New method to determine the total carbonyl functional group content in extractable particulate organic matter by tandem mass spectrometry

A functional group analysis method was developed to determine the quantitative content of carbonyl functional groups in atmospheric particulate organic matter (POM) using constant neutral loss scanning-tandem mass spectrometry (CNLS-MS/MS). The neutral loss method consists in monitoring the loss of a neutral fragment produced by the fragmentation of a precursor ion in a collision cell. The only ions detected are the daughter ions resulting from the loss of the neutral fragment under study. Then, scanning the loss of a neutral fragment characteristic of a functional group enables the selective detection of the compounds bearing the chemical function under study within a complex mixture. The selective detection of carbonyl functional groups was achieved after derivatization with pentafluorophenylhydrazine (PFPH) by monitoring the neutral loss of C(6)F(5)N (181 amu), which was characteristic of a large panel of derivatized carbonyl compounds. The method was tested on 25 reference mixtures of different composition, all containing 24 carbonyl compounds at randomly determined concentrations. The repeatability and calibration tests were satisfying as they resulted in a relative standard deviation below 5% and a linear range between 0.01 and 0.65 mM with a calculated detection limit of 0.0035 mM. Also, the relative deviation induced by changing the composition of the mixture while keeping the total concentration of carbonyl functional groups constant was less than 20%. These reliability experiments demonstrate the high robustness of the developed procedure for accurate carbonyl functional group measurement, which was applied to atmospheric POM samples.     

Spectral signatures and molecular origin of acid dissociation intermediates

The existence of a broad, mid-infrared absorption ranging from 1000 to 3000 cm(-1) is usually interpreted as a signature for the existence of protonated water networks. Herein, we use cryogenic mixtures of water and hydrogen fluoride (HF) and show experimental and computational evidence that similarly wide absorptions can be generated by a broad distribution of proton-shared and ion pair complexes. In the present case, we demonstrate that the broadening is mainly inhomogeneous, reflecting the fact that the topology of the first solvation shell determines the local degree of ionization and the shared-proton asymmetric stretching frequency within H2O x HF complexes. The extreme sensitivity of the proton transfer potential energy hypersurface to local hydrogen bonding topologies modulates its vibrational frequency from 2800 down to approximately 1300 cm(-1), the latter value being characteristic of solvation geometries that yield similar condensed-phase proton affinities for H2O and fluoride. By linking the local degree of ionization to the solvation pattern, we are able to propose a mechanism of ionization for HF in aqueous solutions and to explain some of their unusual properties at large concentrations. However, an important conclusion of broad scientific interest is our prediction that spectral signatures that are normally attributed to protonated water networks could also reveal the presence of strong hydrogen bonds between un-ionized acids and water molecules, with important consequences to spectroscopic investigations of biologically relevant proton channels and pumps.     

Reaction rates as a function of scale within ionic liquids: microscale in droplet microreactors versus macroscale reactions in the case of the Grieco three-component condensation reaction

Task-specific ionic liquids (TSILs) and more specifically binary task-specific ionic liquids (BTSILs), a unique subclass, have been shown to be excellent supports for solution-phase chemistry. The negligible volatility of ionic liquids enables their use as stable droplet microreactors in atmospheric environments without oil protection or confinement. These droplets can be moved, merged and mixed by electrowetting on a chip. Solution-phase synthesis can be performed on these open digital microfluidic labs-on-a-chip as illustrated by a study of the Grieco three-component reaction in [tmba][NTf(2)]-droplet (tmba=N-trimethyl-N-butylammonium NTf(2)=bis(trifluoromethylsulfonyl)imide) microreactors. A detailed study of matrices and scale effects on conversion and kinetic rates of this three-component condensation is presented in this paper. Reactions have been shown to be slower in droplets than in batches in the absence of additional mixing. Also, a significant influence of the ionic-liquid matrix has been observed. Finally, an increase of droplet's temperature resulted in a kinetics enhancement so as to reach macroscale reaction rates, probably because of a much better mixing of reaction's components involving a Marangoni's effect.     

Carboxylic acid functional group analysis using constant neutral loss scanning-mass spectrometry

The present study describes the development of a new analytical technique for the functional group determination of the carboxylic moiety using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS/MS) operated in the constant neutral loss scanning (CNLS) mode. Carboxylic groups were first derivatized into their corresponding methyl esters by reacting with BF₃/methanol mix and the reaction mixture was then directly injected into the APCI chamber. The loss of methanol (m/z = 32 amu) resulting from the fragmentation of the protonated methyl esters was then monitored. Applying this method together with a statistical approach to reference mixtures containing 31 different carboxylic acids at randomly calculated concentrations demonstrated its suitability for quantitative functional group measurements with relative standard deviations below 15% and a detection limit of 0.005 mmol L⁻¹. Its applicability to environmental matrices was also shown through the determination of carboxylic acid concentrations inside atmospheric aerosol samples. To the best of our knowledge, it is the first time that the tandem mass spectrometry was successfully applied to functional group analysis, offering great perspectives in the characterization of complex mixtures which are prevailing in the field of environmental analysis as well as in the understanding of the chemical processes occurring in these matrices.     

Trichloroethylene Combustion in a Submerged Thermal Plasma: Results and Chemical Kinetics Model

This work deals with incineration of organic liquid wastes using an oxygen thermal plasma jet, submerged in water. The results presented here concern incineration of trichloroethylene (TCE). During a trial run, the CO₂ and CO content in the exhaust gas is continuously measured; samples taken periodically from the solution are analyzed by appropriate methods: total organic carbon and chlorine content are measured. Process efficiency during tests with a few L/h of TCE is given by the mineralization rate. The trapping rate of chlorine as HCl is near 100 %. The TCE destruction and removal efficiency, measured by MS/GC, is better than 99.9999 %. A simplified kinetic model of gas quenching was constructed from a single-phase plug-flow reactor model taking into account 14 species and 34 reactions. It satisfies the requirements of heat balance and major components analysis, and reveals the major role of the OH radical on the concentrations of CO as well as HCl and/or Cl₂ in the off-gas stream.     

Generation of Silicone Poly‐HIPEs with Controlled Pore Sizes via Reactive Emulsion Stabilization

Macrocellular silicone polymers are obtained after solidification of the continuous phase of a poly(dimethylsiloxane) emulsion, which contains poly(ethylene glycol) drops of sub‐millimetric dimensions. Coalescence of the liquid template emulsion is prohibited by a reactive blending approach. The relationship is investigated in detail between the interfacial properties and the emulsion stability, and micro‐ and millifluidic techniques are used to generate macrocellular polymers with controlled structural properties over a wider range of cell sizes (0.2–2 mm) and volume fractions of the continuous phase (0.1%–40%). This approach could easily be transferred to a wide range of polymeric systems.

     

Studying variations in the PCDD/PCDF profile across various food products using multivariate statistical analysis

Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) are widely recognized by the scientific community as persistent organic pollutants due to their toxicity and adverse effects on wildlife and human health. The actual regulation dedicated to the monitoring of dioxins in food is based on the measurement of 17 congener concentrations. The final result is reported as a toxic equivalent value that takes into account the relative toxicity of each congener. This procedure can minimize the qualitative information available from the abundances of each PCDD/PCDF congener: the characteristic contamination profile of the sample. Multivariate statistical techniques, such as principal component analysis (PCA) or linear discriminant analysis (LDA), represent an interesting way to investigate this qualitative information. Nevertheless, they have only been applied to the analysis of contamination data from food products and biological matrices infrequently. The objective of the present study was to analyze a large data set from dioxin analyses performed on various food products of animal origin. The results demonstrate the existence of differences in congener-specific patterns between the analyzed samples. Variability was first demonstrated in terms of the food type (fish, meat, milk, fatty products). Then a variability was observed that was related to the specific animal species for meat and milk samples (bovine, ovine, porcine, caprine and poultry). Some practical applications of these results are discussed. The origin(s) of the observed differences, as well as their significance, now remain to be investigated, both in terms of environmental factors and transfer through living organisms. A better knowledge of the relation between a contamination profile and its specific source and/or food product should be of great interest to scientists working in the fields of contaminant analysis, toxicology and metabolism, as well as to regulatory bodies and risk assessors in charge of final decisions regarding the eventual hazards associated with theses substances.