The Structural Influence of Graphene Oxide on Its Fragmentation during Laser Desorption/Ionization Mass Spectrometry for Efficient Small‐Molecule Analysis

The structural influence of graphene oxide (GO) on laser desorption/ionization mass spectrometry (LDI‐MS) analysis of small molecules was systematically investigated by using size‐fractionated GO. For fractionation of GO, pH‐assisted centrifugation, sequential vacuum filtration, and sonochemical cutting processes were employed and the size‐fractionated GO was thoroughly characterized to understand their size‐dependent optochemical properties. Then, the fractionated GO was applied to the analysis of various small molecules by LDI‐MS to investigate the relationship between their optochemical properties and LDI‐MS performance. We found that large GO sheets (>0.5 μm) were more prone to fragmentation under laser irradiation during LDI‐MS analysis than small GO sheets (<0.5 μm). In this regard, the LDI‐MS analysis efficiency of various small molecules was significantly improved by using nanosized GO (NGO) as a matrix without background interference. In particular, NGO was successfully applied to the sensitive detection of hydrophobic pollutant molecules without requiring any surface‐functionalization, enrichment, and separation process. Therefore, the present study could provide important basic information and be a practical tool for the development of simple and efficient LDI‐MS platforms by using GO derivatives.     

Positive and negative‐mode laser desorption/ionization‐mass spectrometry (LDI‐MS) for the detection of indigoids in archaeological purple

Laser‐based ionization techniques have demonstrated to be a valuable analytical tool to study organic pigments by mass spectrometric analyses. Though laser‐based ionization techniques have identified several natural and synthetic organic dyes and pigments, they have never been used in the characterization of purple. In this work, positive and negative‐mode laser desorption/ionization mass spectrometry (LDI‐MS) was used for the first time to detect indigoids in shellfish purple. The method was used to study organic residues collected from archaeological ceramic fragments that were known to contain purple, as determined by a classical high‐performance liquid chromatography‐based procedure. LDI‐MS provides a mass spectral fingerprint of shellfish purple, and it was found to be a rapid and successful tool for the identification of purple. In addition, a comparison between positive and negative mode ionization highlighted the complementarity of the two ionization modes. On the one hand, the negative‐ion mode LDI‐MS showed a better selectivity and sensitivity to brominated molecules, such as 6,6'‐dibromoindigo, 6‐monobromoindigo, 6,6'‐dibromoindirubin, 6‐ and 6’‐monobromoindirubin, thanks to their electronegativity, and produced simpler mass spectra. On the other hand, negative‐ion mode LDI‐MS was found to have a lower sensitivity to non‐brominated compounds, such as indigo and indirubin, whose presence can be established in any case by collecting the complementary positive‐ion LDI mass spectrum. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of substrate surfaces in matrix‐assisted laser desorption/ionization mass spectrometry

For matrix‐assisted laser desorption/ionization (MALDI) mass spectra, undesirable ion contamination can occur due to the direct laser excitation of substrate materials (i.e., laser desorption/ionization (LDI)) if the samples do not completely cover the substrate surfaces. In this study, comparison is made of LDI processes on substrates of indium and silver, which easily emit their own ions upon laser irradiation, and conventional materials, stainless steel and gold. A simultaneous decrease of ion intensities with the number of laser pulses is observed as a common feature. By the application of an indium substrate to the MALDI mass spectrometry of alkali salts and alkylammonium salts mixed with matrices, 2,5‐dihydroxybenzoic acid (DHB) or N‐(4‐methoxybenzylidene)‐4‐butylaniline (MBBA), the mixing of LDI processes can be detected by the presence of indium ions in the mass spectra. This method has also been found to be useful for investigating the intrinsic properties of the MALDI matrices: DHB samples show an increase in the abundance of fragment ions of matrix molecules and cesium ions with the number of laser pulses irradiating the same sample spot; MBBA samples reveal a decrease in the level of background noise with an increase in the thickness of the sample layer. Copyright © 2009 John Wiley & Sons, Ltd.     

Mass spectrometry of rhenium complexes: a comparative study by using LDI‐MS,MALDI‐MS,PESI‐MS and ESI‐MS

A group of rhenium (I) complexes including in their structure ligands such as CF₃SO₃‐, CH₃CO₂‐, CO, 2,2′‐bipyridine, dipyridil[3,2‐a:2′3′‐c]phenazine, naphthalene‐2‐carboxylate, anthracene‐9‐carboxylate, pyrene‐1‐carboxylate and 1,10‐phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF‐ESI‐CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M]^+. and to produce their reduction yielding the gas species [M]^–.. It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV–visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix‐assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor‐harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M]^–. species. Results obtained with 2‐[(2E)‐3‐(4‐tert‐buthylphenyl)‐2‐methylprop‐2‐enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.     

Matrix-assisted laser desorption/ionization mass spectrometry using porous silicon and silica gel as matrix

Porous silicon powder and silica gel particles have been applied as inorganic matrices for the analysis of small molecules in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOFMS). In contrast to conventional MALDI-TOFMS, the signal interference of low-molecular analytes by the matrix has been eliminated. Almost no fragmentations of the analytes were observed. Effects of various factors, such as the particle and pore size, the suspending solution, and sample preparation procedures, on the intensity of mass spectra have been investigated. The pore structure of the inorganic matrix and penetration of the analytes into the pores must be optimized for effective desorption and ionization of the analytes. Matrices (DHB and HCCA) were covalently bound to silica gel for improvement of spectrum intensity. Copyright © 2001 John Wiley & Sons, Ltd.     

A laser desorption ionization/matrix‐assisted laser desorption ionization target system applicable for three distinct types of instruments (LinTOF/curved field RTOF,LinTOF/RTOF and QqRTOF) with different performance characteristics from three vendors

Rationale

We have developed a target system which enables the use of only one target (i.e. target preparation set) for three different laser desorption ionization (LDI)/matrix‐assisted laser desorption ionization (MALDI) mass spectrometric instruments. The focus was on analysing small biomolecules with LDI for future use of the system for the study of meteorite samples (carbonaceous chondrites) using devices with different mass spectrometric performance characteristics.

Methods

Three compounds were selected due to their potential presence in meteoritic chondrites: tryptophan, 2‐deoxy‐d ‐ribose and triphenylene. They were prepared (with and without MALDI matrix, i.e. MALDI and LDI) and analysed with three different mass spectrometers (LinTOF/curved field RTOF, LinTOF/RTOF and QqRTOF). The ion sources of two of the instruments were run at high vacuum, and one at intermediate pressure. Two devices used a laser wavelength of 355 nm and one a wavelength of 337 nm.

Results

The developed target system operated smoothly with all devices. Tryptophan, 2‐deoxy‐d ‐ribose and triphenylene showed similar desorption/ionization behaviour for all instruments using the LDI mode. Interestingly, protonated tryptophan could be observed only with the LinTOF/curved field RTOF device in LDI and MALDI mode, while sodiated molecules were observed with all three instruments (in both ion modes). Deprotonated tryptophan was almost completely obscured by matrix ions in the MALDI mode whereas LDI yielded abundant deprotonated molecules.

Conclusions

The presented target system allowed successful analyses of the three compounds using instruments from different vendors with only one preparation showing different analyser performance characteristics. The elemental composition with the QqRTOF analyser and the high‐energy 20 keV collision‐induced dissociation fragmentation will be important in identifying unknown compounds in chondrites.

     

Matrix‐free thin‐layer chromatography/laser desorption ionization mass spectrometry for facile separation and identification of medicinal alkaloids

Quaternary protoberberine alkaloids belong to a pharmaceutically important class of isoquinoline alkaloids associated with bactericidal, fungicidal, insecticidal and antiviral activities. As traditional medicine gains wider acceptance, quick and robust analytical methods for the screening and analysis of plants containing these compounds attract considerable interest. Thin‐layer chromatography (TLC) combined with matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) is a powerful technique but suffers from dilution of the TLC bands resulting in decreased sensitivity and masking of signals in the low‐mass region both due to addition of matrix. This study integrates for the first time conventional silica gel TLC and laser desorption ionization mass spectrometry (LDI‐MS) thus eliminating the need for any external matrix. Successful separation of berberine (R_f = 0.56) and palmatine (R_f = 0.46) from Berberis barandana including their identification by MS are demonstrated. Furthermore, a robust electrospray ionization (ESI)‐MS method utilizing residual sample from TLC for quantification of berberine applying selected reaction monitoring and standard addition method is presented. The amount of berberine in the plant root prepared for the study was determined to be 0.70% (w/w). Copyright © 2009 John Wiley & Sons, Ltd.     

Online coupling of thin layer chromatography with matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry: synthesis and application of a new material for the identification of carbohydrates by thin layer chromatography/matrix free material enhanced laser desorption/ionization mass spectrometry

This article describes the online hyphenation of thin layer chromatography with matrix free material enhanced laser desorption/ionization mass spectrometry (mf‐MELDI‐MS), the preparation of new material for MELDI and application of this newly synthesized material using TLC/MELDI‐MS for the analysis of carbohydrate reference standards and plant extracts. Samples included within these analyses are standard solutions of glucose, sucrose, raffinose and a plant extract of Quercus robur, which is used for its anti‐inflammatory, anti‐viral and anthelminitc properties in phytomedicine. A new material for mf‐MELDI‐MS is prepared by immobilizing bradykinin – a peptide, on silica gel coupled to 4‐(3‐triethoxysilylpropylureido)azobenzene. This modification enables the absorption of laser energy sufficient for desorption and ionization of low molecular weight molecules like carbohydrates and amino acids. The newly synthesized material delivered excellent results in respect to signal‐to‐noise (S/N) ratio (S/N ratio: >9/1) and sensitivity (limit of detection (LOD): lower to ng/µL). Hyphenation of TLC to MELDI‐MS employing the novel developed material simultaneously as chromatographic and mass spectrometric sorbent was shown for the first time for the analysis of low molecular weight molecules like mono‐ and oligosaccharides. Copyright © 2010 John Wiley & Sons, Ltd.     

Photochemical and Thermal Stability of Some Dihydroxyacetophenones Used as UV‐MALDI‐MS Matrices

2,4‐, 2,5‐, 2,6‐ and 3,5‐dihydroxyacetophenone (DHA) used as matrices in matrix‐assisted ultraviolet laser desorption/ionization mass spectrometry (UV‐MALDI‐MS) were studied by steady‐state and transient absorption spectroscopy, together with DFT calculations at the B3LYP level of theory. All compounds have low fluorescence quantum yields, possibly due to an efficient excited‐state intramolecular proton transfer (ESIPT). Laser flash photolysis (LFP) results showed that, only for 2,4‐DHA, a phototautomer could be detected at λ = 400 nm. Their photochemical stability in solution at different wavelengths and conditions was analyzed by UV–Vis and ¹H nuclear magnetic resonance spectroscopy (¹H‐NMR), together with thin layer chromatography and ultraviolet laser desorption/ionization mass spectrometry (UV‐LDI‐MS). Only 3,5‐DHA showed decomposition when irradiated, probably because phototautomerization is not possible. Thermal stability studies of these compounds in solid state were also conducted.     

Analysis of aquatic‐phase natural organic matter by optimized LDI‐MS method

The composition and physiochemical properties of aquatic‐phase natural organic matter (NOM) are most important problems for both environmental studies and water industry. Laser desorption/ionization (LDI) mass spectrometry facilitated successful examinations of NOM, as humic and fulvic acids in NOM are readily ionized by the nitrogen laser. In this study, hydrophobic NOMs (HPO NOMs) from river, reservoir and waste water were characterized by this technique. The effect of analytical variables like concentration, solvent composition and laser energy was investigated. The exact masses of small molecular NOM moieties in the range of 200–1200 m/z were determined in reflectron mode. In addition, spectra of post‐source‐decay experiments in this range showed that some compounds from different natural NOMs had the same fragmental ions. In the large mass range of 1200–15 000 Da, macromolecules and their aggregates were found in HPO NOMs from natural waters. Highly humic HPO exhibited mass peaks larger than 8000 Da. On the other hand, the waste water and reservoir water mainly had relatively smaller molecules of about 2000 Da. The LDI‐MS measurements indicated that highly humic river waters were able to form large aggregates and membrane foulants, while the HPO NOMs from waste water and reservoir water were unlikely to form large aggregates. Copyright © 2014 John Wiley & Sons, Ltd.     

Method development for the analysis of resinous materials with MALDI‐FT‐ICR‐MS: novel internal standards and a new matrix material for negative ion mode

Matrix‐assisted laser desorption/ionization (MALDI) is a mass spectrometry (MS) ionization technique suitable for a wide variety of sample types including highly complex ones such as natural resinous materials. Coupled with Fourier transform ion cyclotron resonance (FT‐ICR) mass analyser, which provides mass spectra with high resolution and accuracy, the method gives a wealth of information about the composition of the sample. One of the key aspects in MALDI‐MS is the right choice of matrix compound. We have previously demonstrated that 2,5‐dihydroxybenzoic acid is suitable for the positive ion mode analysis of resinous samples. However, 2,5‐dihydroxybenzoic acid was found to be unsuitable for the analysis of these samples in the negative ion mode. The second problem addressed was the limited choice of calibration standards offering a flexible selection of m/z values under m/z 1000. This study presents a modified MALDI‐FT‐ICR‐MS method for the analysis of resinous materials, which incorporates a novel matrix compound, 2‐aminoacridine for the negative ion mode analysis and extends the selection of internal standards with m/z <1000 for both positive (15 different phosphazenium cations) and negative (anions of four fluorine‐rich sulpho‐compounds) ion mode. The novel internal calibration compounds and matrix material were tested for the analysis of various natural resins and real‐life varnish samples taken from cultural heritage objects. Copyright © 2017 John Wiley & Sons, Ltd.     

Laser desorption/ionization mass spectrometry on porous silica and alumina for peptide mass fingerprinting

We investigated a variant of desorption/ionization on porous silicon (DIOS) mass spectrometry utilizing an aqueous suspension of either porous silica gel or porous alumina (pore size of 60 and 90 A, respectively). Laser desorption/ionization (LDI) from samples directly deposited on a stainless steel surface without any inorganic substrates was also achieved. Synthetic peptides designed to cover large sequence diversity constituted our model compounds. Sample preparation, including material conditioning, peptide solubilization, and deposition protocol onto standard matrix-assisted laser desorption/ionization (MALDI) probe, as well as ionization source tuning were optimized to perform sensitive reproducible LDI analyses. The addition of either a cationizing agent or an alkali metal scavenger to the sample suspension allowed modification of the ionization output. Comparing hydrophilic silica gel to hydrophobic reversed-phase silica gel as well as increasing material pore size provided further insights into desorption/ionization processes. Furthermore, mixtures of peptides were analyzed to probe the spectral suppression phenomenon when no interfering organic matrix was present. The results gathered from synthetic peptide cocktails indicated that LDI mass spectrometry on silica gel or alumina constitutes a promising complementary method to MALDI in proteomics for peptide mass fingerprinting.     

Approaches for the analysis of low molecular weight compounds with laser desorption/ionization techniques and mass spectrometry

This review summarizes various approaches for the analysis of low molecular weight (LMW) compounds by different laser desorption/ionization mass spectrometry techniques (LDI-MS). It is common to use an agent to assist the ionization, and small molecules are normally difficult to analyze by, e.g., matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) using the common matrices available today, because the latter are generally small organic compounds themselves. This often results in severe suppression of analyte peaks, or interference of the matrix and analyte signals in the low mass region. However, intrinsic properties of several LDI techniques such as high sensitivity, low sample consumption, high tolerance towards salts and solid particles, and rapid analysis have stimulated scientists to develop methods to circumvent matrix-related issues in the analysis of LMW molecules. Recent developments within this field as well as historical considerations and future prospects are presented in this review.     

Influence of surface melting effects and availability of reagent ions on LDI‐MS efficiency after UV laser irradiation of Pd nanostructures

In this study, the influence of surface morphology, reagent ions and surface restructuring effects on atmospheric pressure laser desorption/ionization (LDI) for small molecules after laser irradiation of palladium self‐assembled nanoparticular (Pd‐NP) structures has been systematically studied. The dominant role of surface morphology during the LDI process, which was previously shown for silicon‐based substrates, has not been investigated for metal‐based substrates before. In our experiments, we demonstrated that both the presence of reagent ions and surface reorganization effects – in particular, melting – during laser irradiation was required for LDI activity of the substrate. The synthesized Pd nanostructures with diameters ranging from 60 to 180 nm started to melt at similar temperatures, viz. 890–898 K. These materials exhibited different LDI efficiencies, however, with Pd‐NP materials being the most effective surface in our experiments. Pd nanostructures of diameters >400–800 nm started to melt at higher temperatures, >1000 K, making such targets more resistant to laser irradiation, with subsequent loss of LDI activity. Our data demonstrated that both melting of the surface structures and the presence of reagent ions were essential for efficient LDI of the investigated low molecular weight compounds. This dependence of LDI on melting points was exploited further to improve the performance of Pd‐NP‐based sampling targets. For example, adding sodium hypophosphite as reducing agent to Pd electrolyte solutions during synthesis lowered the melting points of the Pd‐NP materials and subsequently gave reduced laser fluence requirements for LDI. Copyright © 2015 John Wiley & Sons, Ltd.     

Microgradient separation technique for purification and fractionation of permethylated N‐glycans before mass spectrometric analyses

Analysis of N‐glycans released enzymatically from patients’ sera or other clinical samples may provide diagnostically and prognostically important information on human disease. Permethylation of these biomolecules simultaneously increases their hydrophobicity and substantially improves their detection parameters in the following mass spectrometric analyses. The overall procedure, from the glycan cleavage to the final mass spectrometric determinations, includes several steps involving extraction, derivatization, and purification. During these steps, certain polymeric contaminants that may have been coincidentally introduced could hamper the final measurements. To understand and counter these interferences and further fractionate or preconcentrate these glycans, we introduce here an effective microgradient chromatographic technique that employs a small reversed‐phase microcolumn connected to a gas‐tight microsyringe delivering a mobile‐phase gradient. After loading the glycan fraction onto the microcolumn, three elution steps are recommended: (1) remove polar contaminants; (2) recover permethylated glycans for either liquid chromatography with electrospray ionization mass spectrometry or matrix‐assisted laser desorption/ionization mass spectrometry; and (3) remove larger polymeric contaminants and regenerate the precolumn. We further demonstrate that the trapped second fraction can be beneficially preconcentrated and further separated to achieve matrix‐assisted laser desorption/ionization mass spectrometric detection of the derivatized N‐glycans up to 6300 Da. The enhanced detection capabilities for tetra‐antennary N‐glycans are of increasing interest in disease biomarker discovery.     

In situ probing of cholesterol in astrocytes at the single‐cell level using laser desorption ionization mass spectrometric imaging with colloidal silver

Mass spectrometric imaging has been utilized to localize individual astrocytes and to obtain cholesterol populations at the single‐cell level in laser desorption ionization (LDI) with colloidal silver. The silver ion adduct of membrane‐bound cholesterol was monitored to detect individual cells. Good correlation between mass spectrometric and optical images at different cell densities indicates the ability to perform single‐cell studies of cholesterol abundance. The feasibility of quantification is confirmed by the agreement between the LDI‐MS ion signals and the results from a traditional enzymatic fluorometric assay. We propose that this approach could be an effective tool to study chemical populations at the cellular level. Published in 2010 by John Wiley & Sons, Ltd.     

Aniline/α‐cyano‐4‐hydroxycinnamic acid is a highly versatile ionic liquid for matrix‐assisted laser desorption/ionization mass spectrometry

The performance of a matrix‐assisted laser desorption/ionization (MALDI) ionic liquid matrix (ILM) consisting of α‐cyano‐4‐hydroxycinnamic acid (CHCA) and aniline (ANI) was evaluated to assess whether it could offer possible advantages over conventional matrices. Ultraviolet (UV), Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR) and laser desorption/ionization mass spectrometry (LDI‐MS) experiments were carried out with the aim of confirming the structure of the ANI‐CHCA ILM. Different model analytes such as amino acids, peptides, proteins, lipids, phospholipids, synthetic polymers, and sugars were tested. Mass spectra with similar or improved signal‐to‐noise (S/N) ratio (compared to CHCA) were invariably obtained demonstrating the potential of this ILM as a general purpose matrix. Furthermore, protein identification by peptide mass fingerprinting (PMF) and database search was facilitated compared to CHCA since higher scores and increased sequence coverage were observed. Finally, a complex lipid mixture (i.e. a raw extract of a milk sample) analysed by MALDI‐MS showed improved S/N ratio, a reduced chemical noise and a limited formation of matrix‐clusters. Copyright © 2009 John Wiley & Sons, Ltd.     

On‐chip solid‐phase extraction pre‐concentration/focusing substrates coupled to atmospheric pressure matrix‐assisted laser desorption/ionization ion trap mass spectrometry for high sensitivity biomolecule analysis

Atmospheric pressure matrix‐assisted laser desorption/ionization (AP‐MALDI) has proven a convenient and rapid method for ion production in the mass spectrometric (MS) analysis of biomolecules. AP‐MALDI and electrospray ionization (ESI) sources are easily interchangeable in most mass spectrometers. However, AP‐MALDI suffers from less‐than‐optimal sensitivity due to ion losses during transport from the atmosphere into the vacuum of the mass spectrometer. Here, we study the signal‐to‐noise ratio (S/N) gains observed when an on‐chip dynamic pre‐concentration/focusing approach is coupled to AP‐MALDI for the MS analysis of neuropeptides and protein digests. It was found that, in comparison with conventional AP‐MALDI targets, focusing targets showed (1) a sensitivity enhancement of approximately two orders of magnitude with S/N gains of 200–900 for hydrophobic substrates, and 150–400 for weak cation‐exchange (WCX) substrates; (2) improved detection limits as low as 5 fmol/µL for standard peptides; (3) significantly reduced matrix background; and (4) higher inter‐day reproducibility. The improved sensitivity allowed successful tandem mass spectrometric (MS/MS) sequencing of dilute solutions of a derivatized tryptic digest of a protein standard, and enabled the first reported AP‐MALDI MS detection of neuropeptides from Aedes aegypti mosquito heads. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of three different types of fullerene derivatives by laser desorption/ionization time‐of‐flight mass spectrometry with new matrices

Three different types of fullerene derivatives, namely methano[60]fullerene dicarboxylate esters, [60]fulleropyrrolidines, and imino[60]fullerenes, were analyzed by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry using trans‐4‐tert‐butyl‐4′‐nitrostilbene (TBNS), 1,8,9‐anthracenetriol (dithranol), 6‐aza‐2‐thiothymine (ATT), 2,5‐dihydroxybenzoic acid (DHB) and carbazole as matrices. Unit mass resolution (sufficient to clearly resolve isotopic peaks), high signal‐to‐noise ratio, and clean mass spectra for all analytes were acquired by the optimization of experimental parameters and choice of optimal solvent for the matrix and molar matrix‐to‐analyte ratio. The new matrix, TBNS, gave the best results in the positive‐ion mode, as it can provide higher yields of analyte molecular ions at a lower laser threshold than the other four matrices, together with a very low degree of unwanted fragmentations. In the negative‐ion mode dithranol was better than TBNS, and the other three matrices gave relatively poor mass spectra for these fullerene derivatives. Copyright © 2005 John Wiley & Sons, Ltd.     

Successful MALDI‐MS Analysis of Synthetic Polymers with Labile End‐Groups: The Case of Nitroxide‐Mediated Polymerization Using the MAMA‐SG1 Alkoxyamine

A sample pretreatment was evaluated to enable the production of intact cationic species of synthetic polymers holding a labile end‐group using matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry. More specifically, polymers obtained by nitroxide‐mediated polymerization involving the MAMA‐SG1 alkoxyamine were stirred for a few hours in trifluoroacetic acid (TFA) to induce the substitution of a tert‐butyl group on the nitrogen of nitroxide end‐group by a hydrogen atom. Nuclear magnetic resonance, electrospray ionization tandem mass spectrometry, and theoretical calculations were combined to scrutinize this sample pretreatment from both mechanistic and energetic points of view. The substitution reaction was found to increase the dissociation energy of the fragile C? ON bond to a sufficient extent to prevent this bond to be spontaneously cleaved during MALDI analysis. This TFA treatment is shown to be very efficient regardless of the nature of the polymer, as evidenced by reliable MALDI mass spectrometric data obtained for poly(ethylene oxide), polystyrene and poly(butylacrylate).