Analysis of polyaniline oligomers by laser desorption ionization and solventless MALDI

Dolan, Anthony R.

doi:10.1016/s1044-0305(04)00177-1

Cited by 10 publications

(15 citation statements)

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“…This fragmentation is inhibited when DHB is employed as matrix, absorbing most of the laser power and protecting the polymer chains from fragmentation [41]. Again, the presence of lateral peaks with Δm/z=15 were observed and attributed to additional NH2 or phenylene terminal groups present from the synthesis [42,43] or generated by the desorption/ionization conditions [40,42].…”

Section: Laser-induced Desorption-mass Spectrometry (Ldi-ms) Maldi-tmentioning

confidence: 99%

Amine-appended polyaniline as a water dispersible electroactive polyelectrolyte and its integration into functional self-assembled multilayers

Marmisollé

Maza

Moya

et al. 2016

Electrochimica Acta

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We present an effective and simple method for the synthesis of poly(3-aminobenzylamine) (PABA) using a chemical oxidation strategy in aqueous solution. The polymer was characterized by NMR, LDI-TOF mass spectrometry, UV-visible, XPS and ATR-FTIR spectroscopies. Stable acidic dispersions were employed for the construction of layer-by-layer assembled films with polyanions, which effectively act as dopants of the electroactive component as revealed by spectroscopic analysis. The assembled films were electroactive in neutral solutions, probably owing to the combination of the doping effect by the polyanions and the self-doping effect of the protonated amino groups of the PABA backbone. These layers showed an electrocatalytic effect on the ascorbic acid oxidation. The advantages of employing PABA instead of polyaniline include improved electroactivity in neutral solution, good processability owing to its higher solubility in acidic solutions and increased interaction with anionic counterparts, which may propel its integration with electroactive biomolecules or conducting nanomaterials for the design of bioelectrochemical devices and energy storage applications.

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Section: Laser-induced Desorption-mass Spectrometry (Ldi-ms) Maldi-tmentioning

confidence: 99%

Amine-appended polyaniline as a water dispersible electroactive polyelectrolyte and its integration into functional self-assembled multilayers

Marmisollé

Maza

Moya

et al. 2016

Electrochimica Acta

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“…For this solventless approach, a true matrix assistance was found for UV-absorbing compounds (e.g., labile side-chain protected synthetic peptides [14] and pigments [15]), and high molecular weight polymers (e.g., poly(methyl methacrylate) and polystyrene) [15], and justified this method as a true MALDI sample preparation method. Subsequently, this solvent-free MALDI method allowed the analysis of pyrolysis products [16], carbonaceous pitches [17], and polyaniline oligomers [18]. The applied mechanical mixing methods, such as ball mill or mortar and pestle treatment, do not appear to have much influence on the success of the solvent-free MALDI analysis, however the transfer method to the MALDI sample holder does which includes improved sensitivity, higher mass resolution, and less restrictive molar analyte:matrix ratios when employing the loose powder transfer [15].…”

mentioning

confidence: 99%

Solvent-free MALDI-MS: Developmental improvements in the reliability and the potential of MALDI in the analysis of synthetic polymers and giant organic molecules

Trimpin¹,

Keune²,

Räder

et al. 2006

J. Am. Soc. Mass Spectrom.

108

161

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A dry sample preparation strategy was previously established as a new method for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS), so-called solvent-free MALDI-MS. In this contribution, we examine systems that have been shown problematic with conventional solvent-based MALDI approaches. Problems frequently encountered are solubility, miscibility, and segregation effects during crystallization as a result of unfavorable analyte and matrix polarities. In all cases studied, solvent-free MALDI-MS simplified the measurement and improved the analysis. Solvent-free MALDI-MS enables more reliable results in well-known problematic systems such as polydimethylsiloxane with its segregation effects. However, even in highly compatible analyte/matrix systems such as polystyrene and dithranol, there were undesirable suppression effects when employing THF as solvent. Generally, the solvent-free method allows for more homogeneous analyte/matrix mixtures as well as higher shot-to-shot and sample-to-sample reproducibility. As a result, less laser power has to be applied, which yields milder MALDI conditions, reduced background signals, and provides better resolution of the analyte signals. Solvent-free MALDI-MS proved valuable for the characterization of nanosized material, e.g., fullereno-based structures, which indicated having an increased fragmentation-susceptibility. New analyte/matrix combinations (e.g., polyvinylpyrrolidone/dithranol) are accessible independent of solubility and compatibility in common solvents. An improved quantitation potential is recognized (e.g., insoluble polycyclic aromatic hydrocarbon against soluble dendrite precursor). The rapid and easy measurement of industrial products demonstrates the solvent-free method capable for improved throughput analysis of a variety of compounds (e.g., poly(butylmethacrylate) diol) in routine industrial analysis. Hence, this new MALDI method leads to qualitative and quantitative improvements, making it a powerful tool for analytical purposes, which may also prove to be valuable in future automation attempts.

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“…The MALDI spectrum is very crowded and each oligomer showed the presence of different peak clusters corresponding to its various redox states and different end groups [41]. As an example, a mass increment of about 15 Da corresponding to polymeric species with loss of -NH 2 , may be the result of fragmentation of the sample in the desorption/ionization process, as reported elsewhere [42][43][44][45]. As for pDANI, the spectra showed the presence of polymeric species in the range from 700 to 1600 Da, with peaks belonging to two families with different abundance (Supporting Information Figure 1B).…”

Section: Maldi Analysismentioning

confidence: 69%

Green synthesis of conductive polyaniline by Trametes versicolor laccase using a DNA template

Giacobbe

Pezzella

Ventura

et al. 2019

Engineering in Life Sciences

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The green synthesis of highly conductive polyaniline by using two biological macromolecules, i.e laccase as biocatalyst, and DNA as template/dopant, was achieved in this work. Trametes versicolor laccase B (TvB) was found effective in oxidizing both aniline and its less toxic/mutagenic dimer N‐phenyl‐p‐phenylenediamine (DANI) to conductive polyaniline. Reaction conditions for synthesis of conductive polyanilines were set‐up, and structural and electrochemical properties of the two polymers were extensively investigated. When the less toxic aniline dimer was used as substrate, the polymerization reaction was faster and gave less‐branched polymer. DNA was proven to work as hard template for both enzymatically synthesized polymers, conferring them a semi‐ordered morphology. Moreover, DNA also acts as dopant leading to polymers with extraordinary conductive properties (∼6 S/cm). It can be envisaged that polymer properties are magnified by the concomitant action of DNA as template and dopant. Herein, the developed combination of laccase and DNA represents a breakthrough in the green synthesis of conductive materials.

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Analysis of polyaniline oligomers by laser desorption ionization and solventless MALDI

Cited by 10 publications

References 0 publications

Amine-appended polyaniline as a water dispersible electroactive polyelectrolyte and its integration into functional self-assembled multilayers

Amine-appended polyaniline as a water dispersible electroactive polyelectrolyte and its integration into functional self-assembled multilayers

Solvent-free MALDI-MS: Developmental improvements in the reliability and the potential of MALDI in the analysis of synthetic polymers and giant organic molecules

Green synthesis of conductive polyaniline by Trametes versicolor laccase using a DNA template

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