Fluorescence lifetime measurements to determine the core-shell nanostructure of FITC-doped silica nanoparticles: An optical approach to evaluate nanoparticle photostability

In this paper, we described a novel fluorescence lifetime-based approach to determine the core-shell nanostructure of FITC-(fluorescein isothiocyanate, isomer I) doped fluorescent silica nanoparticles (FSNPs). Because of phase homogeneity between the core and the shell, electron microscopic technique could not be used to characterize such core-shell nanostructure. Our optical approach not only revealed the core-shell nanostructure of FSNPs but also evaluated photobleaching of FSNPs both in the solvated and non-solvated (dry) states. The FSNPs were produced via Stöber's method by hydrolysis and co-condensation reaction of tetraethylorthosilicate (TEOS) and fluorescein linked (3-aminopropyl)triethoxysilane (FITC-APTS conjugate) in the presence of ammonium hydroxide catalyst. To obtain a pure silica surface coating, FSNPs were then post-coated with TEOS. The average particle size was 135 nm as determined by TEM (transmission electron microscope) measurements. Fluorescence excitation and emission spectral data demonstrated successful doping of FITC dye molecules in FSNPs. Fluorescence lifetime data revealed that approximately 62% of dye molecules remained in the solvated silica shell, while 38% of dye molecules remained in the non-solvated (dry) silica core. Photobleaching experiments of FSNPs were conducted both in DI water (solution state) and in air (dry state). Severe photobleaching of FSNPs was observed in air. However, FSNPs were moderately photostable in the solution state. Photostability of FSNPs in both solution and dry states was explained on the basis of fluorescence lifetime data.     

Relative Quantum Yield Measurements of Coumarin Encapsulated in Core-Shell Silica Nanoparticles

Fluorescent silica nanoparticles encapsulating organic fluorophores provide an attractive materials platform for a wide array of applications where high fluorescent brightness is required. We describe a class of fluorescent silica nanoparticles with a core-shell architecture and narrow particle size distribution, having a diameter of less than 20 nm and covalently incorporating a blue-emitting coumarin dye. A quantitative comparison of the scattering-corrected relative quantum yield of the particles to free dye in water yields an enhancement of approximately an order of magnitude. This enhancement of quantum efficiency is consistent with previous work on rhodamine dye-based particles. It provides support for the argument that improved brightness over free dye in aqueous solution is a more general effect of covalent incorporation of fluorescent organic dyes within rigid silica nanoparticle matrices. These results indicate a synthetic route towards highly fluorescent silica nanoparticles that produces excellent probes for imaging, security, and sensing applications.     

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 characterization of a novel luminescent nanoparticles

In this paper, a new kind of fluorescent nanomaterial with morin modified alumina core and silica shell was prepared. Samples were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), photoluminescent (PL) spectroscopy and fluorescence microscope. TEM results indicated that this material could be synthesized in nanometer range. PL spectra suggested that this new synthesized material was photostable and it showed nearly no dye leakage. This was because the dye molecules could form stable complex with the reactive aluminum cations on the surfaces of the alumina particles. The excitation and emission maxima of this new luminescent material were located at 420 and 493 nm, respectively. This new kind of luminescent nanomaterial was prepared by morin, AlCl₃ and tetraethyl orthosilicate, which was very important for the large-scale and economic preparation luminescent nanoparticles because these precursors were inexpensive and the preparation process was convenient.     

Efficient Entrapment of Dye in Hollow Silica Nanoparticles: Direct Evidence Using Fluorescence Spectroscopy

Using hollow silica nanoparticles we demonstrate a simple and highly efficient way of removing hydrophilic dye (Rhodamine B) from water by encapsulation within these hollow spheres. The hollow silica spheres were obtained by using a surfactant templated procedure. Using fluorescence spectroscopy, we also show the evidence of the dye being absorbed within the hollow core of the silica shell (which is crucial for many applications) and differentiate from the adsorption of dye on the surface of the silica shell. It was found that that up to 94 % of the hydrophilic dye could be entrapped using these hollow shells within 72 h of exposure. Fluorescence spectroscopy shows a red shift in the dye encapsulated in the hollow silica which is due to aggregation of the dye and enables us to follow quantitatively the uptake of the dye molecules by the silica shells with time. The evidence for the encapsulation of the dye in these hollow spheres was reinforced by carrying out a comparative study, using solid silica particles.

丹酰氯SiO2纳米发光标记物的制备

通过合成丹酰氯的荧光单体硅酯前驱物,采用油包水的反相微乳液法,以丹酰氯的荧光单体硅酯前驱物为核材料,成功地制备了丹酰氯的荧光纳米颗粒,克服了传统方法制备核壳荧光纳米颗粒中存在的荧光染料泄漏问题.通过透射电子显微镜表征该纳米粒子呈球形,大小均匀,直径为40nm左右.所制得纳米颗粒荧光性质稳定,受外界环境的影响小,且潜在生物亲和性,是一种新型的荧光标记物.     

Fluorescent monodisperse spherical particles based on mesoporous silica containing rhodamine 6G

Fluorescent monodisperse spherical silica (SiO₂) particles with a regular mesoporous structure containing encapsulated Rhodamine 6G (R6G) dye have been synthesized. The as-synthesized particles have been coated with SiO₂ and SiO₂-CTAB (cetyltrimethylammonium bromide, C₁₆H₃₃N(CH₃)₃Br) shells in order to prevent uncontrolled release of the dye from pores. The kinetics of R6G release from the pores of silica particles has been studied. It has been found that the particles synthesized by adding CTAB and R6G to the reaction mixture, as well as the particles coated with the SiO₂-CTAB shell, are characterized by the maximum duration of dye release from the pores, which is probably associated with the formation of chemical bonds between R6G and CTAB molecules.     

Preparation and characterization of SiO2/ZrO2/Ag multicoated microspheres

A new type of multicoated silica/zirconia/silver (SiO₂/ZrO₂/Ag) core-shell composite microspheres is synthesized in this paper. In the process, ZrO₂-decorated silica (SiO₂/ZrO₂) core-shell composites were firstly fabricated by the modification of zirconia on silica microspheres through the hydrolysis of zirconium precursor. Subsequently, on SiO₂/ZrO₂ composite cores, silver nanoparticles were introduced via ultrasonic irradiation and acted as “Ag seeds” for the formation of integrate silver shell by further reduction of silver ions using formaldehyde as reducer. The resulting samples were characterized by transmission electron microscopy, X-ray diffraction, Fourier-transform infrared, energy-dispersive X-ray, and UV-vis spectroscopy, indicating that zirconia and silver layers were successfully coated on the surfaces of silica microspheres.     

Photocatalytic degradation of methyl orange by gold silver nano-core/silica nano-shell

The silica nanoparticles (SiO₂ NPs), silver (Ag) NPs and gold (Au) NPs coated with SiO₂ NPs (core-shell) were prepared. The sizes and morphology of the particles were indicated. The three prepared NPs were used for photocatalytic degradation of methyl orange (MO) dye by xenon lamp. Rate of photocatalytic degradation reaction constant and lifetime were calculated for each catalyst. Moreover, the mechanism of the photocatalytic reaction was studied.     

Functionalized Ultrabright Fluorescent Mesoporous Silica Nanoparticles

The problem of functionalization of recently reported ultrabright fluorescent mesoporous silica nanoparticles while preserving their fluorescent brightness is solved. This is a serious issue because of the open geometry of mesoporous channels and physical encapsulation of fluorescent dye inside those channels. Amine modification of mesoporous nanoparticles is described to preserve the brightness comparable to that of earlier reported ultrabright silica nanoparticles. Scaling to 40 nm sized particles, amine‐functionalized nanoparticle have fluorescent brightness equivalent to the one of 630 free rhodamine 6G (R6G) dye molecules in water. To demonstrate further most challenging functionalization, which relies on using organic‐solvent‐based chemistry, folic acid conjugation is developed. Two different methods are used to conjugate folites to the amine functionalities. Both methods result in a decrease of fluorescence intensity, which can nonetheless still be called ultrabright. The brightness can drop to either 310 or 80 R6G dye molecules per particle of nominal diameter of 40 nm.     

Effect of polyvinylpyrrolidone on the structure and laser damage resistance of sol–gel silica anti-reflective films

The effect of polyvinylpyrrolidone (PVP) on the structure and laser-induced damage threshold (LIDT) of sol–gel silica anti-reflective films is investigated. The results of dynamic light scattering, transmission electron microscopy, and small angle X-ray scattering, show that the PVP molecules surrounded the silica sol particles through the strong hydrogen bonds between Si-OH groups and the PVP. As a result, the growth of silica particles was restricted and thus the interface layer between the silica particles and the solvent become thickened with PVP content. Furthermore, the PVP reduced the porosity of the film, so the anti-reflection properties of the film were weakened. A multi-fractal analysis showed that the appropriate addition of PVP, 1 weight percent (wt%), could improve the surface fractal structure of the film, but that higher PVP content resulted in reduced surface uniformity. The addition of PVP lead to improved LIDT.     

Nanosized titania encapsulated silica particles using an aqueous TiCl4 solution

In this study, sub-micron sized silica particles were encapsulated with nanosized titania particles using an aqueous TiCl₄ solution. The particle size distribution of the synthesized titania particles in the coating layer was estimated to be 10 nm from X-ray powder diffraction and transmission electron microscopy. The thickness of the coating layer ranged from a few nm to about 30 nm from transmission electron microscopy analysis. Zeta potential analysis demonstrated the presence of a titania particle coating layer and the extent of its coverage on the surface of silica particles. X-ray photoelectron spectroscopy analysis also demonstrated that titania particles were successfully deposited on the surface of core silica particles from the chemical shift of binding energies of O 1s, Ti 2p and Si 2p.     

Preparation of alumina/silica core-shell abrasives and their CMP behavior

Abrasive is one of key influencing factors on the surface quality during the chemical mechanic polishing (CMP). α-Alumina particles, as a kind of widely used abrasive in CMP slurries, often cause to surface defects because of its high hardness. In the present paper, a series of novel alumina/silica core-shell abrasives in slurries were described. The CMP performances of the alumina/silica core-shell abrasives on hard disk substrate were investigated by using a SPEEDFAM-16B-4M CMP equipment. Experimental results indicate that the CMP performances are strong dependent on the coated SiO₂ content of the alumina/silica composite abrasives. Slurries containing the alumina/silica composite abrasives exhibited lower surface roughness and waviness as well as lower topographical variations and less scratch than that containing pure alumina abrasive under the same testing conditions.     

Synthesis and Characterization of Monodispersed SiO2@Y3Al5O12:Er3+ Core-Shell Particles

Submicron core-shell structure particles SiO₂@Y₃Al₅O₁₂:Er³⁺, which silica spherical particles was coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺, were prepared by the modified Pechini-Type sol-gel method for the first time. The structure and morphology of samples were detected by the X-ray powder diffraction (XRD) measurement, field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), respectively. The results indicate that well-crystallized garnet nanocrystallines were formed on the surface of the silica particles. The luminescent spectra in near infrared and visible region of the core-shell structured SiO₂@Y₃Al₅O₁₂:Er³⁺ powders were also investigated and compared with those of the pure Y₃Al₅O₁₂:Er³⁺ and the Er³⁺ doped silicate glass. The results show that mono-dispersed SiO₂@Y₃Al₅O₁₂:Er³⁺ core-shell spherical particles with the near infrared, red and green luminescent emissions under the excitation of 980 nm laser diode have been successfully synthesized.     

An investigation on the behavior of fine-grained magnetite particles as a function of size and surface modification

By using a KNO₃-aging ferrous hydroxide gel method, Fe₃O₄ particles with sizes ranging from 35 to 1500 nm were synthesized. The particles were covered with a silica coating to form Fe₃O₄-SiO₂ core-shell structures by using the improved conventional Stöber polycondensation method. The thickness of the SiO₂ covering on magnetite particles surface varies from 10 to 20 nm. The morphology, size and composition of the particles were determined by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The particles with and without coating with SiO₂ were pressed into slices with an oil press at 10 MPa. Subsequently, the coercive forces H_C of the particles were measured by VSM at room temperature, and the critical size for a single domain was estimated. The shape of the particles is basically spherical when the size is smaller than 800 nm, while it is hexagonal for larger particles. The H_C of Fe₃O₄-SiO₂ core-shell structure was larger than that of the uncoated Fe₃O₄ particles by 20%, which was explained to be due to the reduction of inter-particle magnetostatic interaction, supported by an agreement with the packing factor. The dependence of H_C on magnetic particle size could be explained and fitted by the Heewell-Knozam stacking density equation and object-oriented micromagnetic computing framework (OOMMF) micromagnetic software. the results agree well with the experimental data.     

Spectroscopic and lasing properties of Xanthene dyes encapsulated in silica and polymeric matrices

The photo-physical properties of Xanthene dyes: Basic Rhodamine Yellow (BRY), Rhodamine590perchlorate (R590p), SulforhodamineB (SRB) doped in tetramethylorthosilicate (TMOS) and poly-methylmethacrylate (PMMA) are observed. The various parameters viz. full-width at half-maxima (FWHM), peak emission wavelength, quantum yield and excited state lifetime at different concentrations ranging from ∼0.05 to ∼1 mM of the dye under excitation by Copper Vapor Laser (CVL) of high repetition rate (∼5.6 kHz) of are investigated. In order to identify photostability in dyes, normalized photostability has been studied and found that silica gel samples containing dye are more stable than that of polymeric samples. This has been further understood in terms of number density of unbleached dye molecules that infers that photobleaching of dye molecules is not prominent at higher concentrations in glassy solid matrices. Pump intensity dependent optical gain of the samples has also been reported and efforts have been made to study the efficiency of solid-state laser samples in a cavity for the performance of the dye laser.     

Surface functionalization of silica-coated magnetic nanoparticles for covalent attachment of cholesterol oxidase

A systematic approach towards the fabrication of highly functionalized silica shell magnetic nanoparticles, presently used for enzyme immobilization, is herein fully presented. The synthesis of bare maghemite (γ-Fe₂O₃) nanoparticles was accomplished by thermal co-precipitation of iron ions in ammonia alkaline solution at harsh reaction conditions, respectively. Primary surface engineering of maghemite nanoparticles was successfully performed by the proper deposition of silica onto nanoparticles surface under strictly regulated reaction conditions. Next, the secondary surface functionalization of the particles was achieved by coating the particles with organosilane followed by glutaraldehyde activation in order to enhance protein immobilization. Covalent immobilization of cholesterol oxidase was attempted afterwards. The structural and magnetic properties of magnetic silica nanocomposites were characterized by TEM and vibrating sample magnetometer (VSM) instruments. X-ray diffraction measurements confirmed the spinel structure and average size of uncoated maghemite nanoparticles to be around 20 nm in diameter. SEM-EDS spectra indicated a strong signal for Si, implying the coating procedure of silica onto the particles surface to be successfully accomplished. Fourier transform infrared (FT-IR) spectra analysis confirmed the binding of amino silane molecules onto the surface of the maghemite nanoparticles mediated Si-O-Si chemical bonds. Compared to the free enzyme, the covalently bound cholesterol oxidase retained 50% of its activity. Binding of enzyme onto chemically modified magnetic nanoparticles via glutaraldehyde activation is a promising method for developing biosensing components in biomedicine.     

Synthesis and characterization of core-shell europium(III)-silica nanoparticles

Luminescent core-shell europium(III)-silica nanoparticles were prepared using europium(III) chelate core structure and polyvinylpyrrolidone synthesis strategy for silica shell. Europium(III):naphtoyltrifluoroacetone:trioctylphosphineoxide complex was spontaneously agglomerated from organic solvent to water. Polyvinylpyrrolidone was adsorbed onto the core structure and stable silica shell was synthesized using tetraethylorthosilicate. Nanosized particles with a diameter of 71 ± 5 nm and 11 nm shell thickness were obtained with fluorescence decay rate of 517 μs and excitation and emission wavelengths of 334 and 614 nm, respectively.     

Plasma-activated core-shell gold nanoparticle films with enhanced catalytic properties

Catalytically active gold nanoparticle films have been prepared from core-shell nanoparticles by plasma-activation and characterized by high-resolution transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Methane can be selectively oxidized into formic acid with an O₂–H₂ mixture in a catalytic wall reactor functionalized with plasma-activated gold nanoparticle films containing well-defined Au particles of about 3.5 nm in diameter. No catalytic activity was recorded over gold nanoparticle films prepared by thermal decomposition of core-shell nanoparticles due to particle agglomeration.     

Dually fluorescent silica nanoparticles

The cationic dyes 9-aminoacridine (9AA) and safranine (Sf) were entrapped into silica spheres of about 0.2 μm diameter prepared by modified Stöber method. The fluorescent materials are investigated by steady-state and time-resolved emission, in addition of confocal fluorescence microscopy. Silica particles containing 9-aminoacridine (SP9AA) and safranine (SPSf) or both dyes (SPSf9AA) are emissive particles. When both dyes are present in the same particle but loaded in sequential stages 9AA emission is quenched as a consequence of energy transfer from 9AA (donor) to Sf (acceptor). This result suggests that particle growing processes where the acceptor is incorporated first into the core do not prevent donor/acceptor pairs to be close due to an overlay of the concentration gradients of both dyes in a radial core-shell like distribution.