Boron-doped carbon nanowalls for fast and direct detection of cytochrome C and ricin by matrix-free laser desorption/ionization mass spectrometry.

Detecting proteins via surface assisted laser desorption/ionization mass spectrometry (SALDI-MS) method is still highly challenging, and only few examples of nanomaterials have been demonstrated to perform such detection so far. In this study, carbon nanowalls (CNWs), vertically aligned graphene sheet-based materials, presenting specific morphology, dimensions, and boron doping levels have shown improved performances for both qualitative and quantitative detection of Cytochrome C under optimized experimental conditions. Boron doped carbon nanowalls (B-CNWs) with a [B]/[C] ratio of 5000 ppm and growing time of 4 h have shown the best performance in terms of signal intensity and reliability. Then, the detection of ricin, a ribosomal-inhibiting protein (RIP) classified as category B bioterrorism agent by CDC (Centre of Disease and Control and Prevention), was performed. For the first time, direct SALDI-MS detection of ricin B chain was reported without tedious sample preparation steps or database interrogation, and results were obtained within few minutes and a limit of detection (LOD) of 0.5 pmol/µl was obtained. Thanks to the introduction of galactosamine residues on B-CNW, we were able to selectively detect ricin B chain protein in complex media such as serum and soft drinks with enhanced signal intensity. B-CNWs are not toxic and are adaptable to any commercial MALDI-TOF mass spectrometer, showing their great potential as SALDI based materials.

Comparison of the paracetamol electrochemical determination using boron-doped diamond electrode and boron-doped carbon nanowalls.

Two different type of electrodes, boron-doped diamond electrode (BDD) and boron-doped carbon nanowalls (B:CNW) electrode, were used for the electrochemical determination of paracetamol using the cyclic voltammetry and the differential pulse voltammetry in phosphate buffered saline, pH = 7.0. The main advantage of these electrodes is their utilization without any additional modification of the electrode surface. The peak current was linearly related to the concentration of paracetamol in the range from 0.065 µM to 32 µM for BDD electrode and from 0.032 µM to 32 µM for B:CNW electrode. The limit of detection was 0.430 µM and 0.281 µM for BDD and B:CNW electrode, respectively. Additionally, we studied the effect of pH on the redox reaction of paracetamol at the both electrodes in Britton-Robinson buffer solution in the range of pH 3.0-12.0, indicating the pH 7.0 value as the most suitable for the current experiments. The studies also included the various scan rates in range of 50-500 mV/s. Finally, our team selected the B:CNW electrode for the determination of paracetamol in the artificial urine sample using differential pulse voltammetry method, obtaining the calculated limit of detection on the level of 0.08006 µM.

Carbon nanowalls: a new versatile graphene based interface for the laser desorption/ionization-mass spectrometry detection of small compounds in real samples.

Carbon nanowalls, vertically aligned graphene nanosheets, attract attention owing to their tunable band gap, high conductivity, high mechanical robustness, high optical absorbance and other remarkable properties. In this paper, we report for the first time the use of hydrophobic boron-doped carbon nanowalls (CNWs) for laser desorption/ionization of small compounds and their subsequent detection by mass spectrometry (LDI-MS). The proposed method offers sensitive detection of various small molecules in the absence of an organic matrix. The CNWs were grown by microwave plasma enhanced chemical vapor deposition (MW-PECVD), using a boron-carbon gas flow ratio of 1200 in H2/CH4 plasma, on silicon <100> wafer. The hydrophobicity of the surface offers a straightforward MS sample deposition, consisting of drop casting solutions of analytes and drying in air. Limits of detection in the picomolar and femtomolar ranges (25 fmol µL-1 for neurotensin) were achieved for different types of compounds (fatty acids, lipids, metabolites, saccharides and peptides) having clinical or food industry applications. This rapid and sensitive procedure can also be used for quantitative measurements without internal standards with RSDs <19%, as in the case of glucose in aqueous solutions (LOD = 0.32 ± 0.02 pmol), blood serum or soft drinks. Moreover, melamine (63 ± 8.19 ng µL-1), a toxic compound, together with creatinine and paracetamol, was detected in urine samples, while lecithin was detected in food supplements.

Enhanced capacitance of composite TiO2 nanotube/boron-doped diamond electrodes studied by impedance spectroscopy.

We report on novel composite nanostructures based on boron-doped diamond thin films grown on top of TiO2 nanotubes. The nanostructures made of BDD-modified titania nanotubes showed an increase in activity and performance when used as electrodes in electrochemical environments. The BDD thin films (∼200-500 nm) were deposited using microwave plasma assisted chemical vapor deposition (MW PA CVD) onto anodically fabricated TiO2 nanotube arrays. The influence of boron-doping level, methane admixture and growth time on the performance of the Ti/TiO2/BDD electrode was studied in detail. Scanning electron microscopy (SEM) was applied to investigate the surface morphology and grain size distribution. Moreover, the chemical composition of TiO2/BDD electrodes was investigated by means of micro-Raman spectroscopy. The composite electrodes TiO2/BDD are characterized by a significantly higher capacitive current compared to BDD films deposited directly onto a Ti substrate. The novel composite electrode of TiO2 nanotube arrays overgrown by boron-doped diamond (BDD) immersed in 0.1 M NaNO3 can deliver a specific capacitance of 2.10, 4.79, and 7.46 mF cm(-2) at a scan rate of 10 mV s(-1) for a [B]/[C] ratio of 2k, 5k and 10k, respectively. The substantial improvement of electrochemical performance and the excellent rate capability could be attributed to the synergistic effect of TiO2 treatment in CH4 : H2 plasma and the high electrical conductivity of BDD layers. The analysis of electrochemical impedance spectra using an electric equivalent circuit allowed us to determine the surface area on the basis of the value of constant phase element.