@article{RiebeEderRitscheletal.2016, author = {Riebe, Daniel and Eder, Alexander and Ritschel, Thomas and Beitz, Toralf and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Beil, Andreas and Blaschke, Michael and Ludwig, Thomas}, title = {Atmospheric pressure chemical ionization of explosives induced by soft X-radiation in ion mobility spectrometry: mass spectrometric investigation of the ionization reactions of drift gasses, dopants and alkyl nitrates}, series = {Journal of mass spectrometr}, volume = {51}, journal = {Journal of mass spectrometr}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {1076-5174}, doi = {10.1002/jms.3784}, pages = {566 -- 577}, year = {2016}, abstract = {A promising replacement for the radioactive sources commonly encountered in ion mobility spectrometers is a miniaturized, energy-efficient photoionization source that produce the reactant ions via soft X-radiation (2.8 keV). In order to successfully apply the photoionization source, it is imperative to know the spectrum of reactant ions and the subsequent ionization reactions leading to the detection of analytes. To that end, an ionization chamber based on the photoionization source that reproduces the ionization processes in the ion mobility spectrometer and facilitates efficient transfer of the product ions into a mass spectrometer was developed. Photoionization of pure gasses and gas mixtures containing air, N-2, CO2 and N2O and the dopant CH2Cl2 is discussed. The main product ions of photoionization are identified and compared with the spectrum of reactant ions formed by radioactive and corona discharge sources on the basis of literature data. The results suggest that photoionization by soft X-radiation in the negative mode is more selective than the other sources. In air, adduct ions of O-2 - with H2O and CO2 were exclusively detected. Traces of CO2 impact the formation of adduct ions of O-2 - and Cl -(upon addition of dopant) and are capable of suppressing them almost completely at high CO2 concentrations. Additionally, the ionization products of four alkyl nitrates (ethylene glycol dinitrate, nitroglycerin, erythritol tetranitrate and pentaerythritol tetranitrate) formed by atmospheric pressure chemical ionization induced by X-ray photoionization in different gasses (air, N-2 and N2O) and dopants (CH2Cl2, C2H5Br and CH3I) are investigated. The experimental studies are complemented by density functional theory calculations of the most important adduct ions of the alkyl nitrates (M) used for their spectrometric identification. In addition to the adduct ions [M + NO3](-) and [M + Cl](-), adduct ions such as [M + N2O2](-), [M + Br](-) and [M+ I](-) were detected, and their gas-phase structures and energetics are investigated by density functional theory calculations. Copyright (C) 2016 John Wiley \& Sons, Ltd.}, language = {en} } @phdthesis{Riebe2016, author = {Riebe, Daniel}, title = {Experimental and theoretical investigations of molecular ions by spectroscopy as well as ion mobility and mass spectrometry}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-94632}, school = {Universit{\"a}t Potsdam}, pages = {143}, year = {2016}, abstract = {The aim of this thesis was the elucidation of different ionization methods (resonance-enhanced multiphoton ionization - REMPI, electrospray ionization - ESI, atmospheric pressure chemical ionization - APCI) in ion mobility (IM) spectrometry. In order to gain a better understanding of the ionization processes, several spectroscopic, mass spectrometric and theoretical methods were also used. Another focus was the development of experimental techniques, including a high resolution spectrograph and various combinations of IM and mass spectrometry. The novel high resolution 2D spectrograph facilitates spectroscopic resolutions in the range of commercial echelle spectrographs. The lowest full width at half maximum of a peak achieved was 25 pm. The 2D spectrograph is based on the wavelength separation of light by the combination of a prism and a grating in one dimension, and an etalon in the second dimension. This instrument was successfully employed for the acquisition of Raman and laser-induced breakdown spectra. Different spectroscopic methods (light scattering and fluorescence spectroscopy) permitting a spatial as well as spectral resolution, were used to investigate the release of ions in the electrospray. The investigation is based on the 50 nm shift of the fluorescence band of rhodamine 6G ions of during the transfer from the electrospray droplets to the gas phase. A newly developed ionization chamber operating at reduced pressure (0.5 mbar) was coupled to a time-of-flight mass spectrometer. After REMPI of H2S, an ionization chemistry analogous to H2O was observed with this instrument. Besides H2S+ and its fragments, H3S+ and protonated analyte ions could be observed as a result of proton-transfer reactions. For the elucidation of the peaks in IM spectra, a combination of IM spectrometer and linear quadrupole ion trap mass spectrometer was developed. The instrument can be equipped with various ionization sources (ESI, REMPI, APCI) and was used for the characterization of the peptide bradykinin and the neuroleptic promazine. The ionization of explosive compounds in an APCI source based on soft x-radiation was investigated in a newly developed ionization chamber attached to the ion trap mass spectrometer. The major primary and secondary reactions could be characterized and explosive compound ions could be identified and assigned to the peaks in IM spectra. The assignment is based on the comparison of experimentally determined and calculated IM. The methods of calculation currently available exhibit large deviations, especially in the case of anions. Therefore, on the basis of an assessment of available methods, a novel hybrid method was developed and characterized.}, language = {en} } @phdthesis{MichalikOnichimowska2022, author = {Michalik-Onichimowska, Aleksandra}, title = {Real-time monitoring of (photo)chemical reactions in micro flow reactors and levitated droplets by IR-MALDI ion mobility and mass spectrometry}, doi = {10.25932/publishup-55729}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-557298}, school = {Universit{\"a}t Potsdam}, pages = {v, 68}, year = {2022}, abstract = {Eine nachhaltigere chemische Industrie erfordert eine Minimierung der L{\"o}sungsmittel und Chemikalien. Daher werden Optimierung und Entwicklung chemischer Prozesse vor einer Produktion in großem Maßstab in kleinen Chargen durchgef{\"u}hrt. Der entscheidende Schritt bei diesem Ansatz ist die Skalierbarkeit von kleinen Reaktionssystemen auf große, kosteneffiziente Reaktoren. Die Vergr{\"o}ßerung des Volumens des Reaktionsmediums geht immer mit der Vergr{\"o}ßerung der Oberfl{\"a}che einher, die mit dem begrenzenden Gef{\"a}ß in Kontakt steht. Da das Volumen kubisch, w{\"a}hrend die Oberfl{\"a}che quadratisch mit zunehmendem Radius skaliert, nimmt ihr Verh{\"a}ltnis nicht linear zu. Viele an der Grenzfl{\"a}che zwischen Oberfl{\"a}che und Fl{\"u}ssigkeit auftretende Ph{\"a}nomene k{\"o}nnen die Reaktionsgeschwindigkeiten und Ausbeuten beeinflussen, was zu falschen Prognosen aufgrund der kleinskaligen Optimierung f{\"u}hrt. Die Anwendung von schwebenden Tropfen als beh{\"a}lterlose Reaktionsgef{\"a}ße bietet eine vielversprechende M{\"o}glichkeit, die oben genannten Probleme zu vermeiden. In der vorgestellten Arbeit wurde eine effiziente Kopplung von akustisch schwebenden Tropfen und IM Spektrometer f{\"u}r die Echtzeit{\"u}berwachung chemischer Reaktionen entwickelt, bei denen akustisch schwebende Tropfen als Reaktionsgef{\"a}ße fungieren. Das Design des Systems umfasst die ber{\"u}hrungslose Probenahme und Ionisierung, die durch Laserdesorption und -ionisation bei 2,94 µm realisiert wird. Der Umfang der Arbeit umfasst grundlegende Studien zum Verst{\"a}ndnis der Laserbestrahlung von Tropfen im akustischen Feld. Das Verst{\"a}ndnis dieses Ph{\"a}nomens ist entscheidend, um den Effekt der zeitlichen und r{\"a}umlichen Aufl{\"o}sung der erzeugten Ionenwolke zu verstehen, die die Aufl{\"o}sung des Systems beeinflusst. Der Aufbau umfasst eine akustische Falle, Laserbestrahlung und elektrostatische Linsen, die bei hoher Spannung unter Umgebungsdruck arbeiten. Ein effektiver Ionentransfer im Grenzfl{\"a}chenbereich zwischen dem schwebenden Tropfen und dem IMS muss daher elektrostatische und akustische Felder vollst{\"a}ndig ber{\"u}cksichtigen. F{\"u}r die Probenahme und Ionisation wurden zwei unterschiedliche Laserpulsl{\"a}ngen untersucht, n{\"a}mlich im ns- und µs-Bereich. Die Bestrahlung {\"u}ber µs-Laserpulse bietet gegen{\"u}ber ns-Pulse mehrere Vorteile: i) das Tropfenvolumen wird nicht stark beeinflusst, was es erm{\"o}glichet, nur ein kleines Volumen des Tropfens abzutasten; ii) die geringere Fluenz f{\"u}hrt zu weniger ausgepr{\"a}gten Schwingungen des im akustischen Feld eingeschlossenen Tropfens und der Tropfen wird nicht aus dem akustischen Feld r{\"u}ckgeschlagen, was zum Verlust der Probe f{\"u}hren w{\"u}rde; iii) die milde Laserbestrahlung f{\"u}hrt zu einer besseren r{\"a}umlichen und zeitlichen Begrenzung der Ionenwolken, was zu einer besseren Aufl{\"o}sung der detektierten Ionenpakete f{\"u}hrt. Schließlich erm{\"o}glicht dieses Wissen die Anwendung der Ionenoptik, die erforderlich ist, um den Ionenfluss zwischen dem im akustischen Feld suspendierten Tropfen und dem IM Spektrometer zu induzieren. Die Ionenoptik aus 2 elektrostatischen Linsen in der N{\"a}he des Tropfens erm{\"o}glicht es, die Ionenwolke effektiv zu fokussieren und direkt zum IM Spektrometer-Eingang zu f{\"u}hren. Diese neuartige Kopplung hat sich beim Nachweis einiger basischer Molek{\"u}le als erfolgreich erwiesen. Um die Anwendbarkeit des Systems zu belegen, wurde die Reaktion zwischen N-Boc Cysteine Methylester und Allylalkohol in einem Chargenreaktor durchgef{\"u}hrt und online {\"u}berwacht. F{\"u}r eine Kalibrierung wurde der Reaktionsfortschritt parallel mittels 1H-NMR verfolgt. Der beobachtete Reaktionsumsatz von mehr als 50\% innerhalb der ersten 20 Minuten demonstrierte die Eignung der Reaktion, um die Einsatzpotentiale des entwickelten Systems zu bewerten.}, language = {en} } @article{KopyraWierzbickaTulwinetal.2021, author = {Kopyra, Janina and Wierzbicka, Paulina and Tulwin, Adrian and Thiam, Guillaume and Bald, Ilko and Rabilloud, Franck and Abdoul-Carime, Hassan}, title = {Experimental and theoretical studies of dissociative electron attachment to metabolites oxaloacetic and citric acids}, series = {International Journal of Molecular Sciences (IJMS)}, volume = {22}, journal = {International Journal of Molecular Sciences (IJMS)}, number = {14}, publisher = {MDPI}, address = {Basel}, issn = {1422-0067}, doi = {10.3390/ijms22147676}, pages = {14}, year = {2021}, abstract = {In this contribution the dissociative electron attachment to metabolites found in aerobic organisms, namely oxaloacetic and citric acids, was studied both experimentally by means of a crossed-beam setup and theoretically through density functional theory calculations. Prominent negative ion resonances from both compounds are observed peaking below 0.5 eV resulting in intense formation of fragment anions associated with a decomposition of the carboxyl groups. In addition, resonances at higher energies (3-9 eV) are observed exclusively from the decomposition of the oxaloacetic acid. These fragments are generated with considerably smaller intensities. The striking findings of our calculations indicate the different mechanism by which the near 0 eV electron is trapped by the precursor molecule to form the transitory negative ion prior to dissociation. For the oxaloacetic acid, the transitory anion arises from the capture of the electron directly into some valence states, while, for the citric acid, dipole- or multipole-bound states mediate the transition into the valence states. What is also of high importance is that both compounds while undergoing DEA reactions generate highly reactive neutral species that can lead to severe cell damage in a biological environment.}, language = {en} } @misc{KopyraWierzbickaTulwinetal.2021, author = {Kopyra, Janina and Wierzbicka, Paulina and Tulwin, Adrian and Thiam, Guillaume and Bald, Ilko and Rabilloud, Franck and Abdoul-Carime, Hassan}, title = {Experimental and theoretical studies of dissociative electron attachment to metabolites oxaloacetic and citric acids}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, number = {1156}, issn = {1866-8372}, doi = {10.25932/publishup-52182}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-521829}, pages = {16}, year = {2021}, abstract = {In this contribution the dissociative electron attachment to metabolites found in aerobic organisms, namely oxaloacetic and citric acids, was studied both experimentally by means of a crossed-beam setup and theoretically through density functional theory calculations. Prominent negative ion resonances from both compounds are observed peaking below 0.5 eV resulting in intense formation of fragment anions associated with a decomposition of the carboxyl groups. In addition, resonances at higher energies (3-9 eV) are observed exclusively from the decomposition of the oxaloacetic acid. These fragments are generated with considerably smaller intensities. The striking findings of our calculations indicate the different mechanism by which the near 0 eV electron is trapped by the precursor molecule to form the transitory negative ion prior to dissociation. For the oxaloacetic acid, the transitory anion arises from the capture of the electron directly into some valence states, while, for the citric acid, dipole- or multipole-bound states mediate the transition into the valence states. What is also of high importance is that both compounds while undergoing DEA reactions generate highly reactive neutral species that can lead to severe cell damage in a biological environment.}, language = {en} } @article{ErlerRiebeBeitzetal.2018, author = {Erler, Alexander and Riebe, Daniel and Beitz, Toralf and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Grothusheitkamp, Daniela and Kunz, T. and Methner, Frank-J{\"u}rgen}, title = {Detection of volatile organic compounds in the headspace above mold fungi by GC-soft X-radiation-based APCI-MS}, series = {Journal of mass spectrometr}, volume = {53}, journal = {Journal of mass spectrometr}, number = {10}, publisher = {Wiley}, address = {Hoboken}, issn = {1076-5174}, doi = {10.1002/jms.4210}, pages = {911 -- 920}, year = {2018}, abstract = {Mold fungi on malting barley grains cause major economic loss in malting and brewery facilities. Possible proxies for their detection are volatile and semivolatile metabolites. Among those substances, characteristic marker compounds have to be identified for a confident detection of mold fungi in varying surroundings. The analytical determination is usually performed through passive sampling with solid phase microextraction, gas chromatographic separation, and detection by electron ionization mass spectrometry (EI-MS), which often does not allow a confident determination due to the absence of molecular ions. An alternative is GC-APCI-MS, generally, allowing the determination of protonated molecular ions. Commercial atmospheric pressure chemical ionization (APCI) sources are based on corona discharges, which are often unspecific due to the occurrence of several side reactions and produce complex product ion spectra. To overcome this issue, an APCI source based on soft X-radiation is used here. This source facilitates a more specific ionization by proton transfer reactions only. In the first part, the APCI source is characterized with representative volatile fungus metabolites. Depending on the proton affinity of the metabolites, the limits of detection are up to 2 orders of magnitude below those of EI-MS. In the second part, the volatile metabolites of the mold fungus species Aspergillus, Alternaria, Fusarium, and Penicillium are investigated. In total, 86 compounds were found with GC-EI/APCI-MS. The metabolites identified belong to the substance classes of alcohols, aldehydes, ketones, carboxylic acids, esters, substituted aromatic compounds, terpenes, and sesquiterpenes. In addition to substances unspecific for the individual fungus species, characteristic patterns of metabolites, allowing their confident discrimination, were found for each of the 4 fungus species. Sixty-seven of the 86 metabolites are detected by X-ray-based APCI-MS alone. The discrimination of the fungus species based on these metabolites alone was possible. Therefore, APCI-MS in combination with collision induced dissociation alone could be used as a supervision method for the detection of mold fungi.}, language = {en} }