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  • 1. Bertani, Federico
    et al.
    Riboni, Nicolò
    University of Parma, Italy.
    Bianchi, Federica
    Brancatelli, Giovanna
    Sterner, Elizabeth S.
    Pinalli, Roberta
    Geremia, Silvano
    Swager, Timothy M.
    Dalcanale, Enrico
    Triptycene-Roofed Quinoxaline Cavitands for the Supramolecular Detection of BTEX in Air2016In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, p. 3312-3319Article in journal (Refereed)
    Abstract [en]

    Two novel triptycene quinoxaline cavitands (DiTriptyQxCav and MonoTriptyQxCav) have been designed, synthesized, and applied in the supramolecular detection of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air. The complexation properties of the two cavitands towards aromatics in the solid state are strengthened by the presence of the triptycene moieties at the upper rim of the tetraquinoxaline walls, promoting the confinement of the aromatic hydrocarbons within the cavity. The two cavitands were used as fiber coatings for solid‐phase microextraction (SPME) BTEX monitoring in air. The best performances in terms of enrichment factors, selectivity, and LOD (limit of detection) values were obtained by using the DiTriptyQxCav coating. The corresponding SPME fiber was successfully tested under real urban monitoring conditions, outperforming the commercial divinylbenzene–Carboxen–polydimethylsiloxane (DVB–CAR–PDMS) fiber in BTEX adsorption.

  • 2. Bianchi, Federica
    et al.
    Agazzi, Silvia
    Riboni, Nicolò
    Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry. University of Parma, Italy.
    Erdal, Nejla
    Hakkarainen, Minna
    Ilag, Leopold
    Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.
    Anzillotti, Luca
    Andreoli, Roberta
    Moroni, Fabrizio
    Cecchi, Rossana
    Careri, Maria
    Novel sampling-substrates for the determination of new psychoactive substances in oral fluid by desorption electrospray ionization-high resolution mass spectrometryManuscript (preprint) (Other academic)
  • 3.
    Riboni, Nicolò
    et al.
    Università di Parma, Italy.
    Magrini, Laura
    Bianchi, Federica
    Careri, Maria
    Cappiello, Achille
    Sol-gel coated ion sources for liquid chromatography-direct electronionization mass spectrometry2017In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 978, p. 35-41Article in journal (Refereed)
    Abstract [en]

    Advances in interfacing liquid chromatography and electron ionization mass spectrometry are presented. New ion source coatings synthesized by sol-gel technology were developed and tested as vaporization surfaces in terms of peak intensity, peak width and peak delay for the liquid chromatography-direct electron ionization mass spectrometry (Direct-EI) determination of environmental pollutants like polycyclic aromatic hydrocarbons and steroids. Silica-, titania-, and zirconia-based coatings were sprayed inside the stainless steel ion source and characterized in terms of thermal stability, film thickness and morphology. Negligible weight losses until 350–400 °C were observed for all the materials, with coating thicknesses in the 6 (±1)-11 (±2) μm range for optimal ionization process. The best performances in terms of both peak intensity and peak width were obtained by using the silica-based coating: the detection of the investigated compounds was feasible at low ng μl−1 levels with a good precision (RSD < 9% for polycyclic aromatic hydrocarbons and <11% for hormones).

  • 4.
    Riboni, Nicolò
    et al.
    Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry. University of Parma, Italy.
    Quaranta, Alessandro
    Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.
    Motwani, Hitesh
    Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.
    Österlund, Nicklas
    Stockholm University, Faculty of Science, Department of Biochemistry and Biophysics.
    Gräslund, Astrid
    Stockholm University, Faculty of Science, Department of Biochemistry and Biophysics.
    Bianchi, Federica
    Ilag, Leopold
    Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.
    Solvent-Assisted Paper Spray Ionization (SAPSI) for the Analysis of Biomolecules and BiofluidsManuscript (preprint) (Other academic)
  • 5.
    Riboni, Nicolò
    et al.
    Università degli Studi di Parma, Italy.
    Trzcinski, Jakub W.
    Bianchi, Federica
    Massera, Chiara
    Pinalli, Roberta
    Sidisky, Leonard
    Dalcanale, Enrico
    Careri, Maria
    Conformationally blocked quinoxaline cavitand as solid-phase microextraction coating for the selective detection of BTEX in air2016In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 905, p. 79-84Article in journal (Refereed)
    Abstract [en]

    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 × 103 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.

  • 6. Trzciński, Jakub W.
    et al.
    Pinalli, Roberta
    Riboni, Nicolò
    Università di Parma, Italy.
    Pedrini, Alessandro
    Bianchi, Federica
    Zampolli, Stefano
    Elmi, Ivan
    Massera, Chiara
    Uguzzoli, Franco
    Dalcanale, Enrico
    In Search of the Ultimate Benzene Sensor: The EtQxBox Solution2017In: ACS Sensors, ISSN 2379-3694, Vol. 2, no 4, p. 590-598Article in journal (Refereed)
    Abstract [en]

    In this work we report a comprehensive study leading to the fabrication of a prototype sensor for environmental benzene monitoring. The required high selectivity and ppb-level sensitivity are obtained by coupling a silicon-integrated concentration unit containing the specifically designed EtQxBox cavitand to a miniaturized PID detector. In the resulting stand-alone sensor, the EtQxBox receptor acts at the same time as highly sensitive preconcentrator for BTEX and GC-like separation phase, allowing for the selective desorption of benzene over TEX. The binding energies of the complexes between EtQxBox and BTX are calculated through molecular mechanics calculations. The examination of the corresponding crystal structures confirms the trend determined by computational studies, with the number of C–H···N and CH···π interactions increasing from 6 to 9 along the series from benzene to o-xylene. The analytical performances of EtQxBox are experimentally tested via SPME, using the cavitand as fiber coating for BTEX monitoring in air. The cavitand EFs are noticeably higher than those obtained by using the commercial CAR-DVB-PDMS. The LOD and LOQ are calculated in the ng/m3 range, outperforming the commercial available systems in BTEX adsorption. The desired selective desorption of benzene is achieved by applying a smart temperature program on the EtQxBox mesh, which starts releasing benzene at lower temperatures than TEX, as predicted by the calculated binding energies. The sensor performances are experimentally validated and ppbv level sensitivity toward the carcinogenic target aromatic benzene was demonstrated, as required for environmental benzene exposure monitoring in industrial applications and outdoor environment.

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