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1.
Structural elucidation of glycerophospholipids (GPLs), including the polar head group, the position of double-bond(s) along the fatty acyl substituents, and the positions of acyl groups on the glycerol backbone, using multiple-stage liner ion-trap (LIT) mass spectrometric approach is described in this paper. While the product-ion spectra from MSn (n=2, 3) on the [M+Li]+ or [M-H+2Li]+ ions of GPL are readily applicable for discerning the phospholipid classes and for identifying and locating the fatty acid substituents on the glycerol backbone, the structural information from further dissociation of the dilithiated fatty acid cations produced from MSn (n=3, 4) on the [M-H+2Li]+ ion of GPLs, as well as from further dissociation of the monolithiated fragment ion that bears the unsaturated fatty acid moiety produced from subsequent MSn (n=3,4) on the [M+Li]+ ions of GPLs, affords assignment of the position of double-bond(s) along the fatty acyl groups. The application of the present method in the structural characterization of GPL molecules from the lipid extracts of biological origin, including mixtures of phosphatidylglycerol and of phosphatidylserine without prior chromatographic separation, is also demonstrated. Since lithiated molecular species of GPL are readily formed by ESI, this multiple-stage LIT mass spectrometric approach provides a direct means for the near-complete structural characterization of all the GPLs, including the molecules in the lysophospholipid and plasmalogen subclasses. 相似文献
2.
Hsu FF Turk J Rhoades ER Russell DG Shi Y Groisman EA 《Journal of the American Society for Mass Spectrometry》2005,16(4):491-504
We report negative-ion electrospray tandem mass spectrometric methods for structural characterization of cardiolipin (CL), a four-acyl-chain phospholipid containing two distinct phosphatidyl moieties, of which structural assignment of the fatty acid residues attached to the glycerol backbones performed by low-energy CAD tandem mass spectrometry has not been previously described. The low-energy MS2-spectra of the [M - H]- and [M - 2H]2- ions obtained with ion-trap or with tandem quadrupole instrument combined with ion-trap MS3-spectra or with source CAD product-ion spectra provide complete structural information for CL characterization. The MS2-spectra of the [M - H]- ions contain two sets of prominent fragment ions that comprise a phosphatidic acid, a dehydrated phosphatidylglycerol, and a (phosphatidic acid + 136) anion. The substantial differences in the abundances of the two distinct phosphatidic anions observed in the MS2-spectra of the [M -H]- ions lead to the assignment of the phosphatidyl moieties attached to the 1' or 3' position of central glycerol. Upon further collisional dissociation, the MS3-spectra of the phosphatidic anions provide information to identify the fatty acyl substituents and their position in the glycerol backbone. The MS2-spectra of the [M - 2H]2- ions obtained with TSQ or ITMS contain complementary information to confirm structural assignment. The applications of the above methods in the differentiation of cardiolipin isomers and in the identification of complex cardiolipin species consisting of multiple molecular structures are also demonstrated. 相似文献
3.
Fifteen identified C-18 fatty acyl-containing saponin structures from Quillaja saponaria Molina have been investigated by electrospray ionization ion-trap multiple-stage mass spectrometry (ESI-IT-MS(n)) in positive ion mode. Their MS(1)-MS(3) spectra were analyzed and ions corresponding to useful fragments, important for the structural identification of Quillaja saponins, were recognized. A few key fragments could describe the structural variations in the C-3 and the C-28 oligosaccharides of the Quillaja saponins. A flowchart involving a stepwise procedure based on key fragments from the MS(1)-MS(3) spectra of these saponins, together with key fragments from these saponins and 13 previously investigated saponins, was constructed for the identification of structural elements in Quillaja saponins. Peak intensity ratios in MS(3) spectra were found to be correlated to structural features of the investigated saponins and is therefore of value for the identification of regioisomers. 相似文献
4.
The structures of archaeal glycerophospholipids and glycolipids are unique in that they consist of phytanyl substituents ether linked to the glycerol backbone, imparting stability to the molecules. In this contribution, we described multiple-stage linear ion-trap combined with high resolution mass spectrometry toward structural characterization of this lipid family desorbed as lithiated adduct ions or as the [M−H]− and [M−2H]2− ions by ESI. MSn on various forms of the lithiated adduct ions yielded rich structurally informative ions leading to complete structure identification of this lipid family, including the location of the methyl branches of the phytanyl chain. By contrast, structural information deriving from MSn on the [M−H]− and [M−2H]2− ions is not complete. The fragmentation pathways in an ion-trap, including unusual internal loss of glycerol moiety and internal loss of hexose found for this lipid family were proposed. This mass spectrometric approach provides a simple tool to facilitate confident characterization of this unique lipid family. 相似文献
5.
Ten different samples with 13 previously identified saponin structures from Quillaja saponaria Molina were investigated by electrospray ionization ion trap multiple-stage mass spectrometry (ESI-ITMS(n)) in positive and negative ion modes. Both positive and negative ion mode MS(1)-MS(4) spectra were analyzed, showing that structural information on the two oligosaccharide parts in the saponin can be obtained from positive ion mode spectra whereas negative ion mode spectra mainly gave information on one of the oligosaccharide parts. Analysis of MS(1)-MS(4) spectra identified useful key fragment ions important for the structural elucidation of Quillaja saponins. A flowchart involving a stepwise procedure based on key fragments from MS(1)-MS(3) spectra was constructed for the identification of structural elements in the saponin. Peak intensity ratios in MS(3) spectra were found to be correlated with structural features of the investigated saponins and are therefore of value for the identification of terminal monosaccharide residues. 相似文献
6.
7.
Although marine oysters contain abundant amounts of ether-linked aminophospholipids, the structural identification of the various molecular species has not been reported. We developed a normal-phase silica liquid chromatography/negative-ion electrospray ionization/quadrupole multiple-stage linear ion-trap mass spectrometric (NPLC-NI-ESI/Q-TRAP-MS3) method for the structural elucidation of ether molecular species of serine and ethanolamine phospholipids from marine oysters. The major advantages of the approach are (i) to avoid incorrect selection of isobaric precursor ions derived from different phospholipid classes in a lipid mixture, and to generate informative and clear MSn product ion mass spectra of the species for the identification of the sn-1 plasmanyl or plasmenyl linkages, and (ii) to increase precursor ion intensities by “concentrating” lipid molecules of each phospholipid class for further structural determination of minor molecular species. Employing a combination of NPLC-NI-ESI/MS3 and NPLC-NI-ESI/MS2, we elucidated, for the first time, the chemical structures of docosahexaenoyl and eicosapentaenoyl plasmenyl phosphatidylserine (PS) species and differentiated up to six isobaric species of diacyl/alkylacyl/alkenylacyl phosphatidylethanolamine (PE) in the US pacific oysters. The presence of a high content of both omega-3 plasmenyl PS/plasmenyl PE species and multiple isobaric molecular species isomers is the noteworthy characteristic of the marine oyster. The simple and robust NPLC-NI-ESI/MSn-based methodology should be particularly valuable in the detailed characterization of marine lipid dietary supplements with respect to omega-3 aminophospholipids. 相似文献
8.
Juan José Villaverde Sónia A. O. Santos Elisabete Maciel Mário M. Q. Simões Carlos Pascoal Neto M. Rosário M. Domingues Armando J. D. Silvestre 《Journal of mass spectrometry : JMS》2012,47(2):163-172
This study reports the identification of oligomeric alkenylperoxides by electrospray ionization mass spectrometry (ESI‐MS) and tandem mass spectrometry (ESI‐MS2), during the oxidation of oleic, linoleic and linolenic acids with Fenton's (Fe2+/H2O2) and Fe2+/O2 systems. The reactions were followed by ferrous oxidation‐xylenol orange method together with GC‐MS and GC‐FID, allowing to observe that both oxidation systems are different in terms of hydroperoxide evolution, probably due to the presence of different intermediate reactive species: perferryl ion and OH· radical responsible for the decomposition of lipid hydroperoxides and formation of new compounds. The analysis of ESI‐MS in the negative mode, obtained after oxidation of each fatty acid, confirmed the presence of the monomeric oxidation products together with other compounds at high mass region above m/z 550. These new ions were attributed to oligomeric structures, identified by the fragmentation pathways observed in the tandem mass spectra. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
9.
The antimicrobial moenomycin, commonly used as a growth promoter in livestock, was isolated from medicated chicken feed. The purified extract was subjected to reversed-phase liquid chromatographic separation followed by structural characterization using ion-trap mass spectrometry (ITMS), which allowed identification of five moenomycins (A, A12, C1, C3, and C4) as the major components. The fragmentation patterns of the protonated and deprotonated moenomycin molecules, as well as of a series of sodium adducts, were investigated using ITMS after electrospray ionization. While the protonated molecules [M+H]+ proved highly unstable and underwent extensive in-source fragmentation, isolation and activation of the [M--H]- ions (m/z 1580 for moenomycin-A) yielded simple mass spectra with a dominant base peak corresponding to the loss of the carboxy-glycol and the C25-hydrocarbon chain (m/z 1152 for moenomycin-A). Further study of this fragment ion in an MS3 experiment gave rise to a peculiar product ion (m/z 902 for moenomycin-A) that was attributed to the expulsion of a carbohydrate moiety representing a central building block of the linear molecule. In positive ion mode the generation of the mono-sodiated adduct ions, [M+Na]+, was promoted by amending the mobile phase with 100 microM sodium acetate, but this also resulted in higher adducts of the type [M+2Na--H]+ and [M+3Na--2H]+ arising from the formation of the sodium salts of the phosphate acid diester and subsequently of the carboxylic acid. Substantial differences among the fragment-rich product ion profiles of the three species were observed, and could in part be traced back to the mode of complexation of the additional sodium cation(s). 相似文献
10.
Though liquid chromatography electrospray tandem mass spectrometry (LC-ESI-MS2) has been widely used in the structural elucidation of triacylglycerols (TAG) in vegetable oils, its potentiality for the identification of TAG molecules in omega-3 rich oils remains unexplored till date. Hence, this article investigates the applicability of LC-ESI-MS2 for the structural characterization of naturally occurring TAG in cod liver oil without the TAG fractionation during the sample preparation. A computational algorithm was developed to automatically interpret the mass spectra and elucidate the TAG structures respectively. The results were compared against the lipase benchmark method. A principal component analysis study revealed that it is possible to discriminate genuine from adulterated cod liver oil. 相似文献
11.
Moe MK Anderssen T Strøm MB Jensen E 《Rapid communications in mass spectrometry : RCM》2004,18(18):2121-2130
We report a novel method allowing the complete structural characterization of intact species of the phospholipid classes phosphatidylcholine and phosphatidylethanolamine by utilizing negative electrospray ionization quadrupole tandem mass spectrometry (MS/MS). Information on the molecular weight of the intact phospholipid species, the class to which it belongs, the molecular mass of the fatty acid substituents and their regioisomerism, is easily revealed by MS/MS. Throughout our investigations the R2COO- ions were more abundant than the R1COO- ions, and this observation is used for regioisomeric assignment of the two fatty acids. However, for phospholipid species containing an unsaturated fatty acid, information on the position of the double bond is not achieved in this way. By converting the olefinic sites to their 1,2-dihydroxylated derivatives, information on the position of the hydroxyl groups (and hence of the double bond) is obtained by performing a second MS/MS experiment. Thus, a complete structural characterization of intact phosphatidylcholine and phosphatidylethanolamine species is obtained by performing these two MS/MS experiments. In order to ensure structural distinction of isobaric species, a number of phosphatidylethanolamine and phosphatidylcholine species were synthesized from lyso-phosphatidylcholine and analyzed by the present method. The applicability of the method to real samples is also demonstrated by the complete structural elucidation of the two phosphatidylcholine species 16:0/18:1Delta9 and 16:0/18:1Delta11 from egg yolk. 相似文献
12.
Summary A sensitive, selective, and rapid method is described for analysis of ceramides in the human stratum coracum by direct coupling
of HPLC with an electrospray ion-trap mass spectrometry. Nonaqueous reversed-phase chromatography stabilizes the electrospray
ionization, resulting in sensitivity that enables direct measurement of skin lipid extracts with no special sample preparation.
Assignment of individual signals to the corresponding ceramide species is based on interpretation of the fragment spectra
from MS-MS experiments. This enables much finer differentiation between ceramdies than that achievable by thin-layer chromatography.
Summary A sensitive, selective, and rapid method is described for analysis of ceramides in the human stratum corneum by direct coupling
of HPLC with an electrospray ion-trap mass spectrometry. Nonaqueous reversed-phase chromatography stabilizes the electrospray
ionization, resulting in sensitivity that enables direct measurement of skin lipid extracts with no special sample preparation.
Assignment of individual signals to the corresponding ceramide species is based on interpretation of the fragment spectra
from MS-MS experiments. This enables much finer differentiation between ceramides than that achievable by thin-layer chromatography. 相似文献
13.
Johnson DW 《Rapid communications in mass spectrometry : RCM》2000,14(21):2019-2024
The development of a new class of derivatives, the alkyldimethylaminoethyl ester iodides, for the analysis of fatty acids by electrospray ionization tandem mass spectrometry is described. They are prepared by quaternization of dimethylaminoethyl esters with alkyl iodides. The trimethylaminoethyl (choline) ester iodide affords between 8 and 12 times greater signal intensity than the corresponding dimethylaminoethyl ester used in the analysis of long to very long chain fatty acids in plasma samples. It is a superior derivative for unsaturated and monohydroxylated long chain fatty acids but unsuitable for bile acids and dicarboxylic acids. 相似文献
14.
Linear ion-trap multiple-stage mass spectrometric approach (MS
n
) towards nearly complete structural elucidation of triacylglycerol (TAG) including (1) assignment the fatty acid substituents
on the glycerol backbone and (2) location of the double bond(s) on the unsaturated fatty acyl groups is reported. The characterization
is established by the findings that MS2 on the [M+Li]+ ions of TAG yields more abundant ions reflecting losses of the outer fatty acid substituents either as free acids (i.e.,
[M+Li-R1CO2H]+ and [M+Li-R3CO2H]+ ions) or as lithium salts (i.e., [M+Li-R1CO2Li]+ and [M+Li-R3CO2Li]+ ions) than the ions reflecting the similar losses of the inner fatty acid substituent (i.e., [M+Li-R2CO2Li]+ and [M+Li-R2CO2Li]+ ions). Further dissociation (MS3) of [M+Li-R
n
CO2H]+ (n=1, 2, or 3) gives rise to the ion series locating the double bonds along the fatty acid chain. These ions arise from charge-remote
fragmentations involving β-cleavage with γ-H shift, analogous to those seen for the unsaturated long-chain fatty acids characterized as initiated ions. Significant
differences in abundances in the ion pairs reflecting the additional losses of the fatty acid moieties, respectively, were
also seen in the MS3 spectra of the [M+Li-R
n
CO2H]+ and [M+Li-R
n
CO2Li]+ ions, leading to confirmation of the fatty acid substituents on the glycerol backbone. MS
n
on the [M+Na]+ and [M+NH4]+ adduct ions also affords location of fatty acid substituents on the glycerol backbone, but not the position of the double
bond(s) along the fatty acid chain. Unique ions from internal losses of the glycerol residues were seen in the MS3 spectra of [M+Alk-R
n
CO2H]+ (n=1, 2, 3) and of [M+Alk-R
n
CO2Alk]+ (Alk=Li, Na, NH4; n=1, 3). They are signature ions for glycerides and the pathways leading to their formation may involve rearrangements. 相似文献
15.
Fatty acids have for many years been characterized by mass spectrometry using electron ionization after chemical derivatization. When fatty acids are ionized using desorption/ionization methods such as electrospray ionization or fast atom bombardment, structural information is usually obtained through high-energy collision-induced dissociation (CID) using sector instruments. It has been shown that copper displays very interesting properties in the gas phase during CID. In this study, the reactivity of saturated and unsaturated fatty acid-copper [M-H+Cu(II)]+ complex and the role of the copper ion in promoting fragmentations were investigated under low-energy collisional activation conditions. The decomposition of these species in an ion trap instrument led to diagnostic ion series that reflect C--C bond cleavage, which involves Cu(II) reduction followed by the release of an alkyl radical. It was demonstrated that in this way the localization of one or two homoconjugated double bonds is possible using low-energy CID. Moreover, the distinction of cis and trans isomers is possible through characteristic product ions related to a specific loss of CO2. When these experiments are repeated using a triple-quadrupole instrument with argon as collision gas, a different behavior is observed as in this case, in addition to the product ion distributions observed in the ion trap, other distributions are observed that reflect the influence of the different kinetic shifts and the occurrence of consecutive decompositions. Different examples are presented with various saturated and unsaturated fatty acid chains. Mechanisms are proposed in order to rationalize the experimental observations. 相似文献
16.
17.
Single quadrupole gas chromatography/mass spectrometry (GC/MS) has been widely used for isotopic analysis in metabolic investigations using stable isotopes as tracers. However, its inherent shortcomings prohibit it from broader use, including low isotopic precision and the need for chemical derivatization of the analyte. In order to improve isotopic detection power, liquid chromatography/electrospray ionization ion-trap tandem mass spectrometry (LC/ESI-itMS2) has been evaluated for its isotopic precision and chemical sensitivity for the analysis of [13C]palmitoylcarnitine. Over the enrichment range of 0.4-10 MPE (molar % excess), the isotopic response of LC/ESI-itMS2 to [13C]palmitoylcarnitine was linear (r = 1.00) and the average isotopic precision (standard deviation, SD) was 0.11 MPE with an average coefficient of variation (CV) of 5.6%. At the lower end of isotopic enrichments (0.4-0.9 MPE), the isotopic precision was 0.05 MPE (CV = 8%). Routine analysis of rat skeletal muscle [13C4]palmitoylcarnitine demonstrated an isotopic precision of 0.03 MPE for gastrocnemius (n = 16) and of 0.02 MPE for tibialis anterior (n = 16). The high precision enabled the detection of a small (0.08 MPE) but significant (P = 0.01) difference in [13C4]palmitoylcarnitine enrichments between the two muscles, 0.51 MPE (CV = 5.8%) and 0.43 MPE (CV = 4.6%), respectively. Therefore, the system demonstrated an isotopic lower detection limit (LDL) of < or =0.1 MPE (2 x SD) that has been impossible previously with other organic mass spectrometry instruments. LC/ESI-itMS2 systems have the potential to advance metabolic investigations using stable isotopes to a new level by significantly increasing the isotopic solving power. 相似文献
18.
The electrospray ionization ion trap multiple-stage tandem mass spectrometry (ESI-MSn) and electrospray ionization Fourier transform ion cyclotron resonance multiple-stage tandem mass spectrometry (ESI-FT-ICR-MSn) have been applied successfully to the direct investigation of a number of dibenzocyclooctadiene lignan constituents from the methanol extracts of the Fructus Schisandrae in the positive ion mode. The detailed structural characterization of the same skeleton and different peripheral substituents had been studied and the precise elemental compositions of ions at high mass resolution had been obtained. So the fragmentation mechanisms could be clarified. And the lignan components in Schisandra chinensis (Turcz.) Baill. fruits (SCF) and Schisandra sphenanthera Rehd. et Wils. fruits (SSF) were identified by comparing the structural information and fragmentation mechanisms. Then a pair of isobaric compounds was differentiated. Meanwhile these two similar fruits were distinguished. The research results demonstrated that ESI-MSn technique is a sensitive, selective and effective tool for the direct analysis and rapid determination of constituents in complex mixtures from nature products. And these should be useful for the identification of similar compounds and differentiation of similar species from Chinese herbs. 相似文献
19.
The application of multiple-stage ion-trap (IT) mass spectrometric methods for the structural characterization of cardiolipin (CL), a 1,3-bisphosphatidyl-sn-glycerol that consists of four fatty acyl chains and three glycerol backbones (designated as A, B, and central glycerol, respectively), as the sodiated adduct ions in the positive-ion mode was evaluated. Following collisionally activated dissociation (CAD), the [M - 2H + 3Na]+ ions of CL yield two prominent fragment ion pairs that consist of the phosphatidyl moieties attached to the 1'- and 3'-position of the central glycerol, respectively, resulting from the differential losses of the diacylglycerol moieties containing A and B glycerol, respectively. The results are consistent with those previously described for the [M - H]- and [M - 2H + Na]- ions in the negative-ion mode, thus permitting assignment of the two phosphatidyl moieties attached to the 1'- or 3'-position of the central glycerol. The identities of the fatty acyl substituents and their positions on the glycerol backbones (glycerol A and B) are deduced from further degradation of the above ion pairs that give the fragment ions reflecting the fatty acid substituents at the sn-1 (or sn-1') and sn-2 (or sn-2') positions. The ions that arise from losses of the fatty acid substituents at sn-1 and sn-1', respectively, are prominent, but the analogous ions from losses of the fatty acid substituents at sn-2 and sn-2', respectively, are of low abundance in the MS2 product-ion spectra. This feature further confirms the assignment of the positions of the fatty acid substituents. The similar IT multiple-stage mass spectrometric approaches including MS2 and MS3 for structural characterization of CL using its [M + Na]+ and the [M - H + 2Na]+ ions are also readily applicable. However, their uses for structural characterization are less desirable because formation of the [M + Na]+ and the [M - H + 2Na]+ ions for CL is not predictable. 相似文献
20.
Osaka I Watanabe M Takama M Murakami M Arakawa R 《Journal of mass spectrometry : JMS》2006,41(10):1369-1377
Linear and cyclic polylactic acids (PLAs) were characterized using electrospray ionization mass spectrometry (ESI-MS) as part of our ongoing investigation of the hydrolysis mechanism of biodegradable polymers. The condensation oligomers of linear polylactic acid (LPLA) were synthesized by thermal dehydration of L-lactic acid. The trimer and tetramer base polymers of cyclic polylactic acid (CPLA) were obtained by cyclization reactions of lactic acid trimers and tetramers, respectively. In the ESI-MS/MS measurement, LPLA yielded three types of product ion series, while CPLA yielded only one type, from which the repeated units of CPLA were removed. The MS/MS spectrum of the NH4+ adduct ion for both cyclic and linear PLA showed loss of one ammonia molecule. The postsource decay (PSD) spectrum of CPLA by matrix-assisted laser desorption ionization (MALDI) mass spectrometry was similar to the ESI-MS/MS spectrum, while that of LPLA was different. In addition, the degradation of cyclic and linear PLAs by solvolysis was investigated. Solvolysis with anhydrous MeOH was quite feasible, but did not readily occur in the presence of even a small amount of water in the MeOH solvent. 相似文献