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.

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.

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.

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.

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.

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.

Anticipating the fate and impact of organic environmental contaminants: a new approach applied to the pharmaceutical furosemide.

The presence of trace levels of organic contaminants in the environment is currently an environmental concern. When these contaminants are subjected to environmental transformations, environmental transformation products (ETPs) are obtained, whose structures often remain unknown. The absence of information concerning these new compounds makes them unavailable and consequently makes their environmental detection as well as their (eco)toxicological study impossible.

Photolysis of estrone generates estrogenic photoproducts with higher activity than the parent compound.

In the present study, we aimed to evaluate the effect of UV-visible irradiation on the estrogenicity of an estrone aqueous solution by using chemical analysis associated with an in vitro bioassay and in silico analysis. An estrone aqueous solution was irradiated with an UV-visible high-pressure mercury lamp. By using the MELN in vitro cellular bioassay, based on the induction of a luciferase reporter gene upon the activation of the estrogen receptor by chemicals, we showed that the estrogenic potency of the solution increased after irradiation.

Using mass spectrometry to highlight structures of degradation compounds obtained by photolysis of chloroacetamides: case of acetochlor.

The photooxidation of acetochlor (a pesticide belonging to the acetamides group) using a polychromatic UV irradiation in ultrapure water was studied. This study reports the efficiency of mass spectrometry for the characterization of photodegradation products of acetochlor. Decompositions of protonated ions MH+are proposed in electrospray (ESI) mode for LC–MS, while electron ionization (EI) and chemical ionization modes (CI) are used for GC–MS.

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.

Identification and ecotoxicity of degradation products of chloroacetamide herbicides from UV-treatment of water.

The widespread occurrence of chlorinated herbicides and their degradation products in the aquatic environment raises health and environmental concerns. As a consequence pesticides, and to a lesser degree their degradation products, are monitored by authorities both in surface waters and drinking waters. In this study the formation of degradation products from ultraviolet (UV) treatment of the three chloroacetamide herbicides acetochlor, alachlor and metolachlor and their biological effects were investigated.

Characterization of the photodegradation products of metolachlor: structural elucidation, potential toxicity and persistence.

Aqueous solutions of metolachlor and metolachlor-d(6) were photolyzed with UV-visible radiations. The structures of 15 by-products of metolachlor were determined through gas chromatography-mass spectrometry analyses using electron and chemical ionization combined with multistage mass spectrometry. The photolysis by-products of metolachlor resulted mainly from dehalogenation and hydroxylation, in some cases accompanied by cyclization.

A 'meta effect' in the fragmentation reactions of ionised alkyl phenols and alkyl anisoles.

The competition between benzylic cleavage (simple bond fission [SBF]) and retro-ene rearrangement (RER) from ionised ortho, meta and para RC(6) H(4) OH and RC(6) H(4) OCH(3) (R = n-C(3) H(7) , n-C(4) H(9) , n-C(5) H(11) , n-C(7) H(15) , n-C(9) H(19) , n-C(15) H(31) ) is examined. It is observed that the SBF/RER ratio is significantly influenced by the position of the substituent on the aromatic ring. As a rule, phenols and anisoles substituted by an alkyl group in meta position lead to more abundant methylene-2,4-cyclohexadiene cations (RER fragmentation) than their ortho and para homologues.

GC-MS(n) and LC-MS/MS couplings for the identification of degradation products resulting from the ozonation treatment of Acetochlor.

The degradation of the chloracetamide herbicide acetochlor has been studied under simulated ozonation treatment plant conditions. The degradation of acetochlor included the formation of several degradation products that were identified using GC/ion-trap mass spectrometry with EI and CI and HPLC/electrospray-QqTOF mass spectrometry. Thirteen ozonation products of acetochlor have been identified.

Estrone direct photolysis: by-product identification using LC-Q-TOF.

The identification of degradation products generated upon photolysis of estrone (E1), a natural estrogenic hormone, under simulated UV irradiation conditions was addressed by the use of LC-Q-TOF mass spectrometry. The structures of the main degradation products were elucidated, demonstrating how the use of model molecules 5,6,7,8-tetrahydro-2-naphtol (THN), 2-methylcyclopentanone (MCP), labeled molecule estrone D(4) (E1-D(4)), the investigation of the fragmentation pathways of the parent E1, the concurrent use of CID and exact mass measurements permit the characterization of structural modifications induced by photodegradation processes. In the present study, we identified nine major by-products of which seven photoproducts correspond to E1H(+) modified in positions other than the C-2, C-4 and C-16 of E1.

Molecular criteria for discriminating museum Asian lacquerware from different vegetal origins by pyrolysis gas chromatography/mass spectrometry.

This paper focuses on the identification of several chemical markers of vegetal species of Oriental lacquers with the aim at providing a methodology consistent with sampling restrictions necessarily applied in the field of cultural heritage. The method proposed is based on rapid and easy single step thermally assisted hydrolysis-methylation (THM) pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) analysis that can be carried out with a minimum amount of matter (typically 10 μg for a sample collected on a museum or an archaeological object). The main contribution of this study is to provide multiple molecular criteria for discriminating the three Asian species used for making lacquers, namely Rhus verniciflua Stokes, Rhus succedanea and Melanorrhoea usitata.

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.

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 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.

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.

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.

Characterization by mass spectrometry of an unknown polysiloxane sample used under uncontrolled medical conditions for cosmetic surgery.

For a complete understanding of the raw material used for cosmetic surgery under uncontrolled medical conditions, an unknown sample of polydimethylsiloxanes has been investigated utilizing a combination of analytical techniques: pyrolysis/gas chromatography/mass spectrometry (Py/GC/MS), electrospray ionization (ESI)-MS, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF)MS, and liquid chromatography (LC)/MS. Among these techniques, the LC/APCI-MS coupling allowed the fastest and more effective analysis. In addition, the complexity of the mass spectra deduced from these LC/MS experiments was simplified compared to the mass spectra obtained by MALDI-TOF.

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.