Mass spectrometric analysis of polymers with potassium-ion ionization of desorbed species

Polymers are analyzed by using a new ionization technique for mass spectrometry called K⁺ ionization of desorbed species (K⁺IDS). This technique utilizes the fact that when thermally labile compounds are placed on a potassium thermionic emitter and rapidly heated, ions representative of the sample are formed. Potassium ion adducts of intact molecules and thermal degradation products are observed. Reported here are the K⁺IDS mass spectra for various polymers; Nylon-6, the cyanoethylmethylsilicone XF-1150, polyvinylpyrrolidone, poly(ethylene glycol) s and a poly (propylene glycol) are studied. Interpretation of the spectra is discussed in terms of known thermal degradation pathways for these molecules. Use of the method for obtaining structural and molecular weight information is discussed. K⁺IDS is shown to be a viable ionization method for such polymers.     

Characterization of the primary thermal degradation processes of peptides using the mass spectrometric technique K+IDS,K+ ionization of desorbed species

The mass spectrometric technique of K⁺ ionization of desorbed species, K⁺IDS, is used here to characterize the primary thermal degradation chemistry of small peptides. In this technique, a small amount of a compound is rapidly heated in the condensed phase. Desorption of the intact molecule can occur. Also, thermal degradation products are formed which quickly desorb as well, rather than remain on the surface and undergo subsequent chemistry. The desorbed molecules form adducts with gas phase K⁺ ions, and a mass spectrum is obtained. Deuterium labeling experiments, and the use of derivatizing reagents, allows for the thermal degradation chemistry of small peptides to be elucidated. Apparently, skeletal bond cleavages are accompanied by H-shifts, although the hydrogen atoms shift from “remote” sites, brought into close proximity with the fragmenting skeletal bond via secondary interactions. Experimental results are presented that allow for correlations between thermal degradation chemistry and the resulting K⁺IDS mass spectra to be made.     

Design and fabrication of a shielded interdigital sensor for noninvasive In situ real‐time production monitoring of polymers

Interdigital sensors (IDS) have received great attention for production monitoring of polymers over the past decade. However, conventional IDS are limited by high noise to environment due to the dual side access of the sensor, low nominal capacitance, and sensitivity. In this study, a shielded IDS fabricated by flexible circuit board (FCB) technology is presented to overcome these challenges. Compared to conventional sensors, the environmental dependence of the new sensor is minimized by the copper shield. Furthermore, nominal capacitance of at least 350% higher, and an increase of sensitivity per unit area are achieved. To demonstrate the capabilities of the new IDS, a FCB comprising the proposed sensor is fabricated, attached to a mould, and successfully applied for in situ real‐time production monitoring of an epoxy resin. The resulting flexible sensor is noninvasive towards the fabricated parts, and measures the key stages along the production process. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2028–2037     

Complexation of some environmentally friendly carboxylic acid ligands with La3+ ion in aqueous solution

In search for environmentally friendly metal chelating ligands for industrial applications, protonation, and complex-formation equilibria of iminodisuccinic acid (IDS), 3-hydroxy-2,2′ -iminodisuccinic acid (HIDS), N,N′-ethylenediaminedisuccinic acid (EDDS), and oxydisuccinic acid (ODS) with La³⁺ in aqueous 0.1?mol?L^?1 NaCl solution were studied at 25°C by potentiometric titration. The model for complexation and the stability constants of the different complexes were determined using the computer program SUPERQUAD. Complex formation was dominated by stable LaL^? complexes for all tested ligands.     

Comparison of different search engines using validated MS/MS test datasets

Massive amounts of tandem mass spectra are produced in high-throughput proteomics studies. The manual interpretation of these spectra is not feasible. Instead, search engines are used to match the tandem mass spectra with sequence information contained in proteomics and genomics databases. Typically, these search engines provide a list of the best matching peptide sequences for an individual tandem mass spectrum. As well, they provide scores that are somewhat related to the confidence level in the match. Many peptide tandem mass spectra search engines have been reported. These search engines provide very different results depending on the type of mass spectrometers used and their input parameters. Here we describe a comparative analysis of different search engines using validated test sets of tandem mass spectra. We have defined test sets of MS/MS spectra derived from high throughput proteomics experiments performed by HPLC-ESI-MS/MS on ion trap (LCQ) and tandem quadrupole time-of-flight instruments with a pulsar functionality (Qstar Pulsar) mass spectrometers. We analyzed the ability of the different search engines to identify the correct peptides, and the cross-validations of the different search engines.     

质谱匹配概率方法及结果可靠性评价

质谱匹配概率方法不仅能提供纯样品的分析结果,而且也能区分混合物中的成分。因而为大大提高对质谱数据的分析能力提供了可能性,并扩大了它在有机物鉴定方面的应用。本文介绍该方法作环境空气中有机物质谱分析及与综合控制系统资料的比较,并以美国标准局的标准参考数据库作比较。同时讨论了该方法的优点和不足     

Haloaldehyde polymers,XLIX: Analysis of linear bornyl oxide initiated,acetate endcapped chloral oligomers by potassium ionization of desorbed species mass spectrometry

Linear chloral oligomers initiated with lithium bornyl oxide and acetate endcapped were analyzed by potassium ionization of desorbed species (K⁺ IDS) mass spectrometry. Using this technique we observed ions resulting from the [unimer]K⁺ with a mass of 381 daltons, to the [hexamer]K⁺ with a mass of 1 119 daltons. Furthermore, analysis of the isotope pattern supported our structural assignment. The individual lower oligomers were also investigated by GC and NMR spectroscopy.Previous paper in this series: Haloaldehyde Polymers XL VIII. W. J. Simonsick Jr., K. Hatada, Fu Xi, and O. Vogl [27]     

多齿配体-硅胶色谱介质的制备与评价

以新型环保多齿螯合剂——亚氨基二琥珀酸(IDS)为配体,在优化条件下,合成了IDS-Silica固定相。用电位滴定法测定了固定相上IDS的键合量。考察了IDS-Silica柱的色谱特性以及金属螯合特性。使用制备柱成功地分离了标准蛋白质混合物,该制备柱展现出了典型的阳离子交换特性。用电感耦合等离子体原子发射光谱法考察了金属离子在IDS-Silica固定相上的键合特性。结果表明,金属离子在IDS-Silica固定相上键合量的变化规律与它们同该固定相螯合的强弱顺序一致。通过比较金属Cu~(2+)在4种不同氨羧类配体硅胶柱上的键合量,发现IDS对金属离子具有强的螯合能力。IDS对金属离子的强螯合特性为其今后作为固定金属亲和色谱填料奠定了基础,为缓解亲和柱在使用过程中固定金属离子的流失提供了一种有效的解决方法。     

Identification of polymers by library search of pyrolysis mass spectra and pattern recognition analysis

A library of mass spectra of polymers containing about 200 entries is described. These spectra were obtained by direct pyrolysis-electron-impact mass spectrometry, i.e., by heating the polymers in the direct insertion probe for solid samples at a constant heating rate and recording repetitive mass spectra during the temperature rise. The library can be used both as a data base for library searches and as a training set for a pattern recognition analysis. The algorithm used to generate and search the files and a few applications of the library search and pattern recognition analysis are presented.     

A combined forward—reverse library search system for the identification of low-resolution mass spectra

A combined forward—reverse library search routine for low-resolution mass spectra is described. The routine requires binary-coded spectra. Masses and peak intensities are used for spectral comparison. On the basis of three possible search strategies, this routine is adaptable to analytical problems. The program was tested for 25 000 spectra from the ISAS, MSDC and EPA mass spectra libraries. The program is written completely in FORTRAN IV.     

Complexation of iminodisuccinic acid (IDS) and 3-hydroxy-2,2′-iminodisuccinic acid (HIDS) with Cd2+, Hg2+, and Pb2+ in aqueous solution

In a search for environmentally friendly metal-chelating ligands for industrial applications, the protonation and complex formation equilibria of iminodisuccinic acid (IDS) and 3-hydroxy-2,2′-iminodisuccinic acid (HIDS) with Cd²⁺, Hg²⁺, and Pb²⁺ in aqueous 0.1?mol?L^?1 NaNO₃ solution were studied at 25°C by potentiometric titration. Models for complexation and stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. In all cases, complex formation was dominated by stable ML^2? complexes.     

Spektren —a computer system for the identification and structure elucidation of organic compounds

The spectroscopic information system described consists of a data base of 30 000 nuclear magnetic resonance, infrared and mass spectracombined with a program containing functions for matching spectra and substructure search. Information retrieval with this program uses inverted files; sequential search and various functions for graphic and written output and updating are possible. Hardware configuration and data flow from spectrometers to an IBM 3032 computer are described. Results of matching spectra and substructure search and retrieval operations are presented.     

Data self-recalibration and mixture mass fingerprint searching (DASER-MMF) to enhance protein identification within complex mixtures

A novel algorithm based on Data Self-Recalibration and a subsequent Mixture Mass Fingerprint search (DASER-MMF) has been developed to improve the performance of protein identification from online 1D and 2D-LC-MS/MS experiments conducted on high-resolution mass spectrometers. Recalibration of 40% to 75% of the MS spectra in a human serum dataset is demonstrated with average errors of 0.3±0.3 ppm, regardless of the original calibration quality. With simple protein mixtures, the MMF search identifies new proteins not found in the MS/MS based search and increases the sequence coverage for identified proteins by six times. The high mass accuracy allows proteins to be identified with as little as three peptide mass hits. When applied to very complex samples, the MMF search shows less dramatic performance improvements. However, refinements such as additional discriminating factors utilized within the search space provide significant gains in protein identification ability and indicate that further enhancements are possible in this realm.     

Electron Transfer and Collision Induced Dissociation of Non-Derivatized and Derivatized Desmosine and Isodesmosine

Electron transfer dissociation (ETD) has attracted increasing interest due to its complementarity to collision-induced dissociation (CID). ETD allows the direct localization of labile post-translational modifications, which is of main interest in proteomics where differences and similarities between ETD and CID have been widely studied. However, due to the fact that ETD requires precursor ions to carry at least two charges, little is known about differences in ETD and CID of small molecules such as metabolites. In this work, ETD and CID of desmosine (DES) and isodesmosine (IDS), two isomers that due to the presence of a pyridinium group can carry two charges after protonation, are studied and compared. In addition, the influence of DES/IDS derivatization with propionic anhydride and polyethyleneglycol (PEG) reagents on ETD and CID was studied, since this is a common strategy to increase sensitivity and to facilitate the analysis by reversed-phase chromatography. Clear differences between ETD and CID of non-derivatized and derivatized-DES/IDS were observed. While CID is mainly attributable to charge-directed fragmentation, ETD is initiated by the generation of a hydrogen atom at the initial protonation site and its subsequent transfer to the pyridinium ring of DES/IDS. These differences are reflected in the generation of complex CID spectra dominated by the loss of small, noninformative molecules (NH₃, CO, H₂O), while ETD spectra are simpler and dominated by characteristic side-chain losses. This constitutes a potential advantage of ETD in comparison to CID when employed for the targeted analysis of DES/IDS in biological samples.

Identification of components in mixtures by a mathematical analysis of mass spectral data

Mathematical techniques for the identification of components in mixtures from the mass spectra of a series of related mixtures are described. The approach is analogous to library search methods in that spectra from a reference collection are compared with a multidimensional unknown. Searches are conducted with a library file containing approximately 17000 mass spectra. Results for the analyses of several mixtures are reported, to illustrate the effectiveness of the method.     

GroupFilter: A software tool for efficient filtering of Morpheus search engine results

Morpheus is a search algorithm developed recently for high-resolution tandem mass spectra. According to the developers, its intrinsic property is discriminating short sequence length peptides. Therefore, elimination of direct comparisons between peptide spectrum matches (PSMs) for short and long peptides may potentially increase the search sensitivity for a given FDR level. In the proposed approach, all PSMs are grouped according to the number of matched fragment ions, followed by separate filtering of identifications in each group using target-decoy approach. The approach is applied to Morpheus output results and does not cause a significant increase in the overall data analysis time. The proposed approach was implemented as a Python command-line tool, called GroupFilter. Several data sets from different types of mass spectrometers were used for testing of the software, including the data from the original Morpheus search engine paper. Separate FDR filtering for grouped identifications increased the number of identified peptides by up to 18% compared with the default Morpheus post-processing procedure. The proposed approach can be considered as an addition to the Morpheus search engine.     

Analysis of gas chromatography—mass spectrometry data by reverse library search and the detection of substances not in the library

Computer least-squares methods are used to conduct an automatic reverse search of a library of complete mass spectra for the analysis of the output data matrix from a g.c.—m.s. system. The search is limited to those mass spectra falling within a narrow retention index window about the retention index corresponding to each scan in the datamatrix. The least-squares estimated parameters obtained are proportional to the concentrations of the substances present at each scan and are displayed graphically as the profiles of resolved overlapping g.c. peaks. The precision of the parameters is estimated. The root mean square Values of the residuals of the least-squares fits are used successfully to indicate the presence of substances not in the library. Examples are given of the results produced with data from this laboratory. Possible elaborations and improvements of this computer program are discussed.     

Evaluating electron ionization mass spectral library search results

As the size of various collections of electron ionization mass spectra gets larger, there is a continuing and increasing propensity to rely on the results of computerized library searches. The results of these computerized searches do not necessarily account for a spectrum that is produced by the mixture of two or more different compounds. Sometimes the submitted spectrum is not that of a compound whose spectrum is in the library. The quality of the spectrum submitted to the library is often such that the numerical confidence level reported for the search result is so low that it will cause the result to be disregarded. When the sample spectrum is matched against library spectra that have been condensed, the search result can be misleading. Three different examples of mass spectral search results are examined: one, with a high confidence level that the unknown has been identified, but the results are incorrect; one, where the spectrum of the unknown compound is not in the library; one, where consideration of the numerical search results would cause a positive identity not to be confirmed.     

Search strategy and data compression for a retrieval system with binary-coded mass spectra

A retrieval system for binary-coded mass spectra is described. The data base used contains 9628 low-resolution mass spectra from the Aldermaston Mass Spectra Data Collection. These spectra are reduced to 106 preselected binary-coded m/z values each. Storage of the compound names and formulae is minimized by using a special set of characters and file organization. The search strategy permits fast generation of the N- nearest neighbours. Depending on the number of best matches generated, an average search requires access to only 24—33% of the spectra contained in the data base. Because of its limited storage requirements, this search system can be used even on microcomputers.l]     

Peptide sequencing using a patchwork approach and surface-induced dissociation in sector-TOF and dual quadrupole mass spectrometers

Surface-induced ion activation in combination with a database search strategy based on the Patchwork concept is applied to the determination of peptide sequences. Surface-induced dissociation (SID) is performed in a tandem quadrupole mass spectrometer and in a hybrid sector/time-of-flight mass spectrometer in order to evaluate the importance of accurate mass analysis of the SID fragment ions for peptide identification. The modified Patchwork approach is based on piecing together the peptide blocks in a bidirectional way, simultaneously using low-mass fragments originating from the C-terminus and N-terminus of the molecule, and relying on the measurement of the peptide's molecular weight with moderate mass accuracy. The results from this analysis are used as search filters in MASCOT's (http://www.matrixscience.com) Sequence Query search engine, with the simultaneous addition of the full MS/MS peak list. SID is performed with collision targets coated with pure and mixed composition self-assembled monolayers produced by fluorocarbon and hydrocarbon alkanethiolate solutions of varying chemical composition. The resulting MS/MS spectra produced on pure and mixed hydrocarbon SAMs are submitted to the modified version of Patchwork sequencing. It is found that hydrocarbon surfaces improve the relative abundance of larger fragments. Under the moderate mass accuracy conditions (±0.3 u) offered by our linear-TOF-SID instrument, it is found that increasing the abundance of larger fragments dramatically improves the sequencing scores.