116,928 research outputs found
Synthesis of microporous silica nanoparticles to study water phase transitions by vibrational spectroscopy
Silica can take many forms, and its interaction with water can change dramatically at the interface. Silica based systems offer a rich tapestry to probe the confinement of water as size and volume can be controlled by various templating strategies and synthetic procedures. To this end, microporous silica nanoparticles have been developed by a reverse microemulsion method utilizing zinc nanoclusters encapsulated in hydroxyl-terminated polyamidoamine (PAMAM-OH) dendrimers as a soft template. These nanoparticles were made tunable within the outer diameter range of 20-50 nm with a core mesopore of 2-15 nm. Synthesized nanoparticles were used to study the effects of surface area and microporous volumes on the vibrational spectroscopy of water. These spectra reveal contributions from bulk interfacial/interparticle water, ice-like surface water, liquid-like water, and hydrated silica surfaces suggesting that microporous silica nanoparticles allow a way to probe silica water interactions at the molecular scale
Bulk or surface grafted silylated Ru(ii) complexes on silica as luminescent nanomaterials
A series of Ru(II) complexes with monosilylated-dipyridine ligand have been synthesized and fully characterized and were then covalently attached to silica nanoparticles. Two types of hybrids were obtained depending on the experimental procedure. In the first approach, metal complexes were incorporated inside the silica nanoparticles leaving a free hydroxylated silica surface for further functionalization. These silica based nanohybrids are similar to the well known nanoparticles encapsulating [Ru(bpy)3]2+ complexes preventing the release of the dye when used in aqueous or organic solutions. Size and luminescence properties vary throughout the series of metal complexes. The second approach leads to ruthenium(II) complexes covalently attached to the silica nanoparticle surface via hydrolysis and condensation of the ethoxysilyl group with silanol sites of Ludox type silica nanoparticles. This leads to the grafting of a monolayer for complexes with the monoethoxysilyl dipyridine ligand. In contrast, the complexes with triethoxysilyl ligands can lead to small amounts of oligomers, but their quantity is limited by the sterical constraints imposed by the molecular structure. The size of the hybrids depends on the starting particles. 29Si and 13C solid state NMR are used to characterize silica surface properties whereas TEM and SEM confirm nanosize and morphology of the hybrids. The complexes and the nanohybrids are luminescent, with variations for ruthenium(II) complexes that are covalently incorporated or grafted on the silica surfac
Structure of nanoparticles embedded in micellar polycrystals
We investigate by scattering techniques the structure of water-based soft
composite materials comprising a crystal made of Pluronic block-copolymer
micelles arranged in a face-centered cubic lattice and a small amount (at most
2% by volume) of silica nanoparticles, of size comparable to that of the
micelles. The copolymer is thermosensitive: it is hydrophilic and fully
dissolved in water at low temperature (T ~ 0{\deg}C), and self-assembles into
micelles at room temperature, where the block-copolymer is amphiphilic. We use
contrast matching small-angle neuron scattering experiments to probe
independently the structure of the nanoparticles and that of the polymer. We
find that the nanoparticles do not perturb the crystalline order. In addition,
a structure peak is measured for the silica nanoparticles dispersed in the
polycrystalline samples. This implies that the samples are spatially
heterogeneous and comprise, without macroscopic phase separation, silica-poor
and silica-rich regions. We show that the nanoparticle concentration in the
silica-rich regions is about tenfold the average concentration. These regions
are grain boundaries between crystallites, where nanoparticles concentrate, as
shown by static light scattering and by light microscopy imaging of the
samples. We show that the temperature rate at which the sample is prepared
strongly influence the segregation of the nanoparticles in the
grain-boundaries.Comment: accepted for publication in Langmui
Mechanism of cellular uptake of genotoxic silica nanoparticles.
Mechanisms for cellular uptake of nanoparticles have important implications for nanoparticulate drug delivery and toxicity. We have explored the mechanism of uptake of amorphous silica nanoparticles of 14 nm diameter, which agglomerate in culture medium to hydrodynamic diameters around 500 nm. In HT29, HaCat and A549 cells, cytotoxicity was observed at nanoparticle concentrations ≥ 1 μg/ml, but DNA damage was evident at 0.1 μg/ml and above. Transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectroscopy confirmed entry of the silica particles into A549 cells exposed to 10 μg/ml of nanoparticles. The particles were observed in the cytoplasm but not within membrane bound vesicles or in the nucleus. TEM of cells exposed to nanoparticles at 4°C for 30 minutes showed particles enter cells when activity is low, suggesting a passive mode of entry. Plasma lipid membrane models identified physical interactions between the membrane and the silica NPs. Quartz crystal microbalance experiments on tethered bilayer lipid membrane systems show that the nanoparticles strongly bind to lipid membranes, forming an adherent monolayer on the membrane. Leakage assays on large unilamellar vesicles (400 nm diameter) indicate that binding of the silica NPs transiently disrupts the vesicles which rapidly self-seal. We suggest that an adhesive interaction between silica nanoparticles and lipid membranes could cause passive cellular uptake of the particles
The size and polydispersity of silica nanoparticles under simulated hot spring conditions
The nucleation and growth of silica nanoparticles in supersaturated geothermal waters was simulated using a flow-through geothermal simulator system. The effect of silica concentration ([SiO2]), ionic strength (IS), temperature (T) and organic additives on the size and polydispersity of the forming silica nanoparticles was quantified. A decrease in temperature (58 to 33°C) and the addition of glucose restricted particle growth to sizes <20 nm, while varying [SiO2] or ISdid not affect the size (30-35 nm) and polydispersity (±9 nm) observed at 58°C. Conversely, the addition of xanthan gum induced the development of thin films that enhanced silica aggregation
Inorganic nanoparticles: Possible solution for different problems
Formation and Controlled Growth of Bismuth Titanate Phases into Mesoporous Silica Nanoparticles: An Efficient Self-Sealing Nanosystem for UV Filtering in Cosmetic Formulation. Biocompatible tailored zirconia mesoporous nanoparticles with high surface area for theranostic applications. Structural and photophysical properties of rare-earth complexes encapsulated into surface modified mesoporous silica nanoparticlesUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech
Coating thickness and coverage effects on the forces between silica nanoparticles in water
The structure and interactions of coated silica nanoparticles have been
studied in water using molecular dynamics simulations. For 5 nm diameter
amorphous silica nanoparticles we studied the effects of varying the chain
length and grafting density of polyethylene oxide (PEO) on the nanoparticle
coating's shape and on nanoparticle-nanoparticle effective forces. For short
ligands of length and repeat units, the coatings are radially
symmetric while for longer chains () the coatings are highly
anisotropic. This anisotropy appears to be governed primarily by chain length,
with coverage playing a secondary role. For the largest chain lengths
considered, the strongly anisotropic shape makes fitting to a simple radial
force model impossible. For shorter ligands, where the coatings are isotropic,
we found that the force between pairs of nanoparticles is purely repulsive and
can be fit to the form where is the separation
between the center of the nanoparticles, is the radius of the
silica core, and is measured to be between 2.3 and 4.1.Comment: 20 pages, 6 figure
Native silica nanoparticles are powerful membrane disruptors
Silica nanoparticles are under development for intracellular drug delivery applications but can also have cytotoxic effects including cell membrane damage. In this study, we investigated the interactions of silica nanospheres of different size, surface chemistry and biocoating with membranes of phosphatidylcholine lipids. In liposome leakage assays many, but not all, of these nanoparticles induced dose-dependent dye leakage, indicative of membrane perturbation. It was found that 200 and 500 nm native-silica, aminated and carboxylated nanospheres induce near-total dye release from zwitterionic phosphatidylcholine liposomes at a particle/liposome ratio of ~1, regardless of their surface chemistry, which we interpret as particle-supported bilayer formation following a global rearrangement of the vesicular membrane. In contrast, 50 nm diameter native-silica nanospheres did not induce total dye leakage below a particle/liposome ratio of ~8, whereas amination or carboxylation, respectively, strongly reduced or prevented dye release. We postulate that for the smaller nanospheres, strong silica-bilayer interactions are manifested as bilayer engulfement of membrane-adsorbed particles, with localized lipid depletion eventually leading to collapse of the vesicular membrane. Protein coating of the particles considerably reduced dye leakage and lipid bilayer coating prevented dye release all together, while the inclusion of 33% anionic lipids in the liposomes reduced dye leakage for both native-silica and aminated surfaces. These results, which are compared with the effect of polystyrene nanoparticles and other engineered nanomaterials on lipid bilayers, and which are discussed in relation to nanosilica-induced cell membrane damage and cytotoxicity, indicate that a native-silica nanoparticle surface chemistry is a particularly strong membrane interaction motif
All-inorganic core-shell silica-titania mesoporous colloidal nanoparticles showing orthogonal functionality
Colloidal mesoporous silica (CMS) nanoparticles with a thin titania-enriched outer shell showing a spatially resolved functionality were synthesized by a delayed co-condensation approach. The titaniashell can serve as a selective nucleation site for the growth of nanocrystalline anatase clusters. These fully inorganic pure silica-core titania-enriched shell mesoporous nanoparticles show orthogonal functionality, demonstrated through the selective adsorption of a carboxylate-containing ruthenium N3-dye. UV-Vis and fluorescence spectroscopy indicate the strong interaction of the N3-dye with the titania-phase at the outer shell of the CMS nanoparticles. In particular, this interaction and thus the selective functionalization are greatly enhanced when anatase nanocrystallites are nucleated at the titania-enriched shell surface
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