36 nm are produced initially through the deposition of surface silica nanoparticles onto the silica shell, followed by template removal either by calcination or solvent extraction. The synthesized HHSMs are characterized, and a possible mechanism for the synthesis of HHSMs is proposed.     

Exploring meso-/microporous composite molecular sieves with core-shell structures

A series of core–shell‐structured composite molecular sieves comprising zeolite single crystals (i.e., ZSM‐5) as a core and ordered mesoporous silica as a shell were synthesized by means of a surfactant‐directed sol–gel process in basic medium by using cetyltrimethylammonium bromide (CTAB) as a template and tetraethylorthosilicate (TEOS) as silica precursor. Through this coating method, uniform mesoporous silica shells closely grow around the anisotropic zeolite single crystals, the shell thickness of which can easily be tuned in the range of 15–100 nm by changing the ratio of TEOS/zeolite. The obtained composite molecular sieves have compact meso‐/micropore junctions that form a hierarchical pore structure from ordered mesopore channels (2.4–3.0 nm in diameter) to zeolite micropores (≈0.51 nm). The short‐time kinetic diffusion efficiency of benzene molecules within pristine ZSM‐5 (≈7.88×10^?19 m² s^?1) is almost retainable after covering with 75 nm‐thick mesoporous silica shells (≈7.25×10^?19 m² s^?1), which reflects the greatly opened junctions between closely connected mesopores (shell) and micropores (core). The core–shell composite shows greatly enhanced adsorption capacity (≈1.35 mmol g^?1) for large molecules such as 1,3,5‐triisopropylbenzene relative to that of pristine ZSM‐5 (≈0.4 mmol g^?1) owing to the mesoporous silica shells. When Al species are introduced during the coating process, the core–shell composite molecular sieves demonstrate a graded acidity distribution from weak acidity of mesopores (predominant Lewis acid sites) to accessible strong acidity of zeolite cores (Lewis and Brønsted acid sites). The probe catalytic cracking reaction of n‐dodecane shows the superiority of the unique core–shell structure over pristine ZSM‐5. Insight into the core–shell composite structure with hierarchical pore and graded acidity distribution show great potential for petroleum catalytic processes.     

Characterization and Transport Properties of Surfactant-Templated Silica Layers for Membrane Applications

An intermediate surfactant-templated silica (STS) layer is applied between the supporting mesoporous γ-Al₂O₃ and the amorphous microporous silica overlayer resulting in dual-layered microporous silica membranes for gas separation applications that show improved values for both hydrogen flux and selectivity. Determination of thickness and porosity of as-deposited membrane layers by spectroscopic ellipsometry reveals that the STS layer is present as a distinctive layer of ～20 nm thickness, with penetration up to a depth of ～70 nm into the underlying γ-Al₂O₃support layer, whose thickness and porosity are determined to be 1.3 μm and 50%, respectively.     

应用于热控的壳厚可控核壳结构SiO2@TiO2颗粒制备

利用St觟ber方法合成了平均粒径在800 nm,球形度、单分散性良好的SiO2微球,再将其作为制备核壳结构SiO2@TiO2颗粒的内核。利用钛酸四丁酯水解反应,在SiO2内核上包覆制备了壳厚在30～100 nm的TiO2壳层,TiO2壳层厚度可根据水解反应中钛酸四丁酯的量调控。将制得的SiO2@TiO2核壳结构颗粒在550℃煅烧1 h,氧化钛壳层的晶型转变为锐钛矿相,晶型转变为锐钛矿相的TiO2更适合作为填料应用于近红外反射涂层。本文合成厚度可控SiO2@TiO2微球的方法是一种改进的溶胶凝胶方法,即在溶胶凝胶方法的基础上增加水热合成工艺。另外,本合成方法工艺简单,无表面活性剂或者耦合剂的引入。     

A New Synthetic Route to Microporous Silica with Well‐Defined Pores by Replication of a Metal–Organic Framework

Microporous amorphous hydrophobic silica materials with well‐defined pores were synthesized by replication of the metal–organic framework (MOF) [Cu₃(1,3,5‐benzenetricarboxylate)₂] (HKUST‐1). The silica replicas were obtained by using tetramethoxysilane or tetraethoxysilane as silica precursors and have a micro–meso binary pore system. The BET surface area, the micropore volume, and the mesopore volume of the silica replica, obtained by means of hydrothermal treatment at 423 K with tetraethoxysilane, are 620 m²g^?1, 0.18 mL g^?1, and 0.55 mL g^?1, respectively. Interestingly, the silica has micropores with a pore size of 0.55 nm that corresponds to the pore‐wall thickness of the template MOF. The silica replica is hydrophobic, as confirmed by adsorption analyses, although the replica has a certain amount of silanol groups. This hydrophobicity is due to the unique condensation environment of the silica precursors in the template MOF.     

The effect of iron phosphate,alumina and silica coatings on the morphology of carbonyl iron particles

Carbonyl iron powders were coated with iron phosphate using phosphating method and boehmite (γ‐AlOOH) or silicon hydroxide (Si(OH)₄) nanoparticles derived from the hydrolysis of tri‐sec‐butoxide (Al(OC₄H₉)₃) or tetramethylsilane (Si(OCH₃)₄) using sol–gel method. The coated powders were dried and calcined at 400 °C for 3 h in air. Cross‐section morphology of coated carbonyl iron powders were investigated by scanning electron microscopy energy dispersive X‐ray analysis. Coated Fe micro‐particles were spherical in shape with ‘shell/core’ structures. The shells consisted of an amorphous layer with varying thickness (100–800 nm) and the core represented a carbonyl iron. Gelatinous morphology of dried FePO₄ coating composed from nanoparticles of iron oxyhydroxides and hydrated iron phosphate with a shell thickness of ～100 nm around iron particles was observed. In coatings based on alumina or silica xerogels with a thickness of ～100–150 nm or ～200–500 nm, the coatings were composed of iron oxyhydroxides and γ‐AlOOH or Si(OH)₄. The resulting XRD diffractograms revealed the hematite (α‐Fe₂O₃) and magnetite (Fe₃O₄) that were formed in phosphated and sol–gel coated iron powders. The X‐ray diffraction patterns did not verify the presence of phosphates, alumina or silica and indicate the amorphous or nanocrystalline structure of FePO₄, γ‐Al₂O₃ and SiO₂. Copyright © 2009 John Wiley & Sons, Ltd.     

Mesopore-free hollow silica particles with controllable diameter and shell thickness via additive-free synthesis

Mesopore-free hollow silica particles with a spherical shape, smooth surface, and controllable diameter (from 80 to 300 nm) and shell thickness (from 2 to 25 nm) were successfully prepared using an additive-free synthesis method. Different from other hollow particle developments, a mesopore-free shell was produced because of the absence of additive. Although common reports pointed out the importance of the additional additive in pasting and growing silica on the surface of a template, here we preferred to exploit the effect of the template charge in gaining the silica coating process. To form the silica, basic amino acid (i.e., lysine) was used as a catalyst to replace ammonia or hydrazine, which is harmless and able to control the silica growth and produce hollow particles with smooth surfaces. Control of the particle diameter was drastically achieved by altering the size of the template. The flexibility of the process in controlling the shell thickness was predominantly attained by varying the compositions of the reactants (i.e., silica source and catalyst). The present mesopore-free hollow particles could be efficiently used for various applications, especially for thermal insulator and optical devices because of their tendency not to adsorb large molecules, as confirmed by adsorption analysis.     

Tunable optical stop band of silica shell photonic crystals

In this study, optical stop band of three-dimensional silica shell photonic crystals is tuned by adjusting inner diameter and shell thickness of hollow silica spheres. The silica shell photonic crystals are fabricated by sintering crystalline arrays, which are assembled from polystyrene/silica core–shell spheres by an improved vertical deposition method. The inner diameter and the shell thickness are controlled by diameter of polystyrene spheres and concentration of tetraethoxysilane. The results of transmission spectra show that there is an evident red shift of optical stop band as the inner diameter and the shell thickness increase. The red shift of optical stop band is due to variations in the inter-planar spacing and the effective refractive index of silica shell photonic crystals, which result from the variations of the inner diameter and the shell thickness of hollow silica spheres.     

Fabrication and characterization of mesoporous Co3O4 core/mesoporous silica shell nanocomposites

A mesoporous Co(3)O(4) core/mesoporous silica shell composite with a variable shell thickness of 10-35 nm was fabricated by depositing silica on Co(3)O(4) superlatticed particles. The Brunauer-Emmett-Teller (BET) surface area of the composite with a shell thickness of ca. 2.0 nm was 238.6 m(2)/g, which varied with the shell thickness, and the most frequent pore size of the shell was ca. 2.0 nm. After the shell was eroded with hydrofluoric acid, mesoporous Co(3)O(4) particles with a pore size of ca. 8.7 nm could be obtained, whose BET surface area was 86.4 m(2)/g. It is proposed that in the formation of the composite the electropositive cetyltrimethylammonium bromide (CTAB) micelles were first adsorbed on the electronegative Co(3)O(4) particle surface, which directed the formation of the mesoporous silica on the Co(3)O(4) particle surface. Electrochemical measurements showed that the core/shell composites exhibited a higher discharge capacity compared with that of the bare Co(3)O(4) particles.     

Study on the morphological regulation mechanism of hollow silica microsphere prepared via emulsion droplet template

The morphology regulation of hollow silica microspheres is significant for their properties and applications. In this paper, hollow silica microspheres were formed through the hydrolysis and condensation reaction of tetraethyl orthosilicate (TEOS) at the interface of the emulsion droplet templates composed of liquid paraffin and TEOS, followed by dissolving paraffin with ethanol. The effects of various factors including the emulsifier structure and content, TEOS content, catalyst type, and the ethanol content in the continuous water phase on the particle size, shell thickness and morphology of the prepared hollow silica microspheres were studied in detail. The results show that the diffusion and contact of TEOS and water molecules as well as the hydrolysis condensation reaction of TEOS at the oil-water interface are two critical processes for the synthesis and morphological regulation of hollow silica microspheres. Cationic emulsifier with a hydrophobic chain of appropriate length is the prerequisite for the successful synthesis of hollow silica microspheres. The ethanol content in water phase is the dominant factor to determine the average diameter of hollow microspheres, which can vary from 96 nm to 660 nm with the increase of the volume ratio of alcohol-water from 0 to 0.7. The silica wall thickness varies with the content and the hydrophobic chain length of the emulsifier, TEOS content, and the activity of the catalyst. The component of the soft template will affect the morphology of the silica wall. When the liquid paraffin is replaced by cyclohexane, hollow microspheres with fibrous mesoporous silica wall are fabricated. This work not only enriches the basic theory of interfacial polymerization in the emulsion system, but also provides ideas and methods for expanding the morphology and application of hollow silica microspheres.     

Single quantum dot-micelles coated with silica shell as potentially non-cytotoxic fluorescent cell tracers

The present study describes a stabilization of single quantum dot (QD) micelles by hydrophobic silica precursors and an extension of the silica layer to form a silica shell around the micelle. The obtained product consists of up to 92% of single nanocrystals (CdSe, CdSe/ZnS, or CdSe/ZnSe/ZnS quantum dots) in the silica micelles, coated with silica shell. The thickness of silica shell could vary, starting from 3 to 4 nm. Increasing the shell thickness increases the photoluminescent characteristics of QDs in aqueous solution. The silica-shelled single CdSe/ZnS QD micelles possess a high quantum yield in aqueous solution, a controlled small size, sharp photoluminescence spectra (fwhm approximately 30 nm), an absence of aggregation, and a high transparency. The presence of a hydrophobic layer between the QD and silica shell ensures an incorporation of other hydrophobic molecules (with interesting properties) in the close proximity of nanocrystal. Thus, it is possible to combine the characteristics of hybrid material with the priority of small size. The nanoparticles are amino functionalized and ready for conjugation. A comparatively good biocompatibility is demonstrated. The nanoparticles show ability for intracellular delivery and are noncytotoxic during long-term incubation with viable cells in the absence of light exposure, which makes them appropriate for cell tracing and drug delivery.     

Preparation and characterization of a novel nanocomposite particles via in situ emulsion polymerization of vinyl functionalized silica nanoparticles and vinyl acetate

A new class of poly(vinyl acetate) (PVAc)/silica nanocomposite particles was successfully prepared in aqueous solution through a facile synthetic process. First, vinyl functionalized silica nanoparticles (VFSs) were synthesized using one-step method in aqueous emulsion, and then the vinyl groups located on the surface of VFSs were used to induced in situ polymerization of vinyl acetate. Scanning electron microscopy (SEM) images showed that VFSs and PVAc/silica nanocomposite particles all revealed highly monodispersed and uniform spheres. Especially, PVAc/silica nanocomposite particles obtained from transmission electron microscopy images presented an obvious core–shell structure, and the thickness of PVAc shell grafting on the surface of VFSs core was about 17 nm. In addition, the influence of the hydrolyzed and condensed time of vinyl triethoxysilane on the size and size distribution of VFSs was also investigated. The results of dynamic light scattering and SEM analysis indicated that the size and size distribution of VFSs decreased gradually with the extension of the reaction time from 6 to 48 h. Moreover, the structures and thermal properties of the samples were characterized via FT-IR and heat-flow DSC–TG.     

Metal-enhanced fluoroimmunoassay on a silver film by vapor deposition

We studied a fluoroimmunoassay using metal-enhanced fluorescence (MEF) detection on silver film generated by vapor deposition method. The morphology of the silver film was controlled through the thickness of the film. A silica layer was coated on the silver film to protect the film and separate the fluorophore from the metal surface. Rabbit immunoglobulin G (IgG) was adsorbed on the silica by physiosorption and then dye-labeled anti-rabbit IgG was bound to the immobilized rabbit IgG. It was observed that the fluorophore was quenched on a thin silver film (2 nm), enhanced on a thick film (>5 nm), and reached saturation (ca. 10 times enhancement) at 20 nm. The MEF was also dependent on the thickness of the silica with a maximum at 10 nm. The lowest lifetime was observed on the 20 nm silver film, which was consistent with the saturation of MEF. These results showed the properties of a silver film needed for a maximum increase of fluorescence intensity in a fluoroimmunoassay. Dependence of the MEF on the emission wavelength was also studied using different dye-labeled anti-rabbit IgGs.