A new low-modulus β Ti−Nb alloy with low elastic modulus and excellent corrosion resistance is currently under consideration as a surgical implant material. The usefulness of such materials can be dramatically enhanced if their surface structure and surface chemistry can be controlled. This control is achieved in two stages. Electropolishing and anodic oxidation of the Ti45Nb alloy provide a surface with a uniform oxide layer that is a mixture of TiO2 and Nb2O5. The impact of each of these two steps on the morphology of the surface and on the thickness and chemistry of the oxide layer has been assessed. In addition, as a first step toward controlling the surface chemistry of this material, a self-assembled monolayer (SAM) based on hexadecylphosphonic acid (HDPA) is attached to the anodized surface. The SAM is characterized based on its wetting properties and by Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis. Using variable angle XPS analysis, detailed information is obtained about the orientation and structure of the SAM, its thickness, and the chemistry of its interaction with the metal oxide surface of the alloy. Further support for the creation of a true monolayer film is obtained from FTIR measurements on a model oxide surface analogous to that of the alloy. This is the first report of SAM attachment to this alloy and opens the possibility of monolayer control of its biocompatibility.
Significance Morpho butterflies are a brilliant spectacle of nature’s capability for photonic engineering. Their conspicuous appearance arises from the interference and diffraction of light within tree-like nanostructures on their scales. Scientific lessons learned from these butterflies have already inspired designs of new displays, fabrics, and cosmetics. This study reports a vertical surface polarity gradient in these tree-like structures. This biological pattern design may be applied to numerous technological applications ranging from security tags to self-cleaning surfaces, gas separators, protective clothing, and sensors. Here it has allowed us to unveil a general mechanism of selective vapor response in photonic Morpho nanostructures and to demonstrate attractive opportunities for chemically graded sensing units for high-performance sensing.
Producing large-scale graphene films with controllable patterns is an essential component of graphene-based nanodevice fabrication. Current methods of graphene pattern preparation involve either high cost, low throughput patterning processes or sophisticated instruments, hindering their large-scale fabrication and practical applications. We report a simple, effective, and reproducible approach for patterning graphene films with controllable feature sizes and shapes. The patterns were generated using a versatile photocoupling chemistry. Features from micrometres to centimetres were fabricated using a conventional photolithography process. This method is simple, general, and applicable to a wide range of substrates including silicon wafers, glass slides, and metal films.
X-ray Photoelectron Spectroscopy (XPS) was used to characterize the nitrogen species in perfluorophenylazide (PFPA) self-assembled monolayers. PFPA chemistry is a novel immobilization method for tailoring the surface properties of materials. It is a simple route for the efficient immobilization of graphene, proteins, carbohydrates and synthetic polymers onto a variety of surfaces. Upon light irradiation, the azido group in PFPA is converted to a highly reactive singlet nitrene species that readily undergoes CH insertion and C=C addition reactions. Here, the challenge of characterizing the PFPA modified surfaces was addressed by detailed XPS experimental analyses. The three nitrogen peaks detected in the XPS N1s spectra were assigned to amine/amide (400.5 eV) and azide (402.1 and 405.6 eV) species. The observed 2:1 ratio of the areas from the 402.1 eV to 405.6 eV peaks suggests the assignment of the peak at 402.1 eV to the two outer nitrogen atoms in the azido group and assignment of the peak at 405.6 eV to the central nitrogen atom in the azido group. The azide decomposition as the function of x-ray exposure was also determined. Finally, XPS analyses were conducted on patterned graphene to investigate the covalent bond formation between the PFPA and graphene. This study provides strong evidence for the formation of covalent bonds during the PFPA photocoupling process.
In the biological sciences the use of core-shell quantum dots (QDs) has gained wide usage, but analytical challenges still exist for characterizing the QD structure. The application of energydispersive x-ray spectroscopy and x-ray photoelectron spectroscopy (XPS) to bulk materials is relatively straightforward, however, for meaningful applications of surface science techniques to multilayer nanoparticles requires novel modifications and analysis methods. To experimentally characterize the elemental composition and distribution in CdSe/CdS/ZnS QDs, we first develop a XPS signal subtraction technique capable of separating the overlapped selenium 3s (core) and sulfur 2s (shell) peaks (both peaks have binding energies near 230eV) with higher precision than is typically reported in the nanoparticle literature. This method is valid for any nanoparticle containing selenium and sulfur. Then we apply a correction formula to the XPS data and determine that the 2 nm stoichiometric CdSe core is surrounded by 2 CdS layers and a stoichimetric ZnS monolayer. These findings and the multi-approach methodology represent a significant advancement in the detailed surface science study of multi-layer nanoparticles. In agreement with recent surprising findings, the time-of-flight secondary mass spectrometry measurements suggest that the surface sites of the QDs used in this study are primarily covered with a mixture of octadecylphosphonic acid and trioctylphophine oxide.
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