Effect of substituents and protonation on the mechanism of 1,3-dipolar retro-cycloaddition reaction of pyrrolidino[60]- and [70]fullerenes

The mass spectra of new substituted pyrrolidino[60]- and [70]fullerenes have been obtained using electrospray ionization conditions in the positive and negative mode of detection with two different mass spectrometers, a quadrupole ion trap and a Fourier transform ion cyclotron resonance. Radical anions M(●-) and deprotonated molecules [M-H](-) are formed under negative electrospray ionization mass spectrometry conditions, and the collision-induced dissociations of both ionic species have been studied. Either negative odd-electron ions or negative even-electron ions undergo a retro-cycloaddition process forming the corresponding fullerene product ions C(60)(●-) and C(70)(●-). The generation of fullerene radical anions from deprotonated molecules is a new exception of the "even-electron rule." In contrast, the protonated molecules [M + H](+) obtained from the positive mode of detection do not undergo this cycloreversion reaction, and the MS(n) experiment reveals a variety of eliminations of neutral molecules involving different hydrogen shifts and multiple bond cleavages that lead eventually to substituted methanofullerene fragment ions. The observed fragmentations can be correlated with the electronic character of the substituents attached to the heterocyclic moiety. The results obtained from the thermal reactions of these compounds, carried out under different pH conditions, correlate well with those obtained in gas phase. The different behaviors between protonated and unprotonated molecules and ions can be explained assuming that the retro-cycloaddition reaction takes place only when the nitrogen atom of the pyrrolidine ring (the basic center of the molecule) is unprotonated both in gas and condensed phase. The protonation of the NH group inhibits the cycloreversion process, and therefore different fragmentations take place. The detailed mechanisms of the formation and evolution of the intermediate fragments are described.     

Mass spectral studies of meso-dialkyl, alkyl aryl and cycloalkyl calix(4)pyrroles under positive and negative ion electrospray ionization conditions

A series of meso-dialkyl, alkyl aryl and cycloalkyl calix(4)pyrroles (1-15) are studied under positive and negative ion electrospray ionization (ESI) conditions. The positive ion spectra show abundant [M + H](+) and [M + Na](+) ions and the negative ion spectra show the [M + Cl](-) (the Cl(-) ions from the solvent) and [M - H](-) ions. The collision induced dissociation (CID) spectra of [M + H](+), [M + Na](+), [M + Cl](-) and [M - H](-) ions are studied to understand their dissociation pathway and compared to that reported for M(+) under electron ionization (EI) conditions. The beta-cleavage process that was diagnostic to M(+) is absent in all the CID spectra of the ions studied under ESI. Dissociation of all the studied ions resulted in the fragment ions formed by sequential elimination of pyrrole (A) and/or dialkyl/alkyl aryl/cycloalkyl (B) groups involving hydrogen migration to pyrrole ring at each cleavage of A--B bond, which clearly reveals the arrangement of A and B groups in the calix(4)pyrroles. The source of hydrogen that migrates to pyrrole ring during A--B bond cleavage is investigated by the experiments on deuterated compounds and [M + D](+) ions; and confirmed that the hydrogen attached to pyrrole nitrogen, hydrogen on alpha-carbon of alkyl group and the H(+)/Na(+) ion that added during ESI process to generate [M + H](+)/[M + Na](+) ions involve in the migration. The yields of [M + Na](+) ions are found to be different for the isomeric meso-cycloalkyl compounds (cycloheptyl, and 2-, 3- and 4-methyl cyclohexyl) and for normal and N-confused calix(4)pyrroles. The isomeric methyl and 3-hydroxy/4-hydroxy phenyl calix(4)pyrroles show specific fragmentation pattern during the dissociation of their [M - H](-) ions.     

Electrospray ionization mass spectrometry of ginsenosides

Ginsenosides R(b1), R(b2), R(c), R(d), R(e), R(f), R(g1), R(g2) and F(11) were studied systematically by electrospray ionization mass spectrometry in positive- and negative-ion modes with a mobile-phase additive, ammonium acetate. In general, ion sensitivities for the ginsenosides were greater in the negative-ion mode, but more structural information on the ginsenosides was obtained in the positive-ion mode. [M + H](+), [M + NH(4)](+), [M + Na](+) and [M + K](+) ions were observed for all of the ginsenosides studied, with the exception of R(f) and F(11), for which [M + NH(4)](+) ions were not observed. The signal intensities of [M + H](+), [M + NH(4)](+), [M + Na](+) and [M + K](+) ions varied with the cone voltage. The highest signal intensities for [M + H](+) and [M + NH(4)](+) ions were obtained at low cone voltage (15-30 V), whereas those for [M + Na](+) and [M + K](+) ions were obtained at relatively high cone voltage (70-90 V). Collision-induced dissociation yielded characteristic positively charged fragment ions at m/z 407, 425 and 443 for (20S)-protopanaxadiol, m/z 405, 423 and 441 for (20S)-protopanaxatriol and m/z 421, 439, 457 and 475 for (24R)-pseudoginsenoside F(11). Ginsenoside types were identified by these characteristic ions and the charged saccharide groups. Glycosidic bond cleavage and elimination of H(2)O were the two major fragmentation pathways observed in the product ion mass spectra of [M + H](+) and [M + NH(4)](+). In the product ion mass spectra of [M - H](-), the major fragmentation route observed was glycosidic bond cleavage. Adduct ions [M + 2AcO + Na](-), [M + AcO](-), [M - CH(2)O + AcO](-), [M + 2AcO](2-), [M - H + AcO](2-) and [M - 2H](2-) were observed at low cone voltage (15-30 V) only.     

Mass spectral behavior of the hydrolysis products of sesqui- and oxy-mustard type chemical warfare agents in atmospheric pressure chemical ionization

Bis(2-hydroxyethylthio)alkanes and bis(2-hydroxyethylthioalkyl)ethers are important biological and environmental degradation products of sulfur mustard analogs known as sesqui- and oxy-mustards. We used atmospheric pressure chemical ionization mass spectrometry (APCI MS) to acquire characteristic spectra of these compounds in positive and negative ionization modes. Positive APCI mass spectra exhibited [M + H](+); negative APCI MS generated [M + O(2)](-), [M - H](-), and [M - 3H](-); and both positive and negative APCI mass spectra contained fragment ions due to in-source collision-induced dissociation. Product ion scans confirmed the origin of fragment ions observed in single-stage MS. Although the spectra of these compounds were very similar, positive and negative APCI mass spectra of the oxy-mustard hydrolysis product, bis(2-hydroxyethylthiomethyl)ether, differed from the spectra of the other compounds in a manner that suggested a rearrangement to the sesqui-mustard hydrolysis product, bis(2-hydroxyethylthio)methane. We evaluated the [M + O(2)](-) adduct ion for quantification via liquid chromatography-MS/MS in the multiple-reaction monitoring (MRM) mode by constructing calibration curves from three precursor/product ion transitions for all the analytes. Analytical figures of merit generated from the calibration curves indicated the stability and suitability of these transitions for quantification at concentrations in the low ng/mL range. Thus, we are the first to propose a quantitative method predicated on the measurement of product ions generated from the superoxide adduct anion of the sesqui-and oxy-mustard hydrolysis products.     

Cluster ions of diquat and paraquat in electrospray ionization mass spectra and their collision-induced dissociation spectra

Cluster ions such as [Cat+X+nM](+) (n = 0-4); [Cat-H+nM](+) (n = 1-3); and [2(Cat-H)+X+nM](+) (n = 0-2), where Cat, X, and M are the dication, anion, and neutral salt (CatX(2)), respectively, are observed in electrospray ionization (ESI) mass spectrometry of relatively concentrated solutions of diquat and paraquat. Collision-induced dissociation (CID) reactions of the clusters were observed by tandem mass spectrometry (MS/MS), including deprotonation to form [Cat-H](+), one-electron reduction of the dication to form Cat(+.), demethylation of the paraquat cation to form [Cat-CH(3)](+), and loss of neutral salt to produce smaller clusters. The difference in acidity and reduction power between diquat and paraquat, evaluated by thermodynamical estimates, can rationalize the different fractional yields of even-electron ([Cat-H](+) and its clusters) and odd-electron (mostly Cat(+)) ions in ESI mass spectra of these pesticides. The [Cat+n. Solv](2+) doubly charged cluster ions, where n 相似文献   

Comparative study of organic dyes with time-of-flight static secondary ion mass spectrometry and related techniques

A series of cationic, zwitterionic and anionic fluorinated carbocyanine dyes, spin-coated on Si substrates, were measured with time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) under Ga(+) primary ion bombardment. Detailed fragmentation patterns were developed for all dyes measured. In the positive mode, the resulting spectra showed very intense signals for the precursor ions of the cationic dyes, whereas the protonated signals of the anionic dyes were hardly detected. Differences of three orders of magnitude were repeatedly observed for the secondary ion signal intensities of cationic and anionic dyes, respectively. All measured dyes yielded mass spectra containing several characteristic fragment ions. Although the secondary ion yields were still higher for the cationic than the anionic dye fragments, the difference was reduced to a factor of < or =10. This result and the fact that M(+), [M + H](+) or [M + 2H](+) are even-electron species make it very likely that the recorded fragments were not formed directly out of the (protonated) parent ions M(+), [M + H](+) or [M + 2H](+). In the negative mode, none of the recorded spectra contained molecular information. Only signals originating from some characteristic elements of the molecules (F, Cl), the anionic counter ion signal and some low-mass organic ions were detected. A comparative study was made between TOF-S-SIMS, using Ga(+) primary ions, and other mass spectrometric techniques, namely fast atom bombardment (FAB), electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). The measurements showed that MALDI, ESI and FAB all give rise to spectra containing molecular ion signals. ESI and FAB produced M(+) and [M + H](+) signals, originating from the cationic and zwitterionic dyes, in the positive mode and M(-) and [M - H](-) signals of the anionic and zwitterionic dyes in the negative mode. With MALDI, molecular ion signals were measured in both modes for all the dyes. Structural fragment ions were detected for FAB, ESI and MALDI in both the positive and negative modes. Compared with the other techniques, TOF-S-SIMS induced a higher degree of fragmentation.     

Internal residue loss produced by rearrangement of a novel cationic glycosphingolipid,glyceroplasmalopsychosine, in collision-induced dissociation

A novel plasmal conjugate of galactosylsphingosine (psychosine), Gro1(3)-O-plasmal-O-6Galbeta-sphingosine (glyceroplasmalopsychosine), was analyzed by electrospray ionization and liquid secondary ion mass spectrometry with low- or high-energy collision-induced dissociation (CID). In the product ion spectra of the [M + H](+) ions, [M + H - glycerol](+) ions arising from the loss of a glycerol were predominant. Unexpectedly, CID of the [M + H - glycerol](+) ion produced an outstanding ion, [(M + H - glycerol) - Hex](+), which required the loss of the galactose from inside the molecule. This ion was greatly reduced in the spectra of N,N-dimethyl derivatives, indicating that the [(M + H - glycerol) - Hex](+) ion is formed from an intramolecular rearrangement with migration of the plasmal residue to the free amino group of sphingosine. It would be expected that the rearrangement occurs simultaneously with the elimination of glycerol or a rearranged [M + H](+) ion leads to the elimination of glycerol, to form a Schiff base-type [M + H - glycerol](+) ion, from which the terminal galactose could be removed by the normal mechanism of glycosidic cleavage. On the other hand, the [M + Na - glycerol](+) ion derived from the sodiated molecule did not produce an ion corresponding to the rearrangement reaction, possibly owing to a higher stability of the sodiated ions against conformational changes.     

Intramolecular condensation reactions in protonated dipeptides: Carbon monoxide,water, and ammonia losses in competition

The elimination of carbon monoxide and water from a series of protonated dipeptides, [XxxYyy + H](+), is investigated by tandem mass spectrometry experiments and density functional theory. The combined results show that CO loss occurs on the a(1)-y(1) pathway, which begins by rearrangement of the added proton to the amide N-atom and creates the proton-bound dimer of an amino acid (Yyy) and an imine (that from Xxx residue). The loss of H(2)O is initiated from a tautomer in which the added proton has migrated to the hydroxyl group of the C-terminus, thereby promoting the formation of an ion with protonated oxazolone structure (a nominal b(2) ion). The highest yields of [XxxYyy + H - CO](+) and [XxxYyy + H - H(2)O](+) are observed at threshold energies. As the internal energy of the protonated dipeptides increases, these primary products are depleted by consecutive dissociations yielding mostly backbone fragments. Specifically, [XxxYyy + H - CO](+) decomposes to y(1) (protonated Yyy) and a(1) (immonium ion of Xxx residue), while [XxxYyy + H - H(2)O](+) produces a(2) and the immonium ions of residues Xxx (a(1)) and Yyy ("internal" immonium ion). Water loss takes place more efficiently when the more basic residue is at the C-terminal position. Increasing the basicity of the N-terminal residue enhances the extent of CO versus H(2)O loss and introduces the competitive elimination of NH(3). The dissociations leading to eliminations of small neutrals (CO, H(2)O, etc.) generally proceed over transition states that lie higher in energy than the corresponding dissociation products. The excess energy is disposed of either in translational or rovibrational modes of the products, depending on the stability of the incipient noncovalent assemblies emerging during the cleavage of the small neutrals.     

Characterisation of a series of acetals/ketals of bis(2-nitrophenyl) ethanediol and bis(4,5-dimethoxy-2-nitrophenyl) ethanediol under APCI mass spectrometric conditions

A series acetals/ketals of aldehydes and ketones formed by the reaction of two photolabile protecting groups, bis(2-nitrophenyl) ethanediol and bis(4,5-dimethoxy-2-nitrophenyl) ethanediol (I and II, respectively), were analysed under EI, LSIMS, ESI and APCI conditions to obtain molecular weights as well as structural information. The EI and LSIMS techniques failed to give molecular weight information. The positive ESI yielded [M + H](+) ions only for I; however, with added Na(+) both I and II formed [M + Na](+) adducts. But upon decomposition, the [M + Na](+) ions yielded Na(+) ion as the only product ion. Similarly, under negative ion ESI conditions both I and II gave molecular weight information by forming adduct ions with halide anions (F(-), Cl(-), Br(-) and I(-)); however, they did not give structural information as they resulted in only the halide anion as the abundant fragment ion upon dissociation. All the compounds formed abundant M(-*) ions under negative ion APCI conditions, and their MS/MS spectra showed characteristic fragment ions; hence the acetals/ketals of I and II could be successfully characterized under negative ion APCI conditions.     

Cleavage reactions of the complex ions derived from self-complementary deoxydinucleotides and alkali-metal ions using positive ion electrospray ionization with tandem mass spectrometry

The dissociation reactions of the adduct ions derived from the four self-complementary deoxydinucleotides, d(ApT), d(TpA), d(CpG), d(GpC), and alkali-metal ions were studied in detail by positive ion electrospray ionization multiple-stage mass spectrometry (ESI-MS(n)). For the [M + H](+) ions of the four deoxydinucleotides, elimination of 5'-terminus base or loss of both of 5'-terminus base and a deoxyribose were the major dissociation pathway. The ESI-MS(n) spectra showed that Li(+), Na(+), and Cs(+) bind to deoxydinucleotides mainly by substituting the H(+) of phosphate group, and these alkali-metal ions preferred to bind to pyrimidine bases rather than purine bases. For a given deoxydinucleotide, the dissociation pathway of [M + K](+) ions differed clearly from that of [M + Li](+), [M + Na](+), and [M + Cs](+) ions. Some interesting and characteristic cleavage reactions were observed in the product-ion spectra of [M + K](+) ions, including direct elimination of deoxyribose and HPO(3) from molecular ions. The fragmentation behavior of the [M + K](+) and [M + W](+) (W = Li, Na, Cs) adduct ions depend upon the sequence of bases, the interaction between alkali-metal ions and nucleobases, and the steric hindrance caused by bases.     

Differentiation of a pair of diastereomeric tertiarybutoxycarbonylprolylproline ethyl esters by collision-induced dissociation of sodium adduct ions in electrospray ionization mass spectrometry and evidence for chiral recognition by ab initio molecular orbital calculations

The fragmentation of the sodium adduct ions for tert-butoxycarbonyl-L-prolyl-L-proline ethyl ester (Boc-L-Pro-L-Pro-OEt) was compared with that for Boc-D-Pro-L-Pro-OEt in positive-ion electrospray ionization (ESI) mass spectrometry. In the collision-induced dissociation (CID) mass spectra of the [M + Na](+) ions, the abundance of the [M + Na - C(CH(3))(3) + H](+) ion, which is due to the loss of a tert-butyl group from the [M + Na](+) ion for Boc-D-Pro-L-Pro-OEt, was about eight times higher than that for Boc-L-Pro-L-Pro-OEt. In addition, in the CID spectra of the sodium adduct fragment ion ([M + Na - Boc + H](+)), the abundance of the [M + Na - Boc - prolylresidue + H](+) ion, which is due to the loss of prolyl residue from the [M + Na - Boc + H](+) ion for Boc-L-Pro-L-Pro-OEt, was about five times higher than that for Boc-D-Pro-L-Pro-OEt. These results indicate that Boc-L-Pro-L-Pro-OEt was distinguished from Boc-D-Pro-L-Pro-OEt by the CID mass spectra of the sodium adduct ions in ESI mass spectrometry. The optimized geometries of the [M + Na](+) and the [M + Na - Boc + H](+) ions calculated by ab initio molecular orbital calculations suggest that the chiral recognition of these diastereomers was due to the difference of the orientation of a sodium ion to the oxygen and nitrogen atoms in dipeptide derivatives, and to the difference of the total energies between them.     

Mass spectral study of Boc-carbo-beta3-peptides: differentiation of two pairs of positional and diastereomeric isomers

A mass spectral study of a series of new Boc-C-linked carbo-beta(3)-peptides prepared from C-linked carbo-beta(3)-amino acids (Caa) was carried out using liquid secondary ion mass spectrometry (LSIMS), electrospray ionization (ESI) and tandem mass spectrometry. Using the nomenclature of Roepstorff and Fohlman, the positive ion high- and low energy collision-induced dissociation (CID) of [M + H - Boc + H](+) ions of the peptides produce both N- and C-terminus ions, y(n) (+) and b(n) (+) ions, with high abundance and other ions of low abundance. Further, characteristic fragment ions of carbohydrate moiety are observed. In contrast to the CID of protonated peptide acids, the CID of [M - H](-) ions of the beta(3)-peptide acids do not give b(n)(-) ions and show abundant z(n)(-) and c(n) (-) ions which are insignificant in the former. Two pairs of positionally isomeric Boc-carbo-beta(3)-dipeptides were differentiated by the CID of [M + H](+) ions in LSIMS and ESIMS. The fragment ion [M + H - C(CH(3))(3) + H](+) formed from [M + H](+) by the loss of 2-methylprop-2-ene is relatively more abundant in the dipeptide Boc-NH-beta-hGly-Caa(S)-OCH(3) (14) containing the sugar moiety at the C-terminus whereas it is insignificant in Boc-NH-Caa(S)-beta-hGly-OCH(3) (13), which has the sugar moiety at the N-terminus. Similarly, two pairs of diastereomeric dipeptides were distinguished by the high- and low-energy CID of [M + H](+) ions. The loss of 2-methylprop-2-ene is more pronounced for Boc-NH-Caa(R)-beta-hGly-OCH(3) (17) and Boc-NH-Caa(R)-Caa(S)-OCH(3) (18) isomers whereas it is insignificant for Boc-NH-Caa(S)-beta-hGly-OCH(3) (13) and Boc-NH-Caa(S)-Caa(S)-OCH(3) (2) isomers. This was attributed to a favorable configuration of the carbohydrate moiety favoring the 'H' migration involved in the loss of 2-methylprop-2-ene from the [M + H](+) ions of isomers 17 and 18 compared with the unfavorable configuration of the carbohydrate moiety in isomers 13 and 2.     

Characterization of inositol phosphorylceramides from <Emphasis Type="Italic">Leishmania major</Emphasis> by tandem mass spectrometry with electrospray ionization

We describe tandem mass spectrometric approaches, including multiple stage ion-trap and source collisionally activated dissociation (CAD) tandem mass spectrometry with electrospray ionization (ESI) to characterize inositol phosphorylceramide (IPC) species seen as [M - H](-) and [M - 2H + Li](-) ions in the negative-ion mode as well as [M + H](+), [M + Li](+), and [M - H + 2Li](+) ions in the positive-ion mode. Following CAD in an ion-trap or a triple-stage quadrupole instrument, the [M - H](-) ions of IPC yielded fragment ions reflecting only the inositol and the fatty acyl substituent of the molecule. In contrast, the mass spectra from MS(3) of [M - H - Inositol](-) ions contained abundant ions that are readily applicable for assignment of the fatty acid and long-chain base (LCB) moieties. Both the product-ion spectra from MS(2) and MS(3) of the [M - 2H + Alk](-), [M + H](+), [M + Alk](+), and [M - H + 2Alk](+) ions also contained rich fragment ions informative for unambiguous assignment of the fatty acyl substituent and the LCB. However, the sensitivity of the ions observed in the forms of [M - 2H + Alk](-), [M + H](+), [M + Alk](+), and [M - H + 2Alk](+) (Alk = Li, Na) is nearly 10 times less than that observed in the [M - H](-) form. In addition to the major fragmentation pathways leading to elimination of the inositol or inositol monophosphate moiety, several structurally informative ions resulting from rearrangement processes were observed. The fragmentation processes are similar to those previously reported for ceramides. While the tandem mass spectrometric approach using MS(n) (n = 2, 3) permits the structures of the Leishmania major IPCs consisting of two isomeric structures to be unveiled in detail, tandem mass spectra from constant neutral loss scans may provide a simple method for detecting IPC in mixtures.     

Collisionally-induced dissociation of substituted pyrimidine antiviral agents: Mechanisms of ion formation using gas phase hydrogen/deuterium exchange and electrospray ionization tandem mass spectrometry

ESI and CID mass spectra were obtained for four pyrimidine nucleoside antiviral agents and the corresponding compounds in which the labile hydrogens were replaced by deuterium using gas-phase exchange. The number of labile hydrogens, x, was determined from a comparison of ESI spectra obtained with N(2) and with ND(3) as the nebulizer gas. CID mass spectra were obtained for [M + H](+) and [M - H](-) ions and the exchanged analogs, [M(D(x)) + D](+) and [M(D(x)) - D](-), produced by ESI using a SCIEX API-III(plus) mass spectrometer. Protonated pyrimidine antiviral agents dissociate through rearrangement decompositions of base-protonated [M + H](+) ions by cleavage of the glycosidic bonds to give the protonated bases with a sugar moiety as the neutral fragment. Cleavage of the glycosidic bonds with charge retention on the sugar moiety eliminates the base moiety as a neutral molecule and produces characteristic sugar ions. CID of protonated pyrimidine bases, [B + H](+), occurs through three major pathways: (1) elimination of NH(3) (ND(3)), (2) loss of H(2)O (D(2)O), and (3) elimination of HNCO (DNCO). Protonated trifluoromethyl uracil, however, dissociates primarily through elimination of HF followed by the loss of HNCO. CID mass spectra of [M - H](-) ions of all four antiviral agents show NCO(-) as the principal decomposition product. A small amount of deprotonated base is also observed, but no sugar ions. Elimination of HNCO, HN(3), HF, CO, and formation of iodide ion are minor dissociation pathways from [M - H](-) ions.     

Effects of transition metal ion coordination on the collision-induced dissociation of polyalanines

Transition metal-polyalanine complexes were analyzed in a high-capacity quadrupole ion trap after electrospray ionization. Polyalanines have no polar amino acid side chains to coordinate metal ions, thus allowing the effects metal ion interaction with the peptide backbone to be explored. Positive mode mass spectra produced from peptides mixed with salts of the first row transition metals Cr(III), Fe(II), Fe(III), Co(II), Ni(II), Cu(I), and Cu(II) yield singly and doubly charged metallated ions. These precursor ions undergo collision-induced dissociation (CID) to give almost exclusively metallated N-terminal product ions whose types and relative abundances depend on the identity of the transition metal. For example, Cr(III)-cationized peptides yield CID spectra that are complex and have several neutral losses, whereas Fe(III)-cationized peptides dissociate to give intense non-metallated products. The addition of Cu(II) shows the most promise for sequencing. Spectra obtained from the CID of singly and doubly charged Cu-heptaalanine ions, [M + Cu - H](+) and [M + Cu](2+) , are complimentary and together provide cleavage at every residue and no neutral losses. (This contrasts with [M + H](+) of heptaalanine, where CID does not provide backbone ions to sequence the first three residues.) Transition metal cationization produces abundant metallated a-ions by CID, unlike protonated peptides that produce primarily b- and y-ions. The prominence of metallated a-ions is interesting because they do not always form from b-ions. Tandem mass spectrometry on metallated (Met = metal) a- and b-ions indicate that [b(n) + Met - H](2+) lose CO to form [a(n) + Met - H](2+), mimicking protonated structures. In contrast, [a(n) + Met - H](2+) eliminate an amino acid residue to form [a(n-1) + Met - H](2+), which may be useful in sequencing.     

Characterization of alkylacyl,alk-1-enylacyl and lyso subclasses of glycerophosphocholine by tandem quadrupole mass spectrometry with electrospray ionization

Positive ion tandem quadrupole mass spectrometric methods for structural characterization of the subclasses of sn-glycero-3-phosphocholine (PC), including alkylacyl- and alk-1-enylacylphosphocholine and lysophosphatidylcholine (LPC), are described. Following collisionally activated dissociation, the [M + Li](+) ions generated by electrospray ionization yield abundant informative fragment ions that permit structural determination, and distinction of regioisomers among lysophosphatidylcholine can be easily achieved. In contrast, structurally informative ions arising from [M + H](+) or [M + Na](+) ions are less prominent. The most abundant ion observed in the product-ion spectra of the [M + Li](+) ions of plasmenyl- and plasmanyl-PC and of LPC arises from loss of N(CH(3))(3) ([M + Li - 59](+)). This feature permits their distinction from a product-ion spectrum arising from a diacylphosphatidylcholine, in which the [M + Li - 183](+) ion reflecting loss of phosphocholine is the most prominent. Examples for identification of various subclasses of PC in biological extracts by tandem mass spectrometry applying various constant neutral loss scannings are also shown.     

A comparison of EDI with solvent-free MALDI and LDI for the analysis of organic pigments

To evaluate the applicability of EDI to material analysis as a new ionization method, a comparison of EDI with solvent-free matrix-assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) was made for the analysis of organic pigments, e.g. Pigment Yellow 93, Pigment Yellow 180, and Pigment Green 36, as test samples, which are poorly soluble in standard solvents. In EDI, the samples were prepared in two ways: deposition of suspended samples in appropriate solvents and dried on the substrate, and the direct deposition of the powder samples on the substrate. No matrices were used. Both sample preparation methods gave similar mass spectra. Equally strong signals of [M + H](+) and [M - H](-) ions were observed with some fragment ions for azo pigments in the respective positive or negative mode of operation. For the powder sample of the phthalocyanine pigment PG36, M(+*) and [M + H](+) in the positive mode and M(-*) in the negative mode of operation were observed as major ions. Positive-mode, solvent-free MALDI gave M(+), [M + H](+) and [M + Na](+) and negative mode gave [M - H](-) depending on the sample preparation. As solvent-free MALDI, EDI was also found to be an easy-to-operate, versatile method for the samples as received.     

Linear free energy relationships in C-N bond dissociations in molecular ions of 4-substituted N-(2-furylmethyl)anilines in the gas phase

The substituent effect on the reactivity of the C-N bond of molecular ions of 4-substituted N-(2-furylmethyl)anilines toward two dissociation pathways was studied. With this aim, six of these compounds were analyzed by mass spectrometry using electron ionization with energies between 7.8 and 69.9 eV. Also, the UB3LYP/6-31G (d,p) and UHF/6-31G (d, p) levels of theory were used to calculate the critical energies (reaction enthalpies at 0 K) of the processes that lead to the complementary ions [C(5)H(5)O](+) and [M - C(5)H(5)O](+), assuming structures that result from the heterolytic and homolytic C-N bond cleavages of the molecular ions, respectively. A kinetic approach proposed in the 1960s was applied to the mass spectral data to obtain the relative rate coefficients for both dissociation channels from ratios of the peak intensities of these ions. Linear relationships were obtained between the logarithms of the relative rate coefficients and the calculated critical energies and other thermochemical properties, whose slopes showed to be conditioned by the energy provided to the compounds within the ion source. Moreover, it was found that the dissociation that leads to [C(5)H(5)O](+) is a process strongly dependent upon the electron withdrawing or donating properties of the substituent, favored by those factors that destabilize the molecular ion. On the contrary, the dissociation that leads to [M - C(5)H(5)O](+) is indifferent to the polar electronic effects of the substituent. The abundance of both products was governed by the rule of Stevenson-Audier, according to which the major ion is the one of less negative electronic affinity.     

Mass spectral analysis of N-oxides of Chemical Weapons Convention related aminoethanols under electrospray ionization conditions

N,N'-Dialkylaminoethanols are the hydrolyzed products or precursors of chemical warfare agents such as V-agents and nitrogen mustards, and they are prone to undergo oxidation in environmental matrices or during decontamination processes. Consequently, screening of the oxidized products of aminoethanols in aqueous samples is an important task in the verification of chemical weapons convention-related chemicals. Here we report the successful characterization of the N-oxides of N,N'-dialkylaminoethanols, alkyl diethanolamines, and triethanolamine using positive ion electrospray ionization mass spectrometry. The collision-induced dissociation (CID) spectra of the [M+H](+) and [M+Na](+) ions show diagnostic product ions that enable the unambiguous identification of the studied N-oxides, including those of isomeric compounds. The proposed fragmentation pathways are supported by high-resolution mass spectrometry data and product/precursor ion spectra. The CID spectra of [M+H](+) ions included [MH-CH(4)O(2)](+) as the key product ion, in addition to a distinctive alkene loss that allowed us to recognize the alkyl group attached to the nitrogen. The [M+Na](+) ions show characteristic product ions due to the loss of groups (R) attached to nitrogen either as a radical (R) or as a molecule [R+H or (R-H)] after hydrogen migration.     

Differentiation of the diastereomeric synthetic precursors of isofebrifugine and febrifugine by electrospray ionization tandem mass spectrometry

Febrifugine is an alkaloid with potent antimalarial activity isolated from Dichroa febrifuga and Hydrangea umbellate, and it exists naturally with its diastereomeric component, isofebrifugine. Here we report the differentiation of diastereomeric synthetic precursors of isofebrifugine (1, cis) and febrifugine (2, trans) and a structurally similar model diastereomeric pair without a halogen substituent (3 and 4) by electrospray ionization (ESI) tandem mass spectrometry. Compounds 1-4 contain a tert-butoxycarbonyl (BOC) substituent, and the collision-induced dissociation (CID) spectra of the [M+H](+), [M+Na](+) and [M+Li](+) ions of 1-4 include the expected product ions corresponding to the loss of C(4)H(8) (isobutene) and of C(5)H(8)O(2) (BOC-H). Loss of C(5)H(8)O(2) is dominant in cis isomers (1 and 3) and/or loss of C(4)H(8) ions is dominant in trans isomers (2 and 4). The decomposition of [M+H](+) ions shows stereoselectivity in the formation of the [M+H-(BOC-H)-C(3)H(5)OBr](+) and [M+H-(BOC-H)-C(6)H(5)CH(2)OH](+) ions. The [M+Cat](+) ions (where Cat = Na or Li) additionally show loss of NaBr and HBr from [M+Cat-(BOC-H)](+), and these product ions are constantly more abundant in cis isomers than in trans isomers. The stereoselectivity for the product ion corresponding to the loss of [(BOC-H)+C(3)H(5)OBr] from [M+H](+) ions differs from that from [M+Cat](+) ions.