Atomistic Origins of Various Luminescent Centers and n-Type Conductivity in GaN: Exploring the Point Defects Induced by Cr, Mn, and O through an Ab Initio Thermodynamic Approach.

GaN is a technologically indispensable material for various optoelectronic properties, mainly due to the dopant-induced or native atomic-scale point defects that can create single photon emitters, a range of luminescence bands, and n- or p-type conductivities. Among the various dopants, chromium and manganese-induced defects have been of particular interest over the past few years, because some of them contribute to our present-day light-emitting diode (LED) and spintronic technologies. However, the nature of such atomistic centers in Cr and Mn-doped GaN is yet to be understood. A comprehensive defect thermodynamic analysis of Cr- and Mn-induced defects is essential for their engineering in GaN crystals because by mapping out the defect stabilities as a function of crystal growth parameters, we can maximize the concentration of the target point defects. We therefore investigate chromium and manganese-induced defects in GaN with ab initio methods using the highly accurate exchange-correlation hybrid functionals, and the phase transformations upon excess incorporation of these dopants using the CALPHAD method. We also investigate the impact of oxygen codoping that can be unintentionally incorporated during crystal growth. Our analysis sheds light on the atomistic cause of the unintentional n-type conductivity in GaN, being ON-related. In the case of Cr doping, the formation of CrGa defects is the most dominant, with an E +/0 charge transition at E VBM + 2.19 eV. Increasing nitrogen partial pressure tends to enhance the concentration of CrGa. However, in the case of doping with Mn, several different Mn-related centers can form depending on the growth conditions, with MnGa being the most dominant. MnGa possesses the E 2+/+, E +/0, and E 0/- charge transitions at 0.56, 1.04, and 2.10 eV above the VBM. The incorporation of oxygen tends to cause the formation of the MnGa-VGa center, which explains a series of prior experimental observations in Mn-doped GaN. We provide a powerful tool for point defect engineering in wide band gap binary semiconductors that can be readily used to design optimal crystal growth protocols.

Surface analysis of (Ti,Mg)N coated bone fixation devices following the rabbit femur surgery.

BACKGROUND: Magnesium (Mg) enhances the bone regeneration, mineralization and attachment at the tissue/biomaterial interface. OBJECTIVE: In this study, the effect of Mg on mineralization/osseointegration was determined using (Ti,Mg)N thin film coated Ti6Al4V based plates and screws in vivo. METHODS: TiN and (Ti,Mg)N coated Ti6Al4V plates and screws were prepared using arc-PVD technique and used to fix rabbit femur fractures for 6 weeks. Then, mineralization/osseointegration was assessed by surface analysis including cell attachment, mineralization, and hydroxyapatite deposition on concave and convex sides of the plates along with the attachment between the screw and the bone. RESULTS: According to Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) analyses; cell attachment and mineralization were higher on the concave sides of the plates from both groups in comparison to the convex sides. However, mineralization was significantly higher on Mg-containing ones. The mean gray value indicating mineralized area after von Kossa staining was found as 0.48 ± 0.01 and 0.41 ± 0.04 on Mg containing and free ones respectively. Similarly, Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD) analyses showed that hydroxyapatite growth was abundant on the Mg-containing and concave sides of the plates. Enhanced mineralization and strong attachment to bone were also detected in EDS and SEM analyses of Mg-containing screws. CONCLUSION: These findings indicated that (Ti,Mg)N coatings can be used to increase attachment at the implant tissue interface due to accelerated mineralization, cell attachment, and hydroxyapatite growth.

Biocompatibility and Mechanical Stability of Nanopatterned Titanium Films on Stainless Steel Vascular Stents.

Nanoporous ceramic coatings such as titania are promoted to produce drug-free cardiovascular stents with a low risk of in-stent restenosis (ISR) because of their selectivity towards vascular cell proliferation. The brittle coatings applied on stents are prone to cracking because they are subjected to plastic deformation during implantation. This study aims to overcome this problem by using a unique process without refraining from biocompatibility. Accordingly, a titanium film with 1 µm thickness was deposited on 316 LVM stainless-steel sheets using magnetron sputtering. Then, the samples were anodized to produce nanoporous oxide. The nanoporous oxide was removed by ultrasonication, leaving an approximately 500 nm metallic titanium layer with a nanopatterned surface. XPS studies revealed the presence of a 5 nm-thick TiO2 surface layer with a trace amount of fluorinated titanium on nanopatterned surfaces. Oxygen plasma treatment of the nanopatterned surface produced an additional 5 nm-thick fluoride-free oxide layer. The samples did not exhibit any cracking or spallation during plastic deformation. Cell viability studies showed that nanopatterned surfaces stimulate endothelial cell proliferation while reducing the proliferation of smooth muscle cells. Plasma treatment further accelerated the proliferation of endothelial cells. Activation of blood platelets did not occur on oxygen plasma-treated, fluoride-free nanopatterned surfaces. The presented surface treatment method can also be applied to other stent materials such as CoCr, nitinol, and orthopedic implants.

Effect of Ta2O5 content on the osseointegration and cytotoxicity behaviors in hydroxyapatite-Ta2O5 coatings applied by EPD on superelastic NiTi alloys.

In the present study, the different contents of tantalum pentoxide (Ta2O5: 10, 15, 20 and 30 wt%) nanoparticles were introduced into the natural hydroxyapatite (nHA) coating structure on NiTi substrate through electrophoretic deposition (EPD) method. The phase compositions of coatings were perused before and after the sintering at 800 °C for 1 h by XRD. The incorporation of 30wt%Ta2O5 into nHA matrix induced the formation of undesirable soluble Ca3(PO4)2 phase in composite coating. The FESEM images showed that the density of continuous nHA coating increased by compositing with Ta2O5. The maximum adhesion strength of 28.3 ±â€¯0.7 MPa accomplished from the nHA-20 wt%Ta2O5 composite coating. The Ni ions concentration measurement results from the passivated-NiTi with nHA and nHA-(10, 15 and 20)wt%Ta2O5 coatings during 30 days of immersion in PBS clarified the positive role of Ta2O5 in decreasing the Ni leaching due to the lowering the open porosities of nHA structure. The biological response of the coating surfaces was assessed in vitro by cell culturing and MTS assay. By considering the morphology and density of adsorbed cells on each coating, the improved biocompatibility of nHA coating in the presence of Ta2O5 was justified by scrutinizing the surface roughness, wettability and charge. The highest cell attachment and proliferation on nHA-20 wt%Ta2O5 coating was related to owning the lowest roughness, wetting angle of 34o ±â€¯0.5 and the highest negative surface charge density. Also, the concentration of the highest negative charge density on nHA-20 wt%Ta2O5 coating surface in the SBF solution caused to the enhancement of the amount of the apatite nuclei through providing more sites to calcium absorption.

Self-assembling antimicrobial peptides on nanotubular titanium surfaces coated with calcium phosphate for local therapy.

Bacterial infection is a serious medical problem leading to implant failure. The current antibiotic based therapies rise concerns due to bacterial resistance. The family of antimicrobial peptides (AMP) is one of the promising candidates as local therapy agents due to their broad-spectrum activity. Despite AMPs receive increasing attention to treat infection, their effective delivery to the implantation site has been limited. Here, we developed an engineered dual functional peptide which delivers AMP as a biomolecular therapeutic agent onto calcium phosphate (Ca-P) deposited nanotubular titanium surfaces. Dual functionality of the peptide was achieved by combining a hydroxyapatite binding peptide-1 (HABP1) with an AMP using a flexible linker. HABP functionality of the peptide provided a self-coating property onto the nano-topographies that are designed to improve osteointegration capability, while AMP offered an antimicrobial protection onto the implant surface. We successfully deposited calcium phosphate minerals on nanotubular titanium oxide surface using pulse electrochemical deposition (PECD) and characterized the minerals by XRD, FT-IR, FE-SEM. Antimicrobial activity of the engineered peptide was tested against S. mutans (gram- positive) and E. coli (gram-negative) both in solution and on the Ca-P coated nanotubular titanium surface. In solution activity of AMP and dual functional peptide have the same Minimum Inhibitory Concentration (MIC) (32 mg/mL). The peptide also resulted in the reduction of the number of bacteria both for E.coli and S. mutans compare to control groups on the surface. Antimicrobial features of dual functional peptides are strongly correlated with their structures suggesting tunability in design through linkers regions. The dual-function peptide offers single-step solution for implant surface functionalization that could be applicable to any implant surface having different topographies.

Magnesium doping on TiN coatings affects mesenchymal stem cell differentiation and proliferation positively in a dose-dependent manner.

BACKGROUND: In vitro evaluation of cell-surface interactions for hard tissue implants have mostly been done using osteoblasts. However, when an implant is placed in the body, mesenchymal stem cells (MSCs) play a major role in new bone formation. Therefore, using MSCs in cell-surface investigations may provide more reliable information on the prediction of in vivo behavior of implants. OBJECTIVE: In this study, Mg doped TiN coatings ((Ti,Mg)N) were prepared and tested for their effect on MSC differentiation and mineralization. METHODS: MSCs were isolated from rat bone marrow (rBMSCs) and seeded onto bare Ti, TiN and Mg containing (Ti,Mg)N surfaces. Cell proliferation, osteogenic differentiation (collagen type 1, alkaline phosphatase activity), calcium phosphate deposition (von Kossa staining, Scanning Electron Microscopy) analysis were conducted. RESULTS: Differentiation towards osteoblast lineage was significantly improved with the increment in Mg presence. Collagen type I deposition, mineralization, and the ALP activity were higher on high Mg containing (>10 at% Mg) surfaces but differentiation of rBMSCs were found to be delayed. CONCLUSIONS: Mg presence affected rBMSCs proliferation and differentiation positively in a dose-dependent manner. However, high Mg amounts delayed both proliferation and differentiation.

Photocatalytical Antibacterial Activity of Mixed-Phase TiO2 Nanocomposite Thin Films against Aggregatibacter actinomycetemcomitans.

Mixed-phase TiO2 nanocomposite thin films consisting of anatase and rutile prepared on commercially pure Ti sheets via the electrochemical anodization and annealing treatments were investigated in terms of their photocatalytic activity for antibacterial use around dental implants. The resulting films were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). The topology was assessed by White Light Optical Profiling (WLOP) in the Vertical Scanning Interferometer (VSI) mode. Representative height descriptive parameters of roughness R a and R z were calculated. The photocatalytic activity of the resulting TiO2 films was evaluated by the photodegradation of Rhodamine B (RhB) dye solution. The antibacterial ability of the photocatalyst was examined by Aggregatibacter actinomycetemcomitans suspensions in a colony-forming assay. XRD showed that anatase/rutile mixed-phase TiO2 thin films were predominantly in anatase and rutile that were 54.6 wt% and 41.9 wt%, respectively. Craters (2-5 µm) and protruding hills (10-50 µm) on Ti substrates were produced after electrochemical anodization with higher R a and R z surface roughness values. Anatase/rutile mixed-phase TiO2 thin films showed 26% photocatalytic decolorization toward RhB dye solution. The number of colonizing bacteria on anatase/rutile mixed-phase TiO2 thin films was decreased significantly in vitro. The photocatalyst was effective against A. actinomycetemcomitans colonization.

Behavior of mammalian cells on magnesium substituted bare and hydroxyapatite deposited (Ti,Mg)N coatings.

TiN and (Ti,Mg)N thin film coatings were deposited on titanium substrates by using cathodic arc physical vapor deposition (arc-PVD) technique with magnesium contents of 0, 4.24 at% (low Mg) and 10.42 at% (high Mg). The presence of magnesium on both normal (hFOB) and cancer (SaOS-2) osteoblast cell behavior was investigated in (Ti,Mg)N surfaces with or without prior hydroxyapatite (HA) deposition (in simulated body fluid, SBF). Mg incorporation on TiN films was found to have no apparent effect on the cell proliferation in bare surfaces but cell spreading was better on low Mg content surface for hFOB cells. SaOS-2 cells, on the other hand, showed an increased extra cellular matrix (ECM) deposition on low Mg surfaces but ECM deposition almost disappeared when Mg content was increased above 10 at%. HA deposited surfaces with high Mg content was shown to cause a significant decrease in cell viability. While the cells were flattened, elongated and spread over the surface in contact with each other via cellular extensions on unmodified and low Mg doped surfaces, unhealthy morphologies of cells with round shape with a limited number of extended arms was visualized on high Mg containing samples. In summary, Mg incorporation into the TiN coatings by arc-PVD technique and successive HA deposition led to promising cell responses on low Mg content surfaces for a better osteointegration performance.

Antibacterial Activity of As-Annealed TiO2 Nanotubes Doped with Ag Nanoparticles against Periodontal Pathogens.

It is important to develop functional transmucosal implant surfaces that reduce the number of initially adhering bacteria and they need to be modified to improve the anti-bacterial performance. Commercially pure Ti sheets were anodized in an electrolyte containing ethylene glycol, distilled water and ammonium fluoride at room temperature to produce TiO2 nanotubes. These structures were then annealed at 450°C to transform them to anatase. As-annealed TiO2 nanotubes were then treated in an electrolyte containing 80.7 g/L NiSO4 ·7H2O, 41 g/L MgSO4 ·7H2O, 45 g/L H3BO3, and 1.44 g/L Ag2SO4 at 20°C by the application of 9 V AC voltage for doping them with silver. As-annealed TiO2 nanotubes and as-annealed Ag doped TiO2 nanotubes were evaluated by SEM, FESEM, and XRD. Antibacterial activity was assessed by determining the adherence of A. actinomycetemcomitans, T. forsythia, and C. rectus to the surface of the nanotubes. Bacterial morphology was examined using an SEM. As-annealed Ag doped TiO2 nanotubes revealed intense peak of Ag. Bacterial death against the as-annealed Ag doped TiO2 nanotubes were detected against A. actinomycetemcomitans, T. forsythia, and C. rectus indicating antibacterial efficacy.

Magnesium substituted hydroxyapatite formation on (Ti,Mg)N coatings produced by cathodic arc PVD technique.

In this study, formation of magnesium substituted hydroxyapatite (Ca10-xMgx(PO4)6(OH)2) on (Ti,Mg)N and TiN coating surfaces were investigated. The (Ti1-x,Mgx)N (x=0.064) coatings were deposited on titanium substrates by using cathodic arc physical vapor deposition technique. TiN coated grade 2 titanium substrates were used as reference to understand the role of magnesium on hydroxyapatite (HA) formation. The HA formation experiments was carried out in simulated body fluids (SBF) with three different concentrations (1X SBF, 5X SBF and 5X SBF without magnesium ions) at 37 °C. The coatings and hydroxyapatite films formed were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) and FTIR Spectroscopy techniques. The energy dispersive X-ray spectroscopy (EDS) analyses and XRD investigations of the coatings indicated that magnesium was incorporated in the TiN structure rather than forming a separate phase. The comparison between the TiN and (Ti, Mg)N coatings showed that the presence of magnesium in TiN structure facilitated magnesium substituted HA formation on the surface. The (Ti,Mg)N coatings can potentially be used to accelerate the HA formation in vivo conditions without any prior hydroxyapatite coating procedure.

Addressable self-immobilization of lactate dehydrogenase across multiple length scales.

Successful nanobiotechnology implementation largely depends on control over the interfaces between inorganic materials and biological molecules. Controlling the orientations of biomolecules and their spatial arrangements on the surface may transform many technologies including sensors, to energy. Here, we demonstrate the self-organization of L-lactate dehydrogenase (LDH), which exhibits enhanced enzymatic activity and stability on a variety of gold surfaces ranging from nanoparticles to electrodes, by incorporating a gold-binding peptide tag (AuBP2) as the fusion partner for Bacillus stearothermophilus LDH (bsLDH). Binding kinetics and enzymatic assays verified orientation control of the enzyme on the gold surface through the genetically incorporated peptide tag. Finally, redox catalysis efficiency of the immobilized enzyme was detected using cyclic voltammetry analysis in enzyme-based biosensors for lactate detection as well as in biofuel cell energy systems as the anodic counterpart. Our results demonstrate that the LDH enzyme can be self-immobilized onto different gold substrates using the short peptide tag under a biologically friendly environment. Depending on the desired inorganic surface, the proposed peptide-mediated path could be extended to any surface to achieve single-step oriented enzyme immobilization for a wide range of applications.

Effect of solid surface charge on the binding behaviour of a metal-binding peptide.

Over the last decade, solid-binding peptides have been increasingly used as molecular building blocks coupling bio- and nanotechnology. Despite considerable research being invested in this field, the effects of many surface-related parameters that define the binding of peptide to solids are still unknown. In the quest to control biological molecules at solid interfaces and, thereby, tailoring the binding characteristics of the peptides, the use of surface charge of the solid surface may probably play an important role, which then can be used as a potential tuning parameter of peptide adsorption. Here, we report quantitative investigation on the viscoelastic properties and binding kinetics of an engineered gold-binding peptide, 3RGBP(1), adsorbed onto the gold surface at different surface charge densities. The experiments were performed in aqueous solutions using an electrochemical dissipative quartz crystal microbalance system. Hydrodynamic mass, hydration state and surface coverage of the adsorbed peptide films were determined as a function of surface charge density of the gold metal substrate. Under each charged condition, binding of 3rGBP(1) displayed quantitative differences in terms of adsorbed peptide amount, surface coverage ratio and hydration state. Based on the intrinsically disordered structure of the peptide, we propose a possible mechanism for binding of the peptide that can be used for tuning surface adsorption in further studies. Controlled alteration of peptide binding on solid surfaces, as shown here, may provide novel methods for surface functionalization used for bioenabled processing and fabrication of future micro- and nanodevices.

Bioassay-guided isolation of antibacterial and cytotoxic compounds from the mesophilic Actinomycete M-33-5.

One hundred and twenty-six mesophilic Actinomycete cultures were isolated from the Aegean region of Turkey. The antimicrobial activities of pure isolates were tested using the agar-plaque method. Based on high antimicrobial activity against methicillin resistant Staphylococcus aureus (MRSA) and Escherichia coli O157-H7 (E. coli), the isolate M-33-5 was selected for bioactivity-guided isolation. Fermentation, followed by solvent partition (H2O-EtOAc, H2O-n-BuOH), showed that the highest activity was present in the EtOAc extract. By using chromatographic methods, two bioactive compounds were isolated and their structures were determined by spectral methods to be 4'-deacetyl griseusin A and griseusin A. The MIC values of griseusin A and 4'-deacetyl griseusin A against MRSA and E. coli were < or = 1.0 microg/mL. The cytotoxicities of the EtOAc extract and 4'-deacetyl griseusin A were also evaluated against two cancer cell lines (human servical cancer: HeLa; murine fibroblastic cells: L-929). The EtOAc extract showed strong cytotoxic activity against HeLa and L-929 lines with IC50 values of 1.57 and 2.43 microg/mL, respectively, whereas 4'-deacetyl griseusin A was very potent with IC50 values of 0.43 versus HeLa, and 0.12 microg/mL against L-929. The active strain M-33-5 was identified as Streptomyces griseus by 16SrDNA sequence data.