An Electrolyte-Gated Graphene Field-Effect Transistor for Detection of Gadolinium(III) in Aqueous Media.

In this work, an electrolyte-gated graphene field-effect transistor is developed for Gd3+ ion detection in water. The source and drain electrodes of the transistor are fabricated by photolithography on polyimide, while the graphene channel is obtained by inkjet-printing a graphene oxide ink subsequently electro-reduced to give reduced graphene oxide. The Gd3+-selective ligand DOTA is functionalized by an alkyne linker to be grafted by click chemistry on a gold electrode without losing its affinity for Gd3+. The synthesis route is fully described, and the ligand, the linker and the functionalized surface are characterized by electrochemical analysis and spectroscopy. The as functionalized electrode is used as gate in the graphene transistor so to modulate the source-drain current as a function of its potential, which is itself modulated by the concentration of Gd3+captured on the gate surface. The obtained sensor is able to quantify Gd3+ even in a sample containing several other potentially interfering ions such as Ni2+, Ca2+, Na+ and In3+. The quantification range is from 1 pM to 10 mM, with a sensitivity of 20 mV dec-1 expected for a trivalent ion. This paves the way for Gd3+ quantification in hospital or industrial wastewater.

Development of a novel functional core-shell-shell nanoparticles: From design to anti-bacterial applications.

This article reports the synthesis and functionalization of a novel CuO@SiO2-APTES@Ag0 core-shell-shell material using a simple and low-cost process. The growth, design strategies and synthesis approach are the key factors for the development of CuO@SiO2-APTES@Ag0 as efficient material with enhanced antibacterial activity. We investigated the morphology, surface charge, structure and stability of our new core-shell-shell by atomic force microscopy, scanning electron microscopy, energy dispersive X-ray, Fourier transform infrared and UV-visible spectroscopies, zeta potential measurements, and differential scanning calorimetry. The covalent surface grafting of APTES (3-(aminopropyl)triethoxysilane) onto CuO@SiO2 involving electrostatic interactions was confirmed. Size measurements and Scanning electron images showed that both APTES grafting and SiO2/Ag shells dropped on the surface of CuO produced structural compaction. UV-Vis spectroscopy proved to be a fast and convenient way to optically detect SiO2 shell on the surface of colloids. Additionally, the Ag-decorated CuO@SiO2-APTES surfaces were found to possess antibacterial activity and thermally more stable than undecorated surfaces. CuO@SiO2-APTES@Ag0 core-shell had antibacterial properties against Gram-positive bacteria making it a promising candidate for antibacterial applications.

Chemical modification of the cocoa shell surface using diazonium salts.

The outer portion of the cocoa bean, also known as cocoa husk or cocoa shell (CS), is an agrowaste material from the cocoa industry. Even though raw CS is used as food additive, garden mulch, and soil conditioner or even burnt for fuel, this biomass material has hardly ever been investigated for further modification. This article proposes a strategy of chemical modification of cocoa shell to add value to this natural material. The study investigates the grafting of aryl diazonium salt on cocoa shell. Different diazonium salts were grafted on the shell surface and characterized by infrared spectroscopy and scanning electronic microscopy imaging. Strategies were developed to demonstrate the spontaneous grafting of aryl diazonium salt on cocoa shell and to elucidate that lignin is mainly involved in immobilizing the phenyl layer.

Ionic liquids and cyclodextrin inclusion complexes: limitation of the affinity capillary electrophoresis technique.

The state of the art of inclusion complex formation between cyclodextrins and ionic liquids is reported. Mechanisms, stoichiometries, and binding constants are summarized and classified by anion. We investigated the supramolecular interactions between the ß-cyclodextrin cavity and six ionic liquids based on 1-dodecyl-3-methylimidazolium by affinity capillary electrophoresis and compared the results with those obtained by isothermal titration calorimetry. We show that the presence of basic or acidic buffers leads to a metathesis reaction, underlining the limitation of the affinity capillary electrophoresis technique.

Atmospheric Solid Analysis Probe-Ion Mobility Mass Spectrometry: An Original Approach to Characterize Grafting on Cyclic Olefin Copolymer Surfaces.

A cyclic olefin copolymer (COC) was grafted with aryl layers from aryldiazonium salts, and then we combined infrared spectrometry, atomic force microscopy (AFM), and ion mobility mass spectrometry with atmospheric solid analysis probe ionization (ASAP-IM-MS) to characterize the aryl layers. ASAP is a recent atmospheric ionization method dedicated to the direct analysis of solid samples. We demonstrated that ASAP-IM-MS is complementary to other techniques for characterizing bromine and sulfur derivatives of COC on surfaces. ASAP-IM-MS was useful for optimizing experimental grafting conditions and to elucidate hypotheses around aryl layer formation during the grafting process. Thus, ASAP-IM-MS is a good candidate tool to characterize covalent grafting on COC surfaces.

Structure-Binding Effects: Comparative Binding of 2-Anilino-6-naphthalenesulfonate by a Series of Alkyl- and Hydroxyalkyl-Substituted ß-Cyclodextrins.

Cyclodextrins (CDs) are the most widely used organic hosts for the inclusion of guest molecules. CDs can be readily modified through substitutions of the hydroxyl groups, and these modified CDs can have different host binding properties compared to those of parent CDs. However, only relatively few systematic studies of the effects of chemical substitution on CD binding ability have been reported thus far. In this paper, we report the study of the binding properties of five different analytically pure modified ß-cyclodextrin (ß-CD) hosts (substituted with alkyl and/or hydroxyalkyl groups) with 2-anilino-6-naphthalenesulfonate (2,6-ANS) as guest. Binding constants for the formation of the inclusion complex between 2,6-ANS and each CD were determined using both fluorescence spectroscopy and capillary electrophoresis. Addition of modified CDs to an aqueous solution of 2,6-ANS resulted in significant enhancement of the fluorescence intensity of 2,6-ANS, as well as a significant spectral blue shift, indicative of inclusion. Inclusion of 2,6-ANS within the CD cavity was confirmed by NMR spectroscopy. Substitution at position 3 decreased the magnitude of the binding constants, while alkyl or hydroxylalkyl substitution of the primary hydroxyl at position 6 increased the magnitude of the binding constant in all cases, in relation with increasing length of the alkyl chain linker. In addition, binding constants decreased with solvent polarity when increasing amounts of methanol were added. Structure-binding correlations for CDs based on these binding constant results are presented and discussed.

Enantioseparation of underivatised amino acids by ligand exchange capillary electrophoresis in a counter-electroosmotic mode.

Enantiomer separations of underivatised amino acids were carried out by using ligand exchange capillary electrophoresis (LECE). Chiral discrimination is based on the formation of ternary complexes between copper(II), a chiral selector (L-proline or trans-4-hydroxy-L-proline) and an amino acid. All amino acids containing aromatic moieties or not were detected at 214 nm because of their interactions with copper(II). In order to reduce copper(II) adsorption onto capillary walls, we used hexadimethrine bromide to reverse the electroosmotic flow. Using this original strategy, the studied enantiomers migrated in the opposite direction of the anodic electroosmosis. After optimising the analytical conditions taking into account the chiral resolution and the detection sensitivity, we performed very satisfactory enantioseparations not only of aromatic amino acids (tryptophan, tyrosine, phenylalanine and histidine) but also of aliphatic amino acids (threonine, serine, isoleucine and valine). These enantioseparations were performed in a short analysis time at 35 degrees C. In order to rationalise the obtained results, we evaluated the complexation constants corresponding to the formed ternary complexes by capillary electrophoresis and we used molecular mechanics modelling.