The use of Raman spectroscopy to detect nano-sized diamond crystals is controversial; the origins of peaks at in chemical vapor deposition nanodiamond films and in nanodiamond particles, which have both been suggested as evidence for nanophase material, remain uncertain. Many studies have produced evidence showing that the peak is in fact due to polyacetylenelike structures at grain boundaries and interfaces, but little work has been done to confirm the assignment of the peak. In this paper we approach the problem from the molecular level, using Hartree-Fock theory to calculate the Raman spectra of diamond hydrocarbons, and observe the variation of the spectra with molecular size. Molecules with symmetry are studied, varying in size from adamantane to , an octahedral -sized diamond crystallite. For comparison with nanodiamond thin films, the mass of the terminal hydrogen atoms were artificially increased to , approximating the effects of matrix isolation. The calculated spectra are discussed in terms of the signals commonly observed in the Raman spectra of nanocrystalline diamond samples. This study finds no evidence for Raman active vibrations of diamond nanocrystals at either or , whether hydrogen terminated or confined in a matrix. Further, it appears that the only signals produced by a nanodiamond crystal are the broadened zone-center mode and low frequency deformations/Lamb-type vibrations. This suggests any other peaks observed in the Raman spectra of nanocrystalline diamond are due to defects, surface structures, amorphous material, or any other nondiamond material in the sample, and should not be taken as definitive evidence of nanocrystalline diamond.
This report describes a method to fabricate high-surface-area boron-doped diamond (BDD) electrodes using so-called ‘black silicon’ (bSi) as a substrate. This is a synthetic nanostructured material that contains high-aspect-ratio nano-protrusions, such as spikes or needles, on the Si surface produced via plasma etching. We now show that coating a bSi surface composed of 15 μm-high needles conformably with BDD produces a robust electrochemical electrode with high sensitivity and high electroactive area. A clinically relevant demonstration of the efficacy of these electrodes is shown by measuring their sensitivity for detection of dopamine (DA) in the presence of an excess of uric acid (UA). Finally, the nanostructured surface of bSi has recently been found to generate a mechanical bactericidal effect, killing both Gram-negative and Gram-positive bacteria at high rates. We will show that BDD-coated bSi also acts as an effective antibacterial surface, with the added advantage that being diamond-coated it is far more robust and less likely to become damaged than Si.
20 September 2017 in Journal of The Royal Society Interface
Progress made in the last two decades in chemical vapour deposition technology has enabled the production of inexpensive, high-quality coatings made from diamond to become a scientific and commercial reality. Two properties of diamond make it a highly desirable candidate material for biomedical applications: first, it is bioinert, meaning that there is minimal immune response when diamond is implanted into the body, and second, its electrical conductivity can be altered in a controlled manner, from insulating to near-metallic. In vitro, diamond can be used as a substrate upon which a range of biological cells can be cultured. In vivo , diamond thin films have been proposed as coatings for implants and prostheses. Here, we review a large body of data regarding the use of diamond substrates for in vitro cell culture. We also detail more recent work exploring diamond-coated implants with the main targets being bone and neural tissue. We conclude that diamond emerges as one of the major new biomaterials of the twenty-first century that could shape the way medical treatment will be performed, especially when invasive procedures are required.
‘Black silicon’ (bSi) samples with surfaces covered in nanoneedles of varying length, areal density and sharpness, have been fabricated using a plasma etching process. These nanostructures were then coated with a conformal uniform layer of diamond using hot filament chemical vapour deposition to produce ‘black diamond’ (bD) surfaces. The effectiveness of these bSi and bD surfaces in killing Gram-negative (E. coli) and Gram-positive (S. gordonii) bacteria was investigated by culturing the bacteria on the surfaces for a set time and then measuring the live-to-dead ratio. All the nanostructured surfaces killed E. coli at a significantly higher rate than the respective flat Si or diamond control samples. The length of the needles was found to be less important than their separation, i.e. areal density. This is consistent with a model for mechanical bacteria death based on the stretching and disruption of the cell membrane, enhanced by the cells motility on the surfaces. In contrast, S. gordonii were unaffected by the nanostructured surfaces, possibly due to their smaller size, thicker cell membrane and/or their lack of motility.
Brain Computer Interfaces (BCI) currently represent a field of intense research aimed both at understanding neural circuit physiology and at providing functional therapy for traumatic or degenerative neurological conditions. Due to its chemical inertness, biocompatibility and stability, diamond is currently being actively investigated as a potential substrate material for culturing cells and for use as the electrically active component of a neural sensor. Here we provide a protocol for the differentiation of mature, electrically active neurons on microcrystalline synthetic thin-film diamond substrates starting from undifferentiated pluripotent stem cells. Furthermore, we investigate the optimal characteristics of the diamond microstructure for long-term neuronal sustainability. We also analyze the effect of boron as a dopant for such a culture. We found that the diamond crystalline structure has a significant influence on the neuronal culture unlike the boron doping. Specifically, small diamond microcrystals promote higher neurite density formation. We find that boron incorporated into the diamond does not influence the neurite density and has no deleterious effect on cell survival.