Surface Complexation Model for Strontium Sorption to Amorphous Silica and Goethite

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25 C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr{sup 2+} and SrOH{sup +} complexes on the {beta}-plane and a monodentate Sr{sup 2+} complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH{sup +} complexes and a tetradentate binuclear Sr{sup 2+} species on the {beta}-plane. The binuclear complex is needed to account for enhanced sorption at high strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr{sup 2+} and SrOH{sup +} carbonate surface complexes on the {beta}-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate concentrations for the development of a robust surface complexation database to estimate alkaline earth sorption in the environment

Triphasic scaffolds for the regeneration of the bone-ligament interface

A triphasic scaffold (TPS) for the regeneration of the bone-ligament interface was fabricated combining a 3D fiber deposited polycaprolactone structure and a polylactic co-glycolic acid electrospun. The scaffold presented a gradient of physical and mechanical properties which elicited different biological responses from human mesenchymal stem cells. Biological test were performed on the whole TPS and on scaffolds comprised of each single part of the TPS, considered as the controls. The TPS showed an increase of the metabolic activity with culturing time that seemed to be an average of the controls at each time point. The importance of differentiation media for bone and ligament regeneration was further investigated. Metabolic activity analysis on the different areas of the TPS showed a similar trend after 7 days in both differentiation media. Total alkaline phosphatase (ALP) activity analysis showed a statistically higher activity of the TPS in mineralization medium compared to the controls. A different glycosaminoglycans amount between the TPS and its controls was detected, displaying a similar trend with respect to ALP activity. Results clearly indicated that the integration of electrospinning and additive manufacturing represents a promising approach for the fabrication of scaffolds for the regeneration of tissue interfaces, such as the bone-to-ligament one, because it allows mimicking the structural environment combining different biomaterials at different scales

Solution-based nanoengineering of materials.

Solution-based synthesis is a powerful approach for creating nano-structured materials. Although there have been significant recent successes in its application to fabricating nanomaterials, the general principles that control solution synthesis are not well understood. The purpose of this LDRD project was to develop the scientific principles required to design and build unique nanostructures in crystalline oxides and II/VI semiconductors using solution-based molecular self-assembly techniques. The ability to synthesize these materials in a range of different nano-architectures (from controlled morphology nanocrystals to surface templated 3-D structures) has provided the foundation for new opportunities in such areas as interactive interfaces for optics, electronics, and sensors. The homogeneous precipitation of ZnO in aqueous solution was used primarily as the model system for the project. We developed a low temperature, aqueous solution synthesis route for preparation of large arrays of oriented ZnO nanostructures. Through control of heterogeneous nucleation and growth, methods to predicatively alter the ZnO microstructures by tailoring the surface chemistry of the crystals were established. Molecular mechanics simulations, involving single point energy calculations and full geometry optimizations, were developed to assist in selecting appropriate chemical systems and understanding physical adsorption and ultimately growth mechanisms in the design of oxide nanoarrays. The versatility of peptide chemistry in controlling the formation of cadmium sulfide nanoparticles and zinc oxide/cadmium sulfide heterostructures was also demonstrated

Surface Structure and Stability of Partially Hydroxylated Silica Surfaces

Surface energies of silicates influence crack propagation during brittle fracture and decrease with surface relaxation caused by annealing and hydroxylation. Molecular-level simulations are particularly suited for the investigation of surface processes. In this work, classical MD simulations of silica surfaces are performed with two force fields (ClayFF and ReaxFF) to investigate the effect of force field reactivity on surface structure and energy as a function of surface hydroxylation. An unhydroxylated fracture surface energy of 5.1 J/m² is calculated with the ClayFF force field, and 2.0 J/m² is calculated for the ReaxFF force field. The ClayFF surface energies are consistent with the experimental results from double cantilever beam fracture tests (4.5 J/m²), whereas ReaxFF underestimated these surface energies. Surface relaxation via annealing and hydroxylation was performed by creating a low-energy equilibrium surface. Annealing condensed neighboring siloxane bonds increased the surface connectivity, and decreased the surface energies by 0.2 J/m² for ClayFF and 0.8 J/m² for ReaxFF. Posthydroxylation surface energies decreased further to 4.6 J/m² with the ClayFF force field and to 0.2 J/m² with the ReaxFF force field. Experimental equilibrium surface energies are ∼0.35 J/m², consistent with the ReaxFF force field. Although neither force field was capable of replicating both the fracture and equilibrium surface energies reported from experiment, each was consistent with one of these conditions. Therefore, future computational investigations that rely on accurate surface energy values should consider the surface state of the system and select the appropriate force field

Impact of Cone Beam Computed Tomography in Advanced Endovascular Aortic Aneurysm Repair Using Last Generation 3D C-arm

Background: To report the early outcomes of cone beam computed tomography (CBCT) using last generation 3D C-arm in patients undergone advanced endovascular aortic aneurysm repair (AdEVAR) and to identify risk factors that may predict any un-planned procedures. Methods: Patients undergone AdEVAR between December 2017 and December 2018 were enrolled. Final CBCT was performed in all patients after digital subtraction angiography. Primary end points were the incidence of any positive findings and the following unplanned procedures intended as any endovascular manoeuvre performed to fix such technical defect. The secondary endpoints were comparison of outcomes between patients with positive findings undergone unplanned procedure (Group A) versus patients without findings (Group B). Results: 132 patients underwent endovascular treatment for aortic aneurysm. Of these, 22 (33%) fenestrated-branched endovascular aneurysm repairs (F-BEVAR), 21 (29%) EVAR with iliac branch devices, 19 (26%) abdominal and 10 (14%) thoracic EVAR were included in the study. Unplanned procedures after CBCT were necessary in 22 patients (31%). Patients in both groups were similar excepted for BMI >25 kg/m2 (55% vs. 26%), hostile iliac anatomy (64% vs. 32%) and previous aortic treatment (73% vs. 32%) (P < 0.05). The odds ratios for unplanned procedure in case of previous aortic treatment was 6.76 (95% CI, 1.97–23.16; P = 0.002). Conclusion: The use of CBCT, especially in challenging scenarios, can reveal technical defects and may potentially limit the need for late reintervention. Patients undergone previous aortic surgery should be carefully evaluated and routine CBCT should be performed