436:
thermodynamically stable, which will tend to produce a higher abundance of the doubly substituted (or “clumped”) species than predicted by the statistical abundance of each heavy isotope (known as a stochastic distribution of isotopes). This effect increases in magnitude with decreasing temperature, so the abundance of the clumped species is related to the temperature at which the gas was formed or equilibrated. By measuring the abundance of the clumped species in standard gases formed in equilibrium at known temperatures, the thermometer can be calibrated and applied to samples with unknown abundances.
395:(IRMS) of doubly substituted species requires larger volumes of sample gas and longer analysis times than traditional stable isotope measurements, thereby requiring extremely stable instrumentation. Also, the doubly-substituted isotopologues are often subject to isobaric interferences, as in the methane system where CH
176:
The atom(s) of the different isotope may be anywhere in a molecule, so the difference is in the net chemical formula. If a compound has several atoms of the same element, any one of them could be the altered one, and it would still be the same isotopologue. When considering the different locations of
844:
Young E. D., Kohl I. E., Sherwood Lollar B., Etiope G., Rumble D. III, Li S., Haghnegahdar M. A., Schauble E. A., McCain K. A., Foustoukos D. I., Sutclife C., Warr O., Ballentine C. J., Onstott T. C., Hosgormez H., Neubeck A., Marques J. M., Pérez-Rodríguez I., Rowe A. R., LaRowe D. E., Magnabosco
514:
or mass spectrometry experiments, where isotopologues are used to elucidate metabolic pathways in a qualitative (detect new pathways) or quantitative (detect quantitative share of a pathway) approach. A popular example in biochemistry is the use of uniform labelled glucose (U-C glucose), which is
415:
D species at mass 18. A measurement of such species requires either very high mass resolving power to separate one isobar from another, or modeling of the contributions of the interfering species to the abundance of the species of interest. These analytical challenges are significant: The first
435:
When a light isotope is replaced with a heavy isotope (e.g., C for C), the bond between the two atoms will vibrate more slowly, thereby lowering the zero-point energy of the bond and acting to stabilize the molecule. An isotopologue with a doubly substituted bond is therefore slightly more
444:
The abundances of multiply substituted isotopologues can also be affected by kinetic processes. As for singly substituted isotopologues, departures from thermodynamic equilibrium in a doubly-substituted species can implicate the presence of a particular reaction taking place.
552:
To expand the linear dynamic response range of the mass spectrometer by following multiple isotopologues, with an isotopologue of lower abundance still generating linear response even while the isotopologues of higher abundance giving saturated
543:
The relative mass spectral intensity of natural isotopologues, calculable from the fractional abundances of the constituent elements, is exploited by mass spectrometry practitioners in quantitative analysis and unknown compound identification:
772:
Seeman, Jeffrey I.; Secor, Henry V.; Disselkamp, R.; Bernstein, E. R. (1992). "Conformational analysis through selective isotopic substitution: supersonic jet spectroscopic determination of the minimum energy conformation of o-xylene".
330:(doubly substituted isotopologues) of gases has been used in the field of stable isotope geochemistry to trace equilibrium and kinetic processes in the environment inaccessible by analysis of singly substituted isotopologues alone.
173:. Altogether, there are 9 different stable water isotopologues, and 9 radioactive isotopologues involving tritium, for a total of 18. However only certain ratios are possible in mixture, due to prevalent hydrogen swapping.
548:
To identify the more likely molecular formulas for an unknown compound based on the matching between the observed isotope abundance pattern in an experiment and the expected isotope abundance patterns for given molecular
916:
Stolper, D. A.; Sessions, A. L.; Ferreira, A. A.; Neto, E. V. Santos; Schimmelmann, A.; Shusta, S. S.; Valentine, D. L.; Eiler, J. M. (2014). "Combined C–D and D–D clumping in methane: methods and preliminary results".
1039:
Magyar, P. M.; Orphan, V. J.; and Eiler, J. M. (2016) Measurement of rare isotopologues of nitrous oxide by high-resolution multi-collector mass spectrometry. Rapid Commun. Mass
Spectrom., 30: 1923–1940.
195:
of different elements in a structure. Depending on the formula and the symmetry of the structure, there might be several isotopomers of one isotopologue. For example, ethanol has the molecular formula
1327:
Liu, Hanghui (2011). "Expanding the linear dynamic range for multiple reaction monitoring in quantitative liquid chromatography–tandem mass spectrometry utilizing natural isotopologue transitions".
515:
metabolized by the organism under investigation (e. g. bacterium, plant, or animal) and whose signatures can later be detected in newly formed amino acid or metabolically cycled products.
1356:"Importance of Utilizing Natural Isotopologue Transitions in Expanding the Linear Dynamic Range of LC-MS/MS Assay for Small-Molecule Pharmacokinetic Sample Analysis – A mini-review"
416:
publication precisely measuring doubly substituted isotopologues did not appear until 2004, though singly substituted isotopologues had been measured for decades previously.
1454:
Stokvis, Ellen (2005). "Stable isotopically labeled internal standards in quantitative bioanalysis using liquid chromatography/mass spectrometry: necessity or not?".
423:
has also emerged as a method to measure doubly substituted species free from isobaric interferences, and has been applied to the methane isotopologue CH
618:
835:
Ghosh, Prosenjit, et al. "C–O bonds in carbonate minerals: A new kind of paleothermometer". Geochimica et
Cosmochimica Acta 70.6 (2006): 1439–1456.
952:
Yeung, L. Y.; Young, E. D.; Schauble, E. A. (2012). "Measurements of OO and OO in the atmosphere and the role of isotope-exchange reactions".
420:
1128:
Wang, Z.; Schauble, E. A.; Eiler, J. M. (2004). "Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases".
306:, isotopologues of simple molecules containing rare heavy isotopes of carbon, oxygen, hydrogen, nitrogen, and sulfur are used to trace
562:
A compound tagged by replacing specific atoms with the corresponding isotopes can facilitate the following mass spectrometry methods:
857:
D and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gas". Geochimica et
Cosmochimica Acta 203, 235–264.
989:"A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O
584:
392:
1118:
Urey, H. C., 1947. The thermodynamic properties of isotopic substances. J. Chem. Soc. London 1947, 561–581.
1300:
Bluck, Les. "The Role of
Naturally Occurring Stable Isotopes in Mass Spectrometry, Part I: The Theory".
511:
269:
1049:
Eiler, John M.; et al. (2013). "A high-resolution gas-source isotope ratio mass spectrometer".
579:
188:
311:
285:
845:
C., Yeung L. Y., Ash J. L., and
Bryndzia L. T. (2017) "The relative abundances of resolved CH
273:
1180:
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307:
303:
297:
162:
149:-related isotopologues of water include the commonly available form of heavy-oxygen water (
8:
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327:
78:
47:
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192:
114:
867:
Ono, Shuhei (2014). "Measurement of a Doubly
Substituted Methane Isotopologue,CH
1371:
1070:
1025:
988:
454:
446:
337:
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1105:
938:
814:
1502:
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in the formation of methane, as well as mixing and equilibration of multiple
379:
284:) do not interfere with the solutes' H signals, and in investigations of the
1193:
1164:
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Stable isotopically labeled internal standards for quantitative analysis
1405:"Metabolic Flux Analysis-Linking Isotope Labeling and Metabolic Fluxes"
589:
179:
161:
isotope. Both elements may be replaced by isotopes, for example in the
86:
20:
1278:
884:
627:, 2nd ed. (the "Gold Book") (1997). Online corrected version: (1994) "
449:
occurring in the atmosphere has been shown to alter the abundance of O
1467:
391:
Because of the relative rarity of the heavy isotopes of C, H, and O,
82:
27:
1218:"SIRIUS: Decomposing isotope patterns for metabolite identification"
419:
As an alternative to more conventional gas source IRMS instruments,
370:
66:
39:
1265:
Wang, Yongdong (2010). "The
Concept of Spectral Accuracy for MS".
485:
O isotopologues NNO and {{sup>15}}NNO can distinguish whether N
524:
343:
142:
55:
43:
1084:
Eiler, J. M.; Schauble, E. (2004). "OCO in Earth's atmosphere".
1492:
360:
146:
987:
Young, E. D.; Rumble, D. III; Freedman, P.; Mills, M. (2016).
871:
D, by
Tunable Infrared Laser Direct Absorption Spectroscopy".
771:
333:
Currently measured doubly substituted isotopologues include:
62:
796:
Seeman, Jeffrey I.; Paine, III, John B. (December 7, 1992).
915:
51:
187:
and Paine in 1992, is used. Isotopomerism is analogous to
986:
775:
Journal of the
Chemical Society, Chemical Communications
538:
141:, where some or all of the hydrogen is the radioactive
473:
and have been used to demonstrate the significance of
157:) and the more difficult to separate version with the
500:
481:. Variations in the relative abundances of the two N
263:
231:, is an isotopologue of it. The structural formulas
557:
510:Multiple substituted isotopologues may be used for
321:
258:
951:
798:"Letter to the Editor: 'Isotopomers, Isotopologs'"
69:-related isotopologues are: "light water" (HOH or
54:, but at least one atom has a different number of
16:Molecules which differ only in isotope composition
1493:Fractional abundance of atmospheric isotopologues
1127:
518:
268:Singly substituted isotopologues may be used for
1500:
795:
1165:"Biological signatures in clumped isotopes of O
1163:Yeung, L. Y.; Ash, J. L.; Young, E. D. (2015).
272:experiments, where deuterated solvents such as
1162:
1083:
430:
505:
421:tunable diode laser absorption spectroscopy
403:D ions interfere with measurement of the CH
291:
1051:International Journal of Mass Spectrometry
1005:International Journal of Mass Spectrometry
523:Resulting from either naturally occurring
386:
255:are two isotopomers of that isotopologue.
1456:Rapid Communications in Mass Spectrometry
1430:
1420:
1379:
1241:
1192:
1024:
892:
813:
314:processes in natural environments and in
439:
1453:
531:, isotopologues can be used in various
1501:
1215:
1048:
765:
715:The nine tritiated isotopologues are
539:Applications of natural isotopologues
1402:
1353:
1264:
1326:
866:
13:
1360:Journal of Pharmaceutical Sciences
647:The nine stable isotopologues are
624:Compendium of Chemical Terminology
501:Multiple substituted isotopologues
14:
1520:
1486:
1299:
489:O has been produced by bacterial
264:Analytical chemistry applications
808:(2). American Chemical Society.
558:Applications of isotope labeling
326:Measurement of the abundance of
322:Doubly substituted isotopologues
259:Singly substituted isotopologues
46:composition. They have the same
1447:
1396:
1347:
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1209:
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1121:
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1086:Geochimica et Cosmochimica Acta
1077:
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954:Journal of Geophysical Research
945:
802:Chemical & Engineering News
585:Isotope-ratio mass spectrometry
471:microbial processing of methane
393:isotope-ratio mass spectrometry
85:isotope in equal proportion to
909:
860:
838:
829:
789:
709:
641:
612:
519:Mass spectrometry applications
113:); and "super-heavy water" or
1:
1341:10.1016/j.talanta.2011.09.063
1234:10.1093/bioinformatics/btn603
605:
566:Metabolic flux analysis (MFA)
97:" with two deuterium atoms (
7:
573:
304:stable isotope geochemistry
207:. Mono-deuterated ethanol,
177:the same isotope, the term
50:and bonding arrangement of
10:
1525:
1372:10.1016/j.xphs.2021.12.012
1071:10.1016/j.ijms.2012.10.014
1026:10.1016/j.ijms.2016.01.006
512:nuclear magnetic resonance
295:
270:nuclear magnetic resonance
42:that differ only in their
18:
1150:10.1016/j.gca.2004.05.039
1106:10.1016/j.gca.2004.05.035
939:10.1016/j.gca.2013.10.045
815:10.1021/cen-v070n049.p002
453:from equilibrium, as has
431:Equilibrium fractionation
1130:Geochim. Cosmochim. Acta
919:Geochim. Cosmochim. Acta
580:Mass (mass spectrometry)
506:Biochemical applications
292:Geochemical applications
189:constitutional isomerism
19:Not to be confused with
1194:10.1126/science.aaa6284
637:10.1351/goldbook.I03351
387:Analytical requirements
1422:10.3390/metabo10110447
286:kinetic isotope effect
440:Kinetic fractionation
274:deuterated chloroform
1403:Wang, Yujue (2020).
1354:Bach, Thanh (2022).
974:10.1029/2012JD017992
873:Analytical Chemistry
783:10.1039/C39920000713
457:. Measurements of CH
298:Isotope geochemistry
183:, first proposed by
163:doubly labeled water
1216:Böcker, S. (2009).
1185:2015Sci...348..431Y
1142:2004GeCoA..68.4779W
1098:2004GeCoA..68.4767E
1063:2013IJMSp.335...45E
1017:2016IJMSp.401....1Y
966:2012JGRD..11718306Y
931:2014GeCoA.126..169S
1495:, SpectralCalc.com
479:methane reservoirs
1279:10.1021/ac100888b
1273:(17): 7055–7062.
1179:(6233): 431–434.
1136:(23): 4779–4797.
1092:(23): 4767–4777.
885:10.1021/ac5010579
879:(13): 6487–6494.
533:mass spectrometry
529:isotopic labeling
475:quantum tunneling
58:than the parent.
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1479:
1468:10.1002/rcm.1790
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1001:and other gases"
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382:: NNO and NNO
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139:DTO [HHO]
135:HTO [HHO]
133:, as well as
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629:Isotopologue
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316:Earth's past
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1415:(11): 447.
1409:Metabolites
1335:: 307–310.
925:: 169–191.
600:Isotopocule
308:equilibrium
95:heavy water
81:" with the
36:isotopologs
1308:(10): 36.
1267:Anal. Chem
777:(9): 713.
606:References
590:Isotopomer
180:isotopomer
145:isotope).
21:isotopomer
1057:: 45–56.
821:28 August
549:formulas.
83:deuterium
40:molecules
28:chemistry
1509:Isotopes
1503:Category
1476:15645520
1441:33172051
1390:34919967
1314:23772100
1287:20684651
1252:19015140
1203:25908819
1011:: 1–10.
997:, and CH
903:24895840
574:See also
553:signals.
525:isotopes
461:D and CH
371:Nitrogen
350:D and CH
89:(HDO or
67:hydrogen
65:, whose
56:neutrons
44:isotopic
1432:7694648
1381:9018470
1329:Talanta
1243:2639009
1181:Bibcode
1173:Science
1138:Bibcode
1094:Bibcode
1059:Bibcode
1013:Bibcode
962:Bibcode
927:Bibcode
344:Methane
312:kinetic
280:or CHCl
143:tritium
87:protium
1474:
1439:
1429:
1388:
1378:
1312:
1285:
1250:
1240:
1201:
901:
853:and CH
411:and CH
399:and CH
367:and OO
361:Oxygen
185:Seeman
147:Oxygen
38:) are
619:IUPAC
340:: COO
276:(CDCl
63:water
52:atoms
1472:PMID
1437:PMID
1386:PMID
1310:PMID
1283:PMID
1248:PMID
1199:PMID
899:PMID
823:2020
346:: CH
310:and
253:−O−H
249:D−CH
243:and
241:−O−D
137:and
93:), "
77:), "
1464:doi
1427:PMC
1417:doi
1376:PMC
1368:doi
1364:111
1337:doi
1275:doi
1238:PMC
1230:doi
1189:doi
1177:348
1146:doi
1102:doi
1067:doi
1055:335
1021:doi
1009:401
993:, N
970:doi
958:117
935:doi
923:126
889:hdl
881:doi
810:doi
779:doi
753:DOT
749:HOT
737:DOT
733:HOT
721:DOT
717:HOT
697:HOD
677:HOD
657:HOD
633:doi
631:".
427:D.
373:: N
363:: O
237:−CH
219:or
191:or
125:or
105:or
91:HHO
26:In
1505::
1470:.
1460:19
1458:.
1435:.
1425:.
1413:10
1411:.
1407:.
1384:.
1374:.
1362:.
1358:.
1333:87
1331:.
1306:23
1304:.
1281:.
1271:82
1269:.
1246:.
1236:.
1226:25
1224:.
1220:.
1197:.
1187:.
1175:.
1171:.
1144:.
1134:68
1132:.
1100:.
1090:68
1088:.
1065:.
1053:.
1019:.
1007:.
1003:.
968:.
956:.
933:.
921:.
897:.
887:.
877:86
875:.
806:70
804:.
800:.
755:,
751:,
747:,
739:,
735:,
731:,
723:,
719:,
699:,
695:,
687:,
679:,
675:,
667:,
659:,
655:,
621:,
497:.
318:.
288:.
245:CH
233:CH
229:HO
217:DO
30:,
1478:.
1466::
1443:.
1419::
1392:.
1370::
1343:.
1339::
1316:.
1289:.
1277::
1254:.
1232::
1205:.
1191::
1183::
1169:"
1167:2
1152:.
1148::
1140::
1108:.
1104::
1096::
1073:.
1069::
1061::
1029:.
1023::
1015::
999:4
995:2
991:2
976:.
972::
964::
941:.
937::
929::
905:.
891::
883::
869:3
855:3
851:2
849:D
847:2
825:.
812::
785:.
781::
761:O
759:2
757:T
745:O
743:2
741:T
729:O
727:2
725:T
705:O
703:2
701:D
693:O
691:2
689:H
685:O
683:2
681:D
673:O
671:2
669:H
665:O
663:2
661:D
653:O
651:2
649:H
635::
487:2
483:2
467:2
465:D
463:2
459:3
451:2
425:3
413:3
409:2
407:D
405:2
401:3
397:5
375:2
365:2
356:2
354:D
352:2
348:3
282:3
278:3
251:2
247:2
239:2
235:3
227:5
225:H
223:2
221:C
215:5
213:H
211:2
209:C
205:O
203:6
201:H
199:2
197:C
171:O
169:2
167:D
159:O
155:O
153:2
151:H
131:O
129:2
127:H
123:O
121:2
119:T
117:(
111:O
109:2
107:H
103:O
101:2
99:D
75:O
73:2
71:H
23:.
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