Determination of blood:air, urine:air and plasma:air partition coefficients of selected microbial volatile organic compounds.

Partition coefficients (PCs) are essential parameters for understanding the toxicokinetics of chemicals in the human body since they are used in the description of different processes of absorption, distribution, and excretion in physiologically based pharmacokinetic (PBPK) models used in chemical exposure and risk assessment. The goal of this study was to determine urine:air, blood:air and plasma:air partition coefficients (PCs) of microbial volatile organic compounds (mVOCs) previously selected as having high potential as biomarkers of indoor mold exposure. To achieve this goal, the vial-equilibration technique was used, and quantification was performed using headspace gas chromatography tandem mass spectrometry (HS-GC-MS/MS) analysis. Matrix:air PCs of 19 different mVOCs have been successfully determined and their values ranged between 14 and 3586 for urine:air, 78 and 4721 for blood:air and 64 and 5604 for plasma:air PCs. Water:air PCs were also determined, and their values varied between 16 and 2210, showing a good correlation with urine:air PCs for 17 compounds of the selected mVOCs (R2 = 0.97, slope close to unity) indicating that water:air PCs below 103 may be a good surrogate for urine:air PCs. All studied mVOCs have high blood:air PCs (greater than 78) indicating strong pulmonary uptake. Due to their high blood:urine PCs, some mVOCs may be more easily measured in blood than in urine. This work is an important preliminary step toward the use of mVOCs as potential biomarkers of indoor mold exposure. The data obtained in this study will help to determine the most appropriate matrix to use in this biomonitoring approach and will eventually facilitate the development of PBPK models for these chemicals.

A new headspace solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry method for the simultaneous quantification of 21 microbial volatile organic compounds in urine and blood.

Mold growth can cause the development of several metabolites including microbial volatile organic compounds (mVOCs). These latter may be considered as potential biomarkers of fungal presence and have been detected in human biological matrices such as urine and blood. Exposure to molds and their metabolites (e.g., mVOCs, mycotoxins) in occupational settings, is responsible for several health effects. Thus, this exposure cannot be neglected and must be evaluated. Herein, a method has been developed to quantify 21 mVOCs in urine and human blood by headspace solid phase micro-extraction (HS-SPME) coupled with gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). The parameters influencing the extraction process, such as the type of fiber, the incubation and extraction time and temperature and the desorption time, have been optimized to ensure better mVOCs extraction. The developed method showed good linearity over the concentration range of the compounds (R2 ˃ 0.995) for all the mVOCs in all the matrices. The low limits of detection (LOD) ranging from 0.7 to 417 ng/L in urine and from 1 to 507 ng/L in blood, make the developed methods sensitive and effective for biomonitoring of exposure at low levels. Recoveries, at low and high concentrations, were between 87% and 120% in urine and between 83% and 118% in blood. The repeatability and the intermediate precision in terms of coefficients of variation (CV%) was lower than 13% and 8.58% respectively for all compounds in all matrices. These values show satisfactory accuracy and precision of the developed method. Thus, this practical, simple, and sensitive method is well suited for the simultaneous quantification of target mVOCs.

Temporal and spatial variations in the levels of prominent airborne disinfection by-products at four indoor swimming pools.

Exposure to airborne disinfection by-products, especially trichloramine and trichloromethane, may cause various adverse health effects for the workers and users of indoor swimming pools. This study aims to evaluate the spatial and temporal variations in trichloramine and trichloromethane concentrations within and between swimming pools. Workplace measurements were carried out at four indoor swimming pools in Quebec (Canada) during the cold season. To fully represent daily operating conditions, sampling started 2 hr before the swimming pool opened and continued until 2 hr after closing. To quantify trichloramine and trichloromethane concentrations, 304 air samples have been collected. Temperature, humidity, and CO2 were measured-simultaneously every 2 hr. The results showed that both trichloramine and trichloromethane concentrations varied significantly in time. The observed daily variations in trichloramine and trichloromethane concentrations suggest that the common practice of collecting a single 2-hr air sample does not represent daily pool trichloramine and trichloromethane contamination levels and, consequently, does not represent the true exposure and health risks for workers that are present for a full 8-hr shift. This study recommends a new 8-hr sampling strategy or a full-shift strategy using a cassette with three impregnated filters as a valid and cost-effective solution for comparing time-weighted average (TWA) concentrations to permissible trichloramine exposure limits.

Building large supramolecular nanocapsules with europium cations.

A new tripodal ligand has been designed by connecting pyridine-based coordination units to a rigid triptycene moiety. Its reaction with europium(III) provides three-dimensional tetranuclear edifices, whose structural and photophysical characteristics as well as host-guest interactions are discussed in this contribution.

Lanthanide-mediated supramolecular cages and host-guest interactions.

The structure and thermodynamic properties of lanthanide complexes with a new tripodal ligand L2 have been elucidated using different physicochemical methods. At stoichiometric ratios, the tetrahedral three-dimensional complexes with lanthanide cations are formed in acetonitrile with good stabilities. Despite minor structural changes comparing to previously investigated tripodal ligands, the resulting assembly exhibits different features revealed with the crystal structure of [Eu(4)L2(4)](OH)(ClO(4))(11) (orthorhombic, Pbcn). Interestingly, the highly charged edifice contains an inner cage encapsulating a perchlorate anion. Such lanthanide mediated cage-like assemblies are rare, and may be of interest for different sensing applications. Indeed, the anionic guest can be exchanged with different anions. The related host-guest equilibria were investigated with NMR techniques. Various aspects of these reactions are qualitatively discussed.

Rational design of a ternary supramolecular system: self-assembly of pentanuclear lanthanide helicates.

The self-assembly of the first pentanuclear helicate was predicted on the structural basis obtained for linear and tetranuclear parent supramolecular compounds. Accordingly, the designed ternary supramolecular system requires appropriate polytopic organic receptors, which were successfully synthesized. Indeed, the formation of pentanuclear complexes was experimentally evidenced with NMR and ESMS spectra that perfectly reflect the expected pattern. The structural features in the europium pentanuclear complex are highlighted with semiempirical molecular modeling. The present work validates the combinatorial approach leading to the thermodynamically driven formation of tower-like pentanuclear edifices.

Unsymmetrical tripodal ligand for lanthanide complexation: structural, thermodynamic, and photophysical studies.

Two tridentate and one bidentate binding strands have been anchored on a carbon atom to provide a new unsymmetrical tripodal ligand L for Ln(III) coordination. The ligand itself adopts a single conformation in solution stabilized by intramolecular hydrogen bonds evidenced in the solid state. The reaction of L with trivalent lanthanides provides different coordination complexes depending on the metal/ligand ratio. The speciation studies with selected lanthanides were performed in solution by means of NMR, ESMS, and spectrophotometric titrations. Differences in coordination properties along the lanthanide series were evidenced and may be associated with the changes in the ionic size. However, thermodynamic stability constants for the species of the same stoichiometry do not significantly vary. In addition, the structure of the dinuclear complex [Eu(2)L(2)](6+) has been elucidated in the solid state, where the complex crystallizes predominantly as an M-isomer. The crystal structure shows the coordination of two different ligands to each europium cation through tridentate strands, and the europium nine-coordinate sphere is completed with three solvent molecules. Finally, the results of photophysical investigations of [Eu(2)L(2)](6+) are in close agreement with the structural parameters determined by crystallography.