Resonant dissociative electron capture by the simplest amino acids and dipeptides

The formation of ions from amino acids (glycine and alanine) and dipeptides (glycylglycine, alanylalanine, and glycylalanine) under the resonant electron capture conditions was studied by negative ion resonant electron capture mass spectrometry. The isobaric ions were found, their effective yield curves were experimentally separated, and the elemental composition was determined. The thermochemical aspect of ion formation was considered, and probable dissociative channels of fragmentation ion formation and their structures were established on the basis of this aspect. Bond cleavage reactions only and H-shift processes were revealed. The rearrangements occur presumably through the stage of formation of intramolecular hydrogen bonds. The cross-sections of formation of ions [M − H]⁻ were measured in the energy range 1.1–1.3 eV. The metastable decay channels of ions [M − H]⁻ and [M − COOH]⁻ were found in the energy range 4.5–7.5 eV for dipeptides, which enabled establishing the genetic relationship between the parental and daughter ions and revealing hidden fragmentation pathways.     

Electron capture negative ion (ECNI) mass spectrometry of complex mixtures of chlorinated decanes and dodecanes: An approach to ECNI mass spectra of chlorinated paraffins in technical mixtures

The electron capture negative ion (ECNI) mass spectra of two complex mixtures of polychlorinated decanes (PCDe) and polychlorinated dodecanes (PCDo) are presented. The number of isomers in these mixtures is still high but is drastically reduced in comparison to technical products of chlorinated paraffins (CP), due to their fixed chain length. As a result, the mass spectra are simplified and less complex. Different modes of negative ion formation were observed in the spectra of the PCDe and PCDo. [M+Cl]^– adduct ions were the most abundant ions in the spectra of lower chlorinated molecules. Higher chlorinated isomers formed prominently [M-Cl]^– and [M-HCl]^– fragments besides [M+Cl]^–. Possible consequences for the determination of chlorinated paraffins by ECNI-MS that result from the variation in ion formation are addressed. Received: 18 August 1997 / Revised: 26 January 1998 / Accepted: 31 January 1998     

Resonance-enhanced photon excitation spectroscopy of the even-parity autoionizing Rydberg states of Kr

Kr atoms were produced in their metastable states 4p⁵5s [3/2]₂ and 4p⁵5s’ [1/2]₀ in a pulsed DC discharge in a beam, and subsequently excited to the even-parity autoionizing Rydberg states 4p⁵ np′ [3/2]_1,2, [1/2]₁ and 4p⁵ nf′ [5/2]₃ using single photon excitation. The excitation spectra of the even-parity autoionizing resonance series from the metastable Kr were obtained by recording the autoionized Kr⁺ ions with time-of-flight ion detection in the photon energy range of 29000–40000 cm⁻¹. A wealth of autoionizing resonances were newly observed, from which more precise and more systematic spectroscopic data of the level energy and quantum defects were derived. Supported by the National Natural Science Foundation of China (Grant No. 20673107), the National Key Basic Research Special Foundation of China (Grant No. 2007CB815203), and Chinese Academy of Sciences (Grant No. KJCX2-SW-H08)     

Characterization of Tyrosine Nitration and Cysteine Nitrosylation Modifications by Metastable Atom-Activation Dissociation Mass Spectrometry

The fragmentation behavior of nitrated and S-nitrosylated peptides were studied using collision induced dissociation (CID) and metastable atom-activated dissociation mass spectrometry (MAD-MS). Various charge states, such as 1+, 2+, 3+, 2–, of modified and unmodified peptides were exposed to a beam of high kinetic energy helium (He) metastable atoms resulting in extensive backbone fragmentation with significant retention of the post-translation modifications (PTMs). Whereas the high electron affinity of the nitrotyrosine moiety quenches radical chemistry and fragmentation in electron capture dissociation (ECD) and electron transfer dissociation (ETD), MAD does produce numerous backbone cleavages in the vicinity of the modification. Fragment ions of nitrosylated cysteine modifications typically exhibit more abundant neutral losses than nitrated tyrosine modifications because of the extremely labile nature of the nitrosylated cysteine residues. However, compared with CID, MAD produced between 66% and 86% more fragment ions, which preserved the labile –NO modification. MAD was also able to differentiate I/L residues in the modified peptides. MAD is able to induce radical ion chemistry even in the presence of strong radical traps and therefore offers unique advantages to ECD, ETD, and CID for determination of PTMs such as nitrated and S-nitrosylated peptides.     

Sulfur ylides

The mass spectra of negative ions of keto-stabilized sulfur and phosphorus ylides (obtained from amino acids) and products of their thermal conversion are studied. The most characteristic peaks in the mass spectra of ylides belong to negative molecular ions and to [M−H]⁻ ions. Peaks of fragment ions in the mass spectra of ylides and products of their thermal conversion coincide both in mass numbers and resonance energies. For Part 8, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2100–2103, November, 1999.     

Sol–gel synthesis of nanosilver embedded hybrid materials using combined organosilica precursors

A facile sol–gel route to the fabrication of size-controllable nanosilver embedded hybrid materials at room-temperature is presented. The preparation process involves using three kind of organosilica precursors, i.e. tetraethoxysilane, 3-mercaptopropyltrimethoxysilane and polymethylhydrosiloxane, which behaved as framework constructor, complexing agent toward metal ions and in situ reducing agent for Ag⁺ ions, respectively, under alcohol-rich synthesis conditions. The prepared hybrid materials were characterized by Ultraviolet–visible diffuse reflectance spectra, Fourier transform infrared, transmission electron microscopy, X-ray diffraction, nitrogen adsorption–desorption measurements. It was shown that well-dispersed silver nanoparticles (AgNPs) with small particle size were successfully embedded in the hybrid skeleton, and the mean particle size of AgNPs could be controlled at ca. 2–5 nm.     

Metastable Atom-Activated Dissociation Mass Spectrometry of Phosphorylated and Sulfonated Peptides in Negative Ion Mode

The dissociation behavior of phosphorylated and sulfonated peptide anions was explored using metastable atom-activated dissociation mass spectrometry (MAD-MS) and collision-induced dissociation (CID). A beam of high kinetic energy helium (He) metastable atoms was exposed to isolated phosphorylated and sulfonated peptides in the 3– and 2– charge states. Unlike CID, where phosphate losses are dominant, the major dissociation channels observed using MAD were C_α – C peptide backbone cleavages and neutral losses of CO₂, H₂O, and [CO₂ + H₂O] from the charge reduced (oxidized) product ion, consistent with an electron detachment dissociation (EDD) mechanism such as Penning ionization. Regardless of charge state or modification, MAD provides ample backbone cleavages with little modification loss, which allows for unambiguous PTM site determination. The relative abundance of certain fragment ions in MAD is also demonstrated to be somewhat sensitive to the number and location of deprotonation sites, with backbone cleavage somewhat favored adjacent to deprotonated sites like aspartic acid residues. MAD provides a complementary dissociation technique to CID, ECD, ETD, and EDD for peptide sequencing and modification identification. MAD offers the unique ability to analyze highly acidic peptides that contain few to no basic amino acids in either negative or positive ion mode.     

In-source decay and fragmentation characteristics of peptides using 5-aminosalicylic acid as a matrix in matrix-assisted laser desorption/ionization mass spectrometry

The use of 5-aminosalicylic acid (5-ASA) as a new matrix for in-source decay (ISD) of peptides including mono- and di-phosphorylated peptides in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is described. The use of 5-ASA in MALDI-ISD has been evaluated from several standpoints: hydrogen-donating ability, the outstanding sharpness of molecular and fragment ion peaks, and the presence of interference peaks such as metastable peaks and multiply charged ions. The hydrogen-donating ability of several matrices such as α-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), 1,5-diaminonaphthalene (1,5-DAN), sinapinic acid (SA), and 5-ASA was evaluated by using the peak abundance of a reduction product [M + 2H + H]⁺ to that of non-reduced protonated molecule [M + H]⁺ of the cyclic peptide vasopressin which contains a disulfide bond (S-S). The order of hydrogendonating ability was 1,5-DAN > 5-ASA > 2,5-DHB > SA = CHCA. The chemicals 1,5-DAN and 5-ASA in particular can be classified as reductive matrices. 5-ASA gave peaks with higher sharpness for protonated molecules and fragment ions than other matrices and did not give any interference peaks such as multiply-protonated ions and metastable ions in the ISD mass spectra of the peptides used. Particularly, 1,5-DAN and 5-ASA gave very little metastable peaks. This indicates that 1,5-DAN and 5-ASA are more “cool” than other matrices. The 1,5-DAN and 5-ASA can therefore be termed “reductive cool” matrix. Further, it was confirmed that ISD phenomena such as N-Cα bond cleavage and reduction of S-S bond is a single event in the ion source. The characteristic fragmentations, which form a− and (a + 2)-series ions, [M + H − 15]⁺, [M + H − 28]⁺, and [M + H − 44]⁺ ions in the MALDI-ISD are described.     

Half protons or doubly charged protons? The history of metastable ions

The history of metastable ions is intertwined with that of ions formed by collision-induced dissociation (CID), and frequently the genesis of the two ion types cannot be strictly separated. Originally, metastable ions were considered a curiosity or even a nuisance, being responsible for "humps" in the base line of the recorded mass spectra. In their heyday metastable ions were recognized as having importance for establishing fragmentation sequences and for distinguishing between isomeric ion structures. Today, in many respects the utility of metastable ions has been superseded by a systematic application of CID techniques; yet the evaluation of their shape is still of importance for questions of reaction energies and ion thermochemistry.     

A laser desorption ionization time-of-flight mass spectrometry investigation into triacylglycerols oxidation during thermal stressing of edible oils

Laser desorption ionization time-of-flight mass spectrometry (LDI–TOF MS) was used to characterize olive and sunflower oils before and after thermally assisted oxidation in order to develop a rapid fingerprinting method for oil that contains unchanged and oxidized components. No matrix was used to assist laser desorption, and simplified mass spectra were obtained in the mass range of interest (m/z 500–1000), where triacyl- and diacylglycerol ions were observed. Sample preparation was reduced to dissolving oil in chloroform saturated with NaCl. Sodiated triacylglycerols (TAGs), their epoxy/hydroxy and hydroperoxy derivatives, as well as TAGs with shortened chain fatty acids (β-scission products) were clearly observed in the spectra. LDI–TOF MS rapidly provides semiquantitative information about the oxidation level of edible oil, and thus represents a very useful quality control tool. Dedicated to Professor Pier Giorgio Zambonin on the occasion of his 72nd birthday.     

Comparison of Triple Quadrupole and Double Focusing Mass Spectrometers to Investigate Collision-Induced Dissociation and Metastable Ions of Glycoconjugates

Glycoconjugates, such as chromophore-labeled disaccharides and permethylated glycosphingolipids (GSL) were used for comparison of triple quadrupole and double focusing mass spectrometers in analysis of product ions. A profound effect of collision energy was observed in the product ion spectra of ceramide ions (fragment ions of permethylated GSL): more product ions were observed from a double focusing mass spectrometer. Besides collision energy, the structure of the analyte had a significant effect on the formation of product ions. Despite the fact that masses of protonated molecular ions (MH⁺) of permethylated GSL are significantly larger than their ceramide fragments, the low-energy and high-energy product ion spectra of MH⁺ are, in general, similar. In a double focusing mass spectrometer of reversed geometry, more metastable ions were observed in the first field free region (FFR) than in the second FFR. The metastable ions observed in the second FFR were similar to those observed in low-energy collision-induced dissociation (CID). Although a double focusing mass spectrometer is superior to triple quadrupole instrument for detection of product ions, the poor resolution in either the selection of precursor ion or in the product ion spectra can be a serious problem in analysis of a mixture with similar masses.     

The [M?OH]+ ions of m- and p-ethylnitrobenzene: A common structure?

The structures of the [M? OH]⁺ ions of m- and pethylnitrobenzene have been compared by measurements of metastable ion spectra, collisional activation spectra, kinetic energy releases and critical energies for the formation of these ions and their subsequent decomposition. Normalized rates of fragmentation of metastable molecular ions and metastable [M? OH]⁺ ions have been compared for ion lifetimes up to 30 μs. The energy measurements fail to distinguish between the structures of the [M? OH]⁺ ions, but the normalized fragmentation rates and the collisional activation spectra show their structures to be different.     

The mass spectra of alkyl- and phenyl-4-imidazolin-2-ones

The mass spectra of a variety of alkyl- and aryl-4-imidazolin-2-ones have been determined and the fragmentation mechanisms have been analyzed by deuterium labelling, high resolution and metastable transitions allowing certain differentiations of positional isomers. In contrast to the benzoid systems the mass spectra of isomeric alkyl-4-imidazolin-2-ones are distinctive. The influence of the position of substituents is demonstrated by phenyl-4-imidazolin-2-ones establishing an exact prediction of fragmentation pathways. Fragment ions (e.g. [M-HNCO].⁺) which are the result of rearrangement processes were excluded for structure determinations. The ion structures involved were elucidated by collisional activation comparing model ions. Alkyl-phenyl-4-imidazolin-2-ones give almost identical mass spectra, but the positional isomers can easily be distinguished by different fragmentation patterns in both metastable and collisional activation spectra of the molecular ions.     

Proximity effects in mass spectrometry. Electron impact ionization-induced cyclization of 1,2-bis(1,4-dithiafulven-6-yl)benzenes

The electron impact ionization mass spectra of o-, m- and p-bis(1,4-dithiafulven-6-yl)benzenes were studied by means of accurate mass measurements, metastable analysis and collision-induced dissociation. Differences observed in the spectra of the ortho isomers are due to a cyclization reaction leading to molecular ions with the same structure as those generated from certain cyclic compounds, as confirmed by comparison of linked scans at constant B/E of metastable and collisionally activated molecular ions. Parallels of this cyclization of molecular ions with their electrochemical or acid-induced isomerization are also discussed.     

Features of laser desorption/ionization mass spectrometry fragmentation of vitamin B<Subscript>12</Subscript>

A comparative analysis of the laser desorption/ionization of vitamin B₁₂ by matrix-assisted laser desorption/ionization (MALDI) and desorption/ionization on porous silicon (DIOS) was carried out. The mass spectra obtained were interpreted and the pathways for ion formation and decomposition were established. The MALDI fragmentation of the positive vitamin B₁₂ ions is more extensive than the DIOS fragmentation. The most extensive fragmentation was found using the MALDI method for negative vitamin B₁₂ ions, which are lacking when using the DIOS method. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 4, pp. 251–256, July–August, 2007.     

Preconcentration of uranium(VI) and thorium(IV) from aqueous solutions using low-cost abundantly available sorbent

Olive cake as low-cost abundantly available sorbent has been characterized by N₂ at 77 K adsorption, porosity analysis, elemental analysis and IR spectra and has been used for preconcentrating of uranium(VI) and thorium(IV) ions prior to their determination spectrophotometrically. The optimum pH values for quantitative sorption of U(VI) and Th(IV) are 4–7 and 3–7, respectively. The enrichment factor for the preconcentration of U(VI) and Th(IV) were found to be 125 and 75 in the given order. The sorption capacity of olive cake is in the range of 2,260–15,000 μg g⁻¹ for Th(IV) and in the range of 1,090–17,000 μg g⁻¹ for U(VI) at pH 3–7. The sorbent exhibits good reusability and the uptake and stripping of the studied ions were fairly rapid. The elution of U(VI) and Th(IV) was performed with 0.3–1 M HCl/1–2 M HNO₃ and 0.3–0.8 M HCl/1 M HNO₃, respectively. The precision of the method was 1.8 RSD% for U(VI) and 2.5 RSD% for Th(IV) in a concentration of 1.00 μg mL⁻¹ for 10 replicate analysis. The influence of some electrolytes and cations as interferents was discussed. Separation of U(VI) and Th(IV) from other metal ions in synthetic solution was achieved.     

Mass spectrometry in structural and stereochemical problems—CCXXII: Delineation of competing fragmentation pathways of complex molecules from a study of metastable ion transitions of deuterated derivatives

Data on defocused metastable ions have been obtained for a series of structurally significant fragment ions in the mass spectra of the estrogenic steroid, estrone methyl ether and the alkaloid tropine. These data, in conjunction with measurements on defocused metastable ions in the mass spectra of isotopically labeled analogs and complete high resolution mass spectra provide important insights into the details of fragmentation processes, specifically: (a) an enumeration and determination of the frequent multiple origins of fragment ions in the mass spectra of such complex molecules, (b) specification of skeletal atoms lost and retained in concerted (one step) processes, and at each step of stepwise processes, leading to a particular fragment ion and (c) information on the relative contributions of concerted and stepwise processes resulting in the genesis of a given ion.     

Analysis of Cyclic Peptides in Pseudostellaria heterophylla (Miq.) Pax by HPLC–APCI–MS

A new method for the analysis of cyclic peptides (Pseudostellarins) in traditional Chinese medicine, Pseudostellaria heterophylla (Miq.) Pax, was established by high performance liquid chromatography–atmospheric pressure chemical ionization–mass spectrometry (HPLC–APCI–MS). The real samples were separated by a reversed-phase C₁₈ column using a binary eluent under gradient conditions. Six cyclic peptides were isolated and detected with a DAD detector. The Pseudostellarins components were identified by APCI–MS in a negative mode. In the negative ion APCI mode, the best sensitivity and the lowest detection limit for Pseudostellarins were obtained by using a mobile phase consisting of acetonitrile and pure water. The APCI spectra were characterized by [M-H]⁻ peak. The parent ions [M-H]⁻ with highest intensity was used for quantification of one cyclic peptide-Pseudostellarin B.     

Fragmentation of sputtered vanadium and niobium cluster ions,kinetic release and dissociation energy

The generation and unimolecular fragmentation of V _n ⁺ and Nb _n ⁺ clusters formed in sputtering vanadium and niobium surfaces by Xe⁺ ions has been studied. The method of measuring the kinetic energy of fragment ions (kinetic energy release distribution) has been used to determine the dissociation energy. Kinetic energy spectra have been measured in the field-free zone (corresponding to a time window of 10⁻⁵–10⁻⁴ sec after emission) of an ion microanalyzer with double focusing in reverse geometry. The results of spectra measurement were treated using the Rice-Ramsperge-Kassel theory of unimolecular reactions and the “evaporative ensemble”, which allowed us to calculate the dissociation energies of homonuclear V _n ¹ (n= 5–11) and Nb _n ¹ (n = 3–8) clusters.     

Analysis of O-glucuronide conjugates in urine by electrospray ion trap mass spectrometry

The application of electrospray ionization (ESI) ion trap mass spectrometry in the characterization of O-glucuronide conjugates of some drugs in urine is described. The conjugated metabolites formed in rabbit and human were separated by reversed-phase high-performance liquid chromatography (HPLC) and characterized by multi-stage mass spectrometry (MSⁿ) experiments in negative ion mode. The ESI mass spectra showed a deprotonated molecule [M–H]^–, which was chosen as precursor ion. Collision-induced dissociation (CID) of [M–H]^– in MSⁿ experiments resulted in the appearance of glucuronate ‘fingerprint’ ions at m/z 175 and 113 as well as prominent aglycone ions which were the same as those produced from authentic specimens. This information can be used to identify this type of compound directly without the need for derivatization or hydrolysis of enzymes, providing a rapid and specific method for guiding the isolation and characterization of similar compounds in complex matrices with LC/MS. Received: 25 January 1999 / Revised: 19 April 1999 / Accepted: 13 May 1999