Electrochemical Determination of Organic Compounds in Automotive Fuels

This article critically reviews the electroanalytical methods devoted for the determination of organic compounds in automotive fuels that can range from contaminants to additives typically introduced into liquid biofuels and liquid fossil fuels. Contaminants such as aldehydes and ketones in bioethanol, free fatty acids and glycerol in biodiesel, and sulfur and nitrogen organic compounds in gasoline and diesel fuel, and additives such as colour markers and antioxidants added to fuels were determined by electroanalytical methods. Special focus is given to electrodes, electrochemical techniques, and sample preparation strategies. Future directions of research on electroanalysis of liquid fuels are presented.     

Ionic Organic Film Sensor for Determination of Phenolic Compounds

This paper describes the development of a new sensor based on an ionic organic film. The amphiphilic molecule, 4‐[(4‐decyloxyphenyl)‐ethynyl]‐1‐methylpyridinium iodide (10PyI), which has liquid‐crystalline properties, was synthesized and applied in the construction of a GCE/10PyI sensor. Analytical parameters for caffeic acid, repeatability (4.8 %), reproducibility (2.8 %), linearity (two ranges: 9.9×10^?7 to 3.8×10^?5 mol L^?1 and 4.7×10^?5 to 9.9×10^?5 mol L^?1) and detection limits (9.0×10^?7 mol L^?1 and 8.7×10^?6 mol L^?1), were determined. The method was successfully applied in the determination of total phenolic compounds (TPC) in mate herb extracts.     

A study of the aerobic reaction between dopamine and Fe(III) in the presence of S<Subscript>2</Subscript>O<Subscript>3</Subscript><Superscript>2−</Superscript>

The reaction between Fe(III) and dopamine in aqueous solution in the presence of Na₂S₂O₃ was followed through UV–Vis spectroscopy, pH and oxy-reduction potential (Eh) measurements. The formation and quick disappearing of the complex [Fe(III)HL¹⁻]²⁺, HL¹⁻ = monoprotonated dopamine was observed with or without S₂O₃ ²⁻ at pH 3. An unexpected reaction occurs in presence of thiosulfate forming the stable anion complex [Fe(III)(L²⁻)₂]¹⁻, L²⁻ = dopacatecholate (λ = 580 nm) and the auto-increasing of the pH, from 3 to 7. It was proposed that H⁺ and molecular oxygen are consumed by free radical thiosulfate formed during the reaction.     

Photostability of 4,4′‐Dihydroxythioindigo,a Mimetic of Indigo

The photochemical properties of indigo, a widely used industrial dye, has attracted both experimentalists and theoreticians from the beginning. Especially the high photostability of indigo has been the subject of intensive research. Recently, it was proposed that after photoexcitation an intramolecular proton transfer followed by a nonradiative relaxation to the ground state promote photostability. In indigo the hydrogen bond and the proton transfer occur between the opposing hemiindigo parts. Here, we provide experimental and theoretical evidence that a hydrogen transfer within one hemiindigo or hemithioindigo part is sufficient to attain photostability. This concept can serve as an interesting strategy towards new photostable dyes for the visible part of the spectrum.     

Electrophilic aromatic nitration: understanding its mechanism and substituent effects

Theoretical calculations and gas-phase mass spectrometric studies were performed for the reaction of the naked (NO2+) and monosolvated (CH3NO2.NO2+) nitronium ion with several monosubstituted aromatic compounds. From these studies, we propose a general model for regioselectivity based on the single-electron transfer (SET) mechanism and an alternative mechanistic scheme for electrophilic aromatic nitration. This scheme considers the SET and the polar (Ingold-Hughes) mechanisms as extremes in a continuum pathway, the occurrence and extents of both mechanisms being governed mainly by the ability, or lack of ability, of the aromatic compound to transfer an electron to NO2+.     

Synthesis of Novel Ethyl (substituted)phenyl‐4‐oxothiazolidin‐3‐yl)‐1‐ethyl‐4‐oxo‐1,4‐dihydroquinoline‐3‐Carboxylates as Potential Anticancer Agents

A series of ethyl (substituted)phenyl‐4‐oxothiazolidin‐3‐yl)‐1‐ethyl‐4‐oxo‐1,4‐dihydroquinoline‐3‐carboxylates ( 7a , 7b , 7c , 7d , 7e , 7f , 7g ) has been prepared from reactions between aminoquinolones 6 with arenealdehydes and mercaptoacetic acid. The critical intermediates, 6 a and 6b , were obtained from appropriate amines by a sequence of steps involving (i) reaction with diethylethoxymethylenemalonate, (ii) thermal cyclization in diphenyl ether, (iii) ethylation and (iv) Pd/C catalyzed reduction. New compounds 7a , 7b , 7c , 7d , 7e , 7f , 7g were fully identified and characterized by NMR (¹H and ¹³C) and specifically for 7d by X‐ray crystallography. Compounds 7b , 7c , 7d , 7e , 7f were found not to exhibit activity at 10 uM concentrations against gastric ascitis (AGP‐01), gastric adenocarcinoma kind intestinal (ACP‐02), colon (HCT‐116) and murine melanome (B16F10) cancer cells. However, none exhibited cytotoxicity against normal cells human fibroblast (MRC‐5), murine fibroblast (NIH3T3) and normal human melanocyte (Melan‐A).     

Rapid inorganic ion analysis using quantitative microchip capillary electrophoresis

Rapid quantitative microchip capillary electrophoresis (CE) for online monitoring of drinking water enabling inorganic ion separation in less than 15 s is presented. Comparing cationic and anionic standards at different concentrations the analysis of cationic species resulted in non-linear calibration curves. We interpret this effect as a variation in the volume of the injected sample plug caused by changes of the electroosmotic flow (EOF) due to the strong interaction of bivalent cations with the glass surface. This explanation is supported by the observation of severe peak tailing. Conducting microchip CE analysis in a glass microchannel, optimized conditions are received for the cationic species K+, Na+, Ca2+, Mg2+ using a background electrolyte consisting of 30 mmol/L histidine and 2-(N-morpholino)ethanesulfonic acid, containing 0.5 mmol/L potassium chloride to reduce surface interaction and 4 mmol/L tartaric acid as a complexing agent resulting in a pH-value of 5.8. Applying reversed EOF co-migration for the anionic species Cl-, SO42- and HCO3- optimized separation occurs in a background electrolyte consisting of 10 mmol/L 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) and 10 mmol/L HEPES sodium salt, containing 0.05 mmol/L CTAB (cetyltrimethylammonium bromide) resulting in a pH-value of 7.5. The detection limits are 20 micromol/L for the monovalent cationic and anionic species and 10 micromol/L for the divalent species. These values make the method very suitable for many applications including the analysis of abundant ions in tap water as demonstrated in this paper.     

Molecular distillation

Molecular distillation was studied for the separation of tocopherols from soya sludge, both experimentally and by simulation, under different operating conditions, with good agreement. Evaporator temperatures varied from 100°C to 160°C and feed flow rates ranged from 0.1 to 0.8 kg/h. The process pressure was maintained at 10⁻⁶ bar, the feed temperature at 50°C, the condenser temperature at 60°C, and the stirring at 350 rpm. For each process condition, samples of both streams (distillate and residue) were collected and stored at −18°C before tocopherols analyses. Owing to the differences between molecular weights and vapor pressures of free fatty acids and tocopherols, tocopherols preferentially remained in the residue at evaporator temperatures of 100°C and 120°C, whereas for higher temperatures (140°C and 160°C) and lower feed flow rate, tocopherols tended to migrate to the distillate stream.