Kendrick mass

The Kendrick mass is defined by setting the mass of a chosen molecular fragment, typically CH₂, to an integer value in amu (atomic mass units). It is different from the IUPAC definition, which is based on setting the mass of ¹²C isotope to exactly 12 amu. The Kendrick mass is often used to identify homologous compounds differing only by a number of base units in high resolution mass spectra.[1][2] This definition of mass was first suggested in 1963 by chemist Edward Kendrick,[1] and it has been adopted by scientists working in the area of high-resolution mass spectrometry, environmental analysis,[3][4][5][6] proteomics, petroleomics,[2] metabolomics,[7] polymer analysis,[8] etc.

Definition

According to the procedure outlined by Kendrick, the mass of CH₂ is defined as exactly 14 Da, instead of the IUPAC mass of 14.01565 Da.[9][10]

To convert an IUPAC mass of a particular compound to the Kendrick mass, the equation

${\displaystyle {\textrm {Kendrick~mass}}={\textrm {IUPAC~mass}}\times {\frac {14.00000}{14.01565}}}$

is used.[2][11][7][12] The mass in dalton units (Da) can be converted to the Kendrick scale by dividing by 1.0011178.[1][13]

Other groups of atoms in addition to CH₂ can be used define the Kendrick mass, for example CO₂, H₂, H₂O, and O.[12][14][15] In this case, the Kendrick mass for a family of compounds F is given by

${\displaystyle {\textrm {Kendrick~mass~(F)}}={\textrm {(observed~mass)}}\times {\frac {\textrm {nominal~mass~F}}{\textrm {exact~mass~F}}}}$.

For the hydrocarbon analysis, F=CH₂.

As an example, Kendrick analysis has been used for visualizing families of halogenated compounds of environmental interest that differ only by the number of chlorine, bromine or fluorine substitutions.[4][5]

A recent publication has suggested that Kendrick mass be expressed in Kendrick units with symbol Ke.[16]

Kendrick mass defect

The Kendrick mass defect is defined as the exact Kendrick mass subtracted from the nominal (integer) Kendrick mass:[17][18]

${\displaystyle {\textrm {Kendrick~mass~defect}}={\textrm {nominal~Kendrick~mass}}-{\textrm {Kendrick~mass}}}$

In recent years the equation has changed due to rounding errors to:

${\displaystyle {\textrm {Kendrick~mass~defect}}={\textrm {nominal~mass}}-{\textrm {Kendrick~exact~mass}}}$

The members of an alkylation series have the same degree of unsaturation and number of heteroatoms (nitrogen, oxygen and sulfur) but differ in the number of CH₂ units. Members of an alkylation series have the same Kendrick mass defect.

The Kendrick mass defect has also been defined as

${\displaystyle {\textrm {Kendrick~mass~defect}}=({\textrm {nominal~Kendrick~mass}}-{\textrm {Kendrick~mass}})\times 1{,}000}$ .[19]

The abbreviations KM and KMD have been used for Kendrick mass and Kendrick mass defect, respectively.[20]

Kendrick mass analysis

Plot of Kendrick mass defect as function of Kendrick mass; horizontal lines indicate common repeat units. Each dot in the plot corresponds to a peak measured in a mass spectrum.

In a Kendrick mass analysis, the Kendrick mass defect is plotted as function of nominal Kendrick mass for ions observed in a mass spectrum.[11] Ions of the same family, for example the members of an alkylation series, have the same Kendrick mass defect but different nominal Kendrick mass and are positioned along a horizontal line on the plot. If the composition of one ion in the family can be determined, the composition of the other ions can be inferred. Horizontal lines of different Kendrick mass defect correspond to ions of different composition, for example degree of saturation or heteroatom content.

A Kendrick mass analysis is often used in conjunction with a Van Krevelen diagram, a two- or three- dimensional graphical analysis in which the elemental composition of the compounds are plotted according to the atomic ratios H/C, O/C, or N/C.[12][21]

Kendrick mass defect analysis of polymers and alternative base units

Because Kendrick mass defect analysis can be carried out by substituting any repeating unit for CH₂, KMD analysis is particularly useful for the visualizing the data from polymer mass spectra.[8][22] For example, a Kendrick mass defect plot of an ethylene oxide/propylene oxide copolymer can be created by using ethylene oxide (C₂H₄O) as the base unit and calculating the Kendrick mass as:

${\displaystyle {\textrm {Kendrick~mass}}={\textrm {IUPAC~mass}}\times {\frac {44.00000}{44.02621}}}$

where 44.02621 is the calculated IUPAC mass for C₂H₄O. Alternatively, a KMD plot can be constructed for the same copolymer by using propylene oxide as the base unit.

Polymer mass spectra containing multiple charge ions exhibit isotopic splitting.[23]

Fractional base units and referenced KMD plots

Kendrick mass defect plots created by using fractional base units exhibit enhanced resolution.[24] Referenced Kendrick mass defect plots (KMD plots referenced to the terminal group and adduct composition) with fractional base units can be used to obtain an overview of copolymer composition.[25]

See also

• Petroleomics

Notes

1. Kendrick, Edward (1963), "A mass scale based on CH₂ = 14.00000 for high resolution mass spectrometry of organic compounds", Anal. Chem., 35 (13): 2146–2154, doi:10.1021/ac60206a048.
2. Marshall AG, Rodgers RP (January 2004), "Petroleomics: the next grand challenge for chemical analysis", Acc. Chem. Res., 37 (1): 53–9, doi:10.1021/ar020177t, PMID 14730994.
3. Ortiz, Xavier; Jobst, Karl J.; Reiner, Eric J.; Backus, Sean M.; Peru, Kerry M.; McMartin, Dena W.; O’Sullivan, Gwen; Taguchi, Vince Y.; Headley, John V. (2014-08-05). "Characterization of Naphthenic Acids by Gas Chromatography-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry". Analytical Chemistry. 86 (15): 7666–7673. doi:10.1021/ac501549p. ISSN 0003-2700. PMID 25001115.
4. Ubukata, Masaaki; Jobst, Karl J.; Reiner, Eric J.; Reichenbach, Stephen E.; Tao, Qingping; Hang, Jiliang; Wu, Zhanpin; Dane, A. John; Cody, Robert B. (2015). "Non-targeted analysis of electronics waste by comprehensive two-dimensional gas chromatography combined with high-resolution mass spectrometry: Using accurate mass information and mass defect analysis to explore the data". Journal of Chromatography A. 1395: 152–159. doi:10.1016/j.chroma.2015.03.050. PMID 25869800.
5. Myers, Anne L.; Jobst, Karl J.; Mabury, Scott A.; Reiner, Eric J. (2014-04-01). "Using mass defect plots as a discovery tool to identify novel fluoropolymer thermal decomposition products". Journal of Mass Spectrometry. 49 (4): 291–296. Bibcode:2014JMSp...49..291M. doi:10.1002/jms.3340. ISSN 1096-9888. PMID 24719344.
6. Jobst, Karl J.; Shen, Li; Reiner, Eric J.; Taguchi, Vince Y.; Helm, Paul A.; McCrindle, Robert; Backus, Sean (2013-04-01). "The use of mass defect plots for the identification of (novel) halogenated contaminants in the environment". Analytical and Bioanalytical Chemistry. 405 (10): 3289–3297. doi:10.1007/s00216-013-6735-2. ISSN 1618-2642. PMID 23354579.
7. Ohta, Daisaku; Kanaya, Shigehiko; Suzuki, Hideyuki (2010), "Application of Fourier-transform ion cyclotron resonance mass spectrometry to metabolic profiling and metabolite identification", Current Opinion in Biotechnology, 21 (1): 35–44, doi:10.1016/j.copbio.2010.01.012, PMID 20171870
8. Sato, Hiroaki; Nakamura, Sayaka; Teramoto, Kanae; Sato, Takafumi (2014-08-01). "Structural Characterization of Polymers by MALDI Spiral-TOF Mass Spectrometry Combined with Kendrick Mass Defect Analysis". Journal of the American Society for Mass Spectrometry. 25 (8): 1346–1355. Bibcode:2014JASMS..25.1346S. doi:10.1007/s13361-014-0915-y. ISSN 1044-0305. PMC 4105590. PMID 24845357.
9. Mopper, Kenneth; Stubbins, Aron; Ritchie, Jason D.; Bialk, Heidi M.; Hatcher, Patrick G. (2007), "Advanced Instrumental Approaches for Characterization of Marine Dissolved Organic Matter: Extraction Techniques, Mass Spectrometry, and Nuclear Magnetic Resonance Spectroscopy", Chemical Reviews, 107 (2): 419–42, doi:10.1021/cr050359b, PMID 17300139
10. Meija, Juris (2006), "Mathematical tools in analytical mass spectrometry", Analytical and Bioanalytical Chemistry, 385 (3): 486–99, doi:10.1007/s00216-006-0298-4, PMID 16514517
11. Headley, John V.; Peru, Kerry M.; Barrow, Mark P. (2009), "Mass spectrometric characterization of naphthenic acids in environmental samples: A review", Mass Spectrometry Reviews, 28 (1): 121–34, Bibcode:2009MSRv...28..121H, doi:10.1002/mas.20185, PMID 18677766
12. Reemtsma, Thorsten (2009), "Determination of molecular formulas of natural organic matter molecules by (ultra-) high-resolution mass spectrometryStatus and needs", Journal of Chromatography A, 1216 (18): 3687–701, doi:10.1016/j.chroma.2009.02.033, PMID 19264312
13. Panda, Saroj K.; Andersson, Jan T.; Schrader, Wolfgang (2007), "Mass-spectrometric analysis of complex volatile and nonvolatile crude oil components: a challenge", Analytical and Bioanalytical Chemistry, 389 (5): 1329–39, doi:10.1007/s00216-007-1583-6, PMID 17885749
14. Kim, Sunghwan; Kramer, Robert W.; Hatcher, Patrick G. (2003), "Graphical Method for Analysis of Ultrahigh-Resolution Broadband Mass Spectra of Natural Organic Matter, the Van Krevelen Diagram", Analytical Chemistry, 75 (20): 5336–44, doi:10.1021/ac034415p, PMID 14710810
15. Nizkorodov, Sergey A.; Laskin, Julia; Laskin, Alexander (2011), "Molecular chemistry of organic aerosols through the application of high resolution mass spectrometry", Physical Chemistry Chemical Physics, 13 (9): 3612–29, Bibcode:2011PCCP...13.3612N, doi:10.1039/C0CP02032J, PMID 21206953
16. Junninen, H.; Ehn, M.; Petäjä, T.; Luosujärvi, L.; Kotiaho, T.; Kostiainen, R.; Rohner, U.; Gonin, M.; Fuhrer, K.; Kulmala, M.; Worsnop, D. R. (2010), "A high-resolution mass spectrometer to measure atmospheric ion composition", Atmospheric Measurement Techniques, 3 (4): 1039, doi:10.5194/amt-3-1039-2010
17. Hughey CA, Hendrickson CL, Rodgers RP, Marshall AG, Qian K (October 2001), "Kendrick mass defect spectrum: a compact visual analysis for ultrahigh-resolution broadband mass spectra", Anal. Chem., 73 (19): 4676–81, doi:10.1021/ac010560w, PMID 11605846.
18. Marshall, A. G.; Rodgers, R. P. (2008), "Mass Spectrometry Special Feature: Petroleomics: Chemistry of the underworld", Proceedings of the National Academy of Sciences, 105 (47): 18090–5, Bibcode:2008PNAS..10518090M, doi:10.1073/pnas.0805069105, PMC 2587575, PMID 18836082.
19. Panda, Saroj K.; Andersson, Jan T.; Schrader, Wolfgang (2007), "Mass-spectrometric analysis of complex volatile and nonvolatile crude oil components: a challenge", Analytical and Bioanalytical Chemistry, 389 (5): 1329, doi:10.1007/s00216-007-1583-6, PMID 17885749
20. Reemtsma, Thorsten (2009), "Determination of molecular formulas of natural organic matter molecules by (ultra-) high-resolution mass spectrometry Status and needs", Journal of Chromatography A, 1216 (18): 3687–3701, doi:10.1016/j.chroma.2009.02.033, PMID 19264312
21. Wu, Zhigang; Rodgers, Ryan P.; Marshall, Alan G. (2004), "Two- and Three-Dimensional van Krevelen Diagrams: A Graphical Analysis Complementary to the Kendrick Mass Plot for Sorting Elemental Compositions of Complex Organic Mixtures Based on Ultrahigh-Resolution Broadband Fourier Transform Ion Cyclotron Resonance Mass Measurements", Analytical Chemistry, 76 (9): 2511–6, doi:10.1021/ac0355449, PMID 15117191
22. Fouquet, Thierry; Nakamura, Sayaka; Sato, Hiroaki (2016-04-15). "MALDI SpiralTOF high-resolution mass spectrometry and Kendrick mass defect analysis applied to the characterization of poly(ethylene-co-vinyl acetate) copolymers". Rapid Communications in Mass Spectrometry. 30 (7): 973–981. Bibcode:2016RCMS...30..973F. doi:10.1002/rcm.7525. ISSN 1097-0231. PMC 4787217. PMID 26969940.
23. Cody, Robert B.; Fouquet, Thierry (2017). "Paper spray and Kendrick mass defect analysis of block and random ethylene oxide/propylene oxide copolymers". Analytica Chimica Acta. 989: 38–44. doi:10.1016/j.aca.2017.08.005. PMID 28915941.
24. Fouquet, Thierry; Sato, Hiroaki (2017-03-07). "Extension of the Kendrick Mass Defect Analysis of Homopolymers to Low Resolution and High Mass Range Mass Spectra Using Fractional Base Units". Analytical Chemistry. 89 (5): 2682–2686. doi:10.1021/acs.analchem.6b05136. ISSN 0003-2700. PMID 28194938.
25. Fouquet, T.; Cody, R. B.; Sato, H. (2017-09-01). "Capabilities of the remainders of nominal Kendrick masses and the referenced Kendrick mass defects for copolymer ions". Journal of Mass Spectrometry. 52 (9): 618–624. Bibcode:2017JMSp...52..618F. doi:10.1002/jms.3963. ISSN 1096-9888. PMID 28670698.