RESUMEN
HYPOTHESIS: Although many synthetic pathways allow to fine-tune the morphology of dendritic mesoporous silica nanoparticles (DMSNs), the control of their particle size and mesopore diameter remains a challenge. Our study focuses on either increasing the mean particle size or adjusting the pore size distribution, changing only one parameter (particle or pore size) at a time. The dependence of key morphological features (porosity; pore shape and pore dimensions) on radial distance from the particle center has been investigated in detail. EXPERIMENTS: Three-dimensional reconstructions of the particles obtained by scanning transmission electron microscopy (STEM) tomography were adapted as geometrical models for the quantification of intraparticle morphologies by radial porosity and chord length distribution analyses. Structural properties of the different synthesized DMSNs have been complementary characterized using TEM, SEM, nitrogen physisorption, and dynamic light scattering. FINDINGS: The successful independent tuning of particle and pore sizes of the DMSNs could be confirmed by conventional analysis methods. Unique morphological features, which influence the uptake and release of guest molecules in biomedical applications, were uncovered from analyzing the STEM tomography-based reconstructions. It includes the quantification of structural hierarchy, identification of intrawall openings and pores, as well as the distinction of pore shapes (conical vs. cylindrical).
RESUMEN
Quantitative morphology-transport relationships are derived for ordered mesoporous silicas through direct numerical simulation of hindered diffusion in realistic geometrical models of the pore space obtained from physical reconstruction by electron tomography. We monitor accessible porosity and effective diffusion coefficients resulting from steric and hydrodynamic interactions between passive tracers and the pore space confinement as a function of λ = dtracer/dmeso (ratio of tracer diameter to mean mesopore diameter) in SBA-15 (dmeso = 9.1 nm) and KIT-6 (dmeso = 10.5 nm) silica samples. For λ = 0, the pointlike tracers reproduce the true diffusive tortuosities. For 0 ≤λ < 0.5, the derived hindrance factor quantifies the extent to which diffusion of finite-size tracers through the materials is hindered compared with free diffusion in the bulk liquid. The hindrance factor connects the transport properties of the ordered silicas to their mesopore space morphologies and enables quantitative comparison with random mesoporous silicas. Key feature of the ordered silicas is a narrow, symmetric mesopore size distribution (â¼10% relative standard deviation), which engenders a sharper decline of the accessible-porosity window with increasing λ than observed for random silicas with their wide, asymmetric mesopore size distributions. As support structures, ordered mesoporous silicas should offer benefits for applications where spatial confinement effects and molecular size-selectivity are of prime importance. On the other hand, random mesoporous silicas enable higher diffusivities for λ > 0.3, because the larger pores carry most of the diffusive flux and keep pathways open when smaller pores have closed off.
RESUMEN
We present relationships between the multiscale structure and the separation properties of size exclusion chromatography (SEC) columns. Physical bed reconstructions of wall and bulk regions from a 2.1â¯mm i.d. column packed with fully porous 1.7⯵m bridged-ethyl hybrid (BEH) particles, obtained by focused ion-beam scanning electron microscopy, serve as geometrical models for the packing microstructure in wall and central regions of a typical narrow-bore SEC column. In addition, the intraparticle mesopore space morphology of the BEH particles is reconstructed using electron tomography, to ultimately construct a realistic multiscale model of the bed morphology from mesopore level via interparticle macropore space to transcolumn scale. Complemented by the results of eddy dispersion simulations in computer-generated bulk packings, relationships between packing microstructure and transchannel, short-range interchannel, as well as transcolumn eddy dispersion are used to analyze the fluid dynamics in the interparticle macropore space of the model. Further, we simulate hindered diffusion and accessible porosity for passive, finite-size tracers in the intraparticle mesopore space, to finally determine the effective particle and bed diffusion coefficients of these tracers in the hierarchical (macro-mesoporous) bed. Retention and transport properties of polystyrene standards with hydrodynamic diameters from 5 to 95 Å in tetrahydrofuran are subsequently predicted without introducing bias from arbitrary models. These properties include the elution volumes of the polystyrene standards, the global peak capacity (over the entire separation window), and the rate of peak capacity at any fixed elution volume. Optimal flow rates yielding maximal global peak capacity and a nearly uniform rate of peak capacity over the entire separation window are close to 0.04 and 0.20â¯mL/min, respectively. SEC column performance obtained for fully porous and superficially porous particles is compared by varying the core-to-particle diameter ratio ρ from 0 to 0.95. Because the separation window is narrowing more rapidly than the rate of peak capacity is growing with increasing ρ, core-shell particles always provide smaller global peak capacity; they still can be advantageous but only for simple sample mixtures. The presented morphology-performance approach holds great promise for method development in SEC.