Preparation of gold-silica heterogeneous nanocomposite particles by alcohol-reduction method

Au-silica heterogeneous nanocomposite particles were prepared by novel preparation strategy involving alcohol-reduction method using 3-aminopropyltrimethoxysilane (APTMS) as a binder between silica surface and Au nanoparticles, and using PVP as a stabilizer for Au nanoparticles. The evolution of morphology of composite particles was investigated with increasing reaction time at different Au precursor concentrations of 100 ppm and 250 ppm using UV-vis spectrophotometer and TEM. It is shown that the size of immobilized Au particles on silica surface can be controlled with the variation of reaction rate via adjusting Au precursor concentration and reaction time, but the high concentration of Au precursor hinders the immobilization of well-defined Au nanoparticles due to the slow reduction rate of Au precursor. On the basis of experimental results, the role of APTMS and PVP on the formation of composite particles and the effect of Au precursor concentration on the morphological evolution of composite particles are briefly discussed.     

Lateral diffusion of thiol ligands on the surface of au nanoparticles: an electron paramagnetic resonance study

The lateral mobility of the thiolate ligands on the surface of Au nanoparticles was probed by EPR spectroscopy. This was achieved by using bisnitroxide ligands, which contained a disulfide group (to ensure attachment to the Au surface) and a cleavable ester bridge connecting the two spin-labeled branches of the molecule. Upon adsorption of these ligands on the surface of Au nanoparticles, the two spin-labeled branches were held next to each other by the ester bridge as evidenced by the spin-spin interactions. Cleavage of the bridge removed the link that kept the branches together. CW and pulsed EPR (DEER) experiments showed that the average distance between the adjacent thiolate branches on the Au nanoparticle surface only marginally increased after cleaving the bridge and thermal treatment. This implies that the lateral diffusion of thiolate ligands on the nanoparticle surface is very slow at room temperature and takes hours even at elevated temperatures (90 degrees C). The changes in the distance distribution observed at high temperature are likely due to ligands hopping between the nanoparticles rather than diffusing on the particle surface.     

One Step Synthesis of Gold‐Loaded Radial Mesoporous Silica Nanospheres and Supported Lipid Bilayer Functionalization: Towards Bio‐Multifunctional Sensors

A simple synthetic route is developed to achieve gold functionalized radial mesoporous silica nanoparticles (Au‐MsNP) synthesized by a one step procedure fully compatible with basic conditions required for the preparation of monodispersed nanospheres. In a second step, Au‐MsNP particles have been coated with phospholipid bilayers in order to design an advanced biofunctional platform with the gold metallic nanoparticles previously grown into the pore channels and responsible for a plasmonic activity relevant for biosensing. The size of Au‐MsNP is checked by dynamic light scattering while zeta potential measurements reflect their surface charge. The particle morphology is characterized by transmission and scanning electron microscopy and the Si/Au ratios are obtained from energy dispersive X‐ray analysis. The textural properties of Au‐MsNP, specific surface area and pore size, are determined from N₂ adsorption. The supported bilayers are achieved from vesicles of different phospholipids incubated with Au‐MsNP particles. The coating efficiency is investigated by zeta potential and cryo‐ transmission electron microscopy. The plasmonic activities of bare Au‐MsNP particles and coated lipid bilayer Au‐MsNP platform are evidenced for two model systems: direct adsorption of bovine serum albumin and molecular recognition events between avidin molecules and biotin receptors integrated in the supported lipid bilayer.     

Optical organophosphate sensor based upon gold nanoparticle functionalized fumed silica gel

We report on the creation of a high surface area, chemically selective material for the efficient adsorption of organophosphate and organophosphonate species. Using silica microparticles in conjunction with gold nanoparticles and surface modification chemistry, we have demonstrated a material with a binding constant for organophosphonates and organophosphates (OPPs) of K=2x10(6) M-1. The binding of OPPs to the modified gold nanoparticles appears as a spectral shift in the gold nanoparticle resonance. The sensitivity of this technique is limited by scattering losses of suspensions of the particles, and we report on how this sensitivity can be recovered to a significant extent by the use of solvents with a refractive index close to that of the silica particles.     

Preparation of monodispersed mesoporous silica spheres with tunable pore size and pore-size effects on adsorption of Au nanoparticles and urease

Monodispersed mesoporous silica spheres (MMSS) with controllable porosity and pore size were successfully prepared by calcination method in the presence of complex salts. The effect of calcination temperature on the pore size of MMSS was examined. The results show that the pore size of MMSS samples can be tuned in the range from 3.20 to 46.80 nm by varying the calcination temperature. It is worth mentioning that the pore size of MMSS can be controlled on a much larger scale by this method compared to the templating approach, by which the pore size can only be expanded up to 10 nm. It is very advantageous for the application in loading enzymes. Moreover, it could be found that the method is feasible, effective and simple. In addition, the use of various MMSS samples as adsorbents for Au nanoparticles of different sizes as well as urease has also been demonstrated. It was confirmed that MMSS with adequate surface charge and optimum matching pore size showed excellent adsorption properties for Au nanoparticles and urease.     

Regenerating optical properties of individual gold nanoparticles in alcoholic solvents without any surfactant

We compared the optical properties of gold nanoparticles (GNPs) in various solvents with those of strawberry-like composite particles (Au/SiO2) consisting of a silica core and single attached GNPs. The results show that Au/SiO2 without any surfactant could regenerate well optical properties of individual GNPs in alcoholic solvents. By the electrophoretic light-scattering measurements, the high dispersibility of Au/SiO2 composite particles dispersed in alcoholic solvents has been demonstrated. In addition, using Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, we proposed a possible mechanism to qualitatively account for the dispersibility of Au/SiO2 in organic solvents such as alcoholic solvents and cyclohexane, which may provide an opportunity to manipulate optical signals of single nanoparticle in organic solvents.     

A synergistically enhanced photothermal transition effect from mesoporous silica nanoparticles with gold nanorods wrapped in reduced graphene oxide

In this work, near-infrared (NIR)-responsive core–shell gold nanorods/mesoporous silica/reduced graphene oxide (Au/SiO₂/rGO) nanoparticles with synergistically enhanced photothermal stability and transition effect had been prepared via electrostatic interaction. Gold nanorods (AuNRs) and rGO were employed as the NIR-responsive components. UV–Vis–NIR extinction spectra revealed that the surface plasmon resonance peak of AuNRs from Au/SiO₂/rGO nanohybrids remained unchanged after 9 h NIR exposure. UV–Vis–NIR extinction results also showed that thin silica shell was superior to the thick ones in the photothermal stability improvement of Au/SiO₂/rGO nanoparticles. Moreover, the doxorubicin release of Au/SiO₂/rGO was more rapid than that of Au/SiO₂ upon NIR irradiation, indicating that synergistically enhanced photothermal effect between rGO and AuNRs endowed Au/SiO₂/rGO nanoparticles with excellent photothermal transition efficiency. Such novel NIR-responsive core–shell hybrid nanoparticles with enhanced photothermal stability and transition effect are well suited for further biological applications, such as photothermal therapy, bioimaging and drug delivery.     

Fabrication of silica nanocapsules containing Ag/Au alloy nanoparticles by galvanic replacement reaction

A straightforward method has been developed to generate silica nanocapsules containing Ag/Au alloy nanoparticles (Ag/Au@silica) by in-situ galvanic replacement reaction between the silica-coated silver (Ag@silica) nanoparticles with aqueous chloroauric acid (HAuCl4). Ag/Au@silica exhibits an optical absorbance derived from the surface Plasmon resonance of the encapsulated Ag/Au alloy nanoparticle. The behaviour of chemical diffusion across the silica shells of Ag/Au@silica is also investigated. It is worthy to noting that this facile synthetic strategy could be amenable to the other systems that involve the use of different combination of materials for the core (Pd/Ag, Pt/Ag alloy nanoparticles) and for the shell (titania).     

In situ Raman monitoring of competitive adsorption of Ag and Au nanoparticles onto a poly(4-vinyl pyridine) surface

The competitive adsorption of citrate-capped Ag and Au nanoparticles (~25 nm in diameter) onto a poly(4-vinyl pyridine) (P4VP) surface has been investigated by means of Raman scattering spectroscopy. The P4VP film prepared on a glass slide was too thin for its normal Raman spectrum to be observed, but the Raman peaks of P4VP could be detected upon the adsorption of Ag and/or Au nanoparticles onto the film, due to the surface-enhanced Raman scattering (SERS) effect associated with the localized surface plasmon of Ag and/or Au nanoparticles. Neither quartz crystal microbalance nor atomic force microscopy (AFM) nor scanning electron microscopy (SEM) methodologies can distinguish between Ag and Au nanoparticles during their adsorption onto P4VP, but it is possible through Raman scattering spectroscopy because Ag (though not Au) nanoaggregates are SERS active at 514.5 nm excitation, while both Ag and Au nanoaggregates are SERS active at 632.8 nm excitation. Coupled with the AFM data, we were thus able to infer that about 120 Ag nanoparticles per 1 μm(2) were adsorbed, along with 60 Au nanoparticles per 1 μm(2), onto the P4VP film over a period of 1.5 h from a 1 : 1 mixture of Ag and Au sols at 1.6 nM each.     

Sonochemical synthesis of (3-aminopropyl)triethoxysilane-modified monodispersed silica nanoparticles for protein immobilization

3-Aminopropyltriethoxysilane modified monodispersed silica nanoparticles were synthesized by a rapid sonochemical co-condensation synthesis procedure. The chemical nature of surface organic modifier on the obtained modified silica nanoparticle was characterized by ¹³C and ²⁹Si MAS Nuclear Magnetic Resonance (NMR) spectroscopies, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA)- differential scanning calorimetry (DSC). Due to the strengthened positive surface charge of the silica nanoparticles by the modification with aminopropyl groups, the capability for bovine serum albumin (BSA) adsorption was significantly increased as compared with bare silica nanoparticles. 80 mg/g BSA was adsorbed on modified silica nanoparticles, whereas only 20 mg/g BSA could be loaded on pure silica nanoparticles. The enhanced positive surface charge repelled proteins with net positive charge and the modified silica nanoparticles exhibited negligible adsorption of lysozyme, thus a selective adsorption of proteins could be achieved.     

Improving the signal sensitivity and photostability of DNA hybridizations on microarrays by using dye-doped core-shell silica nanoparticles

The development of new highly sensitive and selective methods for microarray-based analysis is a great challenge because, for many bioassays, the amount of genetic material available for analysis is extremely limited. Currently, imaging and detection of DNA microarrays are based primarily on the use of organic dyes. To overcome the problems of photobleaching and low signal intensities of organic dyes, we developed a new class of silica core-shell nanoparticles that encapsulated with cyanine dyes and applied the dye-doped nanoparticles as labeling in the DNA microarray-based bioanalysis. The developed nanoparticles have core-shell structure containing 15-nm Au colloidal cores with 95 dye-alkanethiol (dT)20 oligomers chemisorbed on the each Au particle surface and 10-15-nm silica coatings bearing thiol functional groups. To be utilized for microarray detection, the dye-doped nanoparticles were conjugated with DNA signaling probes by using heterobifunctional cross-linker. The prepared nanoparticle conjugates are stable in both aqueous electrolytes and organic solvents. Two-color DNA microarray-based detection was demonstrated in this work by using Cy3- and Cy5-doped nanoparticles in sandwich hybridization. The use of the fluorophore-doped nanoparticles in high-throughput microarray detection reveals higher sensitivity with a detection limit of 1 pM for target DNA in sandwich hybridization and greater photostable signals than the direct use of organic fluorophore as labeling. A wide dynamic range of approximately 4 orders of magnitude was also found when the dye-doped nanoparticles were applied in microarray-based DNA bioanalysis. In addition, the use of these dye-doped nanoparticles as the labeling in hybridization also improved the differentiation of single-nucleotide polymorphisms. This work offers promising prospects for applying dye-doped nanoparticles as labeling for gene profiling based on DNA microarray technology.     

Effect of acetonitrile/water mobile-phase composition on adsorption characteristics of reversed-phase liquid chromatography

The influence of volumetric composition of acetonitrile in a mobile phase on adsorption characteristics of reversed-phase liquid chromatography using octadecylsilyl (ODS)-modified silica gel was studied by the pulse response method and the moment analysis. The results were compared with those obtained for the reversed-phase system consisting of ODS-silica gel and methanol/water mixtures. In both systems, surface diffusion was dominant for intraparticle diffusion in ODS-silica gel particles. The contributions of three mass transfer steps in a column to peak broadening were of about the same order of magnitude. The activation energy of surface diffusion, E(s), was found to be larger than the isosteric heat of adsorption, Q(st). Because similar tendencies were observed for these adsorption characteristics, adsorption mechanisms may be analogous in both chromatographic systems. However, absolute values of the adsorption equilibrium constant, K, the decreasing ratio of hydrophobic surface area, ΔA/A, Q(st), and E(s) for acetonitrile/water systems were smaller than the corresponding values for methanol/water systems. Oppositely, greater values of D(s) were obtained for acetonitrile/water systems. It was concluded that the interaction between ODS ligands and adsorbate molecules was weaker compared with that in methanol/water mobile-phase systems when acetonitrile was used as an organic modifier in a mobile phase of reversed-phase liquid chromatography.     

Effect of solvents on properties of the ultrasound assisted synthesized ceria nanoparticles and its performance as an adsorbent

The present study revealed a facile, ultrasound assisted ceria nanoparticle synthesis route by the reduction of cerium nitrate hexahydrate in different solvents at room temperature. The different solvents employed were methanol (MeOH), ethylene glycol (EG), water (aq) and isopropyl alcohol (IPA). The ceria nanoparticles were synthesized without the use of any capping agent in 20?min. The yield obtained was around 90% for the synthesized ceria samples. As synthesized ceria nanoparticles were characterized by X-ray diffraction (XRD), Field emission gun scanning electron microscopy (FEG-SEM), Brunauer Emmett Teller (BET) and zeta (ζ) potential in order to determine the influence of solvent on the physical properties of ceria nanoparticles. All the ceria samples illustrated a predominant spherical shape with the size in the range of 5–20?nm. It was found that interaction of the solvent with ceria nanoparticles in the presence of ultrasound plays an important role in modulating crystallite size, surface charge and its adsorption performance for a xylene milling yellow 6G dye. Among all the sonicated ceria samples, IPA mediated ceria exhibited highest positive zeta potential and hence was found to be proficient for the complete removal of dye in 15?min. Furthermore, the adsorption of the yellow milling dye on the surface of (IPA mediated) sonicated ceria sample has shown to follow pseudo-first order kinetic model. The non-sonicated sample (prepared in MeOH solvent without ultrasound) shows negligible dye adsorption while sonicated sample reveals 50% removal of XMY dye due to the difference in zeta potential values resulted from the cavitation effects.     

Reuse of waste silica as adsorbent for metal removal by iron oxide modification

Silica gel is widely used in research laboratories, especially for the purification of organic compounds. Consequently, waste silica gel is generated in increasing amounts. In this work, waste silica was modified by coating its surface with iron oxide aiming to obtain an effective adsorbent for metal removal from wastewater. In the preparation of the adsorbent, the optimal pretreatment temperature and iron concentration were investigated. The coated waste silica was characterized for BET surface area, pore size, specific pore volume and iron content. Iron oxide-coated waste silica was tested for the adsorption of Pb(II), Cu(II), Cd(II) and Ni(II) from solutions in a batch system. The effect of contact time, pH and salt concentration on metal adsorption was investigated. It was found that the adsorption of metals occurred rapidly and reached equilibrium within 30 min. The pH suitable for metal adsorption was between 6 and 7 and leaching of iron from the coating was observed only at pH 3 or lower. The presence of salt reduced the adsorption efficiency of the adsorbent. The adsorption behavior followed both Langmuir and Freundlich isotherms (25 degrees C). Finally, the efficacy of the adsorbents was investigated using aqueous lab waste where removal efficiencies ranging from 62 to 89% were achieved when the initial metal concentrations ranged from 13 to 42 mg L(-1).     

Label-free detection of leptin antibody-antigen interaction by using LSPR-based optical biosensor

In the recent research, the development of optical biosensing devices has been focused on finding new method and technologies to exploit the optical properties of noble metal nanostructure, especially localized surface plasmon resonance (LSPR). In this study, we fabricated a LSPR-based label-free optical biosensor with the multi-spot gold-capped nanoparticle array (MG-NPA) biochip based on the deposition of a thin gold (Au) film on the silica nanoparticles layer with the simple process. The MG-NPA biochip used the silica nanoparticles as the core and a thin Au film as a shell on the surface. This structure can excite the LSPR signal easily with the high reproducibility. The anti-leptin antibody was immobilized on the surface of MG-NPA biochip, which could recognize only leptin antigen. The leptin antibody-antigen interaction was performed by the introduction of different concentration (1 pg/mL-100 microg/mL) of leptin antigen solutions for 1 h. The detection limit was found to be 100 pg/mL by using the anti-leptin antibody immobilized MG-NPA biochip. This LSPR-based label-free optical biosensor employing the MG-NPA biochip brings several advantages such as low cost, easy to fabricate, using a simple optical system and can be applied in a wide immunoassay with the similar antibody-antigen model.     

Au(111)电极表面溴离子吸附诱导的表面应力的理论研究

以Br~-为例,应用格子气模型,建立了阴离子吸附层对Au(111)电极表面应力贡献的统计热力学理论,计算了吸附层Br~-间的相互作用能及表面应力的贡献.计算结果表明,总的表面应力是压缩性的;在高覆盖度区域,表面应力与覆盖度近似呈直线关系;在表面吸附层应力的多种物理起源中,通过底物的分子间作用力有着决定性的贡献,揭示了分子的吸附能间接地起着重要作用.     

Comparative studies between synthetic routes of SiO2@Au composite nanoparticles

We studied two different methods for the deposition of Au nanoparticles (Au NPs) onto the functionalized silica microspheres. One method was to mix the two kinds of particles together and react at room temperature overnight. The other one was to reduce hydrochloroauric acid to Au NPs with sodium citrate in the presence of the functionalized silica microspheres (one for the naked silica microspheres, the other for the Au-attached silica microspheres). We investigated the morphologies of SiO₂@Au composite nanoparticles synthesized by these two methods, and found that the latter achieved a denser Au coverage on silica microspheres. Furthermore, we studied the effect of the pH values in a wide range, respectively, for the two methods. A possible mechanism was put forward to interpret the formation of SiO₂@Au composite nanoparticles and the effects of the synthetic routes and pH values on the morphologies and optical properties.     

Structural verification and optical characterization of SiO2–Au–Cu2O nanoparticles

In this paper, SiO₂–Au–Cu₂O core/shell/shell nanoparticles were synthesized by reducing gold chloride on 3-amino-propyl-triethoxysilane molecules attached silica nanoparticle cores for several stages. Cu₂O nanoparticles were synthesized readily with the size of 4–5 nm using a simple route of sol–gel method Then, they were clung to the surface of Au seeds. The morphology of the resultant particles was studied using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Transmission electron microscopy images demonstrate growth of monodispersed gold seeds and Cu₂O nanoparticles in narrow size up to 10 nm and 5 nm, respectively. The presence of gold and Cu₂O coating was confirmed by X-ray diffraction, Fourier transform infrared spectroscopy and UV–Vis spectroscopy. Absorption spectroscopy shows considerably 40 nm blue shift in absorption edge for SiO₂–Au–Cu₂O nanostructure rather than SiO₂–Au core/shell nanoparticles.     

Luminescence properties of Eu3+ or Dy3+/Au co-doped SiO2 nanoparticles

Silica nanoparticles, prepared by the Stober method, have been doped with Eu³⁺, Dy³⁺, or processed to result in Au nanoparticles on the silica surface. The luminescence of the rare earth (RE)-doped SiO₂ particles has been studied as a function of the nature of the RE, their concentration and also of the presence of Au nanoparticles at the surface of the SiO₂ nanoparticles. We have shown that the Eu³⁺ emission is observable over the experimental conditions examined, whereas it was not possible to observe any emission for Dy³⁺ doped materials. No enhancement of the Eu³⁺ emission was observed following the adsorption of gold nanoparticles at the surface of the SiO₂ nanoparticle, however an excitation at 250 nm leads to both the emission of the matrix and Eu³⁺ showing an energy transfer from the SiO₂ matrix to Eu³⁺ ions.     

Fabrication of silica/PDMS hybrid nanoparticles by a novel solvent adjustment route

The silica/polydimethylsilane (PDMS) hybrid nanoparticles were successfully synthesized by a novel solvent adjustment route. The as-prepared hybrid nanoparticles were characterized by transmission electron microscopy, UV-vis spectra, and IR spectra. The possible mechanism for the formation of silica/PDMS nanoparticles was discussed. The adjustment of solvents is a very important factor since it could tune the surface ligands and improve the coordination ability. On the other hand, it could also tune the interaction between precursors, intermediate or the target hybrid materials and guarantee the monodispersion of prepared nanoparticles. With the merits of PDMS and silica, the as-prepared SiO2-PDMS hybrid nanoparticles have a good application in hard coating material.