Rapid separation and analysis of six organic acids in Bayer liquors by RP-HPLC after solid-phase extraction

A rapid revised phase high-performance liquid chromatographic (RP-HPLC) method for the determination of six organic acids in Bayer liquors is reported. Oxalic, tartaric, acetic, succinic, glutaric and butene dicarboxylic acid were separated and quantified in 10 min. First time repeatability, reproducibility and recoveries were determined out for these acids in Bayer liquors. The organic acids were removed from Bayer liquor by using a solid-phase extraction procedure with anion-exchange cartridges. The chromatographic separation was achieved with only one Kromasil RP-C18 column thermo stated at 25 degrees C. Organic acids were detected with a UV-vis detector (215 nm). The precision results showed that the relative standard deviations of the repeatability and reproducibility were < 2.80% and < 3.74%, respectively. The accuracy of the method was confirmed with an average recovery ranging between 85.2 and 107.3%. Under optimum conditions the detection limits ranged from 50 to 1000 mg/L.     

Development of a fully buffered molybdate electrolyte for capillary electrophoresis with indirect detection and its use for analysis of anions in Bayer liquor

A new counterion-buffered molybdate electrolyte was developed and optimized for simultaneous quantitative determination of up to eight anions (chloride, sulphate, oxalate, fluoride, formate, malonate, succinate, and acetate) in Bayer liquor by capillary electrophoresis with indirect detection at 214 nm. The separation parameters were optimized in respect to separation of the critical analyte group fluoride-formate-malonate, with the optimal electrolyte prepared from molybdic trioxide containing 5.0 mmol/L MoO3, 1.3 mmol/L cetyltrimethylammonium bromide (CTAB), and buffered with diethanolamine (DEA) to pH 9.2 (ca. 20 mM DEA). Total length of separation capillary was 80 cm, resulting in run time of under 4 min. The method is suitable for a wide concentration range of the analytes (1-50 mg/L) with linear calibration plots (R2 = 0.9983-0.9999). Relative standard deviations were 0.05%-0.07% for migration times and 0.67%-2.04% for peak areas. The detection limits were in the range of 0.17-0.51 mg/L or 2-10 micromol/L (hydrostatic injection of 30 s of 1000 x diluted sample). Due to its good buffering capacity, the electrolyte exhibited an excellent ruggedness and good tolerance to the alkaline samples. Consequently, Bayer liquor samples could be diluted as little as 100 x which allows more sensitive determination of minor components over previous methods. The method was successfully applied to analysis of Bayer liquor samples with recoveries in the range of 95-105%.     

Emission of possible odourous low molecular weight compounds in recycled biofibre/polypropylene composites monitored by head-space SPME-GC–MS

A disadvantage of the use of natural fibres to reinforce polypropylene is their poor thermal stability, which results in their degradation at processing temperatures of the composites. As a result of this, there is a formation of low molecular weight compounds that are responsible for undesirable odours. Head-space-solid phase microextraction (HS-SPME) was used as a sample preparation technique and gas chromatography–mass spectrometry (GC–MS) was used to identify the low molecular weight compounds in natural polypropylene/polypropylene composites after simulating degradation. Among the compounds found in the samples, there are fragments of PP chains as heptadecane, compounds from antioxidants such as 2,4-bis(1,1-dimethylethyl)-phenol, and p-tert-butylphenol, and compounds from biofibres ageing, such as ethylparaben and vanillin. Numerous carboxylic acids were also identified, being these most probably the source of the undesirable odours.     

Analysis of anions in alkaline solutions by ion chromatography after solid-phase extraction

An Ion Chromatographic (IC) method for the determination of six organic acids and three inorganic anions in alkaline solutions was reported. Formic, acetic, propionic, oxalic, succinic, glutaric acid, F-, Cl-, and SO4(2-) were separated and determined in 33 min. The analytes were removed from Bayer liquor by using an ion-exchange resin column. The chromatographic separation was achieved with only one IonPac AS11-HC column thermostated at 30 degrees C. Organic acids and inorganic anions were detected with a suppressed conductance detector. The precision results' showed that the repeatability and reproducibility were < 2.94 and < 1.37%, respectively. The accuracy of the method was assessed by the recoveries ranging from 86.3 to 105.6%. Under optimum conditions the detection limits ranged from 0.008 to 0.053 mg/l.     

Studies of Cephalosporin C Purification by Ultrafitration

Cephalosporin C was produced with fermentation technique. There are many impurities (mycelium, protein et al) in its fermentation liquor, which can be removed by ultrafitration membrane separation. The ultrafiltration technique has been used for purifying the fermentation liquid of antibiotics^[1-2],however, its application in extraction of Cephalosporin C from its fermentation liquor has not been reported. In this paper, we use Ultra-flo ultraflitration membrane system (concludes UF-54 pilot plant, flat board membrane module, thin composite membrane of 30 thousand reject molecular weight) to purify #1-#3 fermentation liquors of Cephalosporin C, which were not pretreated except acidification(pH=3).     

Absolute Rate Constants in Free-Radical Polymerization. III. Determination of Propagation and Termination Rate Constants for Styrene and Methyl Methacrylate

A spatially intermittent polymerization (SIP) reactor has been used for determination of absolute rate constants in photo-initiated, free-radical polymerization of styrene (STY) and methyl methacrylate (MMA). Experimental data are reported in the temperature range 15-30°C and in the high molecular weight region for MMA and STY. Additional experimental data are reported at 30° C and various lower molecular weights for STY which indicate that the propagation rate constant K is independent of polymer molecular weight, and K is dependent on molecular weight, especially at low molecular weight, approaching an approximately constant value at high molecular weight.     

Rapid determination of methanol in black liquors by full evaporation headspace gas chromatography

This paper reported a full evaporation headspace gas chromatographic (GC) technique for determination of methanol content in black liquors (pulping spent liquor). In this method, a very small volume (10-20 microL) of liquor sample is introduced into a headspace sample vial (20 mL) and heated up to a temperature of 105 degrees C. A near-complete mass transfer of methanol from the liquid phase to vapor phase (headspace), i.e., a full evaporation, can be achieved within 3 min. The methanol in the headspace of the vial is then measured by GC. The present method is simple, rapid and accurate.     

Separation and determination of organic acids and inorganic anions in Bayer liquors by ion chromatography after solid-phase extraction

An ion chromatographic (IC) method for the determination of six organic acids and three inorganic anions in Bayer liquors was proposed. Formic, acetic, propionic, oxalic, succinic, glutaric acid, F⁻, Cl⁻, and SO ₄ ²⁻ were separated and determined within 33 min. For the first time, repeatability, reproducibility, and recoveries for the determination of these acids in Bayer liquors were estimated. The analytes were removed from a Bayer liquor by using an ion-exchange resin column. The chromatographic separation was achieved with only one IonPac AS11-HC column thermostated at 30°C. Organic acids and inorganic anions were detected with a suppressed conductance detector. The precision results showed that the relative standard deviations of the repeatability and reproducibility were <2.94 and <1.37%, respectively. The accuracy of the method was confirmed with an average recovery ranging between 86.3 and 105.6%. Under optimum conditions the detection limits ranged from 0.008 to 0.053 mg/L. The text was submitted by the authors in English.     

FAST ATOM BOMBARDMENT MASS SPECTROMETRY OF BILE ACIDS AND THEIR SUCCINYL DERIVATIVES

The new technique of fast atom bombardment mass spectrometry has.been applied to the investigation of some free bile acids and their succinyl derivatives using glycerol or thioglycbl as "matrix compatible solvent".The pseudomoiecular species are observed giving molecular weight information.In negative ion mass spectra the(M-1)-ion is the most intense ion which is the base peak for each of the samples.Additionally,dimer ions and adduct ions with species which are from the matrix are obtained with low intensity.The technique allows the determination of the mixture of bile acids and the pseudomoiecular species observed to give molecular weight information for the component.     

Analysis of low molecular weight organic acids in water with capillary zone electrophoresis employing indirect photometric detection

A capillary zone electrophoretic method for the analysis of low molecular weight carboxylic acids in water was developed. The application uses the chromophore trimellitic acid that allows for indirect photometric detection at 254 nm. Selectivity control by the addition of Ca2+ to the carrier electrolyte made possible a baseline resolved separation of 14 carboxylic acids. Good linearity and repeatability were obtained for both electrokinetic and hydrostatic injection modes. The usefulness of the method is demonstrated by the analysis of a snow sample.     

Unit resolution mass spectra of 112 kDa molecules with 3 Da accuracy

Previously, the highest molecular weight for a sample yielding a unit resolution mass spectrum was 67 kDa (marginal at 86 kDa), obtained with a 6. 2 T Fourier-transform mass spectrometer with electrospray ionization. Now with a 9. 4 T instrument, resolving power of 170,000 has been achieved for chondroitinase I (997 amino acids) and II (990 amino acids), making possible molecular weight assignments of 112,509 and 111,714, respectively, versus 112,508 and 111,713 calculated. Assisting these assignments was the noise reduction in the resolved isotopic peaks achieved by the time domain data sampling technique introduced by Senko, Marshall, and co-workers.     

The influence of PPV chain aggregated structure on optical properties

A comparison has been made on the fluorescence of the poly (p-phenylenevinylene) (PPV) that without filtering the low molecular weight molecules (sample A) with the PPV of the low molecular weight molecules filtered (sample B). Although there is no obvious difference found in the FT-IR and Raman spectra between two samples, in the photoluminescence spectrum of the sample A, the peak at 510 nm is not appeared and the fluorescence intensity for the peak at 550 nm is increased. Under the high pressure condition the fluorescence peak at 520 nm, which corresponds to the peak at 510 nm of the usual PPV, is observed. Applying high pressure to the sample A or by filtering the low molecular weight molecules, the chain aggregated structure is modified, resulting in a change in the PPV chain distortion degree.     

Matrix‐less laser desorption/ionisation mass spectrometry of polyphenols in red wine

Matrix‐assisted laser desorption/ionisation (MALDI) of small molecules is challenging and in most cases impossible due to interferences from matrix ions precluding analysis of molecules <300–500 Da. A common matrix such as ferulic acid belongs to an important class of compounds associated with antioxidant activity. If the shared phenolic structure is related to the propensity as an active MALDI matrix then it follows that direct laser desorption/ionisation should be possible for polyphenols. Indeed matrix‐less laser desorption/ionisation mass spectrometry is achieved whereby the analyte functions as a matrix and was used to monitor low molecular weight compounds in wine samples. Sensitivity ranging from 0.12–87 pmol/spot was achieved for eight phenolic acids (4‐coumaric, 4‐hydroxybenzoic, caffeic, ferulic, gallic, protocatechuic, syringic, vanillic) and 0.02 pmol/spot for trans‐resveratrol. Additionally, 4‐coumaric, 4‐hydroxybenzoic, caffeic, ferulic, gallic, syringic, vanillic acids and trans‐resveratrol were identified in wine samples using accurate mass measurements consistent with reported profiles based on liquid chromatography (LC)/MS. Minimal sample pre‐treatment make the technique potentially appropriate for fingerprinting, screening and quality control of wine samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Light scattering and size exclusion chromatography of semi-flexible polyimide precursors

Measurement of the molecular weight, radius, and molecular weight distribution of polyimide precursors (amic acids and easters) is quite difficult due to strong polymer–solvent interactions, electrostatic interactions, and the possibility of partial imidization in solution. The large quantities of solvent and high dilutions necessary in liquid chromatography make this technique the most sensitive to these effects. The distortions in the chromatogram from these effects can make assessment of the molecular weight distribution from a polystyrene calibration very tenuous. Use of a light-scattering detector permits direct measurement of the scattering intensity (and thus the molecular weight), as the sample elutes from the column. For the esters, anomalous peaks and unexpectedly large apparent values for both the molecular weight and molecular weight distribution are shown to be due primarily to partial imidization in solution catalyzed by basic solvent impurities. Chromatographic results obtained in neutralized solvent are in agreement with light-scattering results obtained at higher concentrations.     

Characterisation of dissolved combined amino acids in marine waters

Dissolved combined amino acids (DCAA) are important constituents of the dissolved organic nitrogen (DON) pool in marine environments, although little is known about their sources, dynamics and sinks. The DCAA pool consists of various compounds including proteins and peptides, proteins linked to sugars and amino acids adsorbed to humic and fulvic acids, clays and other materials. The proportions of each of these components and the extent to which they are used by microplankton living within the photic zone are not known. An investigation was carried out, using (15)N isotope dilution techniques, to determine the concentration and composition of dissolved amino acid pools in the marine environment. A near-shore seawater sample was collected and split into fractions to determine the concentrations of dissolved free amino acids (DFAA), DCAA and a <3 kDa dissolved peptide fraction (DPEP; obtained by ultrafiltration). DCAA and DPEP fractions were hydrolysed to yield free amino acids and all samples were analysed by gas chromatography/mass spectrometry (GC/MS) as isobutyloxycarbonyl/tert-butyldimethylsilyl derivatives. The DFAA was the smallest fraction representing approximately 1% of total dissolved amino acids. The majority of DCAA was contained in the low molecular weight DPEP fraction (90%) and was probably as a result of release from phytoplankton and degradation by heterotrophic bacteria.     

Analysis of low molecular weight organic acids in water with capillary zone electrophoresis employing indirect photometric detection

A capillary zone electrophoretic method for the analysis of low molecular weight carboxylic acids in water was developed. The application uses the chromophore trimellitic acid that allows for indirect photometric detection at 254 nm. Selectivity control by the addition of Ca²⁺ to the carrier electrolyte made possible a baseline resolved separation of 14 carboxylic acids. Good linearity and repeatability were obtained for both electrokinetic and hydrostatic injection modes. The usefulness of the method is demonstrated by the analysis of a snow sample.     

Anwendungsmöglichkeiten der HPLC bei der Trennung,Isolierung, Identifizierung und quantitativen Bestimmung von Substanzen aus komplexen Stoffgemischen—am Beispiel von Carbonsäuren in Natriumaluminatlaugen aus dem Bayerprozeß der Aluminiumoxidgewinnung

Zusammenfassung Es wird die Anwendung der Hochdruckflüssigchromatographie (HPLC) in Bezug auf die Identifizierung und quantitative Bestimmung von Carbonsäuren in Aluminatlaugen aus dem Bayerprozeß beschrieben. Die Vorgehensweise besteht in folgenden Teilschritten: Optimierung von HPLC Phasensystemen zur Trennung von synthetischen Gemischen von Carbonsäuren, Aufarbeitung der Aluminatlauge, semi-präparative Isolierung von Substanzen, Identifizierung auf flüssigchromatographischem Wege und durch Massenspektrometrie, quantitative Bestimmung durch Peakhöhenauswertung mit Hilfe externer Standards.

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HPLC of carboxylic acids in sodium aluminate liquors from the Bayer process

Summary The paper describes the application of high performance liquid chromatography (HPLC) to the identification and quantitation of carboxylic acids in aluminate liquors from the Bayer process. The procedure comprises the following consecutive steps: optimization of HPLC phase systems employing synthetic mixtures of carboxylic acids, clean-up of the liquor, semi-preparative isolation of substances, identification by means of HPLC and mass spectrometry and estimation based on peak height measurement using external standards.

Herrn Prof. Dr. I. Halász zum 60. Geburtstag gewidment.     

Phase-distribution chromatography (PDC) of polystyrene

A chromatographic technique is described where the stationary phase is a layer of a very high molecular polystyrene fraction (M = 10⁷) on glass beads (ballotines). The mobile phase is cyclohexane passing the column at a constant temperature below the theta-temperature. A polystyrene sample of sufficiently low molecular weight (M ≤ 10⁶) injected as a small plug at the top of the column is fractionated because the distribution between the mobile and the stationary phase depends on the molecular weight. Since the large molecules preferentially remain in the stationary phase, the smaller molecules leave the column first. The fractionation effect is inverse to that found in GPC experiments. The separation efficiency is rather good and can be described by a simple thermodynamic theory.     

Displacement Chromatography of Proteins using Low Molecular Weight Anionic Displacers

A major impediment to the implementation of displacement chromatography has been the lack of suitable displacer compounds. Recently, it has been shown that low molecular weight dendritic polymers, protected amino acids and antibiotics can be successfully employed for displacement purification in cation-exchange systems. In this paper, a variety of low molecular weight anionic displacers are identified for the resolution of a bovine -lactoglobulin mixture into two closely related forms (A and B). A Dynamic Affinity plot is employed to evaluate the affinity of these low molecular weight compounds under various displacement conditions. In contrast to large polyelectrolyte displacers, the efficacy of these low molecular weight displacers are shown to be dependent on displacer concentration. In fact, the Dynamic Affinity Plot qualitatively predicts the transition from a displacement to a desorption regime with these low molecular weight displacers. In addition to the fundamental interest generated by low molecular weight displacers, it is likely that these displacers will have significant operational advantages as compared to large polyelectrolyte displacers. Furthermore, the ability to carry out selective displacement chromatography with these low molecular weight displacers offers significant potential for developing robust large scale displacement processes.     

Improved SEC-FTIR method for the characterization of multimodal high-density polyethylenes

A size-exclusion chromatography-Fourier transform infrared spectroscopy (SEC-FTIR) method for the analysis of high-density polyethylene copolymers was developed, providing superior resolution for the determination of short-chain branching as a function of time and improved repeatability by hardware adaptation and processing optimization. SEC-FTIR for characterization of polyolefins is a compromising technique. Best resolution in terms of molecular weight and molecular weight distribution requires a very low sample solution concentration in size-exclusion chromatography while best results from online infrared (IR) spectroscopy require as high concentrations as possible. The signal-to-noise ratio at the IR detector could be increased significantly after application of a bandpass filter instead of a steel mesh attenuator and furthermore influences of system instabilities could be decreased by changes in data processing. Reliable short-chain branching information in the high molecular weight section in respect to accuracy and repeatability with better chromatographic resolution could be achieved.