Secondary electrospray ionizationmass spectrometry sesi ms breathprinting of multiple bacterial lung pathogens, a mouse model study jiangjiang zhu, heather d. Secondary electrospray ionization sesi is an ambient ionization technique for the analysis of. Desolvation by gas flow n or gentle capillary 22 2 heating 100heating 100300 deg c. It is especially useful in producing ions from macromolecules because it overcomes the propensity of these molecules to fragment when ionized. Still today, the routine calibration of mass spectral data relies on ubiquitous plasticizes and other contaminants i. Hill school of engineering, university of vermont, burlington, vermont submitted 24 january 20. As a class, sims instruments aka ion microprobes use an internally generated beam of either positive e. The electrospray ionization esi is a soft ionization technique extensively used for production of gas phase ions without fragmentation of thermally labile large supramolecules. Journal of the american society for mass spectrometry. Applications of highresolution electrospray ionization. Originally described by canadianamerican physicist sir arthur j. We determine the sensitivity of several commercial atmospheric pressure ionization mass spectrometers towards ambient vapors, ionized by.
Secondary electrospray ionizationmass spectrometry sesims. Evolution of indoor cooking emissions captured by using. More than 600 compounds have been found during and after cooking, including n. Liquid chromatographymass spectrometry lcms ion chromatogram and the corresponding electrospray mass spectrum are shown. Secondary electrospray ionization sesi of ambient vapors for. Secondary electrospray ionization sesi of ambient vapors for explosive detection at concentrations below parts per trillion. Nizkorodov, department of chemistry, university of california, irvine, california 92617, united states.
Secondary electrospray ionizationmass spectrometry sesi. Bateman, julia laskin, alexander laskin, and sergey a. A secondary electrospray ionization sesi method was developed as a nonradioactive ionization source for ion mobility spectrometry ims. Hill university of vermont, school of engineering, burlington, vermont 054050156 received 25 february 2010returned for modi. A proofofprinciple study, clinical chemistry, volume 62, issue 9, 1 september 2016, pages 12301237. This sesi method relied on the gasphase interaction. Apr 15, 2019 secondary electrospray ionization super sesi the super sesi source was optimized for breath analysis and integrates all components required to control the ionization of the sample flow. Realtime quantification of amino acids in the exhalome by. The aim of this work was to develop and apply a method for the real. Electrospray ionization esi is a method by which solutes present in a solution. Despite the attractiveness of breath analysis as a noninvasive means to retrieve relevant metabolic information, its introduction into routine clinical practice remains a challenge. Applications of highresolution electrospray ionization mass.
Secondary electrospray ionization sesi of ambient vapors. Secondary electrospray ionizationmass spectrometry iopscience. We determine the sensitivity of several commercial atmospheric pressure ionization mass spectrometers towards ambient vapors, ionized by contact with an electrospray of acidified or ammoniated solvent, a technique often referred to as secondary electrospray ionization sesi. A series of fatty acids among other compounds have recently been detected in breath in real time by secondary electrospray. Secondary ionization chemistry and physics britannica. Ions are mostly preformed in solution before desorption. Bentzley1, 1department of chemistry and biochemistry, university of the sciences in philadelphia, 600 south 43rd street, philadelphia, pa 19104, usa, 2laboratory of new drug research and mass spectrometry. Indeed, most laboratories and ms users have databases of identified contaminants, which appear in the mass spectra regardless of the liquid sample. Desorption electrospray ionization desi mass spectrometry. Fast detection of volatile organic compounds from bacterial. Among all the different analytical techniques available to interrogate exhaled breath, secondary electrospray ionization highresolution mass spectrometry sesihrms offers a number of advantages e. The persistence of the signals produced by these commonly known. Pdf liquid chromatographyelectrospray ionization tandem. The effect of solvent on the analysis of secondary organic.
Desorption ionization methods can be performed on solid or liquid samples, and allows for the sample to be nonvolatile or thermally unstable. Schematic diagram of electrospray secondary electrospray ionization ionmobility spectrometry mass spectrometry. Interfacing liquid chromatography with electrospray ionization mass spectrometry. Secondary structures stabilize more highly charged negative ions. Apr 15, 2019 despite the attractiveness of breath analysis as a noninvasive means to retrieve relevant metabolic information, its introduction into routine clinical practice remains a challenge. Electrospray is produced by applying a strong electric field to a liquid passing through a capillary tube with a weak flux. Dempster in an article titled a new method of positive ray analysis. Electrospray ionization esi is a technique used in mass spectrometry to produce ions using an electrospray in which a high voltage is applied to a liquid to create an aerosol. A compilation of articles devoted to electrospray can be found in a recent special issue of the journal of aerosol science 8. Ambient ionization methods for ms enable direct, highthroughput measurements of samples in the open air. Sesims breath analysis was performed in positiveion mode within 1 h of breath collection, as previously described 27, 50 on a modified sciex api 3000 mass spectrometer concord, on, canada. We propose a novel application of secondary electrospray ionization mass spectrometry sesims as a realtime clinical diagnostic tool for bacterial infection. Realtime breath analysis with active capillary plasma ionizationambient mass spectrometry lukas bregy, pablo martinezlozano sinues, maryia m nudnova et. Secondary electrospray ionizationmass spectrometry sesims and breath sampling.
This technique continues to be the method of choice for analyzing thermolabile chemicals. Electrospray ionization mass spectrometry chemistry libretexts. Vapor pressure of hexamethylene triperoxide diamine. Visualizing mass transport in desorption electrospray. In the subsequent reaction, the charge is transferred and vapors get ionized, most molecules get protonated in positive mode and deprotonated in. Translating secondary electrospray ionizationhighresolution. Berchtold and others published secondary electrospray ionization find, read and cite all the research you need on researchgate. We exposed target vapors to electrosprays of either water or deuterated water and mass analyzed them. Esi is different from other ionization processes e. The manufacturers ionization source was modified to enable direct vapor measurements using secondary electrospray ionization sesi by removing the glass window from the. This study examined the effect of solvent on the analysis of organic aerosol extracts using electrospray ionization mass spectrometry esims. Secondary electrospray ionization proceeds via gasphase. Vapor pressure of hexamethylene triperoxide diamine hmtd.
Pdf in secondary electrospray ionization sesi systems, gaseous analytes exposed to an electrospray plume become ionized after charge is. Using realtime mass spectrometry, we investigated the profiles of volatile and semivolatile organic compounds voc, svoc in exhaled breath of patients suffering from chronic obstructive pulmonary disease copd with and without frequent exacerbations. Online breath analysis is a painless, noninvasive method to get insights into the metabolism of patients. A highthroughput and sensitive bioanalytical method using liquid chromatographyelectrospray ionization tandem mass spectrometry lcesimsms has been developed. In this new method, charged droplets and ions produced from the electrospray are directed by a highvelocity gas jet to the surface. Electrospray ionization esi a mechanical syringe pump injects the liquid sample usually less than one mm in a polar volatile solvent into the capillary needle, and thereby nebulizing it into a fine mist 1. Standardization procedures for realtime breath analysis by secondary electrospray ionization. Secondary organic aerosol soa produced by ozonation of dlimonene, as well as several organic molecules with functional groups typical for oa constituents, were extracted in methanol, d3methanol, acetonitrile, and d3acetonitrile to investigate the. Secondary structural characterization of oligonucleotide. This means that ionization of samples such as proteins, peptides, olgiopeptides, and some inorganic molecules can be performed.
Electrospray ionization mass spectrometry chemistry. This sesi method relied on the gasphase interaction between charged particles created by electrospray ionization esi and neutral gaseous sample molecules. Mass spectrometry ms was used as the detection method after ion mobility separation for ion. Sep 01, 2016 diego garciagomez, thomas gaisl, lukas bregy, alessio cremonesi, pablo martinezlozano sinues, malcolm kohler, renato zenobi, realtime quantification of amino acids in the exhalome by secondary electrospray ionizationmass spectrometry. This sesi method relied on the gasphase interaction between charged particles cre ated by electrospray ionization esi and neutral gaseous sample molecules. It is known that volatile organic compounds vocs, produced in different combinations and quantities by bacteria as metabolites, generate characteristic odors for certain bacteria. Secondary electrospray ionization ion mobility spectrometrymass. Standardization procedures for realtime breath analysis. Pdf secondary electrospray ionizationmass spectrometry sesi. Electrospray ionization mass spectrometry is a desorption ionization method. A fraction of the total exhaled flow is passed to the ionizer, which features a sampling line connected to an ionization chamber whereby a nanoelectrospray.
The method was first described by fenn and colleagues 1 and has been applied to the detection of illicit drugs 2 and explosives 34, the characterization of skin volatiles. Deprotonation scheme 2 is an ionization method by which the net negative charge of 1 is achieved through the figure 4. Among all the different analytical techniques available to interrogate exhaled breath, secondary electrospray ionization highresolution mass. Standardization procedures for realtime breath analysis by. Secondary electrospray ionization mass spectrometry sesims for this type of metabolomic analysis, a quadrupole timeofflight instrument was. In secondary electrospray ionization sesi systems, gaseous analytes exposed to an elecrospray plume become ionized after charge is. Our main goal was to gain further insights into the mechanism by which gasphase analytes are ionized by interaction with plumes of electrospray solvents. Pdf secondary electrospray ionization of complex vapor mixtures. Sims offers spatial resolution at the nanometer scale, but the detection is limited to lipids, other metabolites, and elements. Secondary electrospray ionization sesi is an ambient ionization technique for the analysis of trace concentrations of vapors, where a nanoelectrospray produces charging agents that collide with the analyte molecules directly in gasphase.
Typically an analyte will undergo three major processes after injection and transfers into the gas phase. Schematic diagram of electrospraysecondary electrospray ionization ionmobility spectrometry mass spectrometry. Translating secondary electrospray ionization highresolution mass spectrometry to the clinical environment to cite this article. Electrospray ionization mass spectrometry is a technique used to determine molecular weights for proteins, peptides, and other biological macromolecules such as oligosaccharides 1. Bacterial cultures by secondary electrospray ionizationmass spectrometry jiangjiang zhu, heather d. A new method for analyzing the composition of electronic cigarette ec vapors based on secondary electrospray ionization mass spectrometry sesi. Secondary electrospray ionization super sesi the super sesi source was optimized for breath analysis and integrates all components required to control the ionization of the sample flow. Fast atom bombardment, secondary ion mass spectrometry, electrospray, and matrix assisted laser desorption are used to ionize condensed phase samples. Characterizing bacterial volatiles using secondary. Secondary electrospray ionizationmass spectrometry sesims breathprinting of multiple bacterial lung pathogens, a mouse model study. Recent citations gcms application in determination of volatile profiles emitted by infected and. We propose a novel application of secondary electrospray ionizationmass spectrometry sesims as a realtime clinical diagnostic tool for bacterial infection. Secondary structural characterization of oligonucleotide strands using electrospray ionization mass spectrometry xinhua guo1,2, michael f. Applications of highresolution electrospray ionization mass spectrometry to measurements of average oxygen to carbon ratios in secondary organic aerosols adam p.
Translating secondary electrospray ionizationhighresolution mass spectrometry to the clinical environment. In the subsequent reaction, the charge is transferred and vapors get ionized, most molecules get. Electron ionization and chemical ionization are only suitable for gas phase ionization. On a developed photographic emulsion, in which strongly ionizing particles have left dense tracks, delta rays appear as thin wavy spurs or branches. Desorption electrospray ionization mass spectrometry. Among the most used spray ionization techniques is electrospray ionization esi. Secondary electrospray ionization sesi is an ambient ionization technique for the analysis of trace concentrations of vapors, where a nano electrospray produces charging agents that collide with the analyte molecules directly in gasphase. The chamber past the capillary is at a vacuum of a few torr, so that. The three most commonly used msi ion sources are secondary ion mass spectrometry sims, matrixassisted laser desorptionionization maldi msi, and desorption electrospray ionization desi msi. The three most commonly used msi ion sources are secondary ion mass spectrometry sims, matrixassisted laser desorption ionization maldi msi, and desorption electrospray ionization desi msi. Here, we applied secondary electrospray ionization highresolution mass spectrometry for realtime measurements of vocs and particles from cooking peanut oil in the presence of 300 ppbv nitrogen oxides no x generated by a gas stove in an indoor environment.
Molecular ions observed in negative ion chemical ionization mass spectra are usually m or mh. The term delta ray, first used by the british physicist j. Here, we report on one such method, desorption electrospray ionization desi, which is coupled to a linear ion trap mass spectrometer and used to record the spatial intensity distribution of a drug directly from histological sections of brain, lung, kidney, and testis without prior. Mass spectrometry tutorial chemical instrumentation. Secondary electrospray ionization ion mobility spectrometry. Secondary electrospray ionization mass spectrometry sesims is a method developed for the rapid detection of volatile compounds, without the need for sample pretreatment. Electrospray ionization mass spectrometry as a valuable. Oct 19, 2015 secondary electrospray ionization mass spectrometry sesims for this type of metabolomic analysis, a quadrupole timeofflight instrument was chosen because of its high resolution and. To our knowledge, this is the first demonstration of the effect of secondary structure on the electrospray ionization charge state distributions of singlestranded oligonucleotide ions. Realtime breath analysis with active capillary plasma ionization ambient mass spectrometry lukas bregy, pablo martinezlozano sinues, maryia m nudnova et. A fraction of the total exhaled flow is passed to the ionizer, which features a sampling line connected to an ionization chamber whereby a nano electrospray. Other articles where secondary ionization is discussed.
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