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The emergence of new super-insulated buildings to reduce energy consumption places the quality of indoor air at the center of the debate. Among the indoor air pollutants, aldehydes are often present, and formaldehyde is of major interest regarding its multiple sources and its health impact. Therefore, French regulations expect to reduce formaldehyde concentrations below 10 µg m −3 in public buildings by 2023. Formaldehyde and other aldehydes were measured for two weeks during an intensive field campaign conducted in a school recently built and equipped with programmable dual-flow ventilation. Aldehydes were monitored with the ISO 16000-3 reference method based on sampling with 2,4-dinitrophenylhydrazine (DNPH) tubes while formaldehyde concentration was continuously measured by using a sensitive near real-time formaldehyde microanalyzer with a detection limit of 1 µg m −3 . Formaldehyde was the major aldehyde. Its concentrations varied in the range of 2-25 µg m −3 and decreased by half when mechanical ventilation was ON, while the other ones were always below 5 µg m −3 . In addition, an excellent agreement was observed between the different analytical techniques deployed to quantify formaldehyde levels. The microanalyzer was able to measure fast variations of formaldehyde concentration in the studied room, according to the building's ventilation periods.

Highlights • Novel analytical micro-device for quantification of gaseous formaldehyde • Gaseous Formaldehyde uptake through the establishment of a microfluidic annular flow • Formaldehyde detection using colorimetric cell using a liquid-core-waveguide

This paper is focused on the improvement of a microfluidic analytical method for the detection of low airborne formaldehyde concentrations, based on only two distinct steps permitting to reduce the response time and to improve the compactness of the device. First, gaseous formaldehyde is trapped into an acetylacetone solution at 65°C through an annular liquid/gas flow and reacts immediately to form 3,5-Diacetyl-1,4-dihydrolutidine which is then quantified by colorimetry using a liquid core waveguide (LCW). To obtain an annular flow, 3 different hydrophilic silica capillaries of 320, 450 and 530µm ID were tested and the corresponding phase diagrams were obtained in the ranges of liquid and gas flows of 5-35µLmin and 5-35mLmin respectively. Finally, the analytical performances were determined using the lowest flow values of 5µLmin and 5NmLmin, ensuring an annular flow and increasing the microdevice autonomy. If the uptake yield of gaseous formaldehyde into the solution was close to 100%, only the 530µm ID capillary permits to obtain a reaction time long enough for a full conversion of formaldehyde into 3,5-Diacetyl-1,4-dihydrolutidine. With a LCW pathlength of 5cm, the microdevice response was perfectly linear in the range 0-154µgm with a detection limit of 1.8µgm.

It is noted that, for a small series of 3,5-diacetyl-1,4-dihydrolutidine (DDL) derivatives and the corresponding Hantzsch esters, the presence of methyl groups at the 2,6-positions serves to extinguish fluorescence in solution but not in the solid state. Emission is weakly activated and affected by changes in solvent polarity. The latter situation arises because the optical transition involves intramolecular charge transfer. Calculations, both semiempirical and DFT, indicate that, in all cases, rotation of the carbonyl function is facile and that the dihydropyridine ring is planar. These calculations also indicate that the 2,6-methyl groups do not affect the generic structure of the molecule. It is proposed that illumination increases the molecular dipole moment and pushes electron density toward the carbonyl oxygen atom. Proton transfer can now occur from one of the methyl groups, leading to formation of a relatively low-energy, neutral intermediate, followed by a second proton transfer step that forms the enol. Reaction profiles computed for the ground-state species indicate that this route is highly favored relative to hydrogen transfer from the 4-position. The barriers for light-induced proton transfer are greatly reduced relative to the ground-state process but such large-scale structural transformations are hindered in the solid state. A rigid analogue that cannot form an enol is highly emissive in solution, supporting the conclusion that proton transfer is in competition to fluorescence in solution.

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