Comparison of the performance of three ion mobility spectrometers for measurement of biogenic amines

The performance of three different types of ion mobility spectrometer (IMS) devices: GDA2 with a radioactive ion source (Airsense, Germany), UV-IMS with a photo-ionization source (G.A.S. Germany) and VG-Test with a corona discharge source (3QBD, Israel) was studied. The gas-phase ion chemistry in the IMS devices affected the species formed and their measured reduced mobility values. The sensitivity and limit of detection for trimethylamine (TMA), putrescine and cadaverine were compared by continuous monitoring of a stream of air with a given concentration of the analyte and by measurement of headspace vapors of TMA in a sealed vial. Preprocessing of the mobility spectra and the effectiveness of multivariate curve resolution techniques (MCR-LASSO) improved the accuracy of the measurements by correcting baseline effects and adjusting for variations in drift time as well as enhancing the signal to noise ratio and deconvolution of the complex data matrix to their pure components. The limit of detection for measurement of the biogenic amines by the three IMS devices was between 0.1 and 1.2 ppm (for TMA with the VG-Test and GDA, respectively) and between 0.2 and 0.7 ppm for putrescine and cadaverine with all three devices. Considering the uncertainty in the LOD determination there is almost no statistically significant difference between the three devices although they differ in their operating temperature, ionization method, drift tube design and dopant chemistry. This finding may have general implications on the achievable performance of classic IMS devices.     

The structure of protonated diamines and polyamines

The reduced mobilities in air, at 200C, of six isomeric C₇H₁₈N₂ protonated diamines, two triamines (caldine and spermidine), and two tetramines (thermine and spermine) were measured by ion mobility spectrometric (IMS) techniques. The results indicated that all these polyamines undergo proton-induced cyclization, with the proton forming a bridge between two amino groups. It appears as if the favored configuration of the protonated polyamines involves a six- or seven-membered ring rather than a bridge between the terminal amino groups. It is believed that in the tetramines the cyclic structure is formed between the two central, more basic, secondary amine sites.     

Determination of volatile biogenic amines in muscle food products by ion mobility spectrometry

The extent of spoilage of muscle food products was determined through measurement of volatile biogenic amines that emanated from food samples. The release of the amines was enhanced by addition of a few drops of an alkaline solution and the amines were monitored by ion mobility spectrometry (IMS). The limit of detection of the method for trimethylamine (TMA) was 2 ng and the measurement was completed within <2 min with short and long term reproducibility of 15 and 25%, respectively, for replicate samples. The method provides qualitative information as it distinguishes between different amines, as well as quantitative data for the key compounds. A good correlation was found between the IMS results and the microorganism populations in microbiological cultures. The effects of storage time and temperature and of the type of meat on the formation of biogenic amines were examined, and as expected, the higher the storage temperature the faster the spoilage. Thus, this pilot study shows that the measurement of biogenic amines can serve as an indicator for food spoilage or freshness.     

On the structure of water—alcohol and ammonia—alcohol protonated clusters

Collision-induced dissociation (CID) of protonated ammonia-alcohol and water-alcohol heteroclusters was studied using a triple quadrupole mass spectrometer with a corona discharge atmospheric pressure ionization source. CID results suggested that the ammonia-alcohol clusters had NH: at the core of the cluster and that hydrogen-bonded alcohol molecules solvated this central ion. In contrast, CID results in water-alcohol clusters showed that water loss was strongly favored over alcohol loss and that there was a preference for the charge to reside on an alcohol molecule. The results also indicated that a loose chain of hydrogen-bonded molecules was formed in the water-alcohol clusters and that there appeared to be no rigid protonation site or a fixed central ion. (J Am Soc Mass     

Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.     

An ion mobility spectrometry/mass spectrometry (IMS/MS) study of the site of protonation in anilines

Ion mobility spectrometry (IMS) and IMS/MS techniques were used to differentiate between nitrogenprotonated and carbon-protonated anilines, both of which coexist under the conditions of the IMS. Analysis of the results led to the conclusion that the former species had lower mobilities than the latter. This was attributed mainly to charge delocalization in the ring-protonated species, which results in a weaker interaction with the drift gas molecules. Furthermore,meta-alkyl substitution enhanced ring protonation, while in 2-chloroaniline the nitrogenprotonated species was predominant, as expected.     

Collision-induced dissociation studies of protonated alcohol and alcohol—water clusters by atmospheric pressure ionization tandem mass spectrometry. 1?Methanol

Cluster size distribution and collision-induced dissociation (CID) studies of protonated methanol and protonated methanol—water clusters yield information on the structure and energetics of such ions. Ions were formed at atmospheric pressure in a corona discharge source, and were subjected to CID in the center quadrupole of a triple quadrupole mass spectrometer. Cluster ions containing up to 13 molecules of methanol and/or water were observed and examined using CID experiments. The CID of all (CH₃OH)_n · H₂O · H⁺ clusters, where n ? 8, showed that water loss was statistically favored over methanol loss and that the preferred dissociation channel involved loss of water with methanol molecules. These results support a model employing a chain of hydrogen-bonded solvent molecules rather than one in which fused rings of ligands surround a central hydronium ion. However, CID of larger clusters, where n ? 9, showed that loss of one methanol was equal to or less than loss of water, reflecting a change in structure.     

Ion mobility spectrometry: a personal retrospective

With a background in mass spectrometric studies of gas-phase ion chemistry the atmospheric pressure technology of ion mobility spectrometry (IMS) presented me with challenges and opportunities. Fundamental studies of the parameters that influence the mobility of ions in a low electric field yielded insights about the effects of temperature, drift gas composition and the conformation of ions on the collision cross section. The inadequacy of current rigid-sphere, polarization limit and hard-core models to predict the mobility of ions particularly at low temperature and in heavy drift gases, led to inclusion of additional terms to the hard-core model to account for these effects. These studies eventually resulted in the two monographs entitled “Ion Mobility Spectrometry” and “Ion Mobility Spectrometry –Second Edition” co-authored with Prof. Gary Eiceman and published by Taylor & Francis, CRC Press in 1994 and 2005, respectively. Novel applications for biological and medical applications were developed on the basis of measurement of biogenic amines by IMS, in particular the rapid, accurate and inexpensive diagnosis of vaginal infections.     

Biogenic amines in bread as indicators of spoilage

Elevated levels of biogenic amines (trimethylamine, putrescine and cadaverine), measured by ion mobility spectrometry (IMS) were found in a sample of “dark rye” bread that had a pungent odor but not in other bread samples. The odorless breads included three types of rye bread, whole wheat, pita bread and a baguette. Sample preparation was simple and consisted of extraction of the biogenic amines into water followed by filtering the solution. The biogenic amines were measured from a single drop (50 μL) of the extract solution. The progress of spoilage was also monitored in the odorous and odorless “dark rye”. Volatile trimethylamine, readily monitored by IMS, was the main compound responsible for the offensive odor in the spoilt bread. The samples were classified by an automatic algorithm as “fresh”, “intermediate” or “spoilt” on the basis of the total biogenic amine level. Thus, we report the development of a fast and objective method to distinguish between spoilt bread and bread that is suitable for consumption.