CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
New Materials and Improved Ambient Techniques in Mass Spectrometry
Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry. University of Parma, Italy.ORCID iD: 0000-0002-0789-3812
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Mass spectrometry (MS) is used in several fields, e.g. biology, environmental monitoring, medicine and forensics due to excellent qualitative and quantitative capabilities. The development of new instrumental setups and ionization sources is crucial to analyze a variety of compounds at trace levels. The synergy between material science and analytical chemistry allowed the development of new materials characterized by specific features of polarity, porosity and functionalization, able to interact with targeted analytes in complex matrices, resulting in high extraction efficiency even in presence of overwhelming amounts of interfering compounds. New methods based on the use of new materials and MS techniques for analytes extraction and detection have been proposed, providing fast analysis times, enhanced selectivity and increased sensitivity.

In this thesis, the development of new materials and setups for mass spectrometric applications is discussed.

In Paper I-III the design, synthesis, characterization and evaluation of the analytical performances of four new supramolecular receptors for targeted extraction of benzene, toluene, ethylbenzene and xylenes (BTEX) are reported. The synthesized materials were used as solid-phase microextraction coatings (SPME) for the GC-MS determination of BTEX at trace levels in urban air. In addition, a portable device for in-situ and real-time monitoring of BTEX using these receptors in the preconcentration unit is presented.

In Paper IV the development of coated ion sources able to improve the performances of an interface coupling liquid chromatography (LC) and electron ionization (EI), called Direct-EI LC-MS, is discussed. The coatings, obtained by sol-gel technique, were deposited onto commercial stainless steel EI sources to increase the inertness of its vaporization surface.

In Paper V, a rapid screening method for the detection of new psychoactive substances (NPS) in oral fluids is presented. New slides based on polylactide (PLLA), carbon particles and silica were tested as probe materials to promote the ionization of the analytes in desorption electrospray ionization – high resolution mass spectrometry (DESI-HRMS). Microextraction by packed sorbent (MEPS) of the analytes from the saliva samples was required due to the high signal suppression. The developed MEPS-DESI-HRMS method was validated and applied for the determination of NPS in road-collected samples.

In Paper VI the development of a new setup called solvent assisted paper spray ionization (SAPSI) is reported. This integrated solution allowed the increased data acquisition time and a close control over the ionization conditions. It was applied for the analysis of biomolecules, namely proteins, lipids, glycans, and amyloid peptides/aggregates, in aqueous solution as well as in human serum and cerebrospinal fluid. Different oligomeric species of amyloid aggregates were detected and it was possible to perform real-time monitoring of disaggregation processes. Modified protein species of physiological relevance such as oxidation, cysteinylation, glycosylation and glycation, and adduct formation were identified.

In conclusion, the new materials and setups discussed in this thesis allowed the development of selective and sensitive MS methods for the determination of different target compounds in complex matrices at trace levels with reduced sample pretreatment.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science and Analytical Chemistry, Stockholm University , 2019. , p. 100
Keywords [en]
Mass Spectrometry, Solid Phase Microextraction, Ambient Mass Spectrometry, Desorption Electrospray Ionization, Paper Spray Ionization, Cavitands, BTEX, New Psychoactive Substances
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-162306ISBN: 978-91-7797-516-8 (print)ISBN: 978-91-7797-517-5 (electronic)OAI: oai:DiVA.org:su-162306DiVA, id: diva2:1265377
Public defence
2019-01-18, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Manuscript. Paper 6: Manuscript.

Available from: 2018-12-19 Created: 2018-11-23 Last updated: 2019-01-22Bibliographically approved
List of papers
1. Conformationally blocked quinoxaline cavitand as solid-phase microextraction coating for the selective detection of BTEX in air
Open this publication in new window or tab >>Conformationally blocked quinoxaline cavitand as solid-phase microextraction coating for the selective detection of BTEX in air
Show others...
2016 (English)In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 905, p. 79-84Article in journal (Refereed) Published
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.

Keywords
Solid-phase microextraction, BTEX, Cavitands, Air monitoring
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-162290 (URN)10.1016/j.aca.2015.12.005 (DOI)
Available from: 2018-11-22 Created: 2018-11-22 Last updated: 2018-11-23Bibliographically approved
2. Triptycene-Roofed Quinoxaline Cavitands for the Supramolecular Detection of BTEX in Air
Open this publication in new window or tab >>Triptycene-Roofed Quinoxaline Cavitands for the Supramolecular Detection of BTEX in Air
Show others...
2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, p. 3312-3319Article in journal (Refereed) Published
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.

Keywords
cavitands, environmental monitoring, host–guest systems, solid-phase microextraction, volatile organic compounds
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-162292 (URN)10.1002/chem.201504229 (DOI)
Available from: 2018-11-22 Created: 2018-11-22 Last updated: 2018-11-23Bibliographically approved
3. In Search of the Ultimate Benzene Sensor: The EtQxBox Solution
Open this publication in new window or tab >>In Search of the Ultimate Benzene Sensor: The EtQxBox Solution
Show others...
2017 (English)In: ACS Sensors, ISSN 2379-3694, Vol. 2, no 4, p. 590-598Article in journal (Refereed) Published
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.

Keywords
benzene sensor, cavitands, MEMS device, preconcentrators, SPME fiber
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-162296 (URN)10.1021/acssensors.7b00110 (DOI)
Available from: 2018-11-22 Created: 2018-11-22 Last updated: 2018-11-23Bibliographically approved
4. Sol-gel coated ion sources for liquid chromatography-direct electronionization mass spectrometry
Open this publication in new window or tab >>Sol-gel coated ion sources for liquid chromatography-direct electronionization mass spectrometry
Show others...
2017 (English)In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 978, p. 35-41Article in journal (Refereed) Published
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).

Keywords
Ion source, Liquid chromatography-direct electron ionization mass spectrometry, Coatings, Sol-gel
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-162303 (URN)10.1016/j.aca.2017.04.026 (DOI)
Available from: 2018-11-22 Created: 2018-11-22 Last updated: 2018-11-23Bibliographically approved
5. Novel sampling-substrates for the determination of new psychoactive substances in oral fluid by desorption electrospray ionization-high resolution mass spectrometry
Open this publication in new window or tab >>Novel sampling-substrates for the determination of new psychoactive substances in oral fluid by desorption electrospray ionization-high resolution mass spectrometry
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-162304 (URN)
Available from: 2018-11-22 Created: 2018-11-22 Last updated: 2018-11-23Bibliographically approved
6. Solvent-Assisted Paper Spray Ionization (SAPSI) for the Analysis of Biomolecules and Biofluids
Open this publication in new window or tab >>Solvent-Assisted Paper Spray Ionization (SAPSI) for the Analysis of Biomolecules and Biofluids
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-162305 (URN)
Available from: 2018-11-22 Created: 2018-11-22 Last updated: 2019-08-21Bibliographically approved

Open Access in DiVA

New Materials and Improved Ambient Techniques in Mass Spectrometry(3868 kB)55 downloads
File information
File name FULLTEXT01.pdfFile size 3868 kBChecksum SHA-512
0bdf83dd4b7899da8a24fa79f0c1a6817204dda0d78bbd5daabbc42e87b961ce5dc8f141a363426bb1fb1310058cb78bc5b6e4935818adb8e376aef672cdf061
Type fulltextMimetype application/pdf
errata(231 kB)0 downloads
File information
File name ERRATA01.pdfFile size 231 kBChecksum SHA-512
6efadf9c4432ee8691a3440caed960e4cbc1ce9dc93ce5211bba1336f0b8b43cd98d2a6f49b9e42302ca3768658d42b3785941dc215a5c05d59989301301a269
Type errataMimetype application/pdf

Search in DiVA

By author/editor
Riboni, Nicolò
By organisation
Department of Environmental Science and Analytical Chemistry
Analytical Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 55 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 353 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf