We have developed structure/toxicity relationships for amorphous silica nanoparticles (NPs) synthesized through low temperature, colloidal (e.g. Stöber silica) or high temperature pyrolysis (e.g. fumed silica) routes. Through combined spectroscopic and physical analyses, we have determined the state of aggregation, hydroxyl concentration, relative proportion of strained and unstrained siloxane rings, and potential to generate hydroxyl radicals for Stöber and fumed silica NPs with comparable primary particle sizes (16-nm in diameter). Based on erythrocyte hemolytic assays and assessment of the viability and ATP levels in epithelial and macrophage cells, we discovered for fumed silica an important toxicity relationship to post-synthesis thermal annealing or environmental exposure, whereas colloidal silicas were essentially non-toxic under identical treatment conditions. Specifically, we find for fumed silica a positive correlation of toxicity with hydroxyl concentration and its potential to generate reactive oxygen species (ROS) and cause red blood cell hemolysis. We propose fumed silica toxicity stems from its intrinsic population of strained three-membered rings (3MRs) along with its chain-like aggregation and hydroxyl content. Hydrogen-bonding and electrostatic interactions of the silanol surfaces of fumed silica aggregates with the extracellular plasma membrane cause membrane perturbations sensed by the Nalp3 inflammasome, whose subsequent activation leads to secretion of the cytokine IL-1β. Hydroxyl radicals generated by the strained 3MRs in fumed silica but largely absent in colloidal silicas may contribute to the inflammasome activation. Formation of colloidal silica into aggregates mimicking those of fumed silica had no effect on cell viability or hemolysis. This study emphasizes that not all amorphous silica is created equal and that the unusual toxicity of fumed silica compared to colloidal silica derives from its framework and surface chemistry along with its fused chain-like morphology established by high temperature synthesis (>1300°C) and rapid thermal quenching.

Nanocomposites offer unique capabilities of controlling thermal transport through the manipulation of various structural aspects of the material. However, measurements of the thermal properties of these composites are often difficult, especially porous nanomaterials. Optical measurements of these properties, although ideal due to the noncontact nature, are challenging due to the large surface variability of nanoporous structures. In this work, we use a vector-based thermal algorithm to solve for the temperature change and heat transfer in which a thin film subjected to a modulated heat source is sandwiched between two thermally conductive pathways. We validate our solution with time domain thermoreflectance measurements on glass slides and extend the thermal conductivity measurements to SiO2-based nanostructured films.

Although evaporation-induced self-assembly (EISA) has proven to be a convenient method for synthesizing nanoporous silica films (and particles), accessing material structures with pore sizes larger than ca. 10 nm remains experimentally inconvenient. The use of pore swelling agents (SAs), commonly used during the hydrothermal synthesis of mesoporous silicas, results in little or no pore size expansion due to evaporation or phase separation. Moreover, diblock copolymer templates can yield large pores, but are quite expensive and generally require the addition of strong organic cosolvents. Here, we hypothesized that pores templated by the Pluronic triblock polymer F127 could be successfully enlarged, without phase separation, by using a chemically similar, non-volatile, secondary Pluronic (P103) as the SA. We find pore size increased up to 15 nm for a spherical pore morphology, with a phase transition to a multilamellar vesicle (MLV) based nanostructure occurring as the P103/F127 ratio is further increased. This MLV phase produces even larger pore sizes due to collapse of concentric silica shells upon template removal.Remarkably, F127 alone exhibits expansion of pore size (up to ca. 16 nm) as the template/silica ratio is increased. We find appearance of the MLV phase is due to geometric packing considerations, with expansion of F127 micelle size a result of favorable intermolecular interactions driven by the large polyethylene oxide content of F127. Other Pluronic polymers with this feature also exhibit variable pore size based on the template/silica ratio, enabling the synthesis of mesoporous films with 3D pore connectivity and truly variable pore size of ca. 4.5 to almost 20 nm. Particles and films of mesoporous silica (MPS) templated by condensation of solution-phase sol-gel precursors around self-assembled surfactant mesophases, either through solution processing 1,2 or evaporation-induced self-assembly (EISA), 3,4 have become an important class of nanostructured materials, with potential applications ranging from catalytic supports 5 and adsorbents for environmental remediation 6 to drug delivery 7,8 and nanoporous molecular separation membranes. 9,10 A prominent feature of these materials is the ease in which pore size can be engineered through the identity of commonly available off-the-shelf surfactant templates, starting at ca. 2 nm, 11,12 though the use of alkylammonium surfactants such as cetyltrimetylammonium bromide (CTAB), 1 up to approximately 10 nm with amphiphilic block co-polymer templates such as the poloxamer series of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblocks (PEO-PPO-PEO, exemplified by the SBA series of mesoporous silicas). 13-15 However, a need for greater pore size (pushed in part by the use of MPS to deliver large biomolecular cargos such as DNA or functional proteins) 16-19 has driven research into methods for expanding the upper limit of this range. One strategy that has been successful in synthesizing porous materials with pore sizes of even greater than 40...

The fabrication of nanostructured films possessing tricontinuous minimal surface mesophases with well-defined framework and pore connectivity remains a difficult task. As a new route to these structures, we introduce glycerol monooleate (GMO) as a template for evaporation-induced self-assembly. As deposited, a nanostructured double gyroid phase is formed, as indicated by analysis of grazing-incidence small-angle x-ray scattering data. Removal of GMO by UV/O3 treatment or acid extraction induces a phase change to a nanoporous body-centered structure which we tentatively identify as based on the IW-P surface. To improve film quality, we add a co-surfactant to the GMO in a mass ratio of 1:10; when this co-surfactant is cetyltrimethylammonium bromide, we find an unusually large pore size (8-12 nm) in acid extracted films, while UV/O3 treated films yield pores of only ca. 4 nm. Using this pore size dependence on film processing procedure, we create a simple method for patterning pore size in nanoporous films, demonstrating spatially-defined size-selective molecular adsorption.

A bile salt (sodium taurodeoxycholate, NaTDC) was used to prevent phase separation between silica and lipid in self-assembled long-chain diacyl phosphatidylcholine/SiO(2) films. Phase diagrams for NaTDC/didecanoyl phosphatidylcholine/SiO(2) and NaTDC/egg phosphatidylcholine/SiO(2) films were investigated through grazing-incidence small-angle X-ray scattering at a synchrotron source.