Surface Modification of Ti Implant for Enhancing Biotribology and Cells Attachment

Implant success strongly depends on the proper integration of bone to biomaterial surface. By the selected retrieval cases, inadequate integration of bone screws was a dominated factor caused failure. The surface modification technology that improve osteointegration by inducing TiO2 nanotubes (NT) on Ti-based implants has a potential applications in orthopaedic implants. NT generated by anodization method provide a vertically aligned nanotube structure that enhances the integration between bone tissue and implant surface by improving osteoblasts attachment. Although cells to NT is positive, the mechanical weakness of NT has also been well-documented and is an obstacle to its applications. The thesis comprise a detailed method to improve NT mechanical stability, by introducing an interfacial bonding layer at NT bottom and Ti substrate, and retaining vertically aligned nanotubes. The physicochemical properties of this structure optimized TiO2 nanotubes (SO-NT) was systematically characterized, the SO-NT has been demonstrated with improved biotribological and biocorrosive performance. The uniform hyperfine interfacial bonding layer with nano-sized grains exhibited a strong bonding to NT layer and Ti substrate. It was observed, the layer not only effectively dissipates external impacts and shear stress but also acts as a good corrosion resistance barrier to prevent the Ti substrate from corrosion. The SO-NT modified bone screw has also demonstrated with enhanced fretting corrosion resistance than NT and pristine Ti6Al4V on screws. Since the elongated osteoblasts were observed on NT and SO-NT compared with Ti surface, the nanotubes structure has been shown with promoting of osteoblasts attachment. However, the mechanism of cell nanotubes interactions are largely in controversial. In order to reveal the cell-nanomaterial interactions, nanotopographies including Nanoconvex, Nanoconcave and Nanoflat were generated and characterized to evaluate the cell initial attachment behaviour. Human osteoblasts were observed with spindle shape on Nanoconcave, cells on Nanoflat were well-spreading but in sphere shape, while the osteoblasts on Nanoconvex were with the minimum spreading areas. Cell-materials interface is mediated and influenced by the adsorption of ECM on nanomaterials. Thus, a novel fibronectin adsorption model was proposed by calculating Coulomb's force to illustrate the interact mechanism between protein and material that influence cell behaviours. The achievements of thesis are; 1. Retrieval analyzed two cases of implants failure and pointed out one of dominated failure factor, the lack of osteointegration. 2. Introduce the interfacial bonding layer that significantly improve the biotribological and biocorrosive performance of NT, and generated SO-NT. 3. Systematically evaluated the biotribological performance of Ti, NT and SO-NT, and propose a novel methodology to quantify the fretting degradation on bone screws. 4. Propose a novel model to estimate the fibronectin adsorption on Nanoflat, Nanoconvex and Nanoconcave by the Coulomb's force calculation

Unveiling the mechanism of controllable CO2 hydrogenation by group VIB metal single atom anchored on N-doped graphite: A density functional theory study

CO2 hydrogenation has raised considerable interest due to concerns about climate change. Realizing low-temperature reverse water gas shift (rWGS) reaction remains a significant challenge in the context of coupling it with the C–C growth reactions to convert CO2 to C2+ fuels. We carried out systematic DFT simulations to unveil the underlying low-temperature mechanism for the selective hydrogenation of CO2 to produce CO, over a variety of metal-based single atom catalysts (SACs) supported on the nitrogen-doped graphite. Group VIB metal-based SACs outperformed other 15 metal candidates in terms of versatile capacities in both selective activation of CO2 molecule and facilitating escaping of CO and H2O. Mo1/N3-Gt was especially outstanding by giving rise to spontaneous production of CO and O∗ through an effective electron injection into the CO2 molecule. Water formation has been identified as the potential rate-controlling step in such a catalytic reaction over Mo1/N3-Gt with an energy barrier of 1.10 eV. Herein, the H migration played a pivotal role and had tight affinity to the charge of H∗ on the active site of catalyst. The dynamic coordination environment of Moδ+ was revealed to be the dominant factor affecting the surface H∗ charge, leading to a variety of hydrogenation behaviors. The electron-deficient ligands of CO2 and O∗ on Mo1/N3-Gt, as well as additional adsorbed H2, were effective in adjusting the 4d and 5s electronic structure of central Mo and consequently resulted in nearly electric neutral surface H∗s, thus most benefiting the hydrogenation process. The optimal charge of the coordinated Mo for an outstanding selective hydrogenation performance in this scenario was found to be no less than +1.7e

End-to-End Optimization of Scene Layout

We propose an end-to-end variational generative model for scene layout synthesis conditioned on scene graphs. Unlike unconditional scene layout generation, we use scene graphs as an abstract but general representation to guide the synthesis of diverse scene layouts that satisfy relationships included in the scene graph. This gives rise to more flexible control over the synthesis process, allowing various forms of inputs such as scene layouts extracted from sentences or inferred from a single color image. Using our conditional layout synthesizer, we can generate various layouts that share the same structure of the input example. In addition to this conditional generation design, we also integrate a differentiable rendering module that enables layout refinement using only 2D projections of the scene. Given a depth and a semantics map, the differentiable rendering module enables optimizing over the synthesized layout to fit the given input in an analysis-by-synthesis fashion. Experiments suggest that our model achieves higher accuracy and diversity in conditional scene synthesis and allows exemplar-based scene generation from various input forms.Comment: CVPR 2020 (Oral). Project page: http://3dsln.csail.mit.edu

Theoretical modeling approach for adsorption of fibronectin on the nanotopographical implants

The success of orthopedic implants depends on the sufficient integration between tissue and implant, which is influenced by the cellular responses to their microenvironment. The conformation of adsorbed extracellular matrix is crucial for cellular behavior instruction via manipulating the physiochemical features of materials. To investigate the electrostatic adsorption mechanism of fibronectin on nanotopographies, a theoretical model was established to determine surface charge density and Coulomb’s force of nanotopography – fibronectin interactions using a Laplace equation satisfying the boundary conditions. Surface charge density distribution of nanotopographies with multiple random fibronectin was simulated based on random number and Monte Carlo hypothesis. The surface charge density on the nanotopographies was compared to the experimental measurements, to verify the effectiveness of the theoretical model. The model was implemented to calculate the Coulomb’s force generated by nanotopographies to compare the fibronectin adsorption. This model has revealed the multiple random quantitative fibronectin electrostatic adsorption to the nanotopographies, which is beneficial for orthopedic implant surface design. Significance: The conformation and distribution of adsorbed extracellular matrix on biomedical implants are crucial for directing cellular behaviors. However, the Ti nanotopography-ECM interaction mechanism remains largely unknown. This is mostly because of the interactions that are driven by electrostatic force, and any experimental probe could interfere with the electric field between the charged protein and Ti surface. A theoretical model is hereby proposed to simulate the adsorption between nanotopographies and fibronectin. Random number and Monte Carlo hypothesis were applied for multiple random fibronectin simulation, and the Coulomb’s force between nanoconvex and nanoconcave structures was comparatively analyzed