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.

Redox-labelled electrochemical aptasensors with nanosupported cancer cells.

The transfer of redox-labelled bioelectrochemical sensors from proteins to cells is not straightforward because of the cell downward force issue on the surface of the sensors. In this paper, 20-nm-thick nanopillars are introduced to overcome this issue, in a well-controlled manner. We show on both molecular dynamics simulations and experiments that suspending cells a few nanometers above an electrode surface enables redox-labelled tethered DNA aptamer probes to move freely, while remaining at an interaction distance from a target membrane protein, i. e. epithelial cell adhesion molecule (EpCAM), which is typically overexpressed in cancer cells. By this nanopillar configuration, the interaction of aptamer with cancer cells is clearly observable, with 13 cells as the lower limit of detection. Nanoconfinement induced by the gap between the electrode surface and the cell membrane appears to improve the limit of detection and to lower the melting temperature of DNA aptamer hairpins, offering an additional degree of freedom to optimize molecular recognition mechanisms. This novel nanosupported electrochemical DNA cell sensor scheme including Brownian-fluctuating redox species opens new opportunities for the design of all-electrical sensors using redox-labelled probes.

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.

EWOD driven cleaning of bioparticles on hydrophobic and superhydrophobic surfaces.

Environmental air monitoring is of great interest due to the large number of people concerned and exposed to different possible risks. From the most common particles in our environment (e.g. by-products of combustion or pollens) to more specific and dangerous agents (e.g. pathogenic micro-organisms), there are a large range of particles that need to be controlled. In this article we propose an original study on the collection of electrostatically deposited particles using electrowetting droplet displacement. A variety of particles were studied, from synthetic particles (e.g. Polystyrene Latex (PSL) microsphere) to different classes of biological particle (proteins, bacterial spores and a viral simulant). Furthermore, we have compared ElectroWetting-On-Dielectric (EWOD) collecting efficiency using either a hydrophobic or a superhydrophobic counter electrode. We observe different cleaning efficiencies, depending on the hydrophobicity of the substrate (varying from 45% to 99%). Superhydrophobic surfaces show the best cleaning efficiency with water droplets for all investigated particles (MS2 bacteriophage, BG (Bacillus atrophaeus) spores, OA (ovalbumin) proteins, and PSL).

Electrowetting and droplet impalement experiments on superhydrophobic multiscale structures.

The reversible actuation of droplets on superhydrophobic surfaces under ambient conditions is currently an important field of research due to its potential applicability in microfluidic lab-on-a-chip devices. We have recently shown that Si-nanowire (NW) surfaces allow for reversible actuation provided that the surface structures show certain characteristics. In particular it appears that, for such surfaces, the presence of structures with multiple specific length scales is indeed needed to have a robust reversibility of contact angle changes. Here we report on electrowetting (EW) and impalement experiments on double-scale structured surfaces prepared by a combination of silicon micropillars prepared by an association of optical lithography and silicon etching, and nanowire growth on top of these surfaces. We show that while micropillar surfaces have a low impalement threshold and irreversible EW behaviour, a surface with double-scale texture can show both a very high resistance to impalement and a limited reversibility under EW, provided that the roughness of the micro-scale is large enough--i.e. that the pillars are tall enough. The optimal performance is obtained for a space between pillars that is comparable to the height of the nanostructure.

Extreme resistance of superhydrophobic surfaces to impalement: reversible electrowetting related to the impacting/bouncing drop test.

The paper reports on the comparison of the wetting properties of superhydrophobic silicon nanowires (NWs), using drop impact impalement and electrowetting (EW) experiments. A correlation between the resistance to impalement on both EW and drop impact is shown. From the results, it is evident that when increasing the length and density of NWs (i) the thresholds for drop impact and EW irreversibility increase and (ii) the contact-angle hysteresis after impalement decreases. This suggests that the structure of the NW network could allow for partial impalement, hence preserving the reversibility, and that EW acts the same way as an external pressure. The most robust of our surfaces shows a threshold to impalement higher than 35 kPa, while most of the superhydrophobic surfaces tested so far have impalement thresholds smaller than 10 kPa.

Semicarbazide-functionalized Si(111) surfaces for the site-specific immobilization of peptides.

The covalent attachment of semicarbazide-functionalized layers to hydrogen-terminated Si(111) surfaces is reported. The surface modification, based on the photoinduced hydrosilylation of a Si(111) surface with protected semicarbazide-functionalized alkenes, was investigated by means of X-ray photoelectron spectroscopy (XPS), contact angle measurements, and atomic force microscopy (AFM). The removal of the protecting group yielded a semicarbazide-terminated monolayer which was reacted with peptides bearing a glyoxylyl group for site-specific alpha-oxo semicarbazone ligation.