Tetrahedral amorphous carbon (ta-C) consists of a mixture of sp(3)- and sp(2)-bonded carbon ranging from 60 to 40% (sp(3)/sp(3)+sp(2)) depending on the deposition conditions. The physical, chemical, and electrochemical properties depend on the sp(2)/sp(3) bonding ratio as well as the presence of incorporated impurities, such as hydrogen or nitrogen. The ability to grow ta-C at lower temperatures (25-100 °C) on a wider variety of substrates as compared to CVD diamond is an advantage of this material. Herein, we report on the structural and electrochemical properties of nitrogen-incorporated ta-C thin films (ta-C:N). The incorporation of nitrogen into the films decreases the electrical resistivity from 613 ± 60 (0 sccm N(2)) to 1.10 ± 0.07 Ω-cm (50 sccm N(2)), presumably by increasing the sp(2)-bonded carbon content and the connectedness of these domains. Similar to boron-doped diamond, these materials are characterized by a low background voltammetric current, a wide working potential window (~ 3 V), and relatively rapid electron-transfer kinetics for aqueous redox systems, including Fe(CN)(6)(-3/-4) and Ru(NH(3))(6)(+3/+2), without conventional pretreatment. Additionally, there is weak molecular adsorption of polar molecules (methylene blue) on the ta-C surface. Overall, the properties of the ta-C and ta-C:N electrodes are such that they could be excellent new choices for electroanalytical measurements.
Diamond-like carbon (DLC) films are favored for wear components because of diamond-like hardness, low friction, low wear, and high corrosion resistance (Schultz et al., Mat-wiss u Werkstofftech 2004;35:924-928; Lappalainen et al., J Biomed Mater Res B Appl Biomater 2003;66B:410-413; Tiainen, Diam Relat Mater 2001;10:153-160). Several studies have demonstrated their inertness, nontoxicity, and the biocompatibility, which has led to interest among manufacturers of surgical implants (Allen et al., J Biomed Mater Res B Appl Biomater 2001;58:319-328; Uzumaki et al., Diam Relat Mater 2006;15:982-988; Hauert, Diam Relat Mater 2003;12:583-589; Grill, Diam Relat Mater 2003;12:166-170). In this study, hydrogen-free amorphous, tetrahedrally bonded DLC films (ta-C) were deposited at low temperatures by physical vapor deposition on medical grade Co28Cr6Mo steel and the titanium alloy Ti6Al4V (Scheibe et al., Surf Coat Tech 1996;85:209-214). The mechanical performance of the ta-C was characterized by measuring its surface roughness, contact angle, adhesion, and wear behavior, whereas the biocompatibility was assessed by osteoblast (OB) attachment and cell viability via Live/Dead assay. There was no statistical difference found in the wettability as measured by contact angle measurements for the ta-C coated and the uncoated samples of either Co28Cr6Mo or Ti6Al4V. Rockwell C indentation and dynamic scratch testing on 2-10 μm thick ta-C films on Co28Cr6Mo substrates showed excellent adhesion with HF1 grade and up to 48 N for the critical load L(C2) during scratch testing. The ta-C coating reduced the wear from 3.5 × 10(-5) mm(3)/Nm for an uncoated control sample (uncoated Co28Cr6Mo against uncoated stainless steel) to 1.1 × 10(-7) mm(3)/Nm (coated Co28Cr6Mo against uncoated stainless steel) in reciprocating pin-on-disk testing. The lowest wear factor of 3.9 × 10(-10) mm(3)/Nm was measured using a ta-C coated steel ball running against a ta-C coated and polished Co28Cr6Mo disk. Student's t-test found that the ta-C coating had no statistically significant (p < 0.05) effect on OB attachment, when compared with the uncoated control samples. There was no significant difference (p < 0.05) in the Live/Dead assay results in cell death between the ta-C coated Co28Cr6Mo and Ti6Al4V samples and the uncoated controls. Therefore, these ta-C coatings show improved wear and corrosion (Dorner-Reisel et al., Diam Relat Mater 2003;11:823-827; Affato et al., J Biomed Mater Res B Appl Biomater 2000;53:221-226; Dorner-Reisel et al., Surf Coat Tech 2004;177-178:830-837; Kim et al., Diam Relat Mater 2004;14:35-41) performance and excellent in vitro cyto-compatibility, when compared with currently used uncoated Co28Cr6Mo and Ti6Al4V implant materials.
The performance of a nitrogen-incorporated tetrahedral amorphous (ta-C:N) carbon thin-film electrode was evaluated using flow injection analysis with amperometric detection.
Isatin is an endogenous indole compound in humans and rodents that has a wide range of biological activity. In rat models, isatin concentrations have been shown to increase in the heart, brain, blood plasma, and urine with stress. Studies on patients suffering from Parkinson's disease have indicated a correlation between progress of the disease and urinary output of the molecule. Isatin is electrochemically active and can therefore be detected with electrochemical techniques. In this work, we compared the performance of a nitrogen‐incorporated tetrahedral amorphous carbon (ta‐C:N) and a boron‐doped nanocrystalline diamond thin‐film electrode for the oxidative detection of this biomolecule using flow injection analysis with amperometric detection. The measurements were performed in 0.1 phosphate buffer pH 7.2. The ta‐C:N electrode, like boron‐doped nanocrystalline diamond, exhibits some excellent properties for electroanalytical measurements including (i) low background current and noise, (ii) microstructural stability at positive detection potentials, and (iii) good activity for a wide range of bioanalytes without conventional surface pretreatment. The results reveal that both electrodes exhibit a linear dynamic range from 100 to 0.1 μmol L−1, a short‐term response variability 3–4 % RSD (30 injections), a sensitivity of 18 mA M‐1, and a limit of detection (S/N=3) of 1.0×10−7 mol L−1 (14 ng mL−1 or 2.5 fmol).
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