Biosensors designed for environmental and food quality control based on screen-printed graphite electrodes with different configurations

Graphite electrodes fabricated by screen-printing have been used as amperometric detectors in biosensors based on NAD(+)-dependent dehydrogenases, tyrosinase, or genetically modified acetylcholinesterases. The mono-enzyme sensors have been optimized as disposable or reusable devices for detection of a variety of substrates important in the food industry ( D-lactic acid, L-lactic acid, acetaldehyde) or in environmental pollution control (phenols and dithiocarbamate, carbamate and organophosphorus pesticides). The sensors were prepared in four configurations differing in enzyme confinement, enzyme immobilization and location of the immobilization agent in the biosensor assembly. Tests on real samples have been performed with the biosensors; D-lactic acid and acetaldehyde have been detected in wine and phenols in air.     

A Class of Non-associated Materials: n-Monotone Materials—Hooke’s Law of Elasticity Revisited

Generalized Standard Materials are governed by maximal cyclically monotone operators and modeled by convex potentials. Géry de Saxcé’s Implicit Standard Materials are modeled by biconvex bipotentials. We analyze the intermediate class of n-monotone materials governed by maximal n-monotone operators and modeled by Fitzpatrick’s functions. Revisiting the model of elastic materials initiated by Robert Hooke, and insisting on the linearity, coaxiality and monotonicity properties of the constitutive law, we illustrate that Fitzpatrick’s representation of n-monotone operators coming from convex analysis provides a constructive method to discover the best bipotential modeling a n-monotone material. Giving up the symmetry of the linear constitutive laws, we find out that n-monotonicity is a relevant criterion for the materials characterization and classification.     

Mesoporous carbon supported ultrasmall palladium particles as highly active catalyst for Suzuki‐Miyaura reaction

A fast and efficient eco‐friendly two‐step preparation of a palladium‐containing mesoporous carbon catalyst ( C1 ) from green and readily available carbon precursors (phloroglucinol and glyoxal), a porogen template (pluronic F‐127) and PdCl₂ is described. Catalyst C1 contains ultra‐small Pd nanoparticles (1.2 nm) uniformly dispersed in the carbon network and shows an outstanding activity for Suzuki‐Miyaura reactions in pure water: extremely low amounts of palladium (10 μequiv. in most cases) are sufficient to afford almost palladium‐free products (containing <0.25 ppm of precious metal without further purification steps).     

In-syringe magnetic-stirring-assisted liquid–liquid microextraction for the spectrophotometric determination of Cr(VI) in waters

A fully automated method for the determination of chromate is described. It is based on the selective reaction of Cr(VI) with diphenylcarbazide in acidic media to form a colored complex of Cr(III) with the oxidation product diphenylcarbazone. The reaction was performed within the syringe of an automatic burette containing a magnetic stirrer for homogenization of the sample and the required reagents. In-syringe stirring was made possible using a specially designed driving device placed around the syringe barrel to achieve a rotating magnetic field in the syringe, forcing the stirrer to spin. In a second step, the reaction mixture in the syringe was neutralized to allow in-syringe magnetic-stirring-assisted dispersive liquid–liquid microextraction of the complex into 125 μL of n-hexanol. After phase separation by droplet flotation over 30 s, the organic phase was propelled into a coupled spectrophotometric detection cell. The entire multistep procedure including in-system standard preparation was done within 270 s. The method was used for the analysis of natural waters, achieving average analyte recovery of 103 %, a limit of detection of 0.26 μg L^-1, and a repeatability of less than 4 % relative standard deviation.     

Influence of surface chemistry on the adsorption of oxygenated hydrocarbons on activated carbons

The objective of this work was to study the adsorption of different oxygenated hydrocarbons (methanol, ethanol, 1 and 2-butanol, methyl acetate) on activated carbons from organic mixtures with cyclohexane. Three activated carbons prepared by thermal and chemical treatments of a commercial carbon were employed for this purpose. Their textural properties were found to be similar, whereas their surface chemistries were modified, as shown by temperature-programmed desorption coupled to mass spectrometry (TPD-MS) and X-ray photoelectron spectroscopy (XPS). The adsorption isotherms were obtained by depletion method, and the analysis of adsorbed species was evaluated by TPD-MS to obtain new insight into the interactions between the different hydrocarbons and the carbon surface. Ethanol leads to a high-energy interaction between its hydroxyl function and the oxygenated surface groups and also to a lower energy interaction between the aliphatic part of the molecule and the carbon material. The desorption activation energy for this hydrophilic interaction is high (50 to 105 kJ/mol), and it is related to the nature of the carbon surface groups. The relative importance of these two interactions depend on the size of the alcohol/methanol is similar to ethanol, whereas butanols lead to more dispersive interactions. Methyl-acetate cannot undergo this kind of strong interaction and behaves like cyclohexane, having desorption activation energies ranging between 25 and 45 kJ/mol no matter the molecule and the carbon surface chemistry.     

Morphology,structure, and photoactivity of two types of graphene oxide-TiO<Subscript>2</Subscript> composites

Two types of graphene oxide-TiO₂ composites were prepared: one by including graphene oxide flakes in the TiO₂ sol, followed by thermal treatment (GI composite) at 300°C, and the second by including graphene oxide flakes in the calcined (at 500°C) TiO₂ xerogel (GII composite). The composites were characterized by SEM, TEM-EDS, TEM-SADP, STEM-HAADF, HRTEM coupled with FT, XRD, and XPS. Photocatalysis results were fitted to different kinetic models (pseudo-first and pseudo-second kinetics, intraparticle Weber-Morris diffusion, film diffusion, and external mass transfer). The results showed that by introducing graphene oxide flakes in the TiO₂ sol, followed by thermal treatment at 300°C (GI composite), an efficient graphene oxide-TiO₂ catalyst with high specific surface area, heterogeneity, and many graphitized areas can be obtained. Complete crystallization of the composite is not the key issue for the best photoactivity achievement. The rate limiting step in the photocatalytic process is the photooxidation of SA molecules on the TiO₂ surface.     

C0-estimates and smoothness of solutions to the parabolic equation defined by Kimura operators

Kimura diffusions serve as a stochastic model for the evolution of gene frequencies in population genetics. Their infinitesimal generator is an elliptic differential operator whose second-order coefficients matrix degenerates on the boundary of the domain. In this article, we consider the inhomogeneous initial-value problem defined by generators of Kimura diffusions, and we establish $C^0$-estimates, which allows us to prove that solutions to the inhomogeneous initial-value problem are smooth up to the boundary of the domain where the operator degenerates, even when the initial data is only assumed to be continuous.     

Sensitive detection of endocrine disrupters using ionic liquid--single walled carbon nanotubes modified screen-printed based biosensors

Simple and low cost biosensor based on screen-printed electrode for sensitive detection of some alkylphenols was developed, by entrapment of HRP in a nanocomposite gel based on single-walled carbon nanotubes (SWCNTs) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]) ionic liquid. Raman and FTIR spectroscopy, CV and EIS studies demonstrate the interaction between SWCNTs and ionic liquid. The nanocomposite gel, SWCNT-[BMIM][PF₆] provides to the modified sensor a considerable enhanced electrocatalytic activity toward hydrogen peroxide reduction. The HRP based biosensor exhibits high sensitivity and good stability, allowing a detection of the alkylphenols at an applied potential of −0.2 V vs. Ag/AgCl, in linear range from 5.5 to 97.7 μM for 4-t-octylphenol and respectively, between 5.5 and 140 μM for 4-n-nonylphenol, with a response time of about 5 s. The detection limit was 1.1 μM for 4-t-octylphenol, and respectively 0.4 μM for 4-n-nonylphenol (S/N = 3).     

Rheological Study of Some Epiclon‐Based Polyimides

The rheological properties of new partially aliphatic polyimides in N,N‐dimethylformamide were investigated at different concentrations and temperatures comparatively to their corresponding poly(amic acid)s. The rheological functions,i.e., dynamic viscosity, shear rate, elastic shear modulus, and viscous shear modulus, and the parameters obtained from rheological properties such as apparent energy of activation and flow activation entropy reflect the influence of the diamine chemical structures used in the synthesis process.