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The determination of the block sequence of triblock copolymers is difficult without information on the synthetic conditions, such as starting materials and reagents used or analysis using tandem ma...

Because of its speed, sensitivity, and ability to scrutinize individual species, mass spectrometry (MS) has become an essential tool in analytical strategies aimed at studying the degradation behavior of polyesters. MS analyses can be performed prior to the degradation event for structural characterization of initial substrates or after it has occurred to measure the decreasing size of products as a function of time. Here, we show that MS can also be usefully employed during the degradation process by online monitoring the chain solvolysis induced by reactive desorption electrospray ionization (DESI). Cleavage of ester bonds in random copolymers of lactic acid (LA) and glycolic acid (GA) was achieved by electrospraying methanol-containing NaOH onto the substrates. Experimental conditions were optimized to generate methanolysis products of high abundance so that mass spectra can be conveniently processed using Kendrick-based approaches. The same reactive-DESI performance was demonstrated for two sample preparations, solvent casting for soluble samples or pressed pellets for highly crystalline substrates, permitting to compare polymers with LA/GA ratios ranging from 100/0 to 5/95. Analysis of sample fractions collected by size exclusion chromatography showed that methanolysis occurs independently of the original chain size, so data recorded for poly(LA-co-GA) (PLAGA) copolymers with the average molecular weight ranging from 10 to 180 kDa could be safely compared. The average mass of methanolysis products was observed to decrease linearly (R2 = 0.9900) as the GA content increases in PLAGA substrates, consistent with the susceptibility of ester bonds toward solvolysis being higher in GA than in LA. Because DESI only explores the surface of solids, these data do not reflect bulk degradability of the copolymers but, instead, their relative degradability at the molecular level. Based on a "reactive-DESI degradability scale" such as that established here for PLAGA, the proposed method offers interesting perspectives to qualify intrinsic degradability of different polyesters and evaluate their erosion susceptibility or to determine the degradability of those polymers known to degrade via erosion only.

An analytical methodology with mass spectrometry as the core technique was developed for precise characterization of end groups, size, and co-monomeric composition of poly(lactic-co-glycolic acid) (PLGA) copolymers, as a preliminary step to qualify their biodegradability. Four PLGA samples were studied, with GA molar content varying from 0 to 50% and Mw ranging from 18 to 75 kg mol-1 according to the supplier. Size exclusion chromatography (SEC) and liquid state nuclear magnetic resonance (NMR) were used as either complementary or validation techniques. As confirmed by tandem mass spectrometry (MS/MS) experiments, macrocycles were most prominent in the low mass range. Nevertheless, elemental compositions derived from high resolution (HR) mass measurements of linear species were consistent with chain terminations revealed by NMR. Off-line coupling of SEC with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) permitted calibration curves to be built based on absolute molecular weights and, although slightly overestimated, so-obtained Mn and Mw values compared well with SEC and NMR results. Homogeneity of the co-monomeric content of all chains within each PLGA sample was demonstrated using surface-assisted laser desorption/ionization in a reactive mode (reactive-SALDI), a newly developed technique that takes advantage of residual acid on desorption ionization using through-hole alumina membrane (DIUTHAME) chips to induce dissociation of high-molecular-weight polymers containing cleavable C-O bonds. All HRMS data were best handled with Kendrick analysis, which helped reveal minor species and allowed automated computation of congested mass spectra.

The fabrication of supramolecularly engineered two-dimensional (2D) networks using simple molecular building blocks is an effective means for studying host–guest chemistry at surfaces toward the potential application of such systems in nanoelectronics and molecular devices. In this study, halogen-bonded molecular networks were constructed by the combination of linear halogen-bond donor and acceptor ligands, and their 2D structures at the highly oriented pyrolytic graphite/1-phenyloctane interface were studied by scanning tunneling microscopy. The bi-component blend of the molecular building blocks possessing tetradecyloxy chains formed a lozenge structure via halogen bonding. Upon the introduction of an appropriate guest molecule (e.g., coronene) into the system, the 2D structure transformed into a hexagonal array, and the central pore of this array was occupied by the guest molecules. Remarkably, the halogen bonding of the original structure was maintained after the introduction of the guest molecule. Thus, the halogen-bonded molecular networks are applicable for assembling guest species on the substrate without the requirement of the conventional rigid molecular building blocks with C3 symmetry.

In this study, an N-heterocyclic carbene (NHC)-based metal coordinate surfactant (MCS), NHC-Au-MCS, in which the NHC framework afforded the bonding of the Au(I) at the linkage of the hydrophilic and hydrophobic moieties, was synthesized. The structure of NHC-Au-MCS was confirmed by 1H and 13C NMR spectroscopic measurements together with elemental analysis. Matrix-assisted laser desorption/ionization (MALDI), laser desorption/ionization (LDI), and electrospray ionization mass spectrometry (ESI-MS) indicated the distinct reactivity of NHC-Au-MCS, such as the exchange of Br to Cl and the formation of a cationic Au complex, where the two NHC ligands were coordinated to an Au(I) center upon laser activation. The surface tension and dynamic light scattering (DLS) measurements revealed that the coordination of Au(I) to NHC reduced the critical micelle concentration (CMC) of NHC-Au-MCS (1.3×10-5 M), which resulted in the formation of micelles at concentrations higher than the CMC in water. We also confirmed that the surface-active Au(I) complex of NHC-Au-MCS catalyzed the hydration of 1-dodecyne to 2-dodecanone in water in the absence of an organic solvent. On the basis of the detailed mechanistic investigations regarding the reactivity of NHC-Au-MCS, we revealed that NHC-Au-MCS partially translated into Au nanoparticles (AuNPs), which facilitated alkyne hydration. These mechanistic studies were supported by UV-vis measurements, transmission electron microscopy (TEM), and LDI-MS.

Technological advances in mass spectrometry (MS) toward more accurate and faster data acquisition result in highly informative but also more complex data sets. Especially the hyphenation of liquid chromatography (LC) and MS yields large data files containing a high amount of compound specific information. Using electrospray-ionization for compounds such as polymers enables highly sensitive detection, yet results in very complex spectra, containing multiply charged ions and adducts. Recent years have seen the development of novel or updated data mining strategies to reduce the MS spectra complexity and to ultimately simplify the data analysis workflow. Among other techniques, the Kendrick mass defect analysis, which graphically highlights compounds containing a given repeating unit, has been revitalized with applications in multiple fields of study, such as lipids and polymers. Especially for the latter, various data mining concepts have been developed, which extend regular Kendrick mass defect analysis to multiply charged ion series. The aim of this work is to collect and subsequently implement these concepts in one of the most popular open-source MS data mining software, i.e., MZmine 2, to make them rapidly available for different MS based measurement techniques and various vendor formats, with a special focus on hyphenated techniques such as LC-MS. In combination with already existing data mining modules, an example data set was processed and simplified, enabling an ever faster evaluation and polymer characterization.

The mass spectrum of a polymer often displays repetitive patterns with peak series spaced by the repeating unit(s) of the polymeric backbones, sometimes complexified with different adducts, chain terminations, or charge states. Exploring the complex mass spectral data or filtering the unwanted signal is tedious whether performed manually or automatically. In contrast, the now 60-year-old Kendrick (mass defect) analysis, when adapted to polymer ions, produces visual two-dimensional maps with intuitive alignments of the repetitive patterns and favourable deconvolution of features overlaid in the one-dimensional mass spectrum. This special feature article reports on an up-to-date and theoretically sound use of Kendrick plots as a data processing tool. The approach requires no prior knowledge of the sample but offers promising dynamic capabilities for visualizing, filtering, and sometimes assigning congested mass spectra. Examples of applications of the approach to polymers are discussed throughout the text, but the same tools can be readily extended to other applications, including the analysis of polymers present as pollutants/contaminants, and to other analytes incorporating a repetitive moiety, for example, oils or lipids. In each of these instances, data processing can benefit from the application of an updated and interactive Kendrick analysis.

Glucuronoxylanases are endo-xylanases and members of the glycoside hydrolase family 30 subfamilies 7 (GH30-7) and 8 (GH30-8). Unlike for the well-studied GH30-8 enzymes, the structural and functional characteristics of GH30-7 enzymes remain poorly understood. Here, we report the catalytic properties and three-dimensional structure of GH30-7 xylanase B (Xyn30B) identified from the cellulolytic fungus Talaromyces cellulolyticus Xyn30B efficiently degraded glucuronoxylan to acidic xylooligosaccharides (XOSs), including an α-1,2-linked 4-O-methyl-d-glucuronosyl substituent (MeGlcA). Rapid analysis with negative-mode electrospray-ionization multistage MS (ESI(-)-MS n ) revealed that the structures of the acidic XOS products are the same as those of the hydrolysates (MeGlcA2Xyl n , n > 2) obtained with typical glucuronoxylanases. Acidic XOS products were further degraded by Xyn30B, releasing first xylobiose and then xylotetraose and xylohexaose as transglycosylation products. This hydrolase reaction was unique to Xyn30B, and the substrate was cleaved at the xylobiose unit from its nonreducing end, indicating that Xyn30B is a bifunctional enzyme possessing both endo-glucuronoxylanase and exo-xylobiohydrolase activities. The crystal structure of Xyn30B was determined as the first structure of a GH30-7 xylanase at 2.25 A resolution, revealing that Xyn30B is composed of a pseudo-(α/β)8-catalytic domain, lacking an α6 helix, and a small β-rich domain. This structure and site-directed mutagenesis clarified that Arg46, conserved in GH30-7 glucuronoxylanases, is a critical residue for MeGlcA appendage-dependent xylan degradation. The structural comparison between Xyn30B and the GH30-8 enzymes suggests that Asn93 in the β2-α2 loop is involved in xylobiohydrolase activity. In summary, our findings indicate that Xyn30B is a bifunctional endo- and exo-xylanase.

Residual acid found in the desorption ionization using through-holes alumina membranes (DIUTHAME) induces a reproducible protonation/in-source dissociation of polymers made of ester, amide, or siloxane moieties during their surface-assisted laser desorption ionization (SALDI) mass analysis. Deposited on the DIUTHAME chips in solution (solvent-based) or in pure form by melting the polymer powder in situ (solvent-free), high-molecular-weight nylons, silicone, or functionalized celluloses among other polymers are instantly fingerprinted by laser DIUTHAME high-resolution mass spectrometry (MS) with specific patterns resembling their direct analysis in real-time (DART) single-stage or tandem mass spectra. Depending on the polymer, two main types of fingerprints are observed with either the protonated monomer or product ions revealing the nature of the repeating unit or its functionalization. This technique allows a rapid molecular analysis of industrial homopolymers regardless of their molecular weight and complementary to DART with simple or no sample preparation and also promisingly applicable for copolymers.

The Kendrick mass defect (KMD) analysis conveniently turns a complex high-resolution mass spectrum into a compositional map with informative clustering of points depending on the elemental composition of the associated ions. It has nevertheless been left unchanged for thirty years with the use of chemical moieties such as methylene as base units for the computation of “regular” mass defects displayed in condensed plots regardless of the samples. The concept of “resolution-enhanced” KMD analysis using the mass of the repeating unit divided by an integer as the new fractional base unit has been recently introduced for the computation of expanded plots from polymeric mass spectral data with a dramatically improved separation of ion series. This user-friendly data processing is extended to the case of carbonaceous samples for the first time with the analysis of water-insoluble organic microspheres recovered from the hydrothermal extraction of wood and coals. In a didactic discussion with illustrative examples, the direct resolution-enhanced KMD analysis, the consecutive resolution-enhanced analysis of a part of a regular KMD plot or the systematic slicing of plots in a multistep procedure are shown to produce simple resolution-enhanced KMD plots or resolution-enhanced zooming from complex mass spectra. The combination of these techniques in a unique “advanced KMD analysis” toolkit is expected to revolutionize the data processing of high-resolution mass spectra with unprecedented separating and unraveling capabilities.

Base-catalyzed, C-alkylation of potassium (K) enolates with styrenes (CAKES) has recently emerged as a highly practical and convenient method for elaboration or synthesis of pharmaceutically-relevant cores. K enolate-type precursors such as alkyl-substituted heterocycles (pyridines, pyrazines and thiophenes), ketones, imines, nitriles and amides undergo C-alkylation reactions with styrene in the presence of KOtBu or KHMDS. Surprisingly, no studies have probed the reaction mechanism beyond the likely initial formation of a K enolate. Herein, a synergistic approach of computational (DFT), kinetic and deuterium labelling studies rationalizes various experimental observations and supports a metal-ene-type reaction for amide CAKES. Moreover, our approach explains experimental observations in other reported C-alkylation reactions of other enolate-type precursors, thus implicating a general mechanism for CAKES.

Rationale Direct analysis in real time mass spectrometry (DART-MS) provides qualitative information about additives and polymer composition. However, the observed mass spectra are dependent on sampling conditions, in particular the DART gas temperature. This report describes the combination of a heated sample stage with DART-MS for polymer characterization. Methods Industrial polymers with different compositions were examined by thermal desorption and pyrolysis (TDPy) DART. Samples were heated on disposable copper stages from ambient temperature to 600°C, and the evolved gases were introduced directly into a DART ion source through a glass tee. Time- and temperature-dependent mass spectra were acquired using a high-resolution time-of-flight mass spectrometer. Kendrick mass analysis was applied to the interpretation of complex mass spectra observed for fluorinated polymers. Results Positive-ion DART mass spectra of common polymers exhibited peak series differing by monomer masses, often accompanied by a peak corresponding to the protonated monomer. Even polymers that did not exhibit a clear series of peaks produced characteristic mass spectra. Positive-ion and negative-ion mass spectra were recorded for fluorinated polymers, with polytetrafluoroethylene (PTFE) producing only negative ions. Thermal desorption provided characteristic temperature profiles for volatile species such as polymer additives and polymer pyrolysis products. Conclusions In comparison with direct analysis by positioning sample directly in the heated DART gas stream, TDPy DART provides a more versatile sampling method and provides thermal separation and profiling of polymer additives, intact short polymer chains, and pyrolysis fragments.

RATIONALE Matrix-assisted laser desorption/ionization mass spectrometric imaging (MSI) is considered to be a powerful tool for visualizing the spatial distribution of synthetic polymers. However, a conventional method extracting an image of a specific m/z value is not suitable for polymers, which have a mass distribution. It is necessary to develop the visualization method to show the spatial distribution of entire polymer series. METHODS The mass peaks included in polymer series were specified from the average mass spectrum of the entire MSI measurement region by using Kendrick mass defect analysis. The images of those mass peaks were extracted and the number average molecular weight (Mn ), the weight average molecular weight (Mw ) and dispersity (Đ) were calculated for each pixel. Finally, the spatial distribution of the polymer series was summarized to images using Mn , Mw and Đ as indices. RESULTS The effects of the methods were investigated by (i) polymers with different mass distributions and (ii) polymers with different repeat units and end-groups. In both cases, the spatial distribution of specific polymer series including several dozens to hundreds of mass peaks was summarized into three images related to Mn , Mw and Đ, which are familiar indices in polymer analysis. The results are able to provide an overview of the spatial variation of each polymer more intuitively. CONCLUSIONS The visualization of Mn , Mw and Đ will help provide an overview of the spatial distribution of polymer series combined with ion intensity distribution made by conventional methods. It can be also applied to other mass spectrometric imaging methods such as desorption electrospray ionization (DESI) or time-of-flight secondary ion mass spectrometry (TOF-SIMS).

RATIONALE Electrospray ionization (ESI) favors the multiple charging of high molecular weight polymer samples and allows their high-resolution mass analysis in the low-mass range. It also induces the detection of numerous ion series at different charge states with different adducts complicating the interpretation of the mass spectrum which should be facilitated by an appropriate data processing. METHODS An arsenal of tools based on the Kendrick mass defect (KMD) is proposed to process congested ESI high-resolution mass spectra of poly(propylene oxide) (PPO) samples. The combination of regular, charge-dependent, and resolution-enhanced KMD plots in addition to a "remainders" plot and a new three-dimensional plot offers unrivaled capabilities of filtering for any minor series among thousands of points. The sequential data processing is conducted using Kendo, a spreadsheet developed in-house for an advanced KMD analysis. RESULTS The charge-state distribution is easily evaluated by counting the parallel lines in a regular KMD plot. A charge-dependent resolution-enhanced KMD plot instantly reveals the variation of adducted ions at a given charge state, helping the user to choose the best analytical conditions. Ion series at different charge states from PPO oligomers carrying different end-groups are also efficiently extracted using several combinations of KMD and remainders plots and assigned using a new simulator tool. CONCLUSIONS The innovative combination of existing and new KMD-related plots, selection tools, and simulator all combined in a single spreadsheet dramatically facilitates the processing and interpretation of complex ESI mass spectral data. The presented tools may be extended to any other class of homo-, co- and terpolymers.

The analysis of additives and polymers was performed by desorption ionization using through-hole alumina membrane (DIUTHAME) as a functional substrate for both sample pretreatment and surface-assisted laser desorption/ionization (SALDI) mass spectrometry. Using the unique absorbing/filtering capabilities of DIUTHAME and investigating the solubility of analytes/bulk materials in some solvents, three pretreatment techniques were demonstrated with (1) the selective removal of hydrophilic poly(ethylene oxide) (PEO)-based components from a "PEO-monostearate" sample, (2) the on-chip filtration of solubilized decabromodiphenylether (DBDE) from a solution of polystyrene that had been preliminarily precipitated, and (3) the on-chip extraction of antioxidants (Irganox 1010, Irgafos 168, and dimyristyl 3,3'-thiodipropionate) from a suspension of polypropylene powder or from the powder itself. The extracted analytes were further mass-analyzed using a spiral high-resolution time-of-flight analyzer to assess their elemental composition or molecular distribution.

Resolution-enhanced Kendrick Mass Defect (KMD) analysis using the new concept of fractional base units (repeating unit R divided by integer X; R/ X as a mathematical moiety) is now a powerful data-processing tool to unravel complex mass spectra of polymers. It enhances regular KMD analysis using the chemical moiety, R, to compute mass defects with unprecedented separation of ion series differing by their isotopic or comonomeric contents, end-groups, or charge states in highly visual KMD plots. The value of the divisor, X, dictates the gain of separating power from the regular to the resolution-enhanced KMD plot, and its choice strongly affects the ease and speed of data interpretation. A simple tool to help select the best values of X depending on the users' needs is mandatory to rationalize the analysis and avoid a time-consuming trial-and-error methodology. We propose two graphical representations intuitively ranking the well-suited divisors for the appropriate separation of isotopes or co-oligomers for copolymeric mass-spectral data. Rankings are extended to any type of data set from homopolymeric blends to terpolymers by generalizing the formulas with three variables beyond the specific separation of isotopes. The RANK functions are now available in commercial or homemade spreadsheets (available upon request) to interactively select divisors and compute the associated KMD plots.

Coal organic microspheres (COM), a novel material originated from the organic components of coal, were obtained from brown coal directly using a one-step treatment in a flow of water. Here, we studied in detail the effect of hydrothermal conditions on morphology, yield, elemental composition, functional groups, and molecular composition of COM, at temperatures of 250, 300, 350, and 380 °C, pressures of 4, 10, 20, and 24 MPa, and holding times of 0, 30, 60, and 90 min. The holding time influences COM production: longer holding time leads to higher yields and larger particle size. The hydrothermal temperature and pressure, which control the properties of water, have a significant influence on the yield, shape, and particle size of COM. The properties of water affect the COM yields as follows: 1) when the phase of water is liquid, the lower density, viscosity, and static dielectric constant gives higher yields; 2) the yield obtained in supercritical water is higher than that in subcritical water; 3) phase transformation of water from liquid to gas decreases the yield. Additionally, the particle size of COM can be controlled by the temperature, and the pressure affects the shape of COM greatly; even nano-sized particles are produced at 350 °C and 10 MPa. From the molecular composition results, low-molecular weight compounds with small double bond equivalents decompose under supercritical water condition. Large amounts of organic compounds in brown coal are thermally decomposed and extracted under hydrothermal conditions, and then spherical COM particles form and grow from small to big during the cooling process. These results are helpful for clarifying the formation mechanism of COM, and enable control of COM yield and properties.

Matrix-assisted laser desorption ionization high-resolution time-of-flight mass spectrometry (MALDI HR TOF MS) is a powerful tool for the molecular characterization of industrial polymers. However, accurate mass determination and resolution of isobaric ions are possible for oligomer samples only typically below m/z 3000. To cut long polymer chains into oligomers suitable for high-resolution mass spectrometry, we propose a simple “on-plate” alkaline degradation of polyesters as a sample pretreatment technique prior to the MALDI TOF MS measurement. This pretreatment can be performed on a MALDI target using a small amount of sample (μg or less) and 1 μL of alkaline reagent by simple pipetting. Informative mass spectra in the oligomeric mass range are successfully recorded but complicated by the variation of end-groups and the copolymeric composition of the degradation products. Data processing is assisted by a series of advanced Kendrick mass defect (KMD) analyses recently proposed by the authors to plot visually understandable two-dimensional maps. On-plate degradation pretreatment, high-resolution MALDI TOF MS measurements, and advanced KMD analyses are innovatively combined for the compositional characterization of bacterial poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) and industrial poly(ethylene terephthalate) samples. Graphical Abstractᅟ Electronic supplementary material The online version of this article (10.1007/s13361-018-2092-x) contains supplementary material, which is available to authorized users.

A new approach to determining the repeat unit compositions of homopolymers is reported in which a mass defect graph is rotated to zero slope to give a graph identical to a Kendrick mass defect graph. Because the Kendrick mass defect (KMD) is directly related to the elemental composition of the base unit, the process can be reversed. A mass defect graph (fractional m/ z plotted against exact m/ z) of a homopolymer can be rotated until the slope of the data points is zero. This is equivalent to finding a new constant factor by which the measured exact masses would have to be multiplied to create a Kendrick mass defect graph with zero slope. The elemental composition of the repeat unit can be determined by matching the new factor against the calculated factors for candidate compositions. This approach provides some benefits over simply looking for pairs of peaks corresponding to oligomer units. The primary benefit is to assist in visualization of the data. Rotating the data points corresponding to polymer masses to zero slope makes it easier to visualize the polymer data, and it facilitates the graphical isolation of polymer masses from background interferences. The repeat unit composition is determined not from a single pair of peaks but from multiple data points, and systematic errors in mass assignment can be visualized as deviations from linearity. Resolution-enhanced KMD graphs can be constructed for the calculated repeat unit composition by using fractional base units.

A modified Kendrick Mass Defect (KMD) analysis was applied to the analysis of polycyclic aromatic hydrocarbons (PAHs) and fullerenes in the diffusion flame from a handheld butane torch. Graphical Abstract ᅟ.

The Kendrick mass defect (KMD) analysis of multiply charged polymeric distributions has recently revealed a surprising isotopic split in their KMD plots-namely a 1/z difference between KMDs of isotopes of an oligomer at charge state z. Relying on the KMD analysis of actual and simulated distributions of poly(ethylene oxide) (PEO), the isotopic split is mathematically accounted for and found to go with an isotopic misalignment in certain cases. It is demonstrated that the divisibility (resp. indivisibility) of the nominal mass of the repeating unit (R) by z is the condition for homolog ions to line up horizontally (resp. misaligned obliquely) in a KMD plot. Computing KMDs using a fractional base unit R/z eventually corrects the misalignments for the associated charge state while using the least common multiple of all the charge states as the divisor realigns all the points at once. The isotopic split itself can be removed by using either a new charge-dependent KMD plot compatible with any fractional base unit or the remainders of KM (RKM) recently developed for low-resolution data all found to be linked in a unified theory. These original applications of the fractional base units and the RKM plots are of importance theoretically to satisfy the basics of a mass defect analysis and practically for a correct data handling of single stage and tandem mass spectra of multiply charged homo- and copolymers. Graphical Abstract ᅟ.

Its recent adaptation to low-resolution mass spectra of polymers using fractional base units raises the question of the minimal resolution needed for a Kendrick mass defect (KMD) analysis. Intuiting an oligomeric resolution since the mass of a repeat unit is the sole value to be known, it is challenged by the relative failure of the KMD plots computed from an isotopically resolved matrix-assisted laser desorption ionization-time-of-flight (MALDI-TOF) mass spectrum to display clear alignments in the high mass range. Another procedure based on the remainders of Kendrick mass (RKMs) overcomes this pitfall with oligomers perfectly aligned in a new RKM plot. Despite a concomitant degradation of the resolving power and accuracy, with the example of MALDI-TOF/TOF mass spectra of a variety of homo- and copolymer ions, the RKM procedure still allows a rapid enumeration, assignment, and any further manipulation of all the product ion series in visual RKM plots. Successfully extended to the critical case of a MALDI mass spectrum recorded with a linear TOF analyzer allowing a bare oligomeric resolution, the RKM plot turns the distributions differing by their end-groups or adducted ion into clear horizontal lines. It eventually gives intuition its due by answering the original question: the minimal resolution required for a mass defect analysis can be as low as oligomeric with the appropriate formulas.

Paper spray ionization coupled with a high-resolution time-of-flight mass spectrometer was applied to the analysis of 13 block and 2 random ethylene oxide/propylene oxide (EO/PO) copolymers as well as to standard samples of poly(ethylene oxide) and poly(propylene oxide) homopolymers. Paper spray mass spectra could be obtained rapidly and, unlike electrospray ionization, were not subject to contamination and sample carryover. For comparison, polyether samples were also measured on a MALDI/TOF system with ultrahigh mass resolving power. MALDI/high-resolution time-of-flight mass spectrometry exhibited single-charge ions characteristic of the polymer distributions whereas the paper spray mass spectra exhibited charge states ranging from one to six charges. Kendrick mass defect plots of the multiple-charge ions in the paper spray mass spectra exhibit isotopic splitting of the Kendrick mass defects, facilitating visualization of the number of charges in each series. The slope of the KMD plots can be used to estimate the percentage of ethylene oxide in the copolymers. In-source fragmentation permitted the distinction between block and random copolymers.

New biobased plasticizers made of di-functional glycidyl ether epoxy cardanol (ECard) were investigated to improve the ductility of renewable poly(lactide) (PLA). Compatibility between PLA and ECard was achieved out through in situ reactive grafting strategy catalyzed with Ethyltriphenyl phosphonium bromide (ETPB) using twin-screw extruder. In absence of catalyst, ECard forms domain ill-dispersed in the PLA matrix due to the high incompatibility between both phases. When ETPB is added as catalyst domain size distribution of the plasticizer decreased, indicating an enhanced compatibility due to the reactive grafting of a fraction of ECard plasticizer onto PLA backbone. Although all plasticized PLA specimens exhibit lower glass transition temperature, lower elastic/tensile modulus, lower yield stress, and higher strain at break, the reactive blend containing the lowest amount of catalyst, that is, 0.02 phr, exhibited the highest ductility behavior. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers

Beyond the high resolution/low mass range data traditionally used, a Kendrick mass defect analysis (KMD) using the new concept of fractional base units has been successfully conducted on low resolution/low mass range and high resolution/high mass range data for the first time. Relying on a mathematical framework to rationalize the effect of the fractional base units, the electrospray ionization single stage and multistage mass spectra of a poly(vinylpyrrolidone) recorded from a low resolution ion trap analyzer were turned into information-rich KMD plots using vinylpyrrolidone/112 and pyrrolidone/86 as base units. The distributions detected in the matrix assisted laser desorption ionization spiralTOF mass spectra of high molecular weight poly(ethylene oxide) and poly(caprolactone) were conveniently discriminated in KMD plots using (ethylene oxide)/45 and caprolactone/113 as base units with an unprecedented resolution at such a mass range. The high resolution KMD analysis using fractional base units opens new perspectives for the acquisition, visualization, and presentation of mass spectra of polymers with less restrictions in terms of required resolution and molecular weights.

Glycoside hydrolase family 30 subfamily 7 (GH30-7) enzymes include various types of xylanases, such as glucuronoxylanase, endoxylanase, xylobiohydrolase, and reducing-end xylose-releasing exoxylanase. Here, we characterized the mode of action and gene expression of the GH30-7 endoxylanase from the cellulolytic fungus Talaromyces cellulolyticus (TcXyn30C). TcXyn30C has a modular structure consisting of a GH30-7 catalytic domain and a C-terminal cellulose binding module 1, whose cellulose-binding ability has been confirmed. Sequence alignment of GH30-7 xylanases exhibited that TcXyn30C has a conserved Phe residue at the position corresponding to a conserved Arg residue in GH30-7 glucuronoxylanases, which is required for the recognition of the 4-O-methyl-α-d-glucuronic acid (MeGlcA) substituent. TcXyn30C degraded both glucuronoxylan and arabinoxylan with similar kinetic constants and mainly produced linear xylooligosaccharides (XOSs) with 2 to 3 degrees of polymerization, in an endo manner. Notably, the hydrolysis of glucuronoxylan caused an accumulation of 2(2)-(MeGlcA)-xylobiose (U(4m2)X). The production of this acidic XOS is likely to proceed via multistep reactions by putative glucuronoxylanase activity that produces 2(2)-(MeGlcA)-XOSs (X(n)U(4m2)X, n ≥ 0) in the initial stages of the hydrolysis and by specific release of U(4m2)X from a mixture containing X(n)U(4m2)X. Our results suggest that the unique endoxylanase activity of TcXyn30C may be applicable to the production of linear and acidic XOSs. The gene xyn30C was located adjacent to the putative GH62 arabinofuranosidase gene (abf62C) in the T. cellulolyticus genome. The expression of both genes was induced by cellulose. The results suggest that TcXyn30C may be involved in xylan removal in the hydrolysis of lignocellulose by the T. cellulolyticus cellulolytic system. IMPORTANCE Xylooligosaccharides (XOSs), which are composed of xylose units with a β-1,4 linkage, have recently gained interest as prebiotics in the food and feed industry. Apart from linear XOSs, branched XOSs decorated with a substituent such as methyl glucuronic acid and arabinose also have potential applications. Endoxylanase is a promising tool in producing XOSs from xylan. The structural variety of XOSs generated depends on the substrate specificity of the enzyme as well as the distribution of the substituents in xylan. Thus, the exploration of endoxylanases with novel specificities is expected to be useful in the provision of a series of XOSs. In this study, the endoxylanase TcXyn30C from Talaromyces cellulolyticus was characterized as a unique glycoside hydrolase belonging to the family GH30-7, which specifically releases 2(2)-(4-O-methyl-α-d-glucuronosyl)-xylobiose from hardwood xylan. This study provides new insights into the production of linear and branched XOSs by GH30-7 endoxylanase.

RATIONALE Molecular characterization of industrial oligomeric products is performed using surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS), termed desorption ionization using a through-hole alumina membrane (DIUTHAME). This paper describes the unique feature of a DIUTHAME chip applying active SALDI, which generates specific types of fragments of polyglycol samples. METHODS Polyethylene oxide (PEO) and PEO-based materials were subjected to SALDI-MS. The influence of the presence or absence of a cationization salt on the mass spectrum was investigated. The resulting mass spectra composed of fragment ions were compared with those obtained by collision-induced dissociation (CID)-MS/MS. The specific fragment ions generated using the DIUTHAME chip were further subjected to high-energy CID-MS/MS. RESULTS The addition of a cationization salt resulted in SALDI mass spectra with fewer fragment peaks. The mass spectra obtained without adding the cationization salt were composed of many more fragment ions caused by in-source decay. The fragmentation pattern was similar to that seen with low-energy CID. The resulting fragment ions were formed by selective cleavage at the C-O bond. High-energy CID-MS/MS can be performed for the specific fragment ions generated by in-source decay fragmentation. CONCLUSIONS Molecular characterization of PEO-based oligomers by SALDI-MS using the DIUTHAME chip was successfully demonstrated. The selective fragmentation and high-energy CID-MS/MS of the in-source decay fragments made it possible to provide more detailed structural information. This unique feature of DIUTHAME gives it potential for use in new molecular characterization techniques.

Elemental compositions are commonly determined from the exact m/z of the monoisotopic peak, which is often the lightest isotope. However, the lightest isotope peak is often weak or absent and the monoisotopic peak can be difficult to identify for organometallics, polyhalogenated compounds, or large molecules. An alternative approach using the abundant isotope for elemental composition determinations is presented here.

A novel biobased plasticizer made of cardanol is designed for poly(lactide) (PLA). This cardanol-derived plasticizer, i.e., methoxylated hydroxyethyl cardanol (MeCard), is synthesized through methoxylation of the double bonds on the side chain of cardanol, and characterized by 1H NMR and mass spectrometry. The plasticization effect of MeCard on the molecular structure, morphology, thermal and mechanical properties of PLA is evaluated and compared to that of a commercial cardanol, i.e., hydroxyethyl cardanol (pCard). The plasticization efficiency of MeCard is demonstrated by a substantial decrease of the glass transition temperature and storage modulus together with a significant increase of the elongation at break as compared to neat PLA. Moreover, MeCard exhibits higher plasticization performance than pCard toward PLA. Such behavior is related to a higher miscibility and compatibility between PLA and MeCard thanks to the methoxylation of the double bonds on the side chain of cardanol as shown by SEM micrographs.

Highlighting an actual plasma copolymerization remains difficult when using infrared or x-ray photoelectron spectroscopies as they provide no evidence of the formation of covalent bonds between the precursors. The combination of high resolution mass spectrometry and mass defect analysis is proposed to characterize plasma (co)polymers of alkyl and perfluorinated acrylates. The mass spectra of the coatings are readily turned into Kendrick mass defect plots unambiguously demonstrating the occurrence of plasma co-oligomers, as suspected from their thermal behavior. Requiring a proper calibration only, the mass defect analysis elegantly transforms an abstruse mass spectrum of plasma polymer in simple point series and constitutes a user-friendly method for data mining.

Rationale Poly(ethylene-co-vinyl acetate) copolymers – usually referred to as EVA – are first class industrial polymers used for applications ranging from padding to photovoltaics as encapsulant for the silicon solar cells. Various techniques have been used for their characterization but the analysis of intact EVA chains using mass spectrometry (MS) has not been reported so far. Methods Three copolymers containing 18, 25 and 40 wt% vinyl acetate (VA) have been characterized using an off-line coupling of size-exclusion chromatography (SEC) and matrix-assisted laser desorption/ionization (MALDI) spiral-time-of-flight (TOF) high-resolution mass spectrometry (HRMS). The representativeness of those results for the entire samples has been checked using 13C NMR spectroscopy. Lastly, Kendrick mass defect analysis has been proposed as an alternative and user-friendly data treatment method. Results The shortest chains isolated by SEC fractionation and mass-analyzed by HRMS have been thoroughly described in terms of end-groups (found to be hydrogens) and co-monomeric composition. The VA content was successfully derived from the peak assignments in MS spectra for the EVA 40 wt% and 25 wt% while it tended to be overestimated for the latest EVA 18 wt% (increasing poly(ethylene) character). Similar results have been found using a faster data treatment method relying on the Kendrick mass defect analysis of the MS data. Conclusions EVA low molecular weight intact oligomers have been extensively characterized by MS for the first time and the structural features confidently extended to the full sample according to NMR data. The Kendrick mass analysis finally constituted an efficient method for a fast evaluation of their VA content with no need for manual assignment. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd.

International audience; This article reports the use of pulsed remote Ar-O 2 microwave plasma assisted chemical vapor deposition with an −NH 2 containing organosilicon precursor ((3-Aminopropyl)triethoxysilane: APTES). It is shown that modifying the plasma pulses duration (t on) and the plasma off duration (t off) allows to finely tune the deposited layer composition. In addition, the results of this work demonstrate that an important film growth occurs during t off , which results in an increased −NH 2 density. Besides, high resolution MALDI-ORBITRAP Mass spectrometry analysis clearly points out that APTES oligomers up to eight base units, including silsesquioxanes (cages), and cyclosi-loxanes (rings) molecules with intact −NH 2 groups are embedded into the as grown pp-APTES thin film. K E Y W O R D S microwave discharges, plasma-enhanced chemical vapour deposition (PECVD), plasma polymerization, pulsed discharges, remote plasma processes

Direct coal liquefaction residue (DCLR) is the main byproduct during the direct coal liquefaction process. The efficient recovery of organic components from DCLR at low temperatures is beneficial for improving the economy and reducing energy consumption and environmental pollution. Here, DCLR was extracted using liquefied dimethyl ether (DME), acetone, and hexane as the solvents. Compared with the other two solvent Soxhlet extraction, the DME extraction process was performed at room temperature with the shortest extraction time, the lowest energy consumption, and the highest extraction yield (16.2%). Owing to the high carbon contents, low sulfur and oxygen contents, and low ash contents (, ファイル公開：2022-02-15

The Kendrick analysis is used for the processing and visualization of mass spectra obtained from polymers containing C, H, O and/or Si with simple isotopic patterns (monoisotope=lightest isotope=most intense isotope for short chains). In the case of heteroatoms with complex isotopic patterns, the impact of the chosen isotope on point alignments in Kendrick plots has not been examined extensively. Rich isotopic patterns also make the evaluation of the mass and nature of the repeating unit and end-groups more difficult from the mass spectrum in the case of unknown samples due to the number of peaks and the absence of a monoisotopic peak. Using a polybrominated polycarbonate as running example, we report that horizontal point alignments can be obtained in a Kendrick plot using the mass of the most abundant isotope instead of the monoisotopic mass as is usually done. Rotating the plot (“reverse Kendrick analysis”) helps to accurately evaluate the mass of the most abundant isotope of the repeating unit, as well as the nature of the brominated neutral expelled upon gentle heating (debromination or dehydrobromination). The whole procedure is then applied to the characterization of an unknown polybrominated flame retardant in an industrial formulation before and after heating.

Glucuronoxylanases are endo-xylanases and members of the glycoside hydrolase family 30 subfamilies 7 (GH30-7) and 8 (GH30-8). Unlike for the well-studied GH30-8 enzymes, the structural and functional characteristics of GH30-7 enzymes remain poorly understood. Here, we report the catalytic properties and three-dimensional structure of GH30-7 xylanase B (Xyn30B) identified from the cellulolytic fungus Talaromyces cellulolyticus. Xyn30B efficiently degraded glucuronoxylan to acidic xylooligosaccharides (XOSs), including an α-1,2-linked 4-O-methyl-d-glucuronosyl substituent (MeGlcA). Rapid analysis with negative-mode electrospray-ionization multistage MS (ESI(−)-MS(n)) revealed that the structures of the acidic XOS products are the same as those of the hydrolysates (MeGlcA(2)Xyl(n), n > 2) obtained with typical glucuronoxylanases. Acidic XOS products were further degraded by Xyn30B, releasing first xylobiose and then xylotetraose and xylohexaose as transglycosylation products. This hydrolase reaction was unique to Xyn30B, and the substrate was cleaved at the xylobiose unit from its nonreducing end, indicating that Xyn30B is a bifunctional enzyme possessing both endo-glucuronoxylanase and exo-xylobiohydrolase activities. The crystal structure of Xyn30B was determined as the first structure of a GH30-7 xylanase at 2.25 Å resolution, revealing that Xyn30B is composed of a pseudo-(α/β)(8)-catalytic domain, lacking an α6 helix, and a small β-rich domain. This structure and site-directed mutagenesis clarified that Arg(46), conserved in GH30-7 glucuronoxylanases, is a critical residue for MeGlcA appendage–dependent xylan degradation. The structural comparison between Xyn30B and the GH30-8 enzymes suggests that Asn(93) in the β2–α2 loop is involved in xylobiohydrolase activity. In summary, our findings indicate that Xyn30B is a bifunctional endo- and exo-xylanase.

Protective coatings from diethylphosphatoethyltriethoxysilane (DEPETS) have been deposited on different polymer substrates in a plasma discharge operated at atmospheric pressure. Plasma polymer chemistry and structure were characterized by means of Fourier transform infrared spectroscopy (FTIR), laser desorption ionization-mass spectrometry (LDI-MS), nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). A chemical structure of the plasma polymer has been proposed based on the coating molecular characterization. Coatings were deposited on polycarbonate (PC) and polyamide 6 (PA6) substrates. The flame retardant properties of coated substrate samples were assessed using cone calorimetry and compared to those of bare substrates. A significant increase in the time to ignition (TTI), up to +143%, was recorded after coating deposition due to the formation of a high-performance barrier layer at the surface of both polymer substrates.