Regio- and Stereo-Specific Chemical Depolymerization of High Molecular Weight Polybutadiene and Polyisoprene for Their Analysis by High-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Comparison with Pyrolysis-Comprehensive Two-Dimensional Gas Chromatography/Mass Spectrometry, Atmospheric Solid Analysis Probe, Direct Inlet Probe-Atmospheric Pressure Chemical Ionization Mass Spectrometry, and Ion Mobility Spectrometry-Mass Spectrometry.

Polybutadiene (PB) and polyisoprene (PI), the two most common polydienes (PD), are involved in a large number of materials and used in a wide variety of applications. The characterization of these polymers by mass spectrometry (MS) continues to be very challenging due to their high insolubility and the difficulty to ionize them. In this work, a cross-metathesis reaction was used to generate end-functionalized acetoxy ionizable oligomers for the structural deciphering of different commercial PB and PI samples. A cross-metathesis reaction was carried out between polymers and the Z-1,4-diacetoxy-2-butene as a chain transfer agent in dichloromethane using a Hoveyda-Grubbs second-generation catalyst. Well-defined acetoxy telechelic structures were obtained and analyzed by Fourier transform ion cyclotron resonance (FTICR) high-resolution MS. However, after depolymerization, low molar mass polyolefins contained some units with different configurations, suggesting an olefin isomerization reaction due to the decomposition of the catalyst. The addition of an electron-deficient reagent such as 2,6-dichloro-1,4-benzoquinone suppressed this isomerization in the case of both Z- and E-PB and PI. Ion mobility spectrometry-mass spectrometry (IMS-MS) and energy-resolved tandem mass spectrometry (ERMS) analyses confirmed a successful isomerization suppression. For comparing the results obtained by depolymerization with classical methods for polymer analysis, pyrolysis-comprehensive two-dimensional gas chromatography/mass spectrometry (Py-GC × GC-MS), atmospheric solid analysis probe (ASAP), and direct inlet probe-atmospheric pressure chemical ionization (DIP-APCI) analyses were performed on the same polymers. This strategy can be applied on a variety of synthetic and natural not yet characterized polymers.

Identification of traditional East Asian handmade papers through the multivariate data analysis of pyrolysis-GC/MS data.

An analytical approach based on the multivariate analysis of on-line pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) data is proposed for the identification of traditional East Asian handmade papers from different fiber material origins. This approach utilized several biomarkers detected during the Py-GC/MS analysis of paper samples. At first, the total ion chromatogram (TIC) was taken as the response and then the extracted ion chromatograms (EICs) were considered to improve the discrimination of papers. The influence of different data pretreatments (raw responses vs. normalized values) including different weightings of the variables (weighting as 1 vs. weighting as 1/STD, where STD stands for standard deviation) for principal component analysis was also investigated. The results showed that compared to the commonly used microscopy techniques, the Py-GC/MS technique proved to be able to discriminate against handmade paper materials that have similar microscopic morphologies such as Morus species vs. Broussonetia species. The data pretreatment influenced PCA modeling: the analysis based on normalized values showed more interpretable PCA group features for Moraceae species. PCA without weighting resulted unsurprisingly in discrimination through the presence of high intensity response biomarkers, while when applying weight as 1/STD, a PCA loading plot was shown to provide a group of compounds, most of them being present at low levels, to be discriminating. Additionally, the characteristic EICs can provide a data matrix for statistical analysis avoiding the interference from a co-eluting compound and background compared to the data matrix obtained from the TIC. As a result, a quick Py-GC/MS based handmade paper identification procedure using PCA modeling of the characteristic EICs was proposed for the first time in the identification of traditional East Asian handmade papers. This procedure could be very beneficial for cultural heritage applications.

Understanding paper degradation: identification of products of cellulosic paper decomposition at the wet-dry "tideline" interface using GC-MS.

Cellulose paper degradation products forming in the "tideline" area at the wet-dry interface of pure cellulose paper were analyzed using gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) and high-resolution electrospray ionization-mass spectrometry (ESI-MS, LTQ Orbitrap) techniques. Different extraction protocols were employed in order to solubilize the products of oxidative cellulose decomposition, i.e., a direct solvent extraction or a more laborious chromophore release and identification (CRI) technique aiming to reveal products responsible for paper discoloration in the tideline area. Several groups of low molecular weight compounds were identified, suggesting a complex pathway of cellulose decomposition in the tidelines formed at the cellulose-water-oxygen interface. Our findings, namely the appearance of a wide range of linear saturated carboxylic acids (from formic to nonanoic), support the oxidative autocatalytic mechanism of decomposition. In addition, the identification of several furanic compounds (which can be, in part, responsible for paper discoloration) plus anhydro carbohydrate derivatives sheds more light on the pathways of cellulose decomposition. Most notably, the mechanisms of tideline formation in the presence of molecular oxygen appear surprisingly similar to pathways of pyrolytic cellulose degradation. More complex chromophore compounds were not detected in this study, thereby revealing a difference between this short-term tideline experiment and longer-term cellulose aging.

Alteration of Asian lacquer: in-depth insight using a physico-chemical multiscale approach.

Oriental lacquer has been used in Asian countries for thousands of years as a durable and aesthetic coating material for its adhesive, consolidating, protective and decorative properties. Although these objects are made from an unusual material in Occident, Western museum collections host many lacquerwares. Curators, restorers and scientists are daily confronted with questions of their conservation and their alteration. The characterization of their conservation state is usually assessed through visual observations. However deterioration often starts at the microscopic level and cannot be detected by a simple visual inspection. Often, ageing and deterioration of artworks are connected to physical, mechanical and chemical transformations. Thus new insight into alteration of lacquer involves the monitoring of macro-, microscopic and molecular modifications, and this can be assessed from physico-chemical measurements. Non-invasive (microtopography and Scanning Electron Microscopy - SEM) and micro-invasive (infrared micro-spectroscopy using a synchrotron source - SR-µFTIR) investigations were performed to study the degradation processes of lacquers and evaluate their level of alteration. In particular, spectral decomposition and fitting procedure were performed in the 1820-1520 cm(-1) region to follow the shift of the C=O and C=C band positions during lacquer ageing. The present work proves the potential of this physico-chemical approach in conservation studies of lacquers and in the quantification of the state of alteration. It evidences chemical phenomena of alteration such as oxidation and decomposition of a lacquer polymeric network. It also demonstrates for the first time the degradation front of artificially aged lacquer and the chemical imaging of a more than 2000 years old archaeological lacquer by using SR-µFTIR.

Investigation of the unusual behavior of metolachlor under chemical ionization in a hybrid 3D ion trap mass spectrometer.

This article describes the strange behavior of the widely used herbicide metolachlor under chemical ionization conditions in a hybrid source ion trap mass spectrometer in gas chromatography/mass spectrometry (GC/MS) coupling. With the use of ammonia as the reagent gas, metolachlor provides a chlorinated ion at m/z 295/297, almost as abundant as the protonated molecule at m/z 284/286, which cannot be isolated to perform tandem mass spectrometry (MS(n)) experiments. Curiously, this ion at m/z = M + 12 is not observed for the herbicides acetochlor and alachlor, which present very similar chemical structures. The chemical structure of the m/z 295/297 ions and the explanation of the observed phenomenon based on the metastable behavior of these ions were elucidated on the basis of experiments including isotopic labeling and modifications of the operating conditions of the ion trap mass spectrometer. This work allows one to give new recommendations for an optimized use of hybrid source ion trap mass spectrometers.

Investigation of the dissociation pathways of metolachlor, acetochlor and alachlor under electron ionization - application to the identification of ozonation products.

With the future aim of using gas chromatography coupled with mass spectrometry to characterize the transformation products of ozonated herbicides: metolachlor, acetochlor and alachlor, an interpretation of their electron ionization mass spectra is presented. Fragmentation mechanisms are proposed on the basis of isotopic labelling and multiple-stage mass spectrometry experiments carried out on an ion trap mass spectrometer. We also give examples in order to demonstrate how the elucidation of such fragmentation mechanisms for herbicides may simplify the characterization of their ozonation products.

Elucidation of the dissociation pathways of electro-ionized estrone.

With the future aim of using gas chromatography coupled with mass spectrometry to characterize the transformation products of estrone submitted to UV-photolysis or to waste water treatment plants, an interpretation of the electron impact mass spectrum of estrone is presented. Fragmentation mechanisms are proposed on the basis of high-resolution measurements performed with a magnetic sector analyzer. Multiple-stage mass spectrometry experiments were carried out using an ion trap mass spectrometer. The structures proposed for product ions were confirmed by the m/z shifts observed in the estrone-d(4) and estrone methyl ether electron ionization mass spectra. If the formation of some of the most abundant ions may easily be explained by alpha-cleavages and retro-Diels-Alder type rearrangements, complex mechanisms need to be considered to rationalize the formation of others. Isotope labelling allows discrimination of isobaric ions.

Elucidation of the decomposition pathways of protonated and deprotonated estrone ions: application to the identification of photolysis products.

With the future aim of elucidating the unknown structures of estrogen degradation products, we characterized the dissociation pathways of protonated estrone (E1) under collisional activation in liquid chromatography/tandem mass spectrometry (LC/MS/MS) experiments employing a quadrupole time-of-flight mass spectrometer. Positive ion and negative ion modes give information on the protonated and deprotonated molecules and their product ions. The mass spectra of estrone methyl ether (CH(3)-E1) and estrone-d(4) (E1-d(4)) were compared with that of E1 in order (i) to elucidate the dissociation mechanisms of protonated and deprotonated molecules and (ii) to propose likely structures for each product ions. The positive ion acquisition mode yielded more fragmentation. The mass spectra of E1 were compared with those of estradiol (E2), estriol (E3) and 17-ethynylestradiol (EE2). This comparison allowed the identification of marker ions for each ring of the estrogenic structure. Accurate mass measurements have been carried out for all the identified ions. The resulting ions revealed to be useful for the characterization of structural modifications induced by photolysis on each ring of the estrone molecule. These results are very promising for the determination of new metabolites in the environment.

Ion attachment mass spectrometry combined with infrared image furnace for thermal analysis: evolved gas analysis studies.

A well-established ion attachment mass spectrometer (IAMS) is combined with an in-house single-atom infrared image furnace (IIF) specifically for thermal analysis studies. Besides the detection of many chemical species at atmospheric pressure, including free radical intermediates, the ion attachment mass spectrometer can also be used for the analysis of products emanating from temperature-programmed pyrolysis. The performance and applicability of the IIF-IAMS is illustrated with poly(tetrafluoroethylene) (PTFE) samples. The potential of the system for the analysis of oxidative pyrolysis is also considered. Temperature-programmed decomposition of PTFE gave constant slopes of the plots of temperature versus signal intensity in a defined region and provided an apparent activation energy of 28.8 kcal/mol for the PTFE decomposition product (CF(2))(3). A brief comparison with a conventional pyrolysis gas chromatography/mass spectrometry system is also given.

Can electrospray ionization help the characterization of iron gall inks? Investigation on the interactions of gallic acid with iron ions in aqueous solutions.

In the present work, an investigation has been conducted by electrospray ionization (ESI) experiments to characterize the structures of iron gall ink complexes in solution. Simple mono and polyphenolic acid molecules added to iron sulfate salts were chosen to model the recipes of ink composition. Theoretical calculations have been used (1) to determine the stability of the ionic complexes generated in the gas phase, (2) to explain which structures are more likely generated in the electrospray ion source, and (3) to determine which mechanisms are likely involved in their formation. Fragmentation pathways of the derived structures have also been investigated and rationalized to facilitate the interpretation of the data obtained under collisionally induced dissociation (CID) conditions.The present study confirms the assumption that ESI experiments with ions that are preformed in solution must be considered carefully. As a matter of fact, the study of ion formation mechanisms in the ion source is necessary to establish relationships between the ion structures in the condensed phase and the gas phase.

Benefit of the Use of GCxGC/MS Profiles for 1D GC/MS Data Treatment Illustrated by the Analysis of Pyrolysis Products from East Asian Handmade Papers.

In this study, we report the use of pyrolysis-GCxGC/MS profiles for an optimized treatment of data issued from pyrolysis-GC/MS combined with the automatic deconvolution software Automated Mass Spectral Deconvolution and Identification System (AMDIS). The method was illustrated by the characterization of marker compounds of East Asian handmade papers through the examination of pyrolysis-GCxGC/MS data to get information which was used for manually identifying low concentrated and co-eluting compounds in 1D GC/MS data. The results showed that the merits of a higher separation power for co-eluting compounds and a better sensitivity for low concentration compounds offered by a GCxGC system can be used effectively for AMDIS 1D GC/MS data treatment: (i) the compound distribution in pyrolysis-GCxGC/MS profiles can be used as "peak finder" for manual check of low concentration and co-eluting compound identification in 1D GC/MS data, and (ii) pyrolysis-GCxGC/MS profiles can provide better quality mass spectra with observed higher match factors in the AMDIS automatic match process. The combination of 2D profile with AMDIS was shown to contribute efficiently to a better characterization of compound profiles in the chromatograms obtained by 1D analysis in focusing on the mass spectral identification. Graphical abstract.

Application of pyrolysis-comprehensive gas chromatography/mass spectrometry for identification of Asian lacquers.

A new approach based on online pyrolysis-comprehensive gas chromatography/mass spectrometry (Py-GCxGC/MS) is introduced for analysis of lacquer saps with potential applications to analysis of Asian lacquers. The bidimensional GCxGC separation demonstrated its benefits for characterization of the markers of lacquer saps, alkylhydrocarbons, alkylbenzenes, alkylphenols, and alkylcatechols, in a visual way not attainable in monodimensional Py-GC/MS analysis. Moreover, the potentiality offered by GCxGC allows the separation of regioisomers difficult to obtain with a monodimensional separation. Under these circumstances, urushiol (Japanese, Chinese), laccol (Vietnamese), and thitsiol (Myanmar) lacquer sap films were differentiated by their marker fingerprints with a limit of detection in the low µg range. Additionally, thermally assisted pyrolysis with tetramethylammonium hydroxyde (TMAH) clearly differentiated the alkylcatechol markers of the four lacquer samples investigated, with a net separation of stereoisomers particularly well exemplified in the case of the Myanmar lacquer sample. The proposed Py-GCxGC/MS approach greatly facilitates the analysis of Asian lacquer saps, and is very promising for sensitive detection of lacquers in archaeological artifacts.

Does the reagent gas influence collisional activation when performing in situ chemical ionization with an ion trap mass spectrometer?

Users of ion trap mass spectrometers frequently develop methods that associate chemical ionization with tandem mass spectrometry detection. With apparatus using internal ionization, the chemical reagent is present in the trap during the collision induced dissociation (CID) step and one may wonder if the reagent influences the fragmentation ratios in MS/MS. We report a comparison of the fragmentation ratios of protonated molecules when using the most common reagents (methane, ammonia, methanol, acetonitrile, isobutane) for performing in situ chemical ionization. Four molecules were chosen in the medical field to serve as models: alprazolam, diazepam, flunitrazepam and acetaminophen. In the non-resonant CID mode, the influence of the reagent mass is clearly seen in spite of its low partial pressure in the ion trap; the reagent acts as a "heavy target": the degree of fragmentation increases with the molecular weight of the reagent. In the resonant CID mode, there is no evident correlation between the fragmentation ratio of MH+ ions and the nature of the CI reagent; a slight shift of the secular frequency of the precursor ion, which tends to reduce the CID efficiency, could compensate for the "heavy target" effect underscored in the non-resonant mode.

In situ chemical ionization in ion trap mass spectrometry--the beneficial influence of isobutane as a reagent gas.

We report a comparison of the ionization yields provided by the most common reagents (methane, ammonia, methanol, acetonitrile, isobutane) performing in situ chemical ionization with an ion trap mass spectrometer. Four molecules were chosen in the medical field to illustrate experimental results: alprazolam, diazepam, flunitrazepam and acetaminophen. Under usual operational conditions, relative abundances of protonated ions appreciably depend on the reagents. The greatest abundance of MH+ ions was obtained with isobutane while observed intensities for MH+ ions varied from 73% for methanol and ammonia to about 23% for acetonitrile and methane. Results were temptatively rationalized comparing energies of formation of the reagent ions and storage efficiency in the trapping field.

New criteria for the characterization of traditional East Asian papers.

We report a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method capable of analyzing traditional East Asian papers. The method proposed is based on rapid and easy single step Py-GC/MS analysis that can be carried out with a minimum amount of matter, in the few microgram range. Three reference papers manufactured from kozo (Broussonetia kazinoki Siebold & Zucc.), mitsumata (Edgeworthia chrysantha Lindl.), and gampi (Wikstroemia sikokiana Franch. & Sav.) with the traditional hand paper making processes were examined. The method allows discrimination between terpenic and steroid compounds, which were revealed as chemical markers of origin of the plant fibers. Each paper investigated was found to have characteristic pyrolysis fingerprints that were unique to the traditional handmade paper, demonstrating the potential for differentiation of these biochemical components of fiber plants on East Asian papers towards identification and conservation of cultural heritage. The investigation on Py-GC/MS was extended to liquid extraction followed by GC/MS analysis to characterize the biochemical components of fiber plants. The main contribution of this study is to provide molecular criteria for discriminating plant species used for traditional East Asian hand papermaking. Py-GC/MS complements efficiently microscope identification especially for adverse cases. A case study of archaeological Chinese paper painting artefacts was thereafter successfully investigated to address informative potential and efficiency of the criteria of identification on ancient and degraded East Asian paperworks.

Study on the pyrolysis of polyethylene in the presence of iron and copper chlorides.

Pyrolysis experiments were conducted to elucidate the effects of metal chlorides on the thermal degradation of low-density polyethylene on a continuous pyrolysis temperature range of 600 degrees C to 1100 degrees C. The present work focusses on the ratio of aromatics generated on increasing the pyrolysis temperature in the presence of metal salts, iron(II), iron(III) and copper(II) chlorides. It was observed that beside alpha,omega-dienes, alpha-olefins and n-alkanes which are usually observed during the thermal decomposition of polyethylene, the level of aromatics noticeably increases with the addition of metal salts. At high temperatures, the formation of these aromatics took place in such a way that they become the major products when polyethylene is pyrolyzed in presence of FeCl(3) and CuCl(2). Quantification of the effect of metal salts has been tempted comparing the variation of the ratio of aromatics with pyrolysis temperatures. Mechanisms responsible for the formation of these aromatics in presence of metal salts have been tentatively investigated. They are proposed to result from cyclization/dehydrogenation reactions similar to those observed during the thermal decomposition of polyethylene, but with an increased efficiency due to the metal salts.

Obtaining thermochemical data by the extended kinetic method.

A microcanonical analysis of the extended kinetic method is performed using statistical rate calculations based on orbiting transition state theory. The model systems simulate polydentate bases M which exhibit losses of entropy upon protonation of up to 35 kJ mol(-1) K(-1). It is shown that the correlations using the natural logarithm of the ratio of rate constants vs the proton affinity of the reference bases, at several effective temperatures, lead to correct proton affinity and protonation entropy of the base M of interest. A systematic underestimate of the latter quantity (by 5-15%), mainly due to the use of a linear rather than a polynomial curve fitting procedure, is noted, however. When considering experimental data, more severe underestimates are observed for the protonation entropies of polydentate bases (by 50-90%). The origins of these considerable discrepancies are beyond the limits of the present modeling and remain to be determined.

Structure, reactivity and thermochemical properties of protonated lactic acid.

The protonation energetics of lactic acid (LA) were experimentally determined by the kinetic method including the entropy effect. The values (proton affinity, PA(LA) = 817.4 +/- 4.3 kJ mol(-1); protonation entropy, DeltaS degrees (p)(LA) = -2 +/- 5 J K(-1) mol(-1); gas-phase basicity, GB(LA) = 784.5 +/- 4.5 kJ mol(-1)) agree satisfactorily with computed G2(MP2) expectations (PA(LA) = 811.8 kJ mol(-1); DeltaS degrees (p)(LA) = -7.1 J K(-1) mol(-1); GB(LA) = 777.4 kJ mol(-1)). The fragmentation behaviour of protonated lactic acid (LAH(+)) is dominated by carbon monoxide loss followed by elimination of a water molecule. Direct dehydration of LAH(+) is only a high-energy process hardly competitive with the CO loss. A complete mechanistic scheme, based on MP2/6-31G* calculations, is proposed; it involves isomerization of the various protonated forms of LA and the passage through the ion-neutral complex between the 2-hydroxypropyl acylium cation and a water molecule.

Low pressure chemical ionization in ion trap mass spectrometry.

This article presents the specificities of low pressure chemical ionization in ion trap mass spectrometry. One main feature is the ability to perform chemical ionization with liquid reagents as readily as with "conventional" gases (methane, isobutane and ammonia). The reactivities and analytical applications of gas and liquid reagents are summarized from literature data and are compared when possible.

Protonation thermochemistry of alpha-aminoacids bearing a basic residue.

The proton affinity, PA, and protonation entropy, Delta(p)S degree, of glycine (Gly), 1, aspartic acid (Asp), 2, asparagine (Asn), 3, histidine (His), 4, lysine (Lys), 5, glutamic acid (Glu), 6, and glutamine (Gln), 7, have been reinvestigated by the extended kinetic method, using the "isothermal point" method and the orthogonal distance regression, ODR, technique. The proton affinity values of a-aminoacids bearing a basic residue (PA = 926.8; 965.2; 996.0; 993.9; 981.8 and 988.1 kJ.mol(-1) for 2-7, respectively) show significant deviation from the tabulated values. As expected from the effect of a strong intramolecular hydrogen bond in the protonated forms of these peculiar aminoacids, negative protonation entropies are detected (Delta(p)S degree = 36; 43; 37; 29; 95 and 55 J mol(-1) K(-1) for for 27 respectively).