Pascal Blondeau

Molecular recognition of oxoanions based on guanidinium receptors

Guanidinium is a versatile functional group with unique properties. In biological systems, hydrogen-bonding and electrostatic interactions involving the arginine side chains of proteins are critical to stabilise complexes between proteins and nucleic acids, carbohydrates or other proteins. Leading examples of artificial receptors for carboxylates, phosphates and other oxoanions, such as sulfate or nitrate are highlighted in this tutorial review, addressed to readers interested in biology, chemistry and supramolecular chemistry.

Label-free detection of Staphylococcus aureus in skin using real-time potentiometric biosensors based on carbon nanotubes and aptamers

In this paper we report the first biosensor that is able to detect Staphylococcus aureus in real-time. A network of single-walled carbon nanotubes (SWCNTs) acts as an ion-to-electron potentiometric transducer and anti-S. aureus aptamers are the recognition element. Carbon nanotubes were functionalized with aptamers using two different approaches: (1) non-covalent adsorption of drop-casted pyrenil-modified aptamers onto the external walls of the SWCNTs; and (2) covalent bond formation between amine-modified aptamers and carboxylic groups previously introduced by oxidation at the ends of the SWCNTs. Both of these approaches yielded functional biosensors but there were large differences in the minimum detectable bacteria concentration and sensitivity values. With covalent functionalization, the minimum concentration detected was 8×10(2)colony-forming units (CFU)/mL and the sensitivity was 0.36 mV/Decade. With the non-covalent approach, the sensitivity was higher (1.52 mV/Decade) but the minimum concentration detected was greatly affected (10(7) CFU/mL). In both cases, potential as a function of Decade of bacteria concentration was linear. Functional biosensors were used to test real samples from freshly excised pig skin, contaminated with the target microorganism, as a surrogate for human skin.

Potentiometric strip cell based on carbon nanotubes as transducer layer: toward low-cost decentralized measurements.

In this study, we developed a potentiometric planar strip cell based on single-walled carbon nanotubes that aims to exploit the attributes of solid-contact ion-selective electrodes for decentralized measurements. That is, the ion-selective and reference electrodes have been simultaneously miniaturized onto a plastic planar substrate by screen-printing and drop-casting techniques, obtaining disposable strip cells with satisfactory performance characteristics (i.e., the sensitivity is 57.4 ± 1.3 mV/dec, the response time is ≤30 s within the linear range from log a(K+) = -5 to -2, and the limit of detection is -6.5), no need of maintenance during long dry storage, quick signal stabilization, and light insensitivity in short-term measurements. We also show how the new potentiometric strip cell makes it possible to perform decentralized and rapid determinations of ions in real samples, such as saliva or beverages.

Disposable Planar Reference Electrode Based on Carbon Nanotubes and Polyacrylate Membrane

In this technical note, we report a new all-solid-state planar reference electrode based on single-walled carbon nanotubes and photocured poly(n-butylacrylate) (poly(nBA)) membrane containing the Ag/AgCl/Cl(-) ion system. Single-walled carbon nanotubes functionalized with octadecylamide (SWCNT-ODA) and deposited by drop-casting onto a disposable screen-printed electrode are an excellent all-solid-state transducer. The novel potentiometric planar reference electrode shows low potential variability (calibration slopes inferior to 2 mV/dec) for a wide range of chemical species (i.e., ions, small molecules, proteins) in a wide calibration range, redox pairs, changes in pH, and changes in ambient light. Potentiometric medium-term signal stability (-0.9 ± 0.2 mV/h) and electrochemical impedance characterization confirm the correct solid contact between the SWCNT-ODA layer and photocured poly(nBA) membrane. Overall, the materials used and the simple fabrication by screen-printing and drop-casting enable a high throughput and highly parallel and cost-effective mass manufacture of the new disposable reference electrode. Moreover, the reference electrode has a long shelf life, a characteristic that can be of special interest in decentralized and multiplexing potentiometric analysis.

Enthalpy driven nitrate complexation by guanidinium-based macrocycles

NMR and isothermal calorimetric titrations, as well as X-ray structures, show the binding of a nitrate anion inside guanidinium-based macrocycles. All six lone pairs of nitrate are complemented by oriented hydrogen bond donors from a guanidinium and two urea subunits.

Recognition and Sensing of Creatinine

Current methods for creatinine quantification suffer from significant drawbacks when aiming to combine accuracy, simplicity, and affordability. Here, an unprecedented synthetic receptor, an aryl-substituted calix[4]pyrrole with a monophosphonate bridge, is reported that displays remarkable affinity for creatinine and the creatininium cation. The receptor works by including the guest in its deep and polar aromatic cavity and establishing directional interactions in three dimensions. When incorporated into a suitable polymeric membrane, this molecule acts as an ionophore. A highly sensitive and selective potentiometric sensor suitable for the determination of creatinine levels in biological fluids, such as urine or plasma, in an accurate, fast, simple, and cost-effective way has thus been developed.

Paper-based chemiresistor for detection of ultralow concentrations of protein.

A new paper-based chemiresistor composed of a network of single-wall carbon nanotubes (SWCNTs) and anti-human immunoglobulin G (anti-HIgG) is reported herein. SWCNTs act as outstanding transducers because they provide high sensitivity in terms of resistance changes due to immunoreaction. As a result, the resistance-based biosensor reaches concentration detection as low as picomolar. The resulting paper-based biosensor is sensitive, selective and employs low-cost substrate and simple manufacturing stages. Since chemiresistors require low-power equipment and are able to detect low concentrations with inexpensive materials, the present approach may pave the way for the development of resistive biosensors at very low-cost with high performances.

Characterization of a new ionophore-based ion-selective electrode for the potentiometric determination of creatinine in urine

The optimization, analytical characterization and validation of a novel ion-selective electrode for the highly sensitive and selective determination of creatinine in urine is presented. A newly synthesized calix[4]pyrrole-based molecule is used as an ionophore for the enhanced recognition of creatininium cations. The calculation of the complex formation constants in the polymeric membrane with creatininium, potassium and sodium confirms the strong selective interactions between the ionophore and the target. The optimization of the potentiometric sensor presented here yields an outstanding analytical performance, with a linear range that spans from 1µM to 10mM and limit of detection of 10-6.2M. The calculation of the selectivity coefficients against most commonly found interferences also show significant improvements when compared to other sensors already reported. The performance of this novel sensor is tested by measuring creatinine in real urine samples (N=50) and comparing the values against the standard colorimetric approach (Jaffés reaction). The results show that this sensor allows the fast and accurate determination of creatinine in real samples with minimal sample manipulation.

Rubber-based substrates modified with carbon nanotubes inks to build flexible electrochemical sensors

The development of a solid-contact potentiometric sensor based on conducting rubbers using a carbon nanotubes ink is described here. Commercial rubbers are turned into conductive ones by a simple and versatile method, i.e. painting an aqueous dispersion of single-walled carbon nanotubes on the polymer surface. On this substrate, both the working ion-selective electrode and the reference electrode are built in order to form an integrated potentiometric cell. As a proof-of-principle, selective potassium electrodes are fully characterized giving comparable performances to conventional electrodes (sensitivity, selectivity, stability, linear range, limit of detection and reproducibility). As an application of the rubber-based electrodes, a bracelet was constructed to measure potassium levels in artificial sweat. Since rubbers are ubiquitous in our quotidian life, this approach offers great promise for the generation of chemical information through daily objects.

Surface characterisation of phosphine and phosphite stabilised Rh nanoparticles: a model study

Small and well defined Rh nanoparticles (<2 nm) stabilised by the model ligands triphenylphosphine 1 and triphenylphosphite 2 were synthesised using various P/Rh ratios. In all cases, the crystalline NPs exhibited a spherical shape and a fcc structure. During the synthesis of these materials, hydrogenation and oxidation of the stabilisers take place and the degree of hydrogenation of the stabilising ligand increased when low ligand to Rh ratio is used during their synthesis. The Rh1 systems mainly contain adsorbed phosphine oxide species at their surface whereas the Rh2 systems include both phosphite and phosphite oxide species. Analysis of the surface of these nanoparticles by infrared spectroscopy revealed the presence of Rh-H at the surface of the NPs and hydride titration experiments revealed a higher hydride coverage for the phosphine stabilized systems. By CO adsorption/infrared experiments, bridging, terminal and geminal Rh(CO)2 sites were detected. All these systems were active catalysts in the hydrogenation of styrene and the observation of Rh(CO)2 sites could be correlated with the activity of these species for the hydrogenation of the aromatic ring.