Kendrick Mass Defect Analysis Research Articles

Analysis of old master paintings by direct temperature-resolved time-of-flight mass spectrometry: Some recent developments

Direct temperature-resolved mass spectrometry (DTMS) is an analytical technique in which small (μg) amounts of sample are applied to a filament and introduced into the ion source of a mass spectrometer. It is a fast fingerprinting method particularly suitable for the characterization of oils, resins, waxes, and other compound classes in tiny complex samples from paintings. DTMS results reported thus far have been obtained using instruments with nominal mass resolution. Higher mass resolutions can be achieved by magnetic sector mass spectrometers only at the expense of a severe loss of sensitivity. Modern time-of-flight mass spectrometers, however, do provide both high resolution and high sensitivity simultaneously. The availability of accurate mass information adds another dimension to DTMS. The difference between the nominal and accurate mass, the mass defect, may be graphically presented in so-called ‘Kendrick plots’. These can be used as fingerprints, enabling a quick overview of the main features in high-resolution mass spectra of complex mixtures. This paper combines DTMS with Kendrick mass defect analysis applied to a series of reference compounds commonly found in paintings. Finally, we also present the results of analysis of samples taken from the 17th-century painting of Saul and David by Rembrandt van Rijn (Mauritshuis, The Hague) that has been recently subjected to extensive conservation treatment.

Chemical Force Spectroscopy Evidence Supporting the Layer-by-Layer Model of Organic Matter Binding to Iron (oxy)Hydroxide Mineral Surfaces.

The adsorption of dissolved organic matter (DOM) to metal (oxy)hydroxide mineral surfaces is a critical step for C sequestration in soils. Although equilibrium studies have described some of the factors controlling this process, the molecular-scale description of the adsorption process has been more limited. Chemical force spectroscopy revealed differing adhesion strengths of DOM extracted from three soils and a reference peat soil material to an iron (oxy)hydroxide mineral surface. The DOM was characterized using ultrahigh-resolution negative ion mode electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometry. The results indicate that carboxyl-rich aromatic and N-containing aliphatic molecules of DOM are correlated with high adhesion forces. Increasing molecular mass was shown to decrease the adhesion force between the mineral surface and the DOM. Kendrick mass defect analysis suggests that mechanisms involving two carboxyl groups result in the most stable bond to the mineral surface. We conceptualize these results using a layer-by-layer "onion" model of organic matter stabilization on soil mineral surfaces.

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

Comprehensive two-dimensional gas chromatography (GC×GC) and high-resolution mass spectrometry (HRMS) offer the best possible separation of their respective techniques. Recent commercialization of combined GC×GC–HRMS systems offers new possibilities for the analysis of complex mixtures. However, such experiments yield enormous data sets that require new informatics tools to facilitate the interpretation of the rich information content.This study reports on the analysis of dust obtained from an electronics recycling facility by using GC×GC in combination with a new high-resolution time-of-flight (TOF) mass spectrometer. New software tools for (non-traditional) Kendrick mass defect analysis were developed in this research and greatly aided in the identification of compounds containing chlorine and bromine, elements that feature in most persistent organic pollutants (POPs). In essence, the mass defect plot serves as a visual aid from which halogenated compounds are recognizable on the basis of their mass defect and isotope patterns. Mass chromatograms were generated based on specific ions identified in the plots as well as region of the plot predominantly occupied by halogenated contaminants. Tentative identification was aided by database searches, complementary electron-capture negative ionization experiments and elemental composition determinations from the exact mass data. These included known and emerging flame retardants, such as polybrominated diphenyl ethers (PBDEs), hexabromobenzene, tetrabromo bisphenol A and tris (1-chloro-2-propyl) phosphate (TCPP), as well as other legacy contaminants such as polychlorinated biphenyls (PCBs) and polychlorinated terphenyls (PCTs).

Characterization of the chemical composition of soil humic acids using Fourier transform ion cyclotron resonance mass spectrometry

The composition of humic acids (HAs) with varying degrees of humification isolated from 10 common Japanese soils was characterized using negative ion mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry at 12T. In particular, attention was paid to polynuclear aromatic components, which are more associated with the refractory nature of HAs and their resistance to biodegradation in soil than single C ring aromatic entities, such as lignin-like components, and aliphatic functionalities. Thousands of peaks were observed in the m/z range of 200–700, and molecular formulas were assigned to 817–2457 peaks in each sample. The molecular formulas having H/C and O/C ratios similar to those of lipid, protein, and other aliphatics with low double bond equivalents (DBE) of 0–7 were generally observed across the m/z range of 200–700. Although there were a number of molecular formulas having H/C and O/C values similar to those of lignin across the wide m/z range in the HAs with a low degree of humification, most lignin-like molecular formulas in the larger m/z range (450–650) or irrespective of m/z were lacking in the HAs with middle and high degrees of humification, respectively. These observations suggest a longer residence time for lignin monomers/dimers (and their derivatives; m/z 200–400) than larger lignin oligomers (m/z 450–650) in HA structural domains. The number of molecular formulas having H/C and O/C values similar to condensed aromatics increased with increasing degree of humification. The m/z and DBE values of condensed aromatic-like molecular formulas in the HAs with a lower degree of humification were <500 and 10–25, respectively, whilst the ranges expanded to 600 and 30–33, respectively, in the highly-humified black HAs. Kendrick mass defect analysis using a carboxyl group as the characteristic functional group found that 31, 73, and 39 molecular formulas had chain-type, net-type, and biphenyl-type condensed aromatic acids, respectively, as possible structures. Summed peak magnitudes of the condensed aromatic-like molecular formulas, in particular those with higher DBE values (>17) expected to have at least 5 rings, increased with increasing degree of humification and aromatic C content (evaluated by solid-state 13C nuclear magnetic resonance spectroscopy), suggesting their contribution to the intrinsic recalcitrance of HAs in soil.

Understanding molecular formula assignment of Fourier transform ion cyclotron resonance mass spectrometry data of natural organic matter from a chemical point of view.

Formula assignment is one of the key challenges in evaluation of dissolved organic matter analyses using ultrahigh resolution mass spectrometry (FTICR MS). The number of possible solutions for elemental formulas grows exponentially with increasing nominal mass, especially when non-oxygen heteroatoms like N, S or P are considered. Until now, no definitive solution for finding the correct elemental formula has been given. For that reason an approach from the viewpoint of chemical feasibility was elucidated. To illustrate the new chemical formula assignment principle, a literature data set was used and evaluated by simplified chemical constraints. Only formulas containing a maximum of one sulphur and five nitrogen atoms were selected for further data processing. The resulting data table was then divided into mass peaks with unique component solutions (singlets, representing unequivocal formula assignments) and those with two or more solutions (multiple formula assignments, representing equivocal formula assignments). Based on a [double bond equivalent (DBE) versus the number of oxygen atoms (o)] frequency contour plot and a frequency versus [DBE minus o] diagram, a new assessment and decision strategy was developed to differentiate multiple formula assignments into chemically reliable and less reliable molecular formulas. Using this approach a considerable number of reliable components were identified within the equivocal part of the data set. As a control, a considerable proportion of the assigned formulas deemed to be reliable correspond to those which would have been obtained by CH 2 -based Kendrick mass defect analysis. We conclude that formula assignment in complex mixtures can be improved by group-wise decisions based on the frequency and the [DBE minus o] values of multiple formula assignments.

Developments in FT‐ICR MS instrumentation, ionization techniques, and data interpretation methods for petroleomics

Because of the increasing importance of heavy and unconventional crude oil as an energy source, there is a growing need for petroleomics: the pursuit of more complete and detailed knowledge of the chemical compositions of crude oil. Crude oil has an extremely complex nature; hence, techniques with ultra-high resolving capabilities, such as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), are necessary. FT-ICR MS has been successfully applied to the study of heavy and unconventional crude oils such as bitumen and shale oil. However, the analysis of crude oil with FT-ICR MS is not trivial, and it has pushed analysis to the limits of instrumental and methodological capabilities. For example, high-resolution mass spectra of crude oils may contain over 100,000 peaks that require interpretation. To visualize large data sets more effectively, data processing methods such as Kendrick mass defect analysis and statistical analyses have been developed. The successful application of FT-ICR MS to the study of crude oil has been critically dependent on key developments in FT-ICR MS instrumentation and data processing methods. This review offers an introduction to the basic principles, FT-ICR MS instrumentation development, ionization techniques, and data interpretation methods for petroleomics and is intended for readers having no prior experience in this field of study.

Structural characterization of polymers by MALDI spiral-TOF mass spectrometry combined with Kendrick mass defect analysis.

High-resolution mass spectrometry (HRMS) continues to play an important role in the compositional characterization of larger organic molecules. In the field of polymer characterization, however, the application of HRMS has made only slow progress because of lower compatibility between matrix-assisted laser desorption/ionization (MALDI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS). In this study, a newly developed type of MALDI high-resolution time-of-flight mass spectrometry (TOFMS) with a spiral ion trajectory (MALDI spiral-TOFMS) was applied to the structural and compositional characterization of polymers. To create a graphical distribution of polymer components on a two-dimensional plot converted from complex mass spectra, we adopted a slightly modified Kendrick mass defect (KMD) analysis based on accurate masses determined using spiral-TOFMS. By setting the Kendrick mass scale based on the mass of the repeating units of a given polymer, components with common repeat units lined up in the horizontal direction on the KMD plot, whereas those components with different structures were shifted vertically. This combination of MALDI spiral-TOFMS measurement and KMD analysis enabled the successful discrimination of the polymer components in a blend of poly(alkylene oxide)s, the compositional analysis of poly(ethylene oxide)/poly(propylene oxide) block copolymers, and profiling of the end-group distribution of poly(ε-caprolactone)s synthesized under different conditions. ᅟ

Molecular Characterization of Inhibiting Biochar Water-Extractable Substances Using Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Biochar has gained significant interest worldwide for its potential use as both a carbon sequestration technique and soil amendment. Recently, research has shown that pinewood-derived biochar water extracts inhibited the growth of aquatic photosynthetic microorganisms, both prokaryotic and eukaryotic algae, while chicken litter- and peanut shell-derived biochar water extracts showed no growth inhibition. With the use of electrodialysis, the pinewood-derived biochar water extract is separated into 3 fractions (anode-isolated, center chamber retained, and cathode-isolated substances) all with varying toxic effects. Because of its ultrahigh resolution and mass precision, electrospray ionization (ESI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is utilized in this study to analyze biochar water extracts at a molecular level to enhance our understanding of the toxic nature of pinewood-derived biochar water extracts as compared to benign peanut shell-derived biochar water extracts. The molecular composition of pinewood-derived biochar water extracts shows unique carbohydrate ligneous components and sulfur containing condensed ligneous components that are both absent from the peanut shell water extracts and more prevalent in the anode-isolated substances. Using Kendrick mass defect analysis, we also determine that the most likely inhibitor species contain carboxyl and hydroxyl homologous series, both of which are characteristic functional groups hypothesized in our previous research for the inhibitor species. We have suggested that inhibition of aquatic photosynthetic microorganism growth is most likely due to degraded lignin-like species rich in oxygen containing functionalities. From the study conducted here, we show the potential of ultrahigh resolution FTICR-MS as a valuable analytical technique for determining whether certain biochars are safe and benign for use as carbon sequestration and soil amendment.

Elemental Composition of HULIS in the Pearl River Delta Region, China: Results Inferred from Positive and Negative Electrospray High Resolution Mass Spectrometric Data

The HUmic-LIke Substances (HULIS) fraction isolated from aerosol samples collected at a rural location of the Pearl River Delta Region (PRD), China, during the harvest season was analyzed by both positive and negative mode electrospray ionization (ESI) coupled with an ultrahigh resolution mass spectrometer (UHRMS). With the remarkable resolving power and mass accuracy of ESI-UHRMS, thousands of elemental formulas were identified. Formulas detected in the positive (ESI+) and the negative (ESI-) mode complement each other due to differences in the ionization mechanism, and the use of both provides a more complete characterization of HULIS. Compounds composed of C, H, and O atoms were preferentially detected in ESI- by deprotonation, implying their acidic properties. Tandem MS and Kendrick Mass Defect analysis implies that carboxyl groups are abundant in the CHO compounds. This feature is similar to those of natural fulvic acids, but relatively smaller molecular weights are observed in the HULIS samples. A greater number of reduced nitrogen organic compounds were observed in the ESI+ compared to ESI-. Compounds with biomass burning origin including alkaloids, amino acids, and their derivatives are their probable constituents. Sulfur-containing species were dominantly detected in ESI-. The presence of sulfate fragments in the MS/MS spectra of these species and their high O/S ratios implies that they are mainly organosulfates. Organosulfates and nitrooxy-organosulfates were often the most intensive peaks in the ESI- spectra. They are believed to be products of reactive uptake of photooxidation products of reactive volatile organic compounds by acidic sulfate particles. The elemental compositions deduced from the UHRMS analysis confirm the conclusion from our previous study that biomass burning and SOA formation are both important sources of HULIS in the PRD region.

High mass accuracy and resolution facilitate identification of glycosphingolipids and phospholipids

Natural lipid profiling can improve our current understanding of disease mechanism in a systems biology approach combining genomics, proteomics, and phenotypic changes. However, lipid profiling is complicated by the >10,000 combinations of polar head group, hydrocarbon chain length and degree of unsaturation/hydroxylation, and glycan composition and branching pattern. Here, we show how LC separation coupled with high resolution Fourier transform ion cyclotron resonance mass analysis can quickly narrow down the possible phospholipid and glycosphingolipid compositions. That approach necessitates resolution of mass differences as small as 1.8 mDa [ 12C 2 13C 1N 1 (51.0064 Da) vs. H 3O 3 (51.0082 Da)] in phospholipids and 1.6 mDa [ 13C 2S 1H 2 (59.9944 Da) vs. N 2O 2 (59.9960 Da)] in glycosphingolipids. For novel/unknown lipid species, high mass accuracy based Kendrick mass defect analysis enables quick grouping of related lipid species for subsequent tandem MS structural characterization. For sulfur-containing lipid species, high mass resolution can reveal isotopic fine structure to verify assignment.

Method for the Identification of Lipid Classes Based on Referenced Kendrick Mass Analysis

A rapid method for the determination of lipid classes with high sensitivity is described. The referenced Kendrick mass defect (RKMD) and RKMD plots are novel adaptations of the Kendrick mass defect analysis that allows for the rapid identification of members of a homologous series in addition to identifying the lipid class. Assignment of lipid classes by the RKMD method is accomplished by conversion of the lipid masses to the Kendrick mass scale and then referencing the converted masses to each lipid class. Referencing of the masses to a given lipid class is achieved by first subtracting the heteroatom and lipid backbone contributions to the mass defect, leaving behind the contribution to the mass by the fatty acid constituents. The final step in the referencing makes use of spacing differences in mass defects between members of the same Kendrick class to identify members of the lipid class being referenced. The end result of this is that a lipid belonging to the class being referenced will have an integer RKMD with the value of the integer being the degrees of unsaturation in the lipid. The RKMD method was able to successfully identify the lipids in an idealized data set consisting of 160 lipids drawn from the glyceride and phosphoglyceride classes. As a real world example the lipid extract from bovine milk was analyzed using both accurate mass measurements and the RKMD method.

High-resolution mass spectrometric analysis of secondary organic aerosol produced by ozonation of limonene

Chemical composition of secondary organic aerosol (SOA) formed from the ozone-initiated oxidation of limonene is characterized by high-resolution electrospray ionization mass spectrometry in both positive and negative ion modes. The mass spectra reveal a large number of both monomeric (m/z < 300) and oligomeric (m/z > 300) condensed products of oxidation. A combination of high resolving power (m/Deltam approximately 60,000) and Kendrick mass defect analysis makes it possible to unambiguously determine the molecular composition of hundreds of individual compounds in SOA samples. Van Krevelen analysis shows that the SOA compounds are heavily oxidized, with average O : C ratios of 0.43 and 0.50 determined from the positive and negative ion mode spectra, respectively. A possible reaction mechanism for the formation of the first generation SOA molecular components is considered. The discussed mechanism includes known isomerization and addition reactions of the carbonyl oxide intermediates generated during the ozonation of limonene. In addition, it includes isomerization and decomposition pathways for alkoxy radicals resulting from unimolecular decomposition of carbonyl oxides that have been disregarded by previous studies. The isomerization reactions yield numerous products with a progressively increasing number of alcohol and carbonyl groups, whereas C-C bond scission reactions in alkoxy radicals shorten the carbon chain. Together these reactions yield a large number of isomeric products with broadly distributed masses. A qualitative agreement is found between the number and degree of oxidation of the predicted and measured reaction products in the monomer product range.

Method for Lipidomic Analysis: p53 Expression Modulation of Sulfatide, Ganglioside, and Phospholipid Composition of U87 MG Glioblastoma Cells

Lipidomics can complement genomics and proteomics by providing new insight into dynamic changes in biomembranes; however, few reports in the literature have explored, on an organism-wide scale, the functional link between nonenzymatic proteins and cellular lipids. Here, we report changes induced by adenovirus-delivered wild-type p53 gene and chemotherapy of U87 MG glioblastoma cells, a treatment known to trigger apoptosis and cell cycle arrest. We compare polar lipid changes in treated cells and control cells by use of a novel, sensitive method that employs lipid extraction, one-step liquid chromatography separation, high-resolution mass analysis, and Kendrick mass defect analysis. Nano-LC FT-ICR MS and quadrupole linear ion trap MS/MS analysis of polar lipids yields hundreds of unique assignments of glyco- and phospholipids at sub-ppm mass accuracy and high resolving power (m/Deltam50% = 200 000 at m/z 400) at 1 s/scan. MS/MS data confirm molecular structures in many instances. Sulfatides are most highly modulated by wild-type p53 treatment. The treatment also leads to an increase in phospholipids such as phosphatidyl inositols, phosphatidyl serines, phosphatidyl glycerols, and phosphatidyl ethanolamines. An increase in hydroxylated phospholipids is especially noteworthy. Also, a decrease in the longer chain gangliosides, GD1 and GM1b, is observed in wild-type p53 (treated) cells.

The application of electrospray ionization coupled to ultrahigh resolution mass spectrometry for the molecular characterization of natural organic matter

Mass spectrometry has recently played a key role in the understanding of natural organic matter (NOM) by providing molecular-level details about its composition. NOM, a complex assemblage of organic molecules present in natural waters and soils/sediments, has the ability to bind and transport anthropogenic materials. An improved understanding of its composition is crucial in order to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles. In the past, low-resolution (>3000) mass analyzers have offered some insights into the structure of NOM, but emerging ultrahigh resolution (>200,000) techniques such as electrospray ionization (ESI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) have significantly advanced our knowledge of NOM chemistry. Here, a review of the recent literature on the advancements of NOM characterization and the applications of mass spectrometry to this central task is presented. Various methods for the analysis and display of the extremely complex mass spectra, such as the van Krevelen diagram and Kendrick mass defect analysis, are discussed. We also review tandem mass spectrometry techniques employed to gain structural information about NOM components. Finally, we show how ESI-FT-ICR-MS has been applied to examine specific issues that are important to the NOM scientific community, such as NOM reactivity, transport and fate, degradation, and existence of components, which are indicators of NOM origin. In general, ultrahigh resolution provided by FT-ICR-MS is essential for the complete separation of the thousands of peaks present in the complex NOM mixture and will clearly lead to additional future advancements in the areas of aquatic, soil, and analytical chemistry.

Heat-Exchanger Deposits in an Inverted Steam-Assisted Gravity Drainage Operation. Part 2. Organic Acid Analysis by Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

As a complement to the bulk analyses presented in part 1 (Jennings, D. W.; Shaikh, A. Energy Fuels 2007, 21, 176−184), we report detailed compositional analysis of the organic acids from heat-exchanger deposits and produced water from an inverted steam-assisted gravity drainage (SAGD) bitumen production process. The current analyses were performed by ultrahigh-resolution negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry [(−) ESI FT-ICR MS] and reveal distributions of molecular weight, heteroatom content, aromaticity, and carbon number for several thousand organic acids in each sample. High mass accuracy combined with Kendrick mass defect analysis allows for assignment of a unique elemental composition, CcHhNnOoSs, to each mass spectral peak. Three-dimensional mass spectral images generated from the molecular formulas reveal compositional differences that may be rationalized on the basis of sample processing. In particular, we report lower overall heteroatom content, higher average carbon number, and lower aromaticity for early stage deposits and the produced bitumen compared to later stage samples that show increased water solubility. Little was previously known about those species other than the presence of organic acid/acid salt functionality. Moreover, we report the first in vacuo isolation and tandem mass spectrometry of individual components of petroleum mixtures. Tandem mass spectrometry by infrared multiphoton dissociation of trapped ions indicates dicarboxylic acid structures for predominant CcHhO4 and dicarboxylic acid structures with thiophenic sulfur for predominant CcHhSO4 species. In this manner, we provide a highly detailed landscape for the organic acid content of inverted SAGD heat-exchanger deposits, to further illuminate the nature of fouling in those systems.

Identification of black carbon derived structures in a volcanic ash soil humic acid by Fourier transform ion cyclotron resonance mass spectrometry.

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), coupled with cross-polarization magic angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy and Kendrick mass defect analysis, was used to study the molecular composition of an aromatic carbon-rich humic acid extracted from a dark black soil from Iwata, Japan. Black carbon, produced by the incomplete combustion of fossil fuels and organic matter, has been suggested as a major component of humic acids having intense peaks in the aromatic and carboxyl regions of the 13C NMR spectrum. Taking advantage of the high resolving power of FT-ICR MS to make precise formula assignments, three different types of highly carboxylated polycyclic aromatic compounds were identified in the sample: linearly fused aromatic structures, aromatic structures linked by carbon-carbon single bonds, and highly condensed aromatic structures. These carboxylated aromatic structures have a low mass defect in their mass spectra due to their abundance of oxygen and deficiency of hydrogen. This mass defect is observed in the vast majority of peaks present in the entire mass spectrum, differentiating them from structures that are hydrogen-rich (e.g., fatty acids, proteins, carbohydrates). Thus, we conclude that the bulk of the sample analyzed is comprised of these heavily carboxylated, hydrogen-deficient, condensed aromatic structures, features believed to be characteristic of black carbon-like material.