Evaluation of comprehensive on-line liquid chromatography thermally assisted hydrolysis and methylation-gas chromatography-mass spectrometry for characterization of sulfonated lignins.

Sulfonated lignins, used as dispersants in agrochemical formulations, have been characterized by hyphenation of ion-pair RPLC and thermally assisted hydrolysis and methylation-GC-MC (THM-GC-MS). The chemical structure of a series of selected lignins was evaluated, both in terms of overall composition and in terms of composition as a function of molecular size. Some sulfonated lignins give rise to unstable formulations. In the compositional analysis, these samples were found to yield additional fragments. A newly developed comprehensive method made it possible to monitor the occurrence of these fragments as a function of molecular size. In addition to differences in the molecular size between "good" and "bad" batches, clear differences in chemical composition were established.

Comprehensive two-dimensional liquid chromatography: ion chromatography × reversed-phase liquid chromatography for separation of low-molar-mass organic acids.

In the work presented here a novel approach to comprehensive two-dimensional liquid chromatography is evaluated. Ion chromatography is chosen for the first-dimension separation and reversed-phase liquid chromatography is chosen for the second-dimension separation mode. The coupling of these modes is made possible by neutralising the first-dimension effluent, containing KOH, prior to transfer to the second-dimension reversed-phase column. A test mixture of 24 low-molar-mass organic acids is used for optimisation of the system. Three food and beverage samples were analysed in order to evaluate the developed methodology, the resulting two-dimensional separation is near-orthogonal, the set-up is simple and all instrumental components are available commercially. The method proved to be robust and suitable for the analysis of wine, orange juice and yogurt.

Analytical methodology for sulfonated lignins.

There is a significant need to characterize and classify lignins and sulfonated lignins. Lignins have so far received a good deal of attention, whereas this is not true for sulfonated lignins. There is a clear demand for a better understanding of sulfonated lignins on a chemical as well as physical level. Many of the analytical methods have been developed with different goals in mind, for example, detection of sulfonated lignins in pulp-mill effluents, elucidation of structural changes in lignosulfonates during a pulping process, or identification of properties that may affect a formulation when sulfonated lignins are used as a dispersant. When sulfonated lignins are used in industrial applications, analytical data obtained using different techniques may be necessary to enable prediction of their behavior in the target application. In the present review, a critical discussion of established and promising analytical techniques for the characterization of sulfonated lignins is presented.

Fully automated system for the gas chromatographic characterization of polar biopolymers based on thermally assisted hydrolysis and methylation.

Pyrolysis-gas chromatography (Py-GC) is a powerful tool for the detailed compositional analysis of polymers. A major problem of Py-GC is that polar (bio)polymers yield polar pyrolyzates which are not easily accessible to further GC characterization. In the present work, a newly developed fully automated procedure for thermally assisted hydrolysis and methylation (THM) of biopolymers is described. Drying of the sample, addition of the reagent, incubation and pyrolysis are performed inside the liner of a programmable temperature vaporizer injector. The new system not only allows efficient analysis of large series of samples, but also allows automated optimization of the experimental parameters based on an experimental design approach. The performance of the automated THM-procedure was evaluated by performing THM-GC of a poly(acrylic acid)-poly(maleic anhydride) copolymer (PAA/PMAH) and several polysaccharides. The optimized THM-procedure was applied for the structural characterization and differentiation of several lignins and hydroxypropylmethyl-celluloses. It was also applied to proteins. Here myoglobin and cytochrome c were used as the model compounds. Both conventional GC-mass spectrometry (MS) and comprehensive two-dimensional gas chromatography (GCxGC)-time-of-flight (TOF) MS were used for separation and identification of the species formed. The information obtained can aid in structure elucidation of polar biopolymers as well as in providing detailed compositional information which can be used to differentiate structurally similar biopolymers.

One-dimensional and two-dimensional liquid chromatography of sulphonated lignins.

One- and two-dimensional separation methods have been developed for the analysis of lignosulphonates and sulphonated kraft lignins. The evaluated sulphonated lignins are all used as dispersants in agrochemical formulations, where some give rise to physical instabilities of formulations. It is of interest to identify the properties of the sulphonated lignins that determine the formulation characteristics. Tetrapentylammonium bromide has been used as an ion-pair reagent in a gradient-elution reversed-phase liquid-chromatographic (IP-RPLC) method, as well as in aqueous size-exclusion chromatography (SEC). Clear differences in the size distribution were observed between different batches of sulphonated lignins. The RPLC and SEC methods were combined in a comprehensive two-dimensional liquid chromatography system. The retention times in the two dimensions were highly correlated. Therefore, the full potential of comprehensive two-dimensional liquid chromatography was not yet realized. However, the results did reveal that retention in IP-RPLC was not determined by the degree of sulphonation of similar-size molecules. Rather, molecules were separated according to size and the degree of sulphonation appears to be approximately constant. The information obtained in this study represents a significant step towards meaningful correlations between the requirements of surfactants within an agrochemical formulation and structural parameters, such as the size and the degree of sulphonation of lignin oligomers.

Supercritical fluid extraction (SFE) for determination of metalworking fluid aerosols.

A common methodology for analyzing metalworking fluid (MWF) aerosols in workplace air is based on gravimetry before and after organic solvent extraction of the MWFs from a suitable collection filter. Because MWFs have different chemical and physical properties, various mixtures of organic solvents have been used to extract the MWFs from their collection device. An alternative to organic solvents, used in the work presented in this article, is the use of a supercritical fluid. The efficiency of supercritical fluid extraction (SFE) was investigated by weighing conditioned filters before and after extraction of samples spiked with MWFs at different concentrations using the American Society for Testing and Materials method. For three common straight oil MWFs spiked on filters, supercritical carbon dioxide gave recoveries of 92-101% with a low standard deviation (0.2-1.9%). For semisynthetic MWFs, carbon dioxide had to be mixed with methanol to obtain recoveries above 80%. With the optimized method using 7% methanol in carbon dioxide, the 10 investigated MWFs could be extracted in 30 min with a recovery of 90-98%. The amount of MWFs spiked on the filters varied between 0.10-1.65 mg. In Sweden, the limit value for MWFs is 1 mg/m3. Thus, our spike level is in the range of 10-200% of the limit value if sampling for 8 hours with 2 L/min. The use of SFE methodology results in small volume extracts (3 mL) with concentrations at such high levels that analysis of chemical components in the MWF can be carried out without further volume reduction.