Xujie Liu

Intrinsic and extrinsic origins of room temperature ferromagnetism in Ni-doped ZnO films

The structural, electrical and magnetic properties of Ni-doped ZnO films with different Ni concentrations (x = 0–0.11, x: Ni concentration) and thicknesses (d = 15–330 nm, d: film thickness) prepared by radio-frequency magnetron sputtering have been systematically investigated. The structural characterizations indicate that Ni ions in the 2+ valence state, uniformly distributed in the film, almost substitute for the Zn ions when x ≤ 0.07, whereas when x increases up to 0.11, a second phase Ni is formed. Room temperature (RT) ferromagnetism (FM) has been observed for all the Ni-doped ZnO wurtzite films. The saturated magnetization varies drastically with the Ni concentration and the film thickness. A large magnetic moment of 2.80 μB/Ni is obtained in the 15 nm thick Zn0.96Ni0.04O film at RT. The results show that the FM observed is intrinsic for Ni-doped ZnO films and can be explained in terms of the bound magnetic polaron mechanism based on the presence of defects. In addition, the Ni precipitates owing to the excessive doping of Ni in ZnO, as an extrinsic origin, also contribute to the ferromagnetic properties in highly doped samples.

Strain-induced ferromagnetism enhancement in Co:ZnO films

The structural and ferromagnetic properties of Zn0.95Co0.05O films grown on Si and LiNbO3 (LNO) substrates have been studied as a function of thickness (15–900 nm). The structural characterizations indicate that the c-axis lattice constant and Co–O bond length slightly decrease with the increase in film thickness, implying the progressive relaxation of the tensile strain. The magnetic measurements show that a larger strain can result in an enhancement of room temperature ferromagnetism. The thinnest films (15 nm) with the largest lattice strains possess the highest saturated magnetic moments, i.e., 5.52 and 2.96μB/Co in Co:ZnO/LNO and Co:ZnO/Si films, respectively. As the film becomes thicker, the saturated ferromagnetism rapidly decreases, which is about two orders of magnitude smaller than that of the 15-nm-thick film when its thickness is 900 nm. The enhancement of ferromagnetism in Co:ZnO films originates from the combination of enlarged Co–O bond length and increased defect amount induced by strain.

Insight into the high reactivity of commercial Fe–Si–B amorphous zero-valent iron in degrading azo dye solutions

Improving intrinsic reactivity is one of the key requirements in applying zero-valent iron in the field. As a new kind of zero-valent iron, iron based amorphous alloys were recently found to be capable of rapidly remediating wastewater. However, the mechanisms for the rapid degradation have not yet been fully understood. In this study, commercial Fe–Si–B amorphous alloy ribbons (Fe–Si–BAR) were used to degrade azo dyes (Direct Blue 6 and Orange II) to study the reaction kinetics, pathway and mechanism behind the high reactivity of these iron based amorphous alloys. The results show that, under the same conditions, the surface normalized reaction rate constants for the decomposition of Orange II and Direct Blue 6 by Fe–Si–BAR could be 1300 and 60 times larger respectively than those obtained by using 300 mesh iron powders. Through UV-vis spectrophotometry and mass spectrometry, it is found that the intermediate products of the azo dyes degraded by Fe–Si–BAR are similar to those produced in degradation by iron powders. However, the controlling step of the degradation reaction by Fe–Si–BAR turns out to be the diffusion process rather than the surface chemical reaction found in the reaction by iron powders. Further analysis indicates that the high degradation efficiency of Fe–Si–BAR results from its amorphous structure and the metalloid additions, which could enhance the catalytic effect and promote the formation of a non-compact and easily detached oxide layer on the surface. The experiments under different environmental conditions show that the factors that influence the degradation efficiency of crystalline iron powders affect that of Fe–Si–BAR in a similar way, but Fe–Si–BAR is capable of efficiently degrading wastewater under broader conditions than the crystalline iron powders. The results indicate that Fe–Si–BAR is a promising environmental catalyst for wastewater treatment.

Surface Modification by Allylamine Plasma Polymerization Promotes Osteogenic Differentiation of Human Adipose-Derived Stem Cells

Tuning the material properties in order to control the cellular behavior is an important issue in tissue engineering. It is now well-established that the surface chemistry can affect cell adhesion, proliferation, and differentiation. In this study, plasma polymerization, which is an appealing method for surface modification, was employed to generate surfaces with different chemical compositions. Allylamine (AAm), acrylic acid (AAc), 1,7-octadiene (OD), and ethanol (ET) were used as precursors for plasma polymerization in order to generate thin films rich in amine (-NH2), carboxyl (-COOH), methyl (-CH3), and hydroxyl (-OH) functional groups, respectively. The surface chemistry was characterized by X-ray photoelectron spectroscopy (XPS), the wettability was determined by measuring the water contact angles (WCA) and the surface topography was imaged by atomic force microscopy (AFM). The effects of surface chemical compositions on the behavior of human adipose-derive stem cells (hASCs) were evaluated in vitro: Cell Count Kit-8 (CCK-8) analysis for cell proliferation, F-actin staining for cell morphology, alkaline phosphatase (ALP) activity analysis, and Alizarin Red S staining for osteogenic differentiation. The results show that AAm-based plasma-polymerized coatings can promote the attachment, spreading, and, in turn, proliferation of hASCs, as well as promote the osteogenic differentiation of hASCs, suggesting that plasma polymerization is an appealing method for the surface modification of scaffolds used in bone tissue engineering.

Effects of hierarchical micro/nano-topographies on the morphology, proliferation and differentiation of osteoblast-like cells

Coating the surfaces of titanium-based implants with appropriate hierarchical micro/nano-topographies resembling the structure of natural bone significantly enhances their biological performance. However, the relationship between nanostructures surfaces and their effects on modulating cellular response is not clearly understood. Moreover, it is not clear whether the surface chemistry or topography is the main factor on modulating cellular behavior, because the commonly used surface modification techniques for titanium-based implants simultaneously modify surface topography and chemistry. The aim of this study is to investigate osteoblast-like cell adhesion, proliferation and differentiation on hierarchical micro/nano-topographies with similar surface chemistry but different nano-scale features. Micro-arc oxidation and post hydrothermal treatment were employed to fabricate micro/nano-topographies on titanium. According to the morphological features, they were classified as microcrater (micro-topography), nanoplate (hierarchical topography with nanoplates) and nanoleaf (hierarchical topography with nanoleaves). The response of osteoblast like cells (SaOS-2) was studied on each surface after sputtering with a thin layer of gold (Au) to minimize the influence of surface chemistry. The morphological evaluation after histochemical staining revealed that the adherent cells were polygonal-shaped on microcrater surface, roundish on nanoplate surface and elongated on nanoleaf surface. Additionally, compared to microcrater surface, nanoplate surface slowed down cell proliferation and exhibited no enhancement on cell differentiation. However, nanoleaf surface supported cell proliferation and promoted cell differentiation. The results indicate that tuning morphological features of nanostructures on micro-topography can serve as a promising strategy to specifically modulate cellular response, such as cell morphology, proliferation, differentiation and mineralization.

Surface Chemical Gradient Affects the Differentiation of Human Adipose-Derived Stem Cells via ERK1/2 Signaling Pathway

To understand the role of surface chemistry on cell behavior and the associated molecular mechanisms, we developed and utilized a surface chemical gradient of amine functional groups by carefully adjusting the gas composition of 1,7-octadiene (OD) and allylamine (AA) of the plasma phase above a moving substrate. The chemical gradient surface used in the present work shows an increasing N/C ratio and wettability from the OD side toward the AA side with no change in surface topography. Under standard culture conditions (with serum), human adipose-derived stem cells (hASCs) adhesion and spreading area increased toward the AA side of the gradient. However, there were no differences in cell behavior in the absence of serum. These results, supported by the trends in proteins adsorption on the gradient surface, demonstrated that surface chemistry affects the response of hASCs through cell-adhesive serum proteins, rather than interacting directly with the cells. The expression of p-ERK and the osteogenic differentiation increased toward the AA side of the gradient, while adipogenic differentiation decreased in the same direction; however, when the activation of ERK1/2 was blocked by PD98059, the levels of osteogenic or adipogenic differentiation on different regions of the chemical gradient were the same. This indicates that ERK1/2 may be an important downstream signaling pathway of surface chemistry directed stem cell fate.

A novel titania/calcium silicate hydrate hierarchical coating on titanium.

Recently, surface micron/nano-topographical modifications have attracted a great deal of attention because it is capable of mimicking the hierarchical characteristics of bone. In the current work, a novel titania/calcium silicate hydrate (CSH) bi-layer coating with hierarchical surface topography was successfully prepared on titanium substrate through micro-arc oxidation (MAO) and subsequent hydrothermal treatment (HT). MAO treatment could lead to a micron-scale topographical surface with numerous crater-like protuberances. The subsequent HT process enables the in situ nucleation and growth of CSH nanoplates on MAO-fabricated titania surface. The nucleation of CSH nanoplates is considered to follow a dissolution-precipitation mechanism. Compared to MAO-fabricated coating with single-scale surface topography, MAO-HT-fabricated coating with hierarchical surface topography exhibits enhanced hydrophilicity, fibronectin adsorption and initial MG-63 cell attachment. The process of cell-material interactions is considered to be triggered by surface properties of the coated layer and indirectly mediated by protein adsorption on coating surface. These results suggest that MAO-HT treatment is an efficient way to prepare coatings with hierarchical surface topography on titanium surface, which is essential for altering protein adsorption and initial cell attachment.

Specific heat treatment of selective laser melted Ti–6Al–4V for biomedical applications

The ductility of as-fabricated Ti–6Al–4V falls far short of the requirements for biomedical titanium alloy implants and the heat treatment remains the only applicable option for improvement of their mechanical properties. In the present study, the decomposition of as-fabricated martensite was investigated to provide a general understanding on the kinetics of its phase transformation. The decomposition of asfabricated martensite was found to be slower than that of water-quenched martensite. It indicates that specific heat treatment strategy is needed to be explored for as-fabricated Ti–6Al–4V. Three strategies of heat treatment were proposed based on different phase transformation mechanisms and classified as subtransus treatment, supersolvus treatment and mixed treatment. These specific heat treatments were conducted on selective laser melted samples to investigate the evolutions of microstructure and mechanical properties. The subtransus treatment leaded to a basket-weave structure without changing the morphology of columnar prior β grains. The supersolvus treatment resulted in a lamellar structure and equiaxed β grains. The mixed treatment yielded a microstructure that combines both features of the subtransus treatment and supersolvus treatment. The subtransus treatment is found to be the best choice among these three strategies for as-fabricated Ti–6Al–4V to be used as biomedical implants.

Preparation and characterization of TiO2/silicate hierarchical coating on titanium surface for biomedical applications.

In the current work, TiO2/silicate hierarchical coatings with various nanostructure morphologies were successfully prepared on titanium substrates through micro-arc oxidation (MAO) and subsequent hydrothermal treatment (HT). Moreover, the nucleation mechanism and growth behavior of the nanostructures, hydrophilicity, protein adsorption and apatite-inducing ability of various coatings were also explored. The novel TiO2/silicate hierarchical coatings comprised calcium silicate hydrate (CSH) as an outer-layer and TiO2 matrix as an inner-layer. According to the morphological features, the nanostructures were classified as nanorod, nanoplate and nanoleaf. The morphology, degree of crystallinity and crystalline phases of CSH nanostructures could be controlled by optimizing the HT conditions. The nucleation of CSH nanostructures is caused by release and re-precipitation mechanism. The TiO2/CSH hierarchical coatings exhibited some enhanced physical and biological performances compared to MAO-fabricated coating. The improvement of the hydrophilicity, fibronectin adsorption and apatite-inducing ability was found to be morphological dependent according to the following trend: nanoleaf coating>nanoplate coating>nanorod coating>MAO coating. The results indicate that the tuning of physical and morphological properties of nanostructures coated on biomaterial surface could significantly influence the hydrophilicity, protein adsorption and in vitro bioactivity of biomaterial.

The stimulatory effect of silica nanoparticles on osteogenic differentiation of human mesenchymal stem cells

Silica-based materials with favourable biocompatibility are generally considered as excellent candidates for applications in biomedical fields. However, previous researches mainly focused on the safety of silica-based materials, their effects on osteogenic differentiation of human mesenchymal stem cells (hMSCs) still need further investigations. In this study, core-shell fluorescent silica nanoparticles (silica NPs) with three different sizes (S1 ~ 50 nm, S2 ~ 200 nm, S3 ~ 400 nm, respectively) were prepared according to the Stöber method. The silica NPs with different sizes did not affect the cell viability (even up to a concentration of 500 µg ml-1), showing size- and dose-independent cytocompatibility of silica NPs on hMSCs. Uptake of silica NPs significantly enhanced the activity of alkaline phosphatase (ALP) and the formation of bone-like nodules of hMSCs after osteogenic induction. At the concentration of 10 µg ml-1, after treating hMSCs with larger sized silica NPs (S2 and S3), higher ALP activity of hMSCs was measured and larger sized bone-like nodules were formed by hMSCs compared with that treated with smaller sized silica NPs (S1).The enhanced osteogenic potential of hMSCs treated with silica NPs may be attributed to the Si released from silica NPs due to the lysosomal degradation inside hMSCs. These results demonstrate the stimulatory effect of silica NPs on osteogenic differentiation of hMSCs and the application potential of silica NPs in bone tissue engineering.