Biphasic synthesis of colloidal mesoporous silica nanoparticles using primary amine catalysts

Evanescent wave-cavity ring-down spectroscopy (EW-CRDS) is employed to characterize micellization of anionic surfactants and the related capability of removing cationic substance off the silica surface. Crystal violet (CV(+)) cationic dye is used as a molecular probe to effectively determine critical hemimicelle concentration (HMC) of surfactants on the surface. The HMC results are 1×10(-2), 4×10(-3), 8×10(-4), and 2.5×10(-4) mol/L for sodium sulfate salts with a carbon-chain length of C-10, C-12, C-14, and C-16, respectively. A stronger hydrophobic interaction results in a less concentration required to undergo micellization. The HMC values on the surface are about half of those in solution. When NaCl solution is added, the electrolyte helps reduce the electrostatic repulsion between the anionic sulfate heads to facilitate the surfactant aggregation, and thus, the subsequent HMC is reduced. Furthermore, the probable phase change for dye-surfactant interactions on the surface at the concentration below HMC is observed, and the desorption rates of CV(+) are measured as a function of concentration and carbon-chain length of surfactants above HMC. Given each surfactant concentration at its respective HMC, the corresponding desorption rates are along the order of C-12相似文献   

Size-controllable synthesis of monodispersed colloidal silica nanoparticles via hydrolysis of elemental silicon

A new method is presented for preparing monodisperse and uniform-size silica nanoparticles using a two-stage hydrolysis of silicon powder in aqueous medium. The influence of synthesis conditions including solution composition and temperature on the formation of silica nanoparticles were systematically investigated. The structure and morphology of the silica particles were characterized via transmission electron microscopy (TEM) and dynamic light scattering (DLS). Various-sized particles in the range 10–100 nm were synthesized. The size of the nanoparticles can be precisely controlled by using a facile regrowth procedure in the same reaction media.     

Effect of anionic surfactants on synthesis and self-assembly of silica colloidal nanoparticles

Effects of the anionic surfactants, sodium dodecyl sulfate and sodium oleate, on the formation and properties of silica colloidal nanoparticles were investigated. At a concentration of approximately 1 x 10(-3) M, adsorption of anionic surfactants increased particle size, monodispersity, and negative surface charge density of synthesized silica particles. As uniformity of particle size and particle-particle interactions increase, colloidal photonic crystals readily self-assemble without extensive washing of the synthesized silica nanoparticles. The photonic crystals diffract light in the visible region according to Bragg's law. The assembled colloidal particle arrays exhibit a face-centered cubic structure in dried thin films. This study offers a new approach for producing ordered colloidal silica thin films.     

Synthesis of colloidal silica dumbbells

We describe the synthesis and characterization of stable suspensions of monodisperse fluorescently labeled silica dumbbell particles. Pure dispersions of silica dumbbells with center-to-center lengths from 174 nm to 2.3 microm were produced with a variety of aspect ratios. Individual particles in concentrated dispersions of these particles could be imaged with confocal microscopy. These particles can be used as a colloidal model system for addressing fundamental questions about crystal and glass formation of low-aspect-ratio anisotropic particles. They also have potential in photonic applications and electro-optical devices.     

Silver-assisted colloidal synthesis of stable, plasmon resonant gold patches on silica nanospheres

Patchy particles possessing heterogeneous surface composition show great promise as self-organizing building blocks for new classes of hierarchical functional structures. A major hurdle is the scalable synthesis of stable patches on nanosized core particles with arbitrarily defined patch number and coverage. So far, few methods have been reported which could be expected to meet these challenges. Recently, we described the heterogeneous nucleation and growth of silver patches on silica nanospheres via a template free colloidal route. The patches produced, although tunable in size and number and showing interesting plasmon resonant properties, were rather unstable and degraded rapidly during attempts to process them further. In the present work, therefore, we set out to explore if related approaches can be employed to produce patchy particles involving gold, which is known to be more stable. The differences between typical patch precursors Ag(+) and [AuCl(x)(OH)(4-x)](-) and their respective interactions with amorphous silica make this a significant challenge. We show that preformed small silver patches in addition to the presence of a reducing agent are necessary for the formation of gold patches conformal to the silica nanosphere surface. Systematic study of the process parameters and their influence on the patchy particle morphology as well as in-depth analytical transmission electron microscopy investigation of the patch composition reveal that patches spread over the silica surface via a cycle of galvanic dissolution and redeposition of silver. The resulting gold patchy particles remain stable during subsequent storage or washing and display tunable plasmon resonances within the visible and near-IR spectrum.     

Surface modification of colloidal silica particles

Colloidal silica particles in organic solvents were grafted, using several reagents, in order to make them hydrophobic. The hydrophobicity of the beads could be easily varied. Quasielastic light scattering and transmission electron microscopy experiments showed that no aggregation occurs during the reaction when monofunctional agents are used. Elemental analysis and solid-state NMR measurements gave us the rate of surface modification of the silanol groups. We also studied the rheological behaviour of the grafted particles as a function of the volume fraction in solvents of various hydrophobicity. Hexamethyldisilazane-grafted particles display hard-sphere behaviour in polar solvents such as 2-propanol, but not in alkanes, whereas dimethyldodecylchlorosilane-grafted particles flocculated in polar solvents but could easily be dispersed in apolar solvents. Received: 15 March 2000 Accepted: 11 July 2000     

Self-assembly patterning of silica colloidal crystals

We developed a self-assembly process of silica particles to fabricate desired patterns of colloidal crystals having high feature edge acuity and high regularity. A micropattern of colloidal methanol prepared on a self-assembled monolayer in hexane was used as a mold for particle patterning, and slow dissolution of methanol into hexane caused shrinkage of molds to form micropatterns of close-packed SiO2 particle assemblies. This result is a step toward the realization ofnano/micro periodic structures for next-generation photonic devices by a self-assembly process.     

Functionalization of colloidal silica and silica surfaces via silylation reactions

A series of trialkoxysilane compounds tipped with primary amine groups were used to functionalize the surfaces of glass and colloidal silica. Streaming potential and microelectrophoretic mobility measurements were used to monitor the stability of the functionalized surfaces.Hydrolytic breakdown of the surface-to-silane coupling was induced by either successively increasing and decreasing the pH of the solution in contact with the surface, or by aging the derivatised surfaces in aqueous solution over prolonged periods of time. The chemistry of the spacer units between the trialkoxysilane group and the primary amine tip had a major influence on the subsequent hydrolytic stability. Large hydrophobic spacer groups showed small changes in the electrokinetic properties on storage, but large changes when successively titrated with acid and base through the pH range. The behavior observed with small hydrophobic spacer groups was that large changes in electrokinetic properties were obtained on storage and with pH titration.     

High-speed electroseparations inside silica colloidal crystals

Crystals made from 200 nm silica colloids are hardened and chemically modified with chlorodimethyloctadecylsilane for use in electrically driven, reversed-phase separations. A van Deemter plot reveals extremely narrow peak widths for the separation of a cationic hydrophobic dye, DiI, with both the A and C terms 10-fold smaller than those for a conventional HPLC column. Electrically driven separations are demonstrated to be achieved in less than 10 s for three dyes differing in hydrophobicity and also for three peptides differing in electrophoretic mobility. The results show that these media are promising for high-speed separations.     

Hybrids of colloidal silica and waterborne polyurethane

Waterborne polyurethane (WPU) was synthesized and followed by adding colloidal silica to prepare WPU-silica hybrids. The silica content in the hybrid thin films was varied from 0 to 50 wt%. The experimental results revealed that the viscosity of these hybrid solutions increased with increasing silica content and resulted in the aggregation of silica particle in the hybrid films. The latter result was evidenced by SEM examination. The effect of interaction between silica particle and urethane polymer chains is more significant with increasing silica content. The prepared hybrid films show much better thermal stability and mechanical properties than pure WPU. The optical transparence did not linearly decrease with increasing the silica fraction in the hybrid thin film. At below 20% silica content, the film transparence decreased with increasing silica content; the converse is true at above 20% silica content. These results showed that the prepared hybrid films demonstrated tunable transparence with the silica fraction in the films.     

Electrophoresis of megaDalton proteins inside colloidal silica

With the growth of the biopharmaceutical industry, there is a need for rapid size‐analysis of proteins on the megaDalton scale. The large pore sizes needed for such separations cannot be easily reached by pushing the current limits of size‐exclusion chromatography or gel electrophoresis. The concept detailed here is the formation of arbitrarily wide pores by packing nonporous colloidal silica in capillaries. This method can be called packed‐capillary electrophoresis, or “pCE”. Electrophoresis of protein standards (11–155 kDa) by pCE, using 345 nm diameter particles in 100 μm diameter capillaries, gives 2x higher resolution than a typical PAGE gel in 1/6 of the time. The electropherograms show that pCE is highly efficient, with half‐micrometer plate heights for all seven standards, giving 10⁵ plates for a 50 mm length. The large pore radius of 65 nm enables baseline resolution of proteins of 0.72, 1.048 and 1.236 MDa in less than 15 min. The short separation time of pCE is attributed to the absence of small pores that restrict protein migration in gels. The pCE separation is applied to the analysis of a stressed pharmaceutical‐grade IgG4 sample, giving unprecedented baseline resolution of monomer, dimer, trimer and tetramer in less than 10 min.     

Size-selective molecular transport through silica colloidal nanopores

Diffusion rate of dye-labelled PAMAM dendrimers through free-standing silica colloidal crystals was studied as a function of the dendrimer generation and nanopore size to determine the transport selectivity.     

The electro-optic properties of colloidal silica filled nematics

The optical and electro-optical properties of filled nematic liquid crystals, nematic systems with added colloidal silica nanoparticles ( ≤6%), have been studied. The macroscopic near IR birefringence of cells constructed from these materials was measured for wavelengths between 2 and 5 mum, and a wavelength independent value of 0.16 was obtained. The visible optical behaviour of cells formed with untreated ITO substrates using both filled nematic, and filled nematic and dichroic dyes was similar to those observed in polymer dispersed liquid crystals. At an electric field of 1-2 V μm -1 , the cells were highly transmitting, while at low fields they were highly scattering. The effects of colloidal silica nanoparticle concentration, cell thickness, electric field and substrate preparation (rubbed polyimide versus no surface treatment) on the electro-optical behaviour of these cells were studied.     

The electro-optic properties of colloidal silica filled nematics

The optical and electro-optical properties of filled nematic liquid crystals, nematic systems with added colloidal silica nanoparticles (? 6%), have been studied. The macroscopic near IR birefringence of cells constructed from these materials was measured for wavelengths between 2 and 5 mum, and a wavelength independent value of 0.16 was obtained. The visible optical behaviour of cells formed with untreated ITO substrates using both filled nematic, and filled nematic and dichroic dyes was similar to those observed in polymer dispersed liquid crystals. At an electric field of 1–2 V μm ^-1, the cells were highly transmitting, while at low fields they were highly scattering. The effects of colloidal silica nanoparticle concentration, cell thickness, electric field and substrate preparation (rubbed polyimide versus no surface treatment) on the electro-optical behaviour of these cells were studied.     

Photochemical synthesis of colloidal metals

New photochemical method for preparation of colloidal metal particles (Cu, Ag, Au) as a films on the quartz surface and colloidal dispersion in different matrixes has been devised. Possibilities to control the properties of photogenerated colloidal metal particles are discussed.     

Sintered silica colloidal crystals with fully hydroxylated surfaces

Silica colloidal crystals require multiple processing steps before they are useful materials in analytical applications, such as chemical separations, microarrays, sensors, and total internal reflection microscopy. These chemical processing steps include calcination, sintering, surface rehydroxylation, and chemical modification, but these steps have not been fully characterized for colloidal crystals. Silica particles of nominally 200 nm in diameter were prepared, and FTIR, SEM, UV-visible spectroscopy, and refractive index measurements were used to study the changes in chemical composition, particle size, and particle density throughout the process. The final material is shown to be a durable, crack-free crystal of solid particles bearing a fully hydroxylated surface of silanols, which can then be chemically modified.     

纳米二氧化硅的表面改性研究

以γ-缩水甘油醚丙基三甲氧基硅烷(GPTMS)对酸催化水解正硅酸乙酯(TEOS)聚合得到的纳米二氧化硅胶粒表面进行接枝改性,用激光粒径仪测定二氧化硅颗粒的粒径,并用透射电子显微镜(TEM)观察了改性前后二氧化硅胶粒的分散状况,采用傅立叶红外(FTIR)光谱法对改性前后的二氧化硅粉体进行了分析,通过热失重分析(TGA)法对GPTMS接枝改性二氧化硅胶粒表面的接枝度进行分析计算,同时对颗粒溶胶的ζ电位进行了测试,结果表明:改性后二氧化硅胶粒分散性大大提高,硅烷偶联剂浓度对接枝度有显著影响,当GPTMS的浓度为1mL/S iO2(g)时,接枝度达到最大,且颗粒表面的物理化学性能发生显著变化。     

Conformation of preadsorbed polyelectrolyte layers on silica studied by secondary adsorption of colloidal silica

The conformation of cationic polyelectrolytes preadsorbed on macroscopic silica surfaces was studied before and after addition of colloidal silica (CS) and compared to the fixation capacity of CS. The study included two polyelectrolytes of equal charge density, cationic polyacrylamide and cationic dextran. Adsorbed amounts were determined with stagnation point adsorption reflectometry (SPAR) and quartz crystal microgravimetry (QCM). Unsaturated layers of polyelectrolyte were formed in SPAR by stopping the adsorption at a fractional coverage relative to saturation adsorption. These layers were probed by secondary saturation adsorption of colloidal silica (CS). At low salt concentrations a high fractional coverage of polyelectrolyte was required to attain adsorption of CS, while significant adsorption of CS was found also for low fractional coverages of polyelectrolyte at salt concentrations above 10 mM NaCl. Saturation adsorption of cationic polyacrylamide (CPAM) and cationic dextran (Cdextran) onto the silica surface was found to be similar, while the secondary adsorption of CS was significantly higher onto preadsorbed CPAM compared with Cdextran. The QCM and SPAR data together indicated that the adsorbed layer of Cdextran was thinner than CPAM, and that a loose, expanded layer was formed after adsorption of CS on CPAM but not on Cdextran.