We describe a rapid in situ method for detecting agrochemicals on the surface or in the tissue of fruit using a portable mass spectrometer equipped with an ambient ionization source. Two such ionization methods, low temperature plasma (LTP) and paper spray (PS), were employed in experiments performed at a local grocery store. LTP was used to detect diphenylamine (DPA) directly from the skin of apples in the store and those treated after harvest with DPA were recognized by MS and MS/MS. These data therefore allowed ready distinction between organic and non-organic apples. DPA was also found within the internal tissue of purchased apples and its distribution was mapped using LTP. Similarly, thiabendazole residues were detected on the skin of treated oranges in a grocery store experiment in which paper spray was performed by wiping the orange surface with a moist commercial lens wipe and then applying a high voltage to ionize the chemicals directly from the wipe. The handheld mass spectrometer used in these measurements is capable of performing several stages of tandem mass spectrometry (up to MS(5)); the compounds on the fruit were identified by their MS/MS fragmentation patterns. Protonated DPA (m/z 170) produced a characteristic MS(2) fragment ion at m/z 92, while thiabendazole was identified by MS(3) using precursor to fragment ion transitions m/z 202 →m/z 175 →m/z 131. These particular examples exemplify the power of in situ analysis of complex samples using ambient ionization and handheld mass spectrometers.
Ion mobility spectra are initiated when ions, derived from a sample, are pulsed or injected through ion shutters into a drift region. The effect on signal intensity from electric fields arising from the shutter grids (E(s)) and a superimposed electric field of the drift tube (E(d)) was determined experimentally and simulated computationally for ion motion at ambient pressure. The combination of these two fields influenced shutter performance in three ways: (1) intensity of an ion peak was suppressed by increased current in the baseline due to continuous leakage of ions into the drift region from insufficient E(s) to block ion motion when needed, at a given value of E(d); (2) the ion shutter provided maximum peak intensity with some optimal ratio of E(s)/E(d) when ions were fully blocked except using the injection time; (c) the signal intensity was reduced when the blocking voltage of the ion shutter exceeded this optimal E(s)/E(d) ratio from ion depletion at the shutter grids. The optimal ratio from the computer models was equal to 1.50, whereas a value of 2.50 was obtained from the experimental findings. This difference was attributed to nonideal geometry with the grids of the shutter and the conducting elements in the drift tube establishing both E(s) and E(d). As both the experimental and modeling results demonstrated, a mobility dependence of ion yield from the ionization source was found to cause a mobility dependent ion signal at the collector electrode.
Chlorophenols (CPs) as a mixture of fourteen congeners from mono-to pentachlorophenol were determined using liquid chromatography/electrospray ionization/ ion mobility spectrometry (LC/ESI/IMS) to describe the response and analytical performance of a mobility spectrometer as a detector for liquid chromatography. The mobility spectrometer was equipped with an interface so that flows from a large bore column could be electrosprayed directly into the drift tube at flow rates up to 500 μL/min without splitting of flow. A linear gradient of the mobile phase from 40% to 90% methanol and 60% to 10% acetic acid (AcOH)-ammonium acetate buffer solution over 40 min with a C18 column provided baseline separations though mobility spectra for CPs were influenced by mobile phase composition. Product ions formed from CPs with ESI included phenoxide anions CPO − , AcOH·CPO − , CPOH·CPO − , and Na + ·(CPO − ) 2 and were found to be governed by the drift gas temperature. Ions were identified using LC/ESI/mass spectrometry (MS) and supported by results from computational modeling. Quantitative response was affected by congener structure through the acidities of the OH moiety and by the composition of the mobile phase. Limits of detection ranged from 0.135 mg/L for 2,3,5-trichlorophenol and pentachlorophenol to 2.23 mg/L for 2-chlorophenol; corresponding linear ranges were 20 and 70.
A new ambient ionization method--leaf-spray mass spectrometry--is used to detect allergenic urushiols directly from poison ivy (T. radicans) leaves with no sample preparation. These simple measurements show all the urushiols previously reported using liquid chromatography mass spectrometry methods. Tandem mass spectrometry analysis of the leaf spray ions confirms the identifications. Enhanced detection of some urushiols was achieved in the negative mode with the addition of chloride anions to the spray solvent.
Mass spectrometry benefits from a flexible definition which equates it with many aspects of the science of matter in the ionized state. The field continues to expand rapidly, not only to encompass larger and more complex molecules through more powerful instruments, but simultaneously towards in-situ measurements made using smaller, more flexible and just-sufficiently-powerful instruments. The senior author has been fortunate to work in mass spectrometry from 1967 to the present and has been involved in a wide range of efforts which have covered analytical, biological, organic, instrumental and physical aspects of the subject. This effort has been made in the company of a remarkable set of colleagues. From this vantage, it is possible to look both backwards and forwards in this prospective and retrospective piece. This presentation involves a personal look at places, people, instruments and concepts engaged in along a path through Mass Spectrometry. The journey goes from Natal, South Africa, via Cambridge, UK, through Kansas and on to Purdue University, in the great state of Indiana. It starts with natural products chemistry and moves to the physical chemistry of fragmentation and energy partitioning on to complex mixture analysis by tandem mass spectrometry and, hence, to the concepts of thermochemical determination by the kinetic method, preparation of materials by ion soft landing, the possible role of amino acid clusters in the origin of homochiral life and the elaboration of a set of ambient ionization methods for chemical analysis performed using samples in their native state. Special attention is given to novel concepts and instrumentation and to the emerging areas of ambient ionization, molecular imaging and miniature mass spectrometers. Personal mass spectrometers appear to be just over the horizon as is the large-scale use of mass spectrometry in field-based analysis, including point-of-care medical diagnostics.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.