Analytische Chemie
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Infraredmatrix-assisted laser dispersion and ionization(IR-MALDI) in combination with on mobility (IM) spectrometry enables the direct Analysis of biomolecules in aqueous solution. The release of ions directly from an aqueous solution is based on a phase explosion, induced by the Absorption of an IR laser pulse, which disperses the liquid as vapor, nano- and micro-droplets. The ionization process is characterized initially by a broad spatial distribution of the ions, which is a result of complex fluid dynamics and desolvation kinetics. These processes have a profound effect on the shape and width of the peaks in the IM spectra. In this work, the Transport of ions by the phase explosion-induced shockwave could be studied independently from the transport by the electric field. The shockwave-induced mean velocities of the ions at different time scales were determined through IM spectrometry and shadowgraphy. The results show a deceleration of the Ions from 118m∙s−1 at a distance of 400 μm from the liquid surface to 7.1 m∙s−1 at a distance of 10 mm, which is caused by a pileup effect. Furthermore, the desolvation kinetics were investigated
and a first-order desolvation constant of 325 ± 50 s−1
was obtained. In the second part, the IR-MALDI-IM
spectrometer is used as an HPLC detector for the twodimensional separation of a pesticide mixture.
This article describes the application of the ion mobility spectrometry (IMS) as a technical link in the screening within the airfreight transport chain. Air freight is of very important also for German foreign trade. Every year around 4.3 Mt of freight are loaded at German airports and transported by air planes. The average value of a transported metric ton freight was approximately 81,000 € in 2015. Nearly 50 percent of the total air freight is transported in passenger planes as belly freight. Measures are necessary to detect illegal, dangerous items such as weapons, ammunition or improvised explosive devices (IED) to protect against attacks on air traffic security. The aim is to increase security in air traffic and at the same time contemporary increasing or at least unchanged efficiency in the airfreight transport chain.
IMS is a suitable instrumental technology for the trace detection of explosives (ETD) and their precursors orthogonal to radiological x-ray measurements on suspicious freight within 30 seconds and per EU regulation 2015/1998, section 6.2. The ECAC* certified ETD system QS-B220 was used. The IMS performance is demonstrated on three target compounds, TNT, RDX and PETN. The results’ evaluation of this semi-quantitative screening is carried out by using statistical methods for reliability assessment, such as probability of detection (POD) and receiver operating characteristic (ROC). Their detection limits with a POD = 0.90 are determined after swab sampling on various surfaces. These screening results provide an objective decision-making aid to responsible control personnel in addition to x-ray measurements, whether there are or are no dangerous substances or objects in the cargo.
*) ECAC = European Civil Aviation Conference
In many laser based ionization techniques with a subsequent drift time separation, the laser pulse generating the ions is considered as the start time t0. Therefore, an accurate temporal definition of this event is crucial for the resolution of the experiments. In this contribution, the laser induced plume dynamics of liquids evaporating into atmospheric pressure are visualized for two distinctively different laser pulse widths, Δt = 6 nanoseconds and Δτ = 280 microseconds. For ns-pulses the expansion of the generated vapour against atmospheric pressure is found to lead to turbulences inside the gas phase. This results in spatial and temporal broadening of the nascent clouds. A more equilibrated expansion, without artificial smearing of the temporal resolution can, in contrast, be observed to follow μs-pulse excitation. This leads to the counterintuitive finding that longer laser pulses results in an increased temporal vapour formation definition. To examine if this fume expansion also eventually results in a better definition of ion formation, the nascent vapour plumes were expanded into a linear drift tube ion mobility spectrometer (IMS). This time resolved detection of ion formation corroborates the temporal broadening caused by collisional impeding of the supersonic expansion at atmospheric pressure and the overall better defined ion formation by evaporation with long laser pulses. A direct comparison of the observed results strongly suggests the coexistence of two individual ion formation mechanisms that can be specifically addressed by the use of appropriate laser sources.
DNA and locked nucleic acid (LNA) were characterized as single strands, as well as double stranded DNA-DNA duplexes and DNA-LNA hybrids using tandem mass spectrometry with collision-induced dissociation. Additionally, ion mobility spectrometry was carried out on selected species. Oligonucleotide duplexes of different sequences – bearing mismatch positions and abasic sites of complementary DNA 15-mers – were investigated to unravel general trends in their stability in the gas phase. Single stranded LNA oligonucleotides were also investigated with respect to their gas phase behavior and fragmentation upon collision-induced dissociation. In contrast to the collision-induced dissociation of DNA, almost no base loss was observed for LNAs. Here, backbone cleavages were the dominant dissociation pathways. This finding was further underlined by the need for higher activation energies. Base losses from the LNA strand were also absent in fragmentation experiments of the investigated DNA-LNA hybrid duplexes. While DNA-DNA duplexes dissociated easily into single stranded fragments, the high stability of DNA-LNA hybrids resulted in predominant fragmentation of the DNA part rather than the LNA, while base losses were only observed from the DNA single strand of the hybrid.
IMS trägt zur Luftfrachtsicherheit bei Luftsicherheitsgesetze verpflichten Luftsicherheitsbehörden, Flughafenbetreiber und Fluggesellschaften umfassende Sicherheitsmaßnahmen auf den Flughäfen zu ergreifen, um Gefahren z. B. durch potenziell gefährliche Frachtgüter zu erkennen. Von der Europäische Zivilluftfahrt-Konferenz (ECAC) zertifizierte IMS-Geräte werden vor Ort an den Kontrollpunkten orthogonal zur Radiologie eingesetzt, um chemische Informationen von verdächtiger Fracht über Gefahrstoffe wie Sprengstoffe oder Drogen vor dem Verladen zu erhalten.
Vor der Detektion von Sprengstoffen beginnt die Untersuchung eines verdächtigen Objekts mit der Probenahme mittels Wischprobensammlern. Eine Luftsicherheitskontrollkraft wischt dabei Oberflächen des Objekts mit einem Probensammler ab, um Partikel von Gefahrstoffen zu sammeln. Der beladene Probensammler wird anschließend in einen Probeneinlass eingeführt. Nach thermischer Desorption der gesammelten Stoffe erhält der Bediener (z. B. Luftsicherheitskontrollkraft) ein boolesches Ergebnis - "Alarm" oder "Kein Alarm".
Verfahren und Ergebnisse
In dieser Studie wurden drei Verfahren mit vier ECAC-zertifizierten ETD-Geräten zur Identifizierung und Beurteilung der Probenahme (PN) entwickelt:
I) direkte PN durch lösemittelbasierten Auftrag einer bekannten Sprengstoffmenge auf einem Probensammler,
II) Auftrag einer bekannten Menge eines gelösten Sprengstoffs auf einem 10 cm × 10 cm Substrat (Aluminium, Papier, Eisen und Polyvinylchlorid) und manuelle PN nach Lösemittelverdampfung,
III) lösemittelbasierter Sprengstoffauftrag auf eine PTFE- oder PTFE-beschichtete Glasfaseroberfläche, nach Lösemittelverdunstung trockene Übertragung auf das zu beprobende Substrat zur PN.
Der Zusammenhang zwischen vorgelegter Sprengstoffmenge und der Detektionswahrscheinlichkeit (POD) erfolgt durch Anwendung des binären Regressionsverfahrens mit einer Logit-Funktion:
POD=1/(1+exp(-A(m-B)) )·100%
Dabei entspricht m der vorgelegten Sprengstoffmasse bis 1000 ng, Parameter A / ng-1 der logistischen Wachstumsrate der Kurve und Parameter B / ng dem m-Wert des Mittelpunktes des Sigmoids. Die Bestimmung der Parameter wurde nach der Methode der kleinsten Quadrate berechnet.
Das entwickelte Messunsicherheitsmodell kombiniert quantitative Ergebnisse aus Stammlösung und deren Verdünnungen sowie Stoffauftrag und qualitative Ergebnisse nach Anzeige "Alarm" oder "Kein Alarm". Dieses Auswerteverfahren wurde auf die Probenahme angewandt. Identifizierte Unsicherheitsursachen sind die Durchführung der Wischprobenahme, Staub, Lösemitteleffekte und die Unsicherheit bei der Herstellung von Testlösungen.
The ability to controllably move gaseous ions is an essential aspect of ion-based spectrometry (e.g., mass spectrometry and ion mobility spectrometry) as well as materials processing. At higher pressures, ion motion is largely governed by diffusion and multiple collisions with neutral gas molecules. Thus, high-pressure ion optics based on electrostatics require large fields, radio frequency drives, complicated geometries, and/or partially transmissive grids that become contaminated. Here, we demonstrate that low-power standing acoustic waves can be used to guide, block, focus, and separate beams of ions akin to electrostatic ion optics. Ions preferentially travel through the static-pressure regions (“nodes”) while neutral gas does not appear to be impacted by the acoustic field structure and continues along a straight trajectory. This acoustic ion manipulation (AIM) approach has broad implications for ion manipulation techniques at high pressure, while expanding our fundamental understanding of the behavior of ions in gases.