Ambient ionization

573: 17: 7305: 506: 602:(LAESI), laser assisted desorption electrospray ionization (LADESI), laser desorption electrospray ionization (LDESI), laser ablation mass spectrometry (LAMS), and laser desorption spray post-ionization (LDSPI). The term laser electrospray mass spectrometry has been used to denote the use of a femtosecond laser for ablation. Laser ablation into an electrospray produces highly charged ions that are similar to those observed in direct electrospray. 557: 623:(PESI) is a modified version of conventional electrospray ionization in which the capillary for sample solution transferring is replaced by a solid needle with a sharp tip. Compared with conventional electrospray ionization, high salt tolerance, direct sampling, and low sample consumption are found with PESI. PESI is not a continuous process; the needle for sampling and spraying is driven up and down at a frequency of 3–5 Hz. 69: 7329: 7317: 491:, may be formed in the afterglow region. These additional reagent ions are capable of ionizing compounds via charge-transfer processes and, thus, offer alternative routes of ionization besides proton transfer, leading to a broader range of suitable analytes. Nevertheless, these ionization mechanisms may also lead to the formation of adducts and oxidation of the original analyte compounds. 636:(SESI), a nano-electrospray operated at high temperature produces nanodroplets that evaporate very rapidly to produce ions and protonated water clusters that ionize the vapors of interest. SESI is commonly used for the analysis of trace concentrations of vapors being able to detect low volatility species in the gas phase with molecular masses of up to 700 Da. 3037:

Berisha, Arton; Dold, Sebastian; Guenther, Sabine; Desbenoit, Nicolas; Takats, Zoltan; Spengler, Bernhard; Römpp, Andreas (2014). "A comprehensive high-resolution mass spectrometry approach for characterization of metabolites by combination of ambient ionization, chromatography and imaging methods".

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The analytes are in the vapor phase. This includes breath, odors, VOCs, and other molecules with low volatility that, due to the constant improvements in sensitivity, are detectable in the vapor phase despite their low vapor pressure. Analyte ions are produced via gas-phase chemical reactions, where

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using laser desorption atmospheric pressure chemical ionization (LD-APCI). For ambient ionization with a spray, the sample material is deposited on a target near the spray. The laser desorbs or ablates material from the sample that is ejected from the surface and into the spray, which can be an APCI

6280:

Mandal, Mridul Kanti; Yoshimura, Kentaro; Saha, Subhrakanti; Ninomiya, Satoshi; Rahman, Md. Obaidur; Yu, Zhan; Chen, Lee Chuin; Shida, Yasuo; Takeda, Sen; Nonami, Hiroshi; Hiraoka, Kenzo (2012). "Solid probe assisted nanoelectrospray ionization mass spectrometry for biological tissue diagnostics".

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Laser-based ambient ionization is a two-step process in which a pulsed laser is used to desorb or ablate material from a sample and the plume of material interacts with an electrospray or plasma to create ions. Lasers with ultraviolet and infrared wavelengths and nanosecond to femtosecond pulse

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In the table below, ambient ionization techniques are classified in the categories "extraction" (a solid or liquid extraction processes dynamically followed by spray or chemical ionization), "plasma" (thermal or chemical desorption with chemical ionization), "two step" (desorption or ablation

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Ratcliffe, Lucy V.; Rutten, Frank J. M.; Barrett, David A.; Whitmore, Terry; Seymour, David; Greenwood, Claire; Aranda-Gonzalvo, Yolanda; Robinson, Steven; McCoustra, Martin (2007). "Surface Analysis under Ambient Conditions Using Plasma-Assisted Desorption/Ionization Mass Spectrometry".

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Wu, Jin; Hughes, Christopher S.; Picard, Pierre; Letarte, Sylvain; Gaudreault, Mireille; Lévesque, Jean-François; Nicoll-Griffith, Deborah A.; Bateman, Kevin P. (2007). "High-Throughput Cytochrome P450 Inhibition Assays Using Laser Diode Thermal Desorption-Atmospheric Pressure Chemical

5031:

Quarles, C. Derrick; Carado, Anthony J.; Barinaga, Charles J.; Koppenaal, David W.; Marcus, R. Kenneth (2011). "Liquid sampling–atmospheric pressure glow discharge (LS-APGD) ionization source for elemental mass spectrometry: preliminary parametric evaluation and figures of merit".

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Zhang, Jialing; Zhou, Zhigui; Yang, Jianwang; Zhang, Wei; Bai, Yu; Liu, Huwei (2012). "Thin Layer Chromatography/Plasma Assisted Multiwavelength Laser Desorption Ionization Mass Spectrometry for Facile Separation and Selective Identification of Low Molecular Weight Compounds".

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Cheng, Sy-Chyi; Cheng, Tain-Lu; Chang, Hui-Chiu; Shiea, Jentaie (2009). "Using Laser-Induced Acoustic Desorption/Electrospray Ionization Mass Spectrometry To Characterize Small Organic and Large Biological Compounds in the Solid State and in Solution Under Ambient Conditions".

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Corso, Gaetano; D'Apolito, Oceania; Garofalo, Daniela; Paglia, Giuseppe; Dello Russo, Antonio (2011). "Profiling of acylcarnitines and sterols from dried blood or plasma spot by atmospheric pressure thermal desorption chemical ionization (APTDCI) tandem mass spectrometry".

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Feng, Baosheng; Zhang, Jialing; Chang, Cuilan; Li, Liping; Li, Min; Xiong, Xingchuang; Guo, Chengan; Tang, Fei; Bai, Yu; Liu, Huwei (2014). "Ambient Mass Spectrometry Imaging: Plasma Assisted Laser Desorption Ionization Mass Spectrometry Imaging and Its Applications".

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Laser ablation was first coupled with mass spectrometry in the 1980s for the analysis of metals using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The laser ablates the sample material that is introduced into an ICP to create atomic ions.

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Huang, Min-Zong; Hsu, Hsiu-Jung; Wu, Chen-I; Lin, Shu-Yao; Ma, Ya-Lin; Cheng, Tian-Lu; Shiea, Jentaie (2007). "Characterization of the chemical components on the surface of different solids with electrospray-assisted laser desorption ionization mass spectrometry".

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Schäfer, Karl-Christian; Dénes, Júlia; Albrecht, Katalin; Szaniszló, Tamás; Balog, Júlia; Skoumal, Réka; Katona, Mária; Tóth, Miklós; Balogh, Lajos; Takáts, Zoltán (2009). "In Vivo, In Situ Tissue Analysis Using Rapid Evaporative Ionization Mass Spectrometry".

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followed by ionization), "laser" (laser desorption or ablation followed by ionization), "acoustic" (acoustic desorption followed by ionization), multimode (involving two of the above modes), other (techniques that do not fit into the other categories).

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to create a liquid film on the sample surface. Molecules on the surface are extracted into the solvent. The action of the primary droplets hitting the surface produces secondary droplets that are the source of ions for the mass spectrometer.

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Wang, Bo; Ding, Xuelu; Zhao, Zhongjun; Duan, Yixiang (2014). "Method development for directly screening pesticide residues in foodstuffs using ambient microfabricated glow discharge plasma (MFGDP) desorption/ionization mass spectrometry".

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Schematic of a DESI solid-liquid extraction ion source: primary charged droplets hit the sample surface and molecules are extracted into the liquid. Secondary charged droplets removed from the surface produce bare ions as the solvent

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Martin, Audrey N.; Farquar, George R.; Steele, Paul T.; Jones, A. Daniel; Frank, Matthias (2009). "Use of Single Particle Aerosol Mass Spectrometry for the Automated Nondestructive Identification of Drugs in Multicomponent Samples".

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Andrade, Francisco J.; Shelley, Jacob T.; Wetzel, William C.; Webb, Michael R.; Gamez, Gerardo; Ray, Steven J.; Hieftje, Gary M. (2008). "Atmospheric Pressure Chemical Ionization Source. 1. Ionization of Compounds in the Gas Phase".

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Pagnotti, Vincent S.; Inutan, Ellen D.; Marshall, Darrell D.; McEwen, Charles N.; Trimpin, Sarah (2011). "Inlet Ionization: A New Highly Sensitive Approach for Liquid Chromatography/Mass Spectrometry of Small and Large Molecules".

20:

Diagram of ambient ionization in mass spectrometry indicating desorption/extraction (spray, heat, laser), optional post-ionization (electrospray, chemical ionization, plasma), ion formation, and entry into the vacuum of the mass

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source to create charged droplets that are directed at a solid sample. The charged droplets pick up the sample through interaction with the surface and then form highly charged ions that can be sampled into a mass spectrometer.

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Luo, Zhigang; He, Jiuming; Chen, Yi; He, Jingjing; Gong, Tao; Tang, Fei; Wang, Xiaohao; Zhang, Ruiping; Huang, Lan; Zhang, Lianfeng; Lv, Haining; Ma, Shuanggang; Fu, Zhaodi; Chen, Xiaoguang; Yu, Shishan; Abliz, Zeper (2013).

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Bennett, Rachel V.; Morzan, Ezequiel M.; Huckaby, Jacob O.; Monge, María Eugenia; Christensen, Henrick I.; Fernández, Facundo M. (2014). "Robotic plasma probe ionization mass spectrometry (RoPPI-MS) of non-planar surfaces".

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Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo (2013). "Leidenfrost Phenomenon-assisted Thermal Desorption (LPTD) and Its Application to Open Ion Sources at Atmospheric Pressure Mass Spectrometry".

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Ren, Xinxin; Liu, Jia; Zhang, Chengsen; Luo, Hai (2013). "Direct analysis of samples under ambient condition by high-voltage-assisted laser desorption ionization mass spectrometry in both positive and negative ion mode".

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Chen, Huanwen; Wortmann, Arno; Zenobi, Renato (2007). "Neutral desorption sampling coupled to extractive electrospray ionization mass spectrometry for rapid differentiation of biosamples by metabolomic fingerprinting".

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Takats, Zoltan; Cotte-Rodriguez, Ismael; Talaty, Nari; Chen, Huanwen; Cooks, R. Graham (2005). "Direct, trace level detection of explosives on ambient surfaces by desorption electrospray ionization mass spectrometry".

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Sampson, Jason S.; Muddiman, David C. (2009). "Atmospheric pressure infrared (10.6 μm) laser desorption electrospray ionization (IR-LDESI) coupled to a LTQ Fourier transform ion cyclotron resonance mass spectrometer".

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Hecht, Max; Evard, Hanno; Takkis, Kalev; Veigure, Rūta; Aro, Rudolf; Lohmus, Rynno; Herodes, Koit; Leito, Ivo; Kipper, Karin (2017). "Sponge Spray — Reaching New Dimensions of Direct Sampling and Analysis by MS".

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Zhan, Xuefang; Zhao, Zhongjun; Yuan, Xin; Wang, Qihui; Li, Dandan; Xie, Hong; Li, Xuemei; Zhou, Meigui; Duan, Yixiang (2013). "Microwave-Induced Plasma Desorption/Ionization Source for Ambient Mass Spectrometry".

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Haapala, Markus; Pól, Jaroslav; Saarela, Ville; Arvola, Ville; Kotiaho, Tapio; Ketola, Raimo A.; Franssila, Sami; Kauppila, Tiina J.; Kostiainen, Risto (2007). "Desorption Atmospheric Pressure Photoionization".

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He, Jiuming; Tang, Fei; Luo, Zhigang; Chen, Yi; Xu, Jing; Zhang, Ruiping; Wang, Xiaohao; Abliz, Zeper (2011). "Air flow assisted ionization for remote sampling of ambient mass spectrometry and its application".

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desorption/ionization (ELDI) can be accomplished with ultraviolet and infrared lasers to the desorb material into the electrospray plume. Similar approaches to laser desorption/ablation into an electrospray are

3725:

McEwen, Charles N.; McKay, Richard G.; Larsen, Barbara S. (2005). "Analysis of Solids, Liquids, and Biological Tissues Using Solids Probe Introduction at Atmospheric Pressure on Commercial LC/MS Instruments".

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Brady, John J.; Judge, Elizabeth J.; Levis, Robert J. (2009). "Mass spectrometry of intact neutral macromolecules using intense non-resonant femtosecond laser vaporization with electrospray post-ionization".

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Zhou, Yueming; Zhang, Ning; Li, Yafeng; Xiong, Caiqiao; Chen, Suming; Chen, Yongtai; Nie, Zongxiu (2014). "Plasma-based ambient sampling/ionization/transmission integrated source for mass spectrometry".

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Haddad, Renato; Sparrapan, Regina; Kotiaho, Tapio; Eberlin, Marcos N. (2008). "Easy Ambient Sonic-Spray Ionization-Membrane Interface Mass Spectrometry for Direct Analysis of Solution Constituents".

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Although most applications focus on the detection of positive ions, measurements in the negative mode are for most of the plasma-based ion sources also possible. In this case, reagent ions, such as O

462: 5230:"Generation and detection of multiply-charged peptides and proteins by matrix-assisted laser desorption electrospray ionization (MALDESI) fourier transform ion cyclotron resonance mass spectrometry" 2859:"Generation and detection of multiply-charged peptides and proteins by matrix-assisted laser desorption electrospray ionization (MALDESI) Fourier transform ion cyclotron resonance mass spectrometry" 5842:

Huang, Yun-Qing; You, Jin-Qing; Yuan, Bi-Feng; Feng, Yu-Qi (2012). "Sample preparation and direct electrospray ionization on a tip column for rapid mass spectrometry analysis of complex samples".

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Steeb, Jennifer; Galhena, Asiri S.; Nyadong, Leonard; Janata, Jiří; Fernández, Facundo M. (2009). "Beta electron-assisted direct chemical ionization (BADCI) probe for ambient mass spectrometry".

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Brüggemann, Martin; Karu, Einar; Hoffmann, Thorsten (2016-02-01). "Critical assessment of ionization patterns and applications of ambient desorption/ionization mass spectrometry using FAPA–MS".

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Jecklin, Matthias Conradin; Gamez, Gerardo; Touboul, David; Zenobi, Renato (2008). "Atmospheric pressure glow discharge desorption mass spectrometry for rapid screening of pesticides in food".

5185:

McEwen, Charles N.; Pagnotti, Vincent S.; Inutan, Ellen D.; Trimpin, Sarah (2010). "New Paradigm in Ionization: Multiply Charged Ion Formation from a Solid Matrix without a Laser or Voltage".

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Hsu, Hsiu-Jung; Kuo, Tseng-Long; Wu, Shu-Huey; Oung, Jung-Nan; Shiea, Jentaie (2005). "Characterization of Synthetic Polymers by Electrospray-Assisted Pyrolysis Ionization-Mass Spectrometry".

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Chen, Huanwen; Venter, Andre; Cooks, R. Graham (2006). "Extractive electrospray ionization for direct analysis of undiluted urine, milk and other complex mixtures without sample preparation".

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Harper, Jason D.; Charipar, Nicholas A.; Mulligan, Christopher C.; Zhang, Xinrong; Cooks, R. Graham; Ouyang, Zheng (2008). "Low-Temperature Plasma Probe for Ambient Desorption Ionization".

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Coon, Joshua J.; McHale, Kevin J.; Harrison, W. W. (2002). "Atmospheric pressure laser desorption/chemical ionization mass spectrometry: a new ionization method based on existing themes".

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Lin, Jia-Yi; Chen, Tsung-Yi; Chen, Jen-Yi; Chen, Yu-Chie (2010). "Multilayer gold nanoparticle-assisted thermal desorption ambient mass spectrometry for the analysis of small organics".

502:, yielding ions. Measurements in the negative ion mode are especially favorable when the analyte molecules exhibit a high gas-phase acidity, as it is the case e.g. for carboxylic acids. 5942:

Dixon, R. Brent; Sampson, Jason S.; Hawkridge, Adam M.; Muddiman, David C. (2008). "Ambient Aerodynamic Ionization Source for Remote Analyte Sampling and Mass Spectrometric Analysis".

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in a flowing gas that produces metastable atoms and molecules and reactive ions. Heat is often used to assist in the desorption of volatile species from the sample. Ions are formed by

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Liu, Jiangjiang; Wang, He; Manicke, Nicholas E.; Lin, Jin-Ming; Cooks, R. Graham; Ouyang, Zheng (2010). "Development, Characterization, and Application of Paper Spray Ionization".

4095:

Nyadong, Leonard; Galhena, Asiri S.; Fernández, Facundo M. (2009). "Desorption Electrospray/Metastable-Induced Ionization: A Flexible Multimode Ambient Ion Generation Technique".

2749:

Shiea J, Huang MZ, Hsu HJ, Lee CY, Yuan CH, Beech I, Sunner J (2005). "Electrospray-assisted laser desorption/ionization mass spectrometry for direct ambient analysis of solids".

4694:

Van Berkel, Gary J.; Pasilis, Sofie P.; Ovchinnikova, Olga (2008). "Established and emerging atmospheric pressure surface sampling/ionization techniques for mass spectrometry".

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of the protonated water clusters and the gas-phase basicity of the analyte molecule are of crucial importance. However, since especially smaller protonated water clusters with

2536:

Ifa, Demian R.; Wu, Chunping; Ouyang, Zheng; Cooks, R. Graham (2010). "Desorption electrospray ionization and other ambient ionization methods: current progress and preview".

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widths have been used. Although atmospheric pressure MALDI is performed under ambient conditions, it is not generally considered to be an ambient mass spectrometry technique.

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Van Berkel, Gary J.; Sanchez, Amaury D.; Quirke, J. Martin E. (2002). "Thin-Layer Chromatography and Electrospray Mass Spectrometry Coupled Using a Surface Sampling Probe".

476:= 1,2,3... exhibit very high gas-phase acidities, even compounds with a rather low gas-phase basicity are readily ionized by proton transfer, yielding quasimolecular ions. 99:(DAPPI) is a solid-liquid extraction ambient ionization method that enables the direct analysis of samples deposited on surfaces by means of a jet of hot solvent vapour and 1908:

Monge, María Eugenia; Harris, Glenn A.; Dwivedi, Prabha; Fernández, Facundo M. (2013). "Mass Spectrometry: Recent Advances in Direct Open Air Surface Sampling/Ionization".

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Yea-Wenn Liou, Jian-Siang Wang, Chien-Chung Chen and Cheng-Huang Lin (2017). "Development of an on-line microextraction method for use in fiber-spray/mass spectrometry".

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Forbes, Thomas P.; Brewer, Tim M.; Gillen, Greg (2013). "Desorption electro-flow focusing ionization of explosives and narcotics for ambient pressure mass spectrometry".

2049:

Badu-Tawiah, Abraham K.; Eberlin, Livia S.; Ouyang, Zheng; Cooks, R. Graham (2013). "Chemical Aspects of the Extractive Methods of Ambient Ionization Mass Spectrometry".

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Shelley, Jacob T.; Ray, Steven J.; Hieftje, Gary M. (2008). "Laser Ablation Coupled to a Flowing Atmospheric Pressure Afterglow for Ambient Mass Spectral Imaging".

7049: 5085:"Laserspray Ionization, a New Atmospheric Pressure MALDI Method for Producing Highly Charged Gas-phase Ions of Peptides and Proteins Directly from Solid Solutions" 1237: 595: 6093: 2211:

Haapala M, Pól J, Saarela V, Arvola V, Kotiaho T, Ketola RA, Franssila S, Kauppila TJ, Kostiainen R (2007). "Desorption Atmospheric Pressure Photoionization".

2164:"Ambient mass spectrometry using desorption electrospray ionization (DESI): instrumentation, mechanisms and applications in forensics, chemistry, and biology" 3949:

Cody, Robert B.; Laramée, James A.; Durst, H. Dupont (2005). "Versatile New Ion Source for the Analysis of Materials in Open Air under Ambient Conditions".

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Takats, Z.; Wiseman, J. M.; Gologan, B; Cooks, R. G. (2004). "Mass Spectrometry Sampling Under Ambient Conditions with Desorption Electrospray Ionization".

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Zhu, Hongying; Li, Gongyu; Huang, Guangming (2014). "Screening of Complicated Matrixes with Paper Assisted Ultrasonic Spray Ionization Mass Spectrometry".

5369:; Laskin, Alexander (2010). "Nanospray desorption electrospray ionization: an ambient method for liquid-extraction surface sampling in mass spectrometry". 4560:

Qiao, Liang; Tobolkina, Elena; Lesch, Andreas; Bondarenko, Alexandra; Zhong, Xiaoqin; Liu, Baohong; Pick, Horst; Vogel, Horst; Girault, Hubert H. (2014).

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Wu, Ching; Siems, William F.; Hill, Herbert H. (2000). "Secondary Electrospray Ionization Ion Mobility Spectrometry/Mass Spectrometry of Illicit Drugs".

2493:

Laiko, Victor V.; Baldwin, Michael A.; Burlingame, Alma L. (2000). "Atmospheric Pressure Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry".

4238:

Krieger, Sonja; Hayen, Heiko; Schmitz, Oliver J. (2013). "Quantification of coumarin in cinnamon and woodruff beverages using DIP-APCI-MS and LC-MS".

5748:

Hiraoka, Kenzo; Nishidate, Kentaro; Mori, Kunihiko; Asakawa, Daiki; Suzuki, Shigeo (2007). "Development of probe electrospray using a solid needle".

4138:

Haddad, Renato; Sparrapan, Regina; Eberlin, Marcos N. (2006). "Desorption sonic spray ionization for (high) voltage-free ambient mass spectrometry".

3200:

Flanigan, P.; Levis, R. (2014). "Ambient Femtosecond Laser Vaporization and Nanosecond Laser Desorption Electrospray Ionization Mass Spectrometry".

6863: 6814: 7232: 7227: 6979: 96: 2794:"Electrospray-assisted laser desorption ionization mass spectrometry (ELDI-MS) with an infrared laser for characterizing peptides and proteins" 528:

that operates by exposing the sample to a gas stream (typically helium or nitrogen) that contains long-lived electronically or excited neutral

4745:

Nemes, Peter; Vertes, Akos (2007). "Laser Ablation Electrospray Ionization for Atmospheric Pressure, in Vivo, and Imaging Mass Spectrometry".

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Jeng, Jingyueh; Lin, Che-Hsin; Shiea, Jentaie (2005). "Electrospray from Nanostructured Tungsten Oxide Surfaces with Ultralow Sample Volume".

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Rezenom, Yohannes H.; Dong, Jianan; Murray, Kermit K. (2008). "Infrared laser-assisted desorption electrospray ionization mass spectrometry".

5895:"Generation of multiply charged peptides and proteins by radio frequency acoustic desorption and ionization for mass spectrometric detection" 7084: 7034: 7222: 7044: 6895: 560:

Ion source for ambient mass spectrometry employing a combination of laser desorption and electrospray. The sample target is on the left.

7059: 6722:; Jara, Jose Luis Paz; Klitzke, Clécio F.; Coelho, Fernando; Eberlin, Marcos N. (2011). "Venturi Easy Ambient Sonic-Spray Ionization". 7250: 7140: 3399: 3149:

Liu, Jia; Qiu, Bo; Luo, Hai (2010). "Fingerprinting of yogurt products by laser desorption spray post-ionization mass spectrometry".

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Nemes P, Vertes A (2007). "Laser Ablation Electrospray Ionization for Atmospheric Pressure, in Vivo, and Imaging Mass Spectrometry".

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Van Berkel, Gary J.; Kertesz, Vilmos; King, Richard C. (2009). "High-Throughput Mode Liquid Microjunction Surface Sampling Probe".

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Chen, Hao; Ouyang, Zheng; Cooks, R. Graham (2006). "Thermal Production and Reactions of Organic Ions at Atmospheric Pressure".

2251:"Characterization of Direct-Current Atmospheric-Pressure Discharges Useful for Ambient Desorption/Ionization Mass Spectrometry" 2249:

Shelley, Jacob T.; Wiley, Joshua S.; Chan, George C. Y.; Schilling, Gregory D.; Ray, Steven J.; Hieftje, Gary M. (2009-05-01).

1059: 599: 6463:

Neidholdt, Evan L.; Beauchamp, J. L. (2011). "Switched Ferroelectric Plasma Ionizer (SwiFerr) for Ambient Mass Spectrometry".

3497:"Air Flow-Assisted Ionization Imaging Mass Spectrometry Method for Easy Whole-Body Molecular Imaging under Ambient Conditions" 1951:

Huang, Min-Zong; Yuan, Cheng-Hui; Cheng, Sy-Chyi; Cho, Yi-Tzu; Shiea, Jentaie (2010). "Ambient Ionization Mass Spectrometry".

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Gray, Alan L. (1985). "Solid sample introduction by laser ablation for inductively coupled plasma source mass spectrometry".

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An alternative ionization approach following laser desorption is a plasma. UV laser ablation can be combined with a flowing

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Hiraoka K.; Nishidate K.; Mori K.; Asakawa D.; Suzuki S. (2007). "Development of probe electrospray using a solid needle".

6767:"Development and Application of a Brush Spray Derived from a Calligraphy Brush Style Synthetic Hair Pen for Use in ESI/MS" 7202: 7321: 6999: 6989: 6941: 3595:

Neidholdt, Evan L.; Beauchamp, J. L. (2007). "Compact Ambient Pressure Pyroelectric Ion Source for Mass Spectrometry".

937: 859: 85: 7280: 7242: 7064: 4332:Özdemir, Abdil; Chen, Chung-Hsuan (2010). "Electrode-assisted desorption electrospray ionization mass spectrometry". 1466: 633: 3349:"Small Molecule Ambient Mass Spectrometry Imaging by Infrared Laser Ablation Metastable-Induced Chemical Ionization" 609:

for mass spectrometry imaging of small molecules. and IR desorption has been combined with a metastable ion source.

7265: 7120: 7029: 6994: 4191:"Desorption ionization by charge exchange (DICE) for sample analysis under ambient conditions by mass spectrometry" 3091:"Single Droplet Separations and Surface Partition Coefficient Measurements Using Laser Ablation Mass Spectrometry" 7069: 6888: 7270: 7255: 2452: 2003: 7260: 7207: 620: 498:, can deprotonate the analyte molecules to give quasimolecular ions, or form adducts with species such as NO 7290: 7181: 6984: 2004:"Ambient ionisation mass spectrometry for the characterisation of polymers and polymer additives: a review" 787: 617:

In two-step non-laser methods, the material removal from the sample and the ionization steps are separate.

514: 7166: 6673:"Ultrasonication-assisted spray ionization mass spectrometry for on-line monitoring of organic reactions" 1852:

Cooks, R. Graham; Ouyang, Zheng; Takats, Zoltan; Wiseman, Justin M. (2006). "Ambient Mass Spectrometry".

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Galhena, Asiri S.; Harris, Glenn A.; Nyadong, Leonard; Murray, Kermit K.; Fernández, Facundo M. (2010).

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Solid-liquid extraction based ambient ionization is based on the use of a charged spray, for example

6827: 7212: 7197: 7125: 7110: 6915: 5518:"Paint Spray Mass Spectrometry for the Detection of Additives from Polymers on Conducting Surfaces" 6182:"Surface Acoustic Wave Nebulization of Peptides As a Microfluidic Interface for Mass Spectrometry" 2792:

Peng, Ivory X.; Ogorzalek Loo, Rachel R.; Margalith, Eli; Little, Mark W.; Loo, Joseph A. (2010).

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Heron, Scott R.; Wilson, Rab; Shaffer, Scott A.; Goodlett, David R.; Cooper, Jonathan M. (2010).

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Grimm, Ronald L.; Beauchamp, J. L. (2003). "Field-Induced Droplet Ionization Mass Spectrometry".

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Crotti, Sara; Traldi, Pietro (2009). "Aspects of the Role of Surfaces in Ionization Processes".

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A direct analysis in real time (DART) metastable ion source for plasma based ambient ionization.

7079: 4789: 7014: 6857: 6808: 4860:"LESA – A New Mass Spectrometry-based Surface Analysis Technique Using the TriVersa NanoMate" 2453:"Versatile New Ion Source for the Analysis of Materials in Open Air under Ambient Conditions" 2587:

Wu, Chunping; Dill, Allison L.; Eberlin, Livia S.; Cooks, R. Graham; Ifa, Demian R. (2013).

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Gross, Jürgen H. (2013-09-15). "Direct analysis in real time—a critical review on DART-MS".

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light. The hot jet thermally desorbs the sample from a surface and the vaporized sample is

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without sample preparation or separation. Ions can be formed by extraction into charged

7089: 6791: 6766: 6648: 6607: 6214: 6181: 5730: 5119: 5084: 5065: 5013: 4271: 3842: 3809: 3123: 3090: 2834: 2793: 2629: 2588: 2433: 2144: 1885: 1818: 479:

Besides protonated water clusters, other positively charged reagent ions, such as NO, O

127: 6719: 6904: 6796: 6747: 6739: 6700: 6692: 6653: 6635: 6588: 6580: 6539: 6531: 6488: 6480: 6445: 6437: 6402: 6394: 6358: 6350: 6314: 6306: 6262: 6254: 6219: 6201: 6162: 6154: 6118: 6110: 6073: 6065: 6011: 6003: 5967: 5959: 5924: 5916: 5875: 5867: 5824: 5816: 5781: 5773: 5722: 5714: 5671: 5663: 5619: 5611: 5575: 5567: 5498: 5490: 5454: 5446: 5402: 5394: 5347: 5339: 5303: 5259: 5251: 5210: 5202: 5167: 5159: 5124: 5106: 5057: 5049: 5005: 4997: 4953: 4945: 4910: 4902: 4841: 4833: 4795: 4770: 4762: 4727: 4719: 4676: 4668: 4624: 4589: 4581: 4542: 4534: 4499: 4491: 4447: 4439: 4408: 4400: 4365: 4357: 4314: 4306: 4263: 4255: 4220: 4212: 4171: 4163: 4120: 4112: 4077: 4069: 4026: 4018: 3974: 3966: 3931: 3923: 3887: 3879: 3847: 3829: 3790: 3782: 3751: 3743: 3707: 3699: 3664: 3656: 3620: 3612: 3577: 3569: 3526: 3518: 3476: 3468: 3424: 3378: 3370: 3326: 3318: 3280: 3272: 3225: 3182: 3174: 3128: 3110: 3071: 3063: 3016: 3008: 2969: 2961: 2915: 2880: 2839: 2821: 2774: 2731: 2723: 2677: 2634: 2616: 2569: 2561: 2518: 2510: 2475: 2425: 2417: 2379: 2371: 2330: 2322: 2272: 2228: 2193: 2136: 2128: 2082: 2074: 2031: 1984: 1976: 1933: 1925: 1877: 1832: 41: 5069: 5017: 4275: 2148: 1889: 7074: 7054: 7019: 6845: 6786: 6782: 6778: 6765:

Jen-Ying Liu, Pei-Chun Chen, Yea-Wenn Liou, Kai-Yin Chang, Cheng-Huang Lin (2017).

6731: 6684: 6643: 6627: 6570: 6523: 6472: 6429: 6386: 6342: 6298: 6246: 6209: 6193: 6146: 6102: 6055: 6047: 5995: 5951: 5906: 5859: 5808: 5765: 5734: 5706: 5655: 5603: 5559: 5529: 5482: 5438: 5386: 5331: 5295: 5241: 5194: 5151: 5114: 5096: 5041: 4989: 4937: 4894: 4825: 4754: 4711: 4660: 4616: 4573: 4526: 4483: 4431: 4392: 4349: 4298: 4247: 4202: 4189:

Chan, Chang-Ching; Bolgar, Mark S.; Miller, Scott A.; Attygalle, Athula B. (2010).

4155: 4104: 4061: 4008: 3958: 3915: 3871: 3837: 3821: 3774: 3735: 3691: 3648: 3604: 3561: 3508: 3460: 3416: 3360: 3310: 3264: 3217: 3166: 3118: 3102: 3055: 3000: 2953: 2907: 2870: 2829: 2813: 2766: 2715: 2669: 2624: 2608: 2553: 2502: 2467: 2437: 2409: 2363: 2314: 2262: 2220: 2183: 2120: 2066: 2023: 1968: 1917: 1869: 1824: 606: 586: 6390: 3652: 632:

charging agents collide with the analyte molecules and transfer their charge. In

518: 107:

by a vacuum ultraviolet light and consequently sampled into a mass spectrometer.

6575: 6558: 5911: 5894: 5246: 5229: 4207: 4190: 4013: 3996: 3825: 2875: 2858: 2267: 2250: 2002:

Paine, Martin R. L.; Barker, Philip J.; Blanksby, Stephen J. (15 January 2014).

513:

One of the most used plasma-based techniques for ambient ionization is probably

7024: 6849: 6106: 5299: 5101: 545: 57: 6671:

Chen, Tsung-Yi; Chao, Chin-Sheng; Mong, Kwok-Kong Tony; Chen, Yu-Chie (2010).

5710: 5045: 4993: 4251: 2413: 2027: 7349: 7171: 6931: 6743: 6696: 6639: 6584: 6535: 6484: 6441: 6398: 6354: 6310: 6258: 6205: 6158: 6114: 6069: 6007: 5963: 5920: 5871: 5820: 5777: 5718: 5667: 5615: 5571: 5534: 5517: 5494: 5450: 5398: 5343: 5307: 5255: 5206: 5163: 5110: 5053: 5001: 4949: 4906: 4837: 4766: 4723: 4672: 4628: 4585: 4538: 4495: 4443: 4404: 4361: 4310: 4259: 4216: 4167: 4116: 4073: 4022: 3995:

Na, Na; Zhao, Mengxia; Zhang, Sichun; Yang, Chengdui; Zhang, Xinrong (2007).

3970: 3927: 3883: 3833: 3786: 3747: 3703: 3660: 3616: 3573: 3522: 3472: 3374: 3322: 3276: 3178: 3114: 3067: 3012: 2965: 2825: 2727: 2681: 2620: 2565: 2514: 2421: 2375: 2326: 2132: 2078: 1980: 1929: 1613: 834: 541: 469: 16: 2124: 1873: 7135: 6800: 6751: 6704: 6657: 6592: 6543: 6492: 6449: 6406: 6362: 6318: 6266: 6223: 6166: 6122: 6077: 6015: 5999: 5971: 5928: 5879: 5828: 5785: 5726: 5675: 5623: 5579: 5502: 5458: 5406: 5366: 5351: 5263: 5214: 5171: 5128: 5061: 5009: 4957: 4914: 4845: 4774: 4731: 4680: 4593: 4561: 4546: 4503: 4451: 4412: 4369: 4318: 4267: 4224: 4175: 4124: 4081: 4030: 3978: 3935: 3891: 3851: 3810:"Charge Assisted Laser Desorption/Ionization Mass Spectrometry of Droplets" 3794: 3755: 3711: 3695: 3668: 3624: 3581: 3530: 3480: 3428: 3382: 3330: 3284: 3229: 3186: 3132: 3075: 3020: 2973: 2919: 2884: 2843: 2778: 2735: 2638: 2573: 2522: 2479: 2429: 2383: 2334: 2276: 2232: 2197: 2140: 2086: 2035: 1988: 1937: 1881: 89: 78: 45: 3641:

Biochimica et Biophysica Acta (BBA) - Molecular and Cell Biology of Lipids

1828: 321:

The protonated water clusters can then protonate the sample molecules via

7176: 7115: 7094: 2673: 100: 6433: 6951: 6688: 6631: 6608:"Touch spray mass spectrometry for in situ analysis of complex samples" 6527: 6302: 6051: 5863: 5659: 5390: 4065: 3396: 525: 505: 53: 37: 29: 6735: 6476: 6346: 6250: 6197: 6150: 6060: 5955: 5812: 5607: 5563: 5486: 5335: 5198: 5155: 4941: 4898: 4829: 4758: 4620: 4577: 4530: 4396: 4302: 4108: 3962: 3919: 3739: 3608: 3513: 3496: 3365: 3348: 3314: 3106: 2911: 2612: 2506: 2471: 2367: 2224: 1921: 5769: 5516:

Paine, Martin R. L.; Barker, Philip J.; Blanksby, Stephen J. (2012).

5442: 4715: 4664: 4487: 4435: 4353: 4159: 3875: 3778: 3565: 3464: 3420: 3268: 3170: 3059: 3004: 2957: 2817: 2770: 2557: 2318: 533: 88:(DESI) is one of the original ambient ionization sources and uses an 6873: 2719: 2188: 2163: 1810: 556: 7145: 6672: 5228:

Sampson, Jason S.; Hawkridge, Adam M.; Muddiman, David C. (2006).

68: 5083:

Trimpin, S.; Inutan, E. D.; Herath, T. N.; McEwen, C. N. (2009).

1775: 104: 3808:

Jorabchi, Kaveh; Westphall, Michael S.; Smith, Lloyd M. (2008).

3637: 2791: 1649: 589:

or an electrospray. Ambient ionization by electrospray-assisted

5893:

Dixon, R. Brent; Sampson, Jason S.; Muddiman, David C. (2009).

3864: 2450: 1026:

Infrared laser ablation metastable-induced chemical ionization

131: 6606:

Kerian, Kevin S.; Jarmusch, Alan K.; Cooks, R. Graham (2014).

5471: 5030: 310:{\displaystyle {\ce {He^{\ast }{}+->{}+{}+OH^{.}{}+e^{-}}}} 5984: 5941: 4791:

Non-destructive Micro Analysis of Cultural Heritage Materials

4693: 4382: 2048: 590: 529: 6135: 4559: 3395:

PESI was first introduced by Kenzo Hiraoka et al. in 2007 —

3036: 1739: 1703: 1327:

Plasma-assisted multiwavelength laser desorption ionization

894:

Direct inlet probe–atmospheric-pressure chemical ionization

710:

Atmospheric pressure thermal desorption chemical ionization

6279: 5747: 5184: 5141: 1907: 6718:

Santos, Vanessa G.; Regiani, Thaís; Dias, Fernanda F. G.;

6179: 4562:"Electrostatic Spray Ionization Mass Spectrometry Imaging" 3346: 1784:

Soft Ionization by Chemical Reaction In Transfer (SICRIT)

1757: 1667: 1614:

Table of commercially available ambient ionization sources

1160:

Laser-induced acoustic desorption-electrospray ionization

1094:

Laser desorption atmospheric pressure chemical ionization

689:

Atmospheric pressure glow discharge desorption ionization

60:

and post-ionized before they enter the mass spectrometer.

6920: 6028: 5082: 4787: 4188: 3858: 3768: 3543: 2248: 2102: 447: 370: 352: 260: 232: 197: 179: 33: 6331: 5227: 2856: 2352: 1851: 1793: 1685: 1238:

Matrix-assisted laser desorption electrospray ionization

596:

matrix-assisted laser desorption electrospray ionization

457:{\displaystyle {\ce {+{}+M->{}+{}+{\mathit {n}}H2O}}} 6419: 6375: 6094:

Combinatorial Chemistry & High Throughput Screening

4094: 3904: 2210: 1748:

Rapid evaporative Ionization Mass Spectrometry (REIMS)

1402:

Remote analyte sampling transport and ionization relay

6717: 6559:"Transmission mode desorption electrospray ionization" 6456: 4137: 3807: 3631: 3588: 2985: 2983: 2492: 2296: 1721: 1338:

Plasma-based ambient sampling/ionization/transmission

1283:

Neutral desorption extractive electrospray ionization

1072:

Laser ablation flowing atmospheric pressure afterglow

1015:

Helium atmospheric pressure glow discharge ionization

915:

Electrode-assisted desorption electrospray ionization

848:

Desorption electrospray/metastable-induced ionization

626: 6563: