Hybrid nanocarbon, comprised of a diamond core and a graphitic shell with a variable sp(2)-/sp(3)-carbon ratio, is controllably obtained through sequential annealing treatment (550-1300 °C) of nanodiamond. The formation of sp(2) carbon increases with annealing temperature and the nanodiamond surface is reconstructed from amorphous into a well-ordered, onion-like carbon structure via an intermediate composite structure--a diamond core covered by a defective, curved graphene outer shell. Direct dehydrogenation of propane shows that the sp(2)-/sp(3)-nanocomposite exhibits superior catalytic performance to that of individual nanodiamond and graphitic nanocarbon. The optimum catalytic activity of the diamond/graphene composite depends on the maximum structural defectiveness and high chemical reactivity of the ketone groups. Ketone-type functional groups anchored on the defects/vacancies are active for propene formation; nevertheless, once the oxygen functional groups are desorbed, the defects/vacancies alone might be active sites responsible for the C-H bond activation of propane.
α-Fetoprotein (AFP) is an important tumor biomarker. In particular, the overexpression of AFP-L3 is associated with hepatocellular carcinoma (HCC). Accordingly, several hospitals have begun to employ the ratio of AFP-L3 to the total AFP level (AFP-L3%) as new diagnostic evidence for HCC owing to its high diagnostic accuracy. However, current methods of detection for AFP and AFP-L3 are time-consuming, require multiple samples, and lack in sensitivity and specificity. Herein, we present a novel concept for the early diagnosis of HCC based on the combination of Raman frequency shift and intensity change, and developed surface-enhanced Raman scattering (SERS)-based immunochips via AFP-L3%. In the first step of the study, the frequency shift of 4-mercaptobenzoic acid (MBA) was applied for the quantitative determination of total AFP based on the AFP and anti-AFP interaction on MBA-modified silver chips. 5,5-Dithiobis(succinimidyl-2-nitrobenzoate) (DSNB)-modified immunogold was then incorporated with AFP-L3 antibodies for sandwich immunoreaction on the chips. As a result, we found that a typical Raman band intensity of DSNB presented an exponential linear relationship with the concentration of AFP-L3. Thus, the AFP-L3% can be calculated according to the concentrations of AFP-L3 and total AFP. The most important advantage of the proposed method is the combination of AFP-L3% and frequency shifts of SERS, which exhibits excellent reproducibility and high accuracy, and significantly simplifies the conventional detection procedure of AFP-L3%. Application of the proposed method with the serum of patients with HCC demonstrated its great potential in early liver cancer diagnosis.
The basicity of the graphitic, pyridine, and pyrrole nitrogen groups on the graphene and single-walled carbon nanotubes is evaluated and compared in terms of both Brønsted base and Lewis base. It turns out that the pyridine group is the most strong basic site, while the graphitic nitrogen does not bring any improvements over the undoped one.
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