Jaap J. Boon

High resolution end group determination of low molecular weight polymers by matrix-assisted laser desorption ionization on an external ion source fourier transform ion cyclotron resonance mass spectrometer

Matrix-assisted laser desorption ionization was performed on an external ion source Fourier transform ion cyclotron resonance mass spectrometer equipped with a 7-T superconducting magnet to analyze end groups of synthetic polymers in the mass range from 500 to 5000 u. Native, perdeutero methylated, propylated, and acetylated polyethylene glycol and polyvinyl pyrrolidone with unknown end-group elemental composition were investigated in the mass range up to 5000 u by using a 2,5-dihydroxybenzoic acid matrix. A small electrospray setup was used for the deposition of the samples. Two methods to process data were evaluated for the determination of end groups from the measured masses of the component molecules in the molecular weight ranges: a regression method and an averaging method. The averaging method is demonstrated to allow end-group mass determinations with an accuracy within 3 mu for the molecular weight range from 500 to 1400 and within 20 mu for the molecular weight range from 3400 to 5000. This is sufficient to identify the elemental composition of end groups in unknown polymer samples.

Electron capture and collisionally activated dissociation mass spectrometry of doubly charged hyperbranched polyesteramides

Electron capture dissociation (ECD) of doubly protonated hyperbranched polyesteramide oligomers (1100–1900 Da) was examined and compared with the structural information obtained by low energy collisionally activated dissociation (CAD). Both the ester and amide bonds of the protonated species were cleaved easily upon ECD with the formation of odd electron (OE·+) or even electron (EE+) fragment ions. Several mechanistic schemes are proposed that describe the complex ECD fragmentation behavior of the multiply charged oligomers. In contrast to studies of biomolecules, the present results indicate that consecutive cleavages induced by intramolecular H-shifts are significant for ECD and of less importance for low energy CAD. The capture of an electron by the ionized species results in fragmentation associated with a redistribution of the excess internal energy over the products and the subsequent bond cleavage. Low energy, multiple collision CAD is found to be a more selective dissociation method than ECD in view of the observation that only amide bonds are cleaved for most of the hyperbranched polymers examined with CAD in this study. ECD appears not to provide complementary structural information compared to CAD in the study of hyperbranched polymers, even though a significantly more complex ECD fragmentation behavior is observed. ECD is shown to be of use for the structural characterization of large oligomers that may not dissociate upon low energy CAD. This is a direct result of the fact that ECD produces ionized hyperbranched oligomers with a relatively high internal energy.

Rapid microscale analyses with an external ion source Fourier transform ion cyclotron resonance mass spectrometer

Abstract The design of a multi-purpose external ion source Fourier transform ion cyclotron resonance mass spectrometer for rapid microscale analyses of complex mixtures is presented. Rapid microscale analyses are carried out using several desorption and ionisation techniques, and benefit from a hydrocarbon-free UHV (Ultra High Vacuum) system. Two different techniques for polymer analysis will be discussed. “In source” filament pyrolysis is used for high speed, broadband screening of additives in polymer blends, and matrix assisted laser desorption and ionisation (MALDI) is used for endgroup analysis and molecular weight determination. External ion source MALDI measurements of the molecular weight distribution of an amine terminated poly(propyleneglycol) are shown to be extremely sensitive to the ion accumulation time used, as a result of the flight time distribution of the ions from ion source to analyser cell. Deconvolution of the measured transient shows that magnetron motion exhibits a strong mass dependent influence on the measured molecular weight distribution. This deconvolution and 2D-representation of the measured and Fourier transformed data provides additional insight into the ion behaviour inside the ICR cell.

Preparation Methods and Accessories for the Infrared Spectroscopic Analysis of Multi-Layer Paint Films

Abstract Several traditional paint samples were prepared for infrared spectroscopic analysis in a number of different ways. The methods applied include the formation of KBr pellets, squeezing of dissected or multi-layer samples in a diamond cell, embedding in a modern resin, and a new method in which a paint cross-section is embedded in KBr and polished from both sides to obtain a thin layer. Microtoming of a paint cross-section embedded in a modern resin was not successful. The various samples were analysed by infrared spectroscopy to assess the usefulness of these sample preparation techniques in the field of paintings research. The amount of information that can be derived from the infrared spectra obtained appeared optimal for sample preparation methods that allow the application of transmission techniques. The results obtained for specular reflectance techniques were of lesser quality, while no diffuse reflectance spectra could be obtained. The results can best be traced to a specific layer or structure in an inhomogeneous paint system if the layer structure of the sample is left intact, i.e., using specular reflectance of an embedded cross-section or transmission of a thin section obtained by doubly polishing a cross-section embedded in KBr.

Endgroup determination of synthetic polymers by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Electrospray ionization (ESI) was performed on a Fourier transform ion cyclotron resonance mass spectrometer for the endgroup and monomer mass determination of three poly(oxyalkylene)s in the mass range of 400–8000 Da. A combined use of the multiple charge states observed with ESI, leads to a threefold increase in accuracy of the endgroup and monomer determination. The improvement is attributed to the increased number of datapoints used for the regression procedure, yielding more accurate results. Endgroup masses are determined with a mass error better than 5 and 75 millimass units for the molecular weight range of 400–4200 and 6200–8000 Da, respectively. A mass error of better than 1 millimass unit was observed for all monomer mass determinations. With ESI, endgroup and monomer masses have been determined for poly(ethylene glycol) oligomers with a mass higher than 8000 Da. This is almost two times higher than observed with matrix-assisted laser desorption/ ionization on the same instrument.

Structural characterization of hyperbranched polyesteramides: MSn and the origin of species

Four hyperbranched synthetic polyesteramides were synthesized by the polycondensation of the trifunctional diisopropanolamine (D) and difunctional anhydrides (X) of succinic acid, glutaric acid, 1,2-cyclohexane dicarboxylic acid, and phthalic acid. The polymers were analyzed with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The most intense oligomer series observed was XnDn+1 containing diisopropanolamine end groups as expected from the polycondensation conditions. A series of oligomers XnDn+1H2O is observed as well, which can have its origin in the polymerization process or alternatively could result from in-source fragmentation of XnDn+1. Breakdown diagrams of the protonated parent ions X3D4 and additional MSn (n = 1, 2, 3) measurements gave insight in the fragmentation behavior of the polymers. Three main fragmentation pathways have been observed for all polymers of which the loss of H2O to oxazolonium ions has the lowest onset energy followed by the rearrangement of the amide and ester bonds also leading to oxazolonium ions. The loss of a second H2O to allylic or morpholine end groups has highest onset energy. MS3 experiments demonstrated that the presence of a series of oligomers XnDn+1H2O can be attributed to the polymerization process. Most probably an allylic end group has formed from one of the alcohol end groups. The formation of allylic end groups partly terminates the polymerization reaction and results in a change of the composition of the molecular weight distribution and decrease of the number average molecular weight.

Immunological studies on microbial mats from Solar Lake (Sinai)— A contribution to the organic geochemistry of sediments

Immunological and biochemical techniques were used to investigate organic matter in microbial mats from Solar Lake (Sinai, Egypt). Antibodies, elicited in rabbits against samples taken at different depths from a core of these mats, were used for the detection of immunological determinants preserved in these samples. Special attention was given to an antiserum directed against a top mat fraction (3–10 mm depth) and an antiserum against a fraction from a lower section of the core (380–390 mm depth). Both antisera, tested in a dot-blot immunobinding assay, were found to give positive reactions with organic matter from different depths of the sediment. An immunohistochemical experiment with the antisera points to antigenic determinants on Recent and subfossil sheaths of Microcoleus. In addition, extracts of sediment samples were submitted to electrophoresis in polyacrylamide gels in order to characterize the separated macromolecules by immunological means. The results showed a rapid decrease in the number of antigenic determinants from Recent to subfossil samples. However, even in the deepest layers of the sediment (690–700 mm depth) intact biopolymers were detected.

FTIR Imaging Spectroscopy for Organic Surface Analysis of Embedded Paint Cross-Sections

A description of the microscopic analysis of an embedded paint cross section with a novel FTIR imaging technique will be provided. Sample preparation turns out to be crucial for the success of the method used and some of its practical aspects for organic surface analytical techniques will be discussed. FTIR imaging analysis carried out with this novel technique is successfully employed to determine the binding medium type in individual paint layers.