Exploration of polyamide structure-property relationships by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

RATIONALE: Polyamides (PA) are among the most used classes of polymers because of their attractive properties. Depending on the nature and proportion of the co-monomers used for their synthesis, they can exhibit a very large range of melting temperatures (Tm ). This study aims at the correlation of data from mass spectrometry (MS) with differential scanning calorimetry (DSC) and X-ray diffraction analyses to relate molecular structure to physical properties such as melting temperature, enthalpy change and crystallinity rate. METHODS: Six different PA copolymers with molecular weights around 3500 g mol(-1) were synthesized with varying proportions of different co-monomers (amino-acid AB/di-amine AA/di-acid BB). Their melting temperature, enthalpy change and crystallinity rate were measured by DSC and X-ray diffraction. Their structural characterization was carried out by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Because of the poor solubility of PA, a solvent-free sample preparation strategy was used with 2,5-dihydroxybenzoic acid (2,5-DHB) as the matrix and sodium iodide as the cationizing agent. RESULTS: The different proportions of the repeating unit types led to the formation of PA with melting temperatures ranging from 115°C to 185°C. The structural characterization of these samples by MALDI-TOF-MS revealed a collection of different ion distributions with different sequences of repeating units (AA, BB; AB/AA, BB and AB) in different proportions according to the mixture of monomers used in the synthesis. The relative intensities of these ion distributions were related to sample complexity and structure. They were correlated to DSC and X-ray results, to explain the observed physical properties. CONCLUSIONS: The structural information obtained by MALDI-TOF-MS provided a better understanding of the variation of the PA melting temperature and established a structure-properties relationship. This work will allow future PA designs to be monitored.

Atmospheric solid analysis probe-ion mobility mass spectrometry of polypropylene.

Polyolefin, including polypropylene (PP), constitutes an important class of materials. In particular, the recent interest in recycling plastic wastes necessitates their characterization as well as their degradation mechanism being understood. PP materials characterization by mass spectrometry, including polymer and additives parts, is not direct and generally involves a pyrolysis step to produce ionizable species. In this study, we extended the use of atmospheric solid analysis probe (ASAP) in combination with traveling wave ion mobility mass spectrometry (TWIM-MS) for the characterization of PP materials, including polymer as well as additives. Different commercial PP samples, from polymer standard to plastic item, were studied. The use of ASAP allow analysis to be done without any sample preparation, while TWIM-MS permitted a clear separation of polymer ions and additive signals. Several series of polymer pyrolysis residues, similar to those produced by classic pyrolysis, were obtained. Moreover, additive characterization has been done and supported by accurate mass measurements and tandem mass spectrometry experiments. Finally, this strategy put in evidence the role of additives in polymer degradation.

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).

Solvent-based and solvent-free characterization of low solubility and low molecular weight polyamides by mass spectrometry: a complementary approach.

RATIONALE: Polyamides (PA) belong to the most used classes of polymers because of their attractive chemical and mechanical properties. In order to monitor original PA design, it is essential to develop analytical methods for the characterization of these compounds that are mostly insoluble in usual solvents. METHODS: A low molecular weight polyamide (PA11), synthesized with a chain limiter, has been used as a model compound and characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the solvent-based approach, specific solvents for PA, i.e. trifluoroacetic acid (TFA) and hexafluoroisopropanol (HFIP), were tested. Solvent-based sample preparation methods, dried-droplet and thin layer, were optimized through the choice of matrix and salt. Solvent-based (thin layer) and solvent-free methods were then compared for this low solubility polymer. Ultra-high-performance liquid chromatography/electrospray ionization (UHPLC/ESI)-TOF-MS analyses were then used to confirm elemental compositions through accurate mass measurement. RESULTS: Sodium iodide (NaI) and 2,5-dihydroxybenzoic acid (2,5-DHB) are, respectively, the best cationizing agent and matrix. The dried-droplet sample preparation method led to inhomogeneous deposits, but the thin-layer method could overcome this problem. Moreover, the solvent-free approach was the easiest and safest sample preparation method giving equivalent results to solvent-based methods. Linear as well as cyclic oligomers were observed. Although the PA molecular weights obtained by MALDI-TOF-MS were lower than those obtained by (1)H NMR and acido-basic titration, this technique allowed us to determine the presence of cyclic and linear species, not differentiated by the other techniques. TFA was shown to induce modification of linear oligomers that permitted cyclic and linear oligomers to be clearly highlighted in spectra. CONCLUSIONS: Optimal sample preparation conditions were determined for the MALDI-TOF-MS analysis of PA11, a model of polyamide analogues. The advantages of the solvent-free and solvent-based approaches were shown. Molecular weight determination using MALDI was discussed.

Molecular weight determination of block copolymers by pulsed gradient spin echo NMR.

Matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS) is the technique of choice to achieve molecular weight data for synthetic polymers. Because the success of a MALDI-MS analysis critically depends on a proper matrix and cation selection, which in turn relates closely to the polymer chemical nature and size, prior estimation of the polymer size range strongly helps in rationalizing MALDI sample preparation. We recently showed how pulsed gradient spin echo (PGSE) nuclear magnetic resonance could be used as an advantageous alternative to size exclusion chromatography, to rationalize MALDI sample preparation and confidently interpret MALDI mass spectra for homopolymers. Our aim here is to extend this methodology to the demanding case of amphiphilic block copolymers, for which obtaining prior estimates on the Mw values appears as an even more stringent prerequisite. Specifically, by studying poly(ethylene oxide) polystyrene block copolymers of distinct molecular weights and relative block weight fractions, we show how PGSE data can be used to derive the block Mw values. In contrast to homopolymers, such determination requires not only properly recorded calibration curves for each of the polymers constituting the block copolymers but also an appropriate hydrodynamic model to correctly interpret the diffusion data.

Rapid analysis of lubricants by atmospheric solid analysis probe-ion mobility mass spectrometry.

Formulated lubricants are complex mixtures composed of base oil(s) and additives with various functions (detergents, corrosion inhibiter, antioxidant, viscosity modifiers, etc.). Because of the aliphatic nature of base oil and the chemical diversity of additives, the characterization of lubricant is currently a long and complex process. The comprehensive analysis of lubricant samples involves several techniques such as nuclear magnetic resonance, mass spectrometry, chromatography and infrared spectroscopy. The coupling of atmospheric solid analysis probe (ASAP) with ion mobility-mass spectrometry (IM-MS) has been shown to be an efficient tool for the characterization of complex mixture containing vaporizable polar to non-polar compounds. This approach affords the coupling of a direct ionization technique that does not require sample preparation, with a bi-dimensional separation method with high peak capacity. In this work, we show that ASAP-IM-MS is a suitable method for rapid and direct characterization of lubricant samples. Indeed, base oil and additives yielded, by ASAP, ions series which could be separated by IM-MS. Molecular additives such as Zn-dithiocarbamate, phosphite, thiophosphate and Alkyl diphenylamine were ionized as molecular ions [M](+•) or protonated molecules [M + H](+), depending of their polarity. In some cases, fragment ions were observed, confirming the additive identification. In addition, high molecular weight polymeric additives such as poly(alkyl methacrylate) (PAM) were pyrolized in the ASAP source leading to characteristic fragment ions. ASAP-IM-MS is shown to be a powerful tool for studying complex mixtures, allowing the first comprehensive analysis of lubricants in just a few minutes.

Tandem mass spectrometry of low solubility polyamides.

The structural characterization of polyamides (PA) was achieved by tandem mass spectrometry (MS/MS) with a laser induced dissociation (LID) strategy. Because of interferences for precursor ions selection, two chemical modifications of the polymer end groups were proposed as derivatization strategies. The first approach, based on the addition of a trifluoroacetic acid (TFA) molecule, yields principally to complementary bn and yn product ions. This fragmentation types, analogous to those obtained with peptides or other PA, give only poor characterization of polymer end-groups [1]. A second approach, based on the addition of a basic diethylamine (DEA), permits to fix the charge and favorably direct the fragmentation. In this case, bn ions were not observed. The full characterization of ω end group structure was obtained, in addition to the expected yn and consecutive fragment ions.

Acquisition strategy to obtain quantitative diffusion NMR data.

Pulsed Gradient Spin Echo (PGSE) diffusion NMR experiments constitute a powerful tool for analyzing complex mixtures because they can in principle separate the NMR spectra of each mixture component. However, because these experiments intrinsically rely on spin echoes, they are traditionally regarded as non-quantitative, due to the signal attenuation caused by longitudinal (T(1)) and transverse (T(2)) nuclear magnetic relaxation during the rather long delays of the pulse sequence. Alternatively to the quantitative Direct Exponential Curve Resolution Algorithm (qDECRA) approach proposed by Antalek (J. Am. Chem. Soc. 128 (2006) 8402-8403), this work presents an acquisition strategy that renormalizes this relaxation attenuation using estimates of the T(1) and T(2) relaxation times for all the nuclei in the mixture, as obtained directly with the pulse sequence used to record the PGSE experiment. More specifically, it is shown that only three distinct PGSE experiments need to be recorded, each with a specific set of acquisition parameters. For small- and medium-sized molecules, only T(1) is required for obtaining accurate quantification. For larger molecular weight species, which typically exhibit short T(2) values, estimates of T(2) must also be included but only a rough estimation is required. This appears fortunate because these data are especially hard to obtain with good accuracy when analyzing homonuclear scalar-coupled systems. Overall, the proposed methodology is shown to yield a quantification accuracy of ±5%, both in the absence and in the presence of spectral overlap, giving rise--at least, in our hands--to results that superseded those achieved by qDECRA, while requiring substantially less experimental time.

A convenient method for the measurements of transverse relaxation rates in homonuclear scalar coupled spin systems.

A new solution-state NMR method is proposed to determine apparent transverse NMR relaxation rates in both weakly and strongly scalar coupled two-spin systems.

Solid state nuclear magnetic resonance as a tool to explore solvent-free MALDI samples.

Solid-state Nuclear magnetic resonance (NMR) was used here to explore structural characteristics of samples to be subjected to matrix-assisted laser desorption/ionization (MALDI) and prepared without the use of any solvent. The analytical systems scrutinized in NMR were mixtures of a 2,5-dihydroxybenzoic acid (2,5-DHB) matrix and caesium fluoride (CsF), used as the cationization agent in synthetic polymer MALDI mass analysis, at different molar ratios (1:1, 5:1, and 10:1). Complementary information could be obtained from 13C, 133Cs, and 19F NMR spectra. Grinding the matrix together with the salt in the solid state was shown to induce a strong modification in the molecular organization within the MALDI sample. The evidenced mechano-induced reactions allow strong interactions between the matrix and the cation, up to the formation of a salt, and only occur in the presence of some water molecules. Addition of a poly(ethylene oxide) polymer as the analyte did not further modify the observed molecular organizations. Although relative matrix and salt concentrations in the scrutinized samples were unusual for MALDI analysis, mass spectra of good quality could be obtained and revealed that cation attachment on polymers during the MALDI process is not a matrix-independent event since a lower ionization efficiency was obtained from highly organized solid samples, mostly consisting of 2,5-DHB caesium salt species.