Magnetic properties of γ-Fe2O3nanoparticles in a porous SiO2shell for drug delivery.

A method is presented for synthesizing core-shell nanoparticles with a magnetic core and a porous shell suitable for drug delivery and other medical applications. The core contains multiple $\gamma$-Fe$_2$O$_3$ nanoparticles ($\sim$15~nm) enclosed in a SiO$_2$ ($\sim$100-200~nm) matrix using either methyl (denoted TMOS-$\gamma$-Fe$_2$O$_3$) or ethyl (TEOS-$\gamma$-Fe$_2$O$_3$) template groups. Low-temperature M{\"o}ssbauer spectroscopy showed that the magnetic nanoparticles have the maghemite structure, $\gamma$-Fe$_2$O$_3$, with all the vacancies in the octahedral sites. Saturation magnetization measurements revealed that the density of $\gamma$-Fe$_2$O$_3$ was greater in the TMOS-$\gamma$-Fe$_2$O$_3$ nanoparticles than TEOS-$\gamma$-Fe$_2$O$_3$ nanoparticles, presumably because of the smaller methyl group. Magnetization measurements showed that the blocking temperature is around room temperature for the TMOS-$\gamma$-Fe$_2$O$_3$ and around 250~K for the TEOS-$\gamma$-Fe$_2$O$_3$. Three dimensional topography analysis shows clearly that the magnetic nanoparticles are not only at the surface but have penetrated deep in the silica to form the core-shell structure.

Improved controlled release of protein from expanded-pore mesoporous silica nanoparticles modified with co-functionalized poly(n-isopropylacrylamide) and poly(ethylene glycol) (PNIPAM-PEG).

Novel pore-expanded mesoporous silica nanoparticles (MSNs) with pore sizes of approximately 11nm were synthesized and modified with thermoresponsive, poly(n-isopropylacrylamide) (PNIPAM) gating groups on the nanoparticle exterior surface and in addition with poly(ethylene-glycol) (PEG) within the porous interior to minimize protein adsorption. PEG traditionally has been grafted to the nanoparticle exterior to minimize non-specific binding and interactions with the biological environment, but due to the templating mechanism of MSN synthesis, both the pore interior and nanoparticle surface can be separately modified. Here, an improved control release behavior of bovine hemoglobin (BHb) was observed after PEGylating the interior porous framework, compared to the release BHb from unmodified MSNs. This can be attributed to the reduced protein denaturation on PEGylated silica that was observed using circular dichroism spectroscopy.

Response to Extreme Temperatures of Mesoporous Silica MCM-41: Porous Structure Transformation Simulation and Modification of Gas Adsorption Properties.

Molecular dynamics (MD) and Monte Carlo (MC) simulations were applied together for the first time to reveal the porous structure transformation mechanisms of mesoporous silica MCM-41 subjected to temperatures up to 2885 K. Silica was experimentally characterized to inform the models and enable prediction of changes in gas adsorption/separation properties. MD simulations suggest that the pore closure process is activated by a collective diffusion of matrix atoms into the porous region, accompanied by bond reformation at the surface. Degradation is kinetically limited, such that complete pore closure is postponed at high heating rates. We experimentally observe decreased gas adsorption with increasing temperature in mesoporous silica heated at fixed rates, due to pore closure and structural degradation consistent with simulation predictions. Applying the Kissinger equation, we find a strong correlation between the simulated pore collapse temperatures and the experimental values which implies an activation energy of 416 ± 17 kJ/mol for pore closure. MC simulations give the adsorption and selectivity for thermally treated MCM-41, for N2, Ar, Kr, and Xe at room temperature within the 1-10 000 kPa pressure range. Relative to pristine MCM-41, we observe that increased surface roughness due to decreasing pore size amplifies the difference of the absolute adsorption amount differently for different adsorbate molecules. In particular, we find that adsorption of strongly interacting molecules can be enhanced in the low-pressure region while adsorption of weakly interacting molecules is inhibited. This then results in higher selectivity in binary mixture adsorption in mesoporous silica.

Template-based syntheses for shape controlled nanostructures.

A variety of nanostructured materials are produced through template-based synthesis methods, including zero-dimensional, one-dimensional, and two-dimensional structures. These span different forms such as nanoparticles, nanowires, nanotubes, nanoflakes, and nanosheets. Many physical characteristics of these materials such as the shape and size can be finely controlled through template selection and as a result, their properties as well. Reviewed here are several examples of these nanomaterials, with emphasis specifically on the templates and synthesis routes used to produce the final nanostructures. In the first section, the templates have been discussed while in the second section, their corresponding synthesis methods have been briefly reviewed, and lastly in the third section, applications of the materials themselves are highlighted. Some examples of the templates frequently encountered are organic structure directing agents, surfactants, polymers, carbon frameworks, colloidal sol-gels, inorganic frameworks, and nanoporous membranes. Synthesis methods that adopt these templates include emulsion-based routes and template-filling approaches, such as self-assembly, electrodeposition, electroless deposition, vapor deposition, and other methods including layer-by-layer and lithography. Template-based synthesized nanomaterials are frequently encountered in select fields such as solar energy, thermoelectric materials, catalysis, biomedical applications, and magnetowetting of surfaces.

Poly(N-isopropylacrylamide)-gated Fe3O4/SiO2 core shell nanoparticles with expanded mesoporous structures for the temperature triggered release of lysozyme.

Core-shell nanoparticles comprised of Fe3O4 cores and a mesoporous silica shell with an average expanded pore size of 6.07 nm and coated with a poly(N-isopropylacrylamide) (PNIPAM) layer (CS-MSNs-EP-PNIPAM) were prepared and characterized. The nanoparticles was loaded with (Ru(bipy)3(2+)) dye or an antibacterial enzyme, lysozyme, to obtain CS-MSNs-EP-PNIPAM-Ru(bipy)3(2+) and CS-MSNs-EP-PNIPAM-Lys, respectively. The lysozyme loading was determined to be 160 mg/g of nanoparticle. It was seen that Ru(bipy)3(2+) and lysozyme release was minimal at a room temperature of 25 °C while at physiological temperature (37 °C), abrupt release was observed. The applicability of the CS-MSNs-EP-PNIPAM-Lys was further tested with two Gram-positive bacteria samples, Bacillus cereus and Micrococcus luteus. At physiological temperature, the nanoparticles were shown to reduce bacterial growth, indicating a successful release of lysozyme from the nanoparticles. This nanoparticle system shows potential as a nanocarrier for the loading of similarly sized proteins or other species as a drug delivery platform.

Modified release from lipid bilayer coated mesoporous silica nanoparticles using PEO-PPO-PEO triblock copolymers.

Triblock copolymers comprised of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, or trade name Pluronic) interact with lipid bilayers to increase their permeability. Here we demonstrate a novel application of Pluronic L61 and L64 as modification agents in tailoring the release rate of a molecular indicator species from 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayer-coated superparamagnetic Fe3O4/mesoporous silica core-shell nanoparticles. We show there is a direct relationship between the Pluronics' concentration and the indicator molecule release, suggesting Pluronics may be useful for the controlled release of drugs from lipid bilayer-coated carriers.