Ultra-sensitive solid-phase Microextraction-Gas Chromatography-Mass spectrometry determination of polycyclic aromatic hydrocarbons in snow samples using a deep cavity BenzoQxCavitand.

A very sensitive and selective solid-phase microextraction-gas chromatography-mass spectrometry method based on the use of a deep cavity BenzoQxCavitand as innovative coating was developed and validated for the simultaneous determination of the 16 US-EPA priority pollutants polycyclic aromatic hydrocarbons (PAHs) in snow samples at ultra-trace levels. The presence of a 8.3 Å deep hydrophobic cavity allowed the engulfment of all the 16 PAHs, providing enhanced selectivity also in presence of interfering aromatic pollutants at high concentration levels. Validation proved the reliability of the method for the determination of the investigated compounds achieving detection limits in the 0.03-0.30 ng/L range, good precision, with relative standard deviations <18% and recovery rates in the 90.8(±2.1)%-109.6(±1.0)%. The detection of low-molecular weight PAHs in snow samples from Antarctica and Alps confirms the widespread occurrence of these compounds, thus assessing the impact of anthropogenic activities onto the environment.

Conformationally blocked quinoxaline cavitand as solid-phase microextraction coating for the selective detection of BTEX in air.

A tetraquinoxaline cavitand functionalized with methylenoxy bridges at the upper rim is proposed as selective solid-phase microextraction (SPME) coating for the determination of BTEX at trace levels in air. The SPME fibers were characterized in terms of film thickness, morphology, thermal stability and extraction capabilities. An average coating thickness of 35 (±4) µm, a thermal stability up to 350 °C and a good fiber-to-fiber and batch-to-batch repeatability with RSD lower than 15% were obtained. Excellent enrichment factors ranging from 360-700 × 10(3) were obtained for the investigated compounds. Finally, method validation proved the capabilities of the developed coating for the selective sampling of BTEX, achieving LOD values in the 0.4-1.2 ng m(-3) range.

Probing cavitand-organosilane hybrid bilayers via sum-frequency vibrational spectroscopy.

Quinoxaline cavitands (QxCav) are transferred by Langmuir-Schaefer method on self-assembled monolayers (SAMs) of octadecyltrichlorosilane (OTS) and N,N-dimethyl-N-octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) on fused silica substrates. The molecular architectures of both the hydrophobic SAMs templates and the hybrid cavitand-organosilanes bilayers at the solid-air interface are investigated and correlated by sum-frequency vibrational spectroscopy. The results show that QxCav are always in the closed vase configuration and orient with their principal axis normal to the substrates. The role of the alkyl chains density in the SAM templates on the QxCav transfer ratio is pointed out.

Supramolecular Sensors for the Detection of Alcohols.

Cooperativity between different noncovalent host-guest interactions is the key for the successful generation of selective supramolecular sensors. A new class of cavitands capable of synergistic CH small middle dot small middle dot small middle dotpi interactions and hydrogen bonding has been designed and exploited for the detection of alcohol vapors using mass transducers (see schematic representation).