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The Simulacrum System as a Construct for Mass Spectrometry of Triacylglycerols and Others

  • Original Article
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Lipids

Abstract

A construct called a simulacrum is defined that provides all possible solutions to a sum of two mass spectral abundances, based on values (abundances) or ratios of those values. The defined construct is applied to atmospheric pressure chemical ionization mass spectrometry (MS) of triacylglycerols (TAG). A simulacrum has precisely defined components, specifically a simulacrum sum, four Possibilities to Observe, two Cases, and eight solutions. A simulacrum with no restrictions is the First General Form of a Simulacrum. When one value is specified to be 1 (as in MS), the construct is called a Unit Simulacrum, also called the First Specified Form of a Simulacrum. When one value is 1 and no value can be greater than 1 (the two specifications dictated by mass spectrometry), the construct is called the Second Specified Form of a Simulacrum, or the Mass Spectrometry Simulacrum. Simulacra are used with three Critical Ratios calculated from raw abundances in mass spectra of TAG to provide structural information about the degree of unsaturation in TAG, the identity and quantity of regioisomers, and other structural characteristics. Three-level-deep nested simulacrum solutions yield the recently reported Updated Bottom Up Solution, from which the protonated molecule, [MH]+, and all diacylglycerol-like fragments, [DAG]+, of TAG can be reproduced from the Critical Ratios. Thus, the simulacrum solutions constitute a reduced data set in which more information is provided in fewer values than raw abundances, such that the Critical Ratios constitute a compact library of mass spectra.

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Abbreviations

A:

Arachidic acid (20:0) or generic A

B:

Behenic acid (22:0) or generic B

Ce:

Cerotic acid (26:0)

G:

Gadoleic acid (20:1)

L:

Linoleic acid (18:2)

Lg:

Lignoceric acid (24:0)

Ln:

Linolenic acid (18:3)

M:

Myristic acid (14:0)

O:

Oleic acid (18:1)

P:

Palmitic acid (16:0)

Po:

Palmitoleic acid (16:1)

S:

Stearic acid (18:0)

ACN:

Acetonitrile

APCI:

Atmospheric pressure chemical ionization

API:

Atmospheric pressure ionization

APPI:

Atmospheric pressure photoionization

BUS:

Bottom Up Solution

CL:

Critical Limit(s)

CR:

Critical Ratio(s)

CV:

Critical Value(s)

DAG:

Diacylglycerol

[DAG]+ :

Diacylglylcerol-like fragment ion, =[M+H–RCOOH]+

DCM:

Dichloromethane

ESI:

Electrospray ionization

FA:

Fatty acid(s)

FD:

First Decrement or First Deconstruction

FGFS:

First General Form of a Simulacrum

FI:

First Increment

FSFS:

First Specified Form of a Simulacrum

FuGFS:

Full General Form of a Simulacrum

GFAS:

General Form of an Anti-Simulacrum

HPLC:

High-performance liquid chromatography

IUS:

Infinity Unit Simulacrum

MAG:

Monoacylglycerol(s)

[MAG]+ :

Monoacylglycerol-like fragments, =[RCO + 74]+

MALDI-TOF:

Matrix-assisted laser desorption ionization time-of-flight

MeOH:

Methanol

MS:

Mass spectrometry

MSS:

Mass Spectrometry Simulacrum

[MH]+ :

Protonated molecule, =[M+H]+

Poss2Obs:

Possibilities to observe

PtdEtn:

Phosphatidylethanolamine

SFA:

Saturated fatty acid(s)

SimSum:

Simulacrum sum

SSFS:

Second Specified Form of a Simulacrum

sn :

Stereospecific numbering

TAG:

Triacylglycerol(s)

UAS:

Unit Anti-Simulacrum

UBUS:

Updated Bottom Up Solution

UIS:

Unit Identity Simulacrum

US:

Unit Simulacrum

UUS:

Unit Unit Simulacrum

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Acknowledgments

This work was supported by the USDA Agricultural Research Service. Mention or use of specific products or brands do not represent or imply endorsement by the USDA.

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  1. Food Composition and Methods Development Lab, U.S.D.A. Agricultural Research Service, 10300 Baltimore Ave., Bldg. 161, Beltsville, MD, 20705, USA

    William Craig Byrdwell

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  1. William Craig Byrdwell
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Correspondence to William Craig Byrdwell.

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The author owns the trademarks for the name and symbol of the Unit Simulacrum. The author hereby grants full and unrestricted rights to use the name and symbol of the Unit Simulacrum for all purposes educational, commercial, public, private, and otherwise.

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Byrdwell, W.C. The Simulacrum System as a Construct for Mass Spectrometry of Triacylglycerols and Others. Lipids 51, 211–227 (2016). https://doi.org/10.1007/s11745-015-4101-1

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