31:
374:(Houston, TX) demonstrated the advantages of APCI for coupling gas chromatography (GC) and liquid chromatography (LC) to a mass spectrometer. High sensitivity and simple mass spectra were shown in these studies. For LC-MS, the LC eluate was vaporized and ionized in a heated metal block. Initially, a Ni foil was used as a source of electrons to perform ionization. In 1975, a corona discharge electrode was developed, providing a larger dynamic response range. APCI with the corona discharge electrode became the model for modern commercially available APCI interfaces.
79:
which creates a mist of fine droplets. Droplets are vaporized by impact with the heated walls at 350â500 °C and carried by the nebulizer gas and an auxiliary gas into the ion molecule reaction region between the corona electrode and the exit counter-electrode. A constant current of 2â5 microamps is maintained from the corona needle. Sample ions are produced by ion-molecule reactions (as described below), and pass through a small orifice or tube into the ion transfer region leading to the mass spectrometer.
71:
87:
1911:
1935:
1923:
378:
version was produced, allowing real-time direct air monitoring by APCI-MS/MS. A similar platform was used for the SCIEX AROMIC system (part of the CONDOR contraband detection system developed together with
British Aerospace) for the detection of drugs, explosives and alcohol in shipping containers at border crossings, by sampling the interior airspace.
400:
converted to a gaseous state before reaching the corona discharge needle. Because APCI involves a gas-phase chemistry, there is no need to use special conditions such as solvents, conductivity, pH for LC. APCI appears to be more versatile LC/MS interface and more compatible with reversed-phase LC than ESI.
408:
APCI is suited for thermal stable samples with low to medium (less than 1500 Da) molecular weight, and medium to high polarity. It is particularly useful for analytes that are not sufficiently polar for electrospray. The application area of APCI is the analysis of drugs, nonpolar lipids, natural
369:
The origins of atmospheric pressure chemical ionization sources combined with mass spectrometry can be found in the 1960s in studies of ions in flames and of ion chemistry in corona discharges up to atmospheric pressure. The first application of APCI combined with mass spectrometry for trace chemical
360:
In a major distinction from chemical ionization, the electrons needed for the primary ionization are not produced by a heated filament, as a heated filament cannot be used under atmospheric pressure conditions. Instead, the ionization must occur using either corona discharges or β- particle emitters,
82:
Various geometries of ion source are possible, depending on application. When used with liquid chromatography, particularly at higher flow rates, the nebulizer is often positioned orthogonal to (or at a similarly steep angle to) the inlet of the mass spectrometer, so that solvent and neutral material
78:
A typical APCI source usually consists of three main parts: a sample inlet, a corona discharge needle, and an ion transfer region under intermediate pressure. In the case of the heated nebulizer inlet from an LC, as shown in the figure, the eluate flows at 0.2 to 2.0 mL/min into a pneumatic nebulizer
390:
Ionization of the substrate is very efficient as it occurs at atmospheric pressure, and thus has a high collision frequency. Additionally, APCI considerably reduces the thermal decomposition of the analyte because of the rapid desolvation and vaporization of the droplets in the initial stages of the
992:
In early 1971, when IMS was referred to as plasma chromatography (PC), the
Franklin GNO Corporation developed the first commercial ion mobility spectrometerâmass spectrometer (IMSâMS) and demonstrated its use as a detector for the identification and analysis of trace amounts of oxygenated compounds
104:
The ionization can either be carried out in positive or negative ionization mode. In the positive mode, the relative proton affinities of the reactant ions and the gaseous analyte molecules allow either proton transfer or adduction of reactant gas ions to produce the ions of the molecular species.
381:
In the mid-1980s and into the early 1990s, the advantages of performing LC/MS with APCI and with electrospray, both atmospheric pressure ionization techniques, began to capture the attention of the analytical community. Together they have dramatically expanded the role of mass spectrometry in the
394:
Another advantage to using APCI over other ionization methods is that it allows for the high flow rates typical of standard bore HPLC (0.2â2.0 mL/min) to be used directly, often without diverting the larger fraction of volume to waste. Additionally, APCI can often be performed in a modified
377:
In the late 1970s an APCI mass spectrometer system (the TAGA, for Trace
Atmospheric Gas Analyzer), mounted in a van for mobile operation, was introduced by SCIEX, providing high sensitivity for monitoring polar organics in ambient air in real time. In 1981 a triple quadrupole mass spectrometer
399:
source. The ionization occurs in the gas phase, unlike ESI, where the ionization occurs in the liquid phase. A potential advantage of APCI is that it is possible to use a nonpolar solvent as a mobile phase solution, instead of a polar solvent, because the solvent and molecules of interest are
61:
where primary ions are produced on a solvent spray. The main usage of APCI is for polar and relatively less polar thermally stable compounds with molecular weight less than 1500 Da. The application of APCI with HPLC has gained a large popularity in trace analysis detection such as steroids,
1044:
Horning, E. C.; Carroll, D. I.; Dzidic, I.; Haegele, K. D.; Horning, M. G.; Stillwell, R. N. (1974-11-01). "Atmospheric pressure ionization (API) mass spectrometry. Solvent-mediated ionization of samples introduced in solution and in a liquid chromatograph effluent stream".
332:
If the mobile phase contains solvents with a higher proton affinity than water, proton-transfer reactions take place that lead to protonated the solvent with higher proton affinity. For example, when methanol solvent is present, the cluster solvent ions would be
1088:
Carroll, D. I.; Dzidic, I.; Stillwell, R. N.; Haegele, K. D.; Horning, E. C. (1975-12-01). "Atmospheric pressure ionization mass spectrometry. Corona discharge ion source for use in a liquid chromatograph-mass spectrometer-computer analytical system".
90:
Atmospheric pressure chemical ionization (APCI) spray chamber from LC-MS; this ion source (spray chamber) would fit onto a mass spectrometer on the side facing the viewer, with the mass spectrometer's inlet at roughly the level of the corona discharge
382:
pharmaceutical industry for both drug development and drug discovery applications. The sensitivity of APCI combined with the specificity of LC-MS and LC-MS/MS often makes it the method of choice for the quantification of drugs and drug metabolites.
100:
Ionization in the gas phase by APCI follows the sequences: sample in solution, sample vapor, and sample ions. The effluent from the HPLC is evaporated completely. The mixture of solvent and sample vapor is then ionized by ion-molecule reaction.
357:. Fragmentation does not normally occur inside the APCI source. If a fragment ion of a sample is observed, thermal degradation has taken place by the heated nebulizer interface, followed by the ionization of the decomposition products.
760:
1005:
Horning, E. C.; Horning, M. G.; Carroll, D. I.; Dzidic, I.; Stillwell, R. N. (1973-05-01). "New picogram detection system based on a mass spectrometer with an external ionization source at atmospheric pressure".
391:
ionization. This combination of factors most typically results in the production of ions of the molecular species with fewer fragmentations than many other ionization methods, making it a soft ionization method.
453:
Carroll, D. I.; Dzidic, I.; Stillwell, R. N.; Horning, M. G.; Horning, E. C. (1974). "Subpicogram detection system for gas phase analysis based upon atmospheric pressure ionization (API) mass spectrometry".
370:
analysis was by the
Franklin GNO Corporation who in 1971 developed an instrument combining APCI with ion mobility and mass spectrometry. Horning, Carroll and their co-workers in the 1970s at the
1655:
116:. The evaporated mobile phase of LC acts as the ionization gas and reactant ions. If water is the only solvent in the evaporated mobile phase, the excited nitrogen molecular ions N
105:
In the negative mode, ions are produced by either proton abstraction, or ions are produced by anion attachment. Most work on the APCI-MS analysis has been in positive mode.
1281:
1308:
Taylor, Lester C. E.; Johnson, Robert L.; Raso, Roberto (1995-05-01). "Open access atmospheric pressure chemical ionization Mass spectrometry for routine sample analysis".
409:
compounds, pesticides and various organic compounds, but it is of limited use in the analysis of biopolymers, organometallics, ionic compounds and other labile analytes.
1448:
HolÄapek, Michal; JirĂĄsko, Robert; LĂsa, Miroslav (2010-06-18). "Basic rules for the interpretation of atmospheric pressure ionization mass spectra of small molecules".
1838:
1833:
1585:
872:
Knewstubb, PF; Sugden, TM (1960). "Mass-Spectrometric
Studies of Ionization in Flames. I. The Spectrometer and its Application to Ionization in Hydrogen Flames".
148:
takes place at the high vacuum of the mass analyzer. The analyte molecule ions detected by MS are . The chemical reactions of ionization process are shown below.
1690:
1640:
1828:
1650:
1501:
1665:
1939:
1856:
1746:
1823:
1405:
HolÄapek, Michal; JirĂĄsko, Robert; LĂsa, Miroslav (2012). "Recent developments in liquid chromatographyâmass spectrometry and related techniques".
1891:
1881:
1645:
54:
1570:
627:
599:
140:
transfer out from the atmospheric-pressure ion source. Declustering (removal of water molecules from the protonated analyte molecule) of MH(H
1354:
Zaikin, Vladimir G.; Halket, John M. (2017). "Derivatization in Mass
Spectrometryâ8. Soft Ionization Mass Spectrometry of Small Molecules".
1575:
1808:
1605:
1595:
1547:
791:
509:
1886:
1848:
1670:
1264:
1186:
695:
433:
1871:
1726:
1635:
1600:
528:
Thomson, Bruce A. (1998-03-01). "Atmospheric pressure ionization and liquid chromatography/mass spectrometryâtogether at last".
1675:
1494:
1876:
1861:
1124:
Byrdwell, William Craig (2001-04-01). "Atmospheric pressure chemical ionization mass spectrometry for analysis of lipids".
821:
Byrdwell, William Craig (2001-04-01). "Atmospheric pressure chemical ionization mass spectrometry for analysis of lipids".
713:"An Introduction to Mass Spectrometry Ionization: An Excerpt from The Expanding Role of Mass Spectrometry in Biotechnology"
1866:
1813:
30:
1787:
1896:
1590:
1927:
1772:
761:"ATMOSPHERIC-PRESSURE-IONIZATION MASS-SPECTROMETRY .2. APPLICATIONS IN PHARMACY, BIOCHEMISTRY AND GENERAL-CHEMISTRY"
1915:
1542:
1487:
371:
1818:
1803:
1731:
1716:
1521:
1204:"Applications of a Versatile Technique for Trace Analysis: Atmospheric Pressure Negative Chemical Ionization"
1615:
428:
396:
132:. Then, analyte molecules M are protonated by the water cluster ions. Finally, the ionization products MH(H
1685:
108:
In the positive mode, when the discharge current of corona discharge is 1-5 ÎźA on the nebulized solvent, N
1620:
17:
53:
which utilizes gas-phase ion-molecule reactions at atmospheric pressure (10 Pa), commonly coupled with
70:
928:
881:
652:
537:
1961:
1767:
1736:
1610:
1580:
712:
418:
58:
361:
which are both electron sources capable of handling the presence of corrosive or oxidizing gases.
1695:
1387:
1157:
983:
897:
854:
734:
561:
1252:
151:
Primary and secondary reagent ion formation in a nitrogen atmosphere in the presence of water:
1510:
1465:
1430:
1422:
1379:
1371:
1333:
1325:
1260:
1233:
1182:
1149:
1141:
1106:
1070:
1062:
1023:
975:
846:
838:
772:
691:
668:
643:
Bruins, A. P. (1991). "Mass spectrometry with ion sources operating at atmospheric pressure".
623:
595:
553:
505:
471:
50:
1176:
1680:
1660:
1625:
1457:
1414:
1363:
1317:
1223:
1215:
1133:
1098:
1054:
1015:
967:
936:
889:
830:
724:
660:
545:
463:
423:
799:
932:
885:
656:
541:
1630:
1228:
1203:
86:
549:
1955:
1777:
1537:
1321:
738:
1391:
987:
955:
901:
565:
1741:
1161:
858:
1461:
1418:
1058:
589:
1782:
1721:
1700:
917:"MassâSpectrometric Studies of Corona Discharges in Air at Atmospheric Pressure"
729:
1557:
1137:
971:
834:
46:
1426:
1375:
1329:
1145:
1110:
1066:
1027:
842:
776:
672:
557:
475:
1469:
1434:
1383:
1337:
1153:
979:
893:
850:
664:
1237:
1074:
1751:
504:. Boca Raton, FL: CRC Press, Taylor and Francis Group. pp. 249â250.
1102:
1019:
467:
1219:
940:
1367:
1280:
Government of Canada, Public
Services and Procurement Canada (1991).
1479:
1253:"Modern Atmospheric Pressure Surface Sampling/Ionization Techniques"
916:
29:
83:
does not contaminate the actual inlet of the mass spectrometer.
1483:
1526:
686:
Thomson, BA (2007). Gross, Michael; Caprioli, Richard (eds.).
34:
Atmospheric pressure chemical ionization chamber cross section
1452:. Mass Spectrometry: Innovation and Application. Part VI.
62:
pesticides and also in pharmacology for drug metabolites.
588:
Edmond de
Hoffmann; Vincent Stroobant (22 October 2007).
312:
Declustering in the high vacuum of the mass analyzer:
112:
gas molecules are excited and ionized, which produce N
1310:
Journal of the
American Society for Mass Spectrometry
1255:. In Trantor, George E.; Koppenaal, David W. (eds.).
530:
Journal of the
American Society for Mass Spectrometry
717:
Journal of the Association for Laboratory Automation
57:(HPLC). APCI is a soft ionization method similar to
1847:
1796:
1760:
1709:
1556:
1282:"On-Site Sampling and Detection of Drug Particles"
792:"Atmospheric Pressure Chemical Ionisation (APCI)"
956:"Developments in Ion Mobility-Mass Spectrometry"
1251:Pasilis, Sofie P.; Van Berkel, Gary J. (2010).
1202:Thomson, BA; Davidson, WR; Lovett, AM (1980).
796:The University of Bristol, School of Chemistry
620:Fundamentals of Contemporary Mass Spectrometry
591:Mass Spectrometry: Principles and Applications
1495:
1257:Encyclopedia of Spectroscopy and Spectrometry
124:O molecules to produce water cluster ions H(H
8:
1502:
1488:
1480:
622:. John Wiley & Sons, Inc. p. 47.
74:APCI source with heated nebulizer LC inlet
1259:. London: John Lindon. pp. 819â829.
1227:
1181:. Netherlands: Elsevier. pp. 11â26.
728:
85:
69:
39:Atmospheric pressure chemical ionization
18:Atmospheric pressure chemical ionization
688:Encyclopedia of Mass Spectrometry Vol 6
502:Liquid Chromatography Mass spectrometry
445:
1039:
1037:
960:Analytical and Bioanalytical Chemistry
583:
581:
579:
577:
575:
55:high-performance liquid chromatography
1356:European Journal of Mass Spectrometry
1349:
1347:
7:
1922:
613:
611:
523:
521:
495:
493:
491:
489:
487:
485:
1934:
765:TrAC Trends in Analytical Chemistry
1047:Journal of Chromatographic Science
25:
1208:Environmental Health Perspectives
1178:Advances in LC-MS Instrumentation
434:Secondary electrospray ionization
1933:
1921:
1910:
1909:
993:(i.e. 1-octanol and 1-nonanol).
711:Siuzdak, Gary (1 April 2004).
690:. Elsevier. pp. 366â370.
1:
954:Collins, DC; Lee, ML (2002).
550:10.1016/S1044-0305(97)00285-7
1462:10.1016/j.chroma.2010.02.049
1419:10.1016/j.chroma.2012.08.072
1322:10.1016/1044-0305(94)00124-1
284:Ionization of product ions:
1773:Microchannel plate detector
1450:Journal of Chromatography A
1407:Journal of Chromatography A
1175:Cappiello, Achille (2007).
1978:
1059:10.1093/chromsci/12.11.725
730:10.1016/j.jala.2004.01.004
500:Niessen, Wilfried (2006).
372:Baylor College of Medicine
1905:
1517:
1138:10.1007/s11745-001-0725-5
972:10.1007/s00216-001-1195-5
835:10.1007/s11745-001-0725-5
759:AP, BRUINS (1994-01-01).
645:Mass Spectrometry Reviews
1788:LangmuirâTaylor detector
429:Electrospray ionization
1732:Quadrupole mass filter
894:10.1098/rspa.1960.0084
665:10.1002/mas.1280100104
618:Dass, Chhabil (2007).
92:
75:
35:
89:
73:
33:
1091:Analytical Chemistry
1008:Analytical Chemistry
456:Analytical Chemistry
96:Ionization mechanism
66:Instrument structure
1768:Electron multiplier
1737:Quadrupole ion trap
1103:10.1021/ac60364a031
1020:10.1021/ac60328a035
933:1966JChPh..45.2600S
915:Shahin, MM (1966).
886:1960RSPSA.255..520K
657:1991MSRv...10...53B
542:1998JASMS...9..187T
468:10.1021/ac60342a009
419:Chemical ionization
59:chemical ionization
1289:publications.gc.ca
1220:10.1289/ehp.803677
874:Proc. R. Soc. Lond
120:would react with H
93:
76:
36:
1949:
1948:
1511:Mass spectrometry
1456:(25): 3908â3921.
1097:(14): 2369â2373.
941:10.1063/1.1727980
880:(1283): 520â535.
629:978-0-471-68229-5
601:978-0-470-51213-5
51:mass spectrometry
47:ionization method
27:Ionization method
16:(Redirected from
1969:
1937:
1936:
1925:
1924:
1913:
1912:
1504:
1497:
1490:
1481:
1474:
1473:
1445:
1439:
1438:
1402:
1396:
1395:
1368:10.1255/ejms.798
1351:
1342:
1341:
1305:
1299:
1298:
1296:
1295:
1286:
1277:
1271:
1270:
1248:
1242:
1241:
1231:
1199:
1193:
1192:
1172:
1166:
1165:
1121:
1115:
1114:
1085:
1079:
1078:
1041:
1032:
1031:
1002:
996:
995:
951:
945:
944:
927:(7): 2600â2605.
912:
906:
905:
869:
863:
862:
818:
812:
810:
808:
807:
798:. Archived from
787:
781:
780:
756:
750:
749:
747:
745:
732:
708:
702:
701:
683:
677:
676:
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615:
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569:
525:
516:
515:
497:
480:
479:
450:
424:Corona discharge
21:
1977:
1976:
1972:
1971:
1970:
1968:
1967:
1966:
1952:
1951:
1950:
1945:
1901:
1843:
1792:
1756:
1705:
1552:
1513:
1508:
1478:
1477:
1447:
1446:
1442:
1404:
1403:
1399:
1353:
1352:
1345:
1307:
1306:
1302:
1293:
1291:
1284:
1279:
1278:
1274:
1267:
1250:
1249:
1245:
1201:
1200:
1196:
1189:
1174:
1173:
1169:
1123:
1122:
1118:
1087:
1086:
1082:
1053:(11): 725â729.
1043:
1042:
1035:
1004:
1003:
999:
953:
952:
948:
914:
913:
909:
871:
870:
866:
820:
819:
815:
805:
803:
789:
788:
784:
758:
757:
753:
743:
741:
710:
709:
705:
698:
685:
684:
680:
642:
641:
637:
630:
617:
616:
609:
602:
587:
586:
573:
527:
526:
519:
512:
499:
498:
483:
452:
451:
447:
442:
415:
406:
388:
367:
356:
352:
348:
344:
340:
336:
327:
323:
319:
307:
303:
299:
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291:
280:
276:
272:
268:
264:
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183:
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162:
158:
147:
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139:
135:
131:
127:
123:
119:
115:
111:
98:
68:
28:
23:
22:
15:
12:
11:
5:
1975:
1973:
1965:
1964:
1954:
1953:
1947:
1946:
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1943:
1931:
1919:
1906:
1903:
1902:
1900:
1899:
1894:
1889:
1884:
1879:
1874:
1869:
1864:
1859:
1853:
1851:
1845:
1844:
1842:
1841:
1836:
1831:
1826:
1821:
1816:
1811:
1806:
1800:
1798:
1797:MS combination
1794:
1793:
1791:
1790:
1785:
1780:
1775:
1770:
1764:
1762:
1758:
1757:
1755:
1754:
1749:
1744:
1739:
1734:
1729:
1727:Time-of-flight
1724:
1719:
1713:
1711:
1707:
1706:
1704:
1703:
1698:
1693:
1688:
1683:
1678:
1673:
1668:
1663:
1658:
1653:
1648:
1643:
1638:
1633:
1628:
1623:
1618:
1613:
1608:
1603:
1598:
1593:
1588:
1583:
1578:
1573:
1568:
1562:
1560:
1554:
1553:
1551:
1550:
1545:
1540:
1535:
1524:
1518:
1515:
1514:
1509:
1507:
1506:
1499:
1492:
1484:
1476:
1475:
1440:
1397:
1343:
1316:(5): 387â393.
1300:
1272:
1265:
1243:
1194:
1187:
1167:
1132:(4): 327â346.
1116:
1080:
1033:
1014:(6): 936â943.
997:
946:
907:
864:
829:(4): 327â346.
813:
782:
751:
703:
696:
678:
635:
628:
607:
600:
571:
536:(3): 187â193.
517:
511:978-0585138503
510:
481:
462:(6): 706â710.
444:
443:
441:
438:
437:
436:
431:
426:
421:
414:
411:
405:
402:
387:
384:
366:
363:
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346:
342:
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145:
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137:
133:
129:
125:
121:
117:
113:
109:
97:
94:
67:
64:
26:
24:
14:
13:
10:
9:
6:
4:
3:
2:
1974:
1963:
1960:
1959:
1957:
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1941:
1932:
1930:
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1917:
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1870:
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1852:
1850:
1849:Fragmentation
1846:
1840:
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1832:
1830:
1827:
1825:
1822:
1820:
1817:
1815:
1812:
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1807:
1805:
1802:
1801:
1799:
1795:
1789:
1786:
1784:
1781:
1779:
1778:Daly detector
1776:
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1722:Wien filter
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1962:Ion source
1558:Ion source
1294:2022-04-21
806:2013-12-06
440:References
386:Advantages
296:+ M â MH(H
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1829:LC/MS
1824:GC/MS
1804:MS/MS
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