Ion chromatographic determination of hydrolysis products of hexafluorophosphate salts in aqueous solution

In this work, hydrolysis of three different hexafluorophosphate salts in purified water was investigated. Aqueous samples of lithium hexafluorophosphate (LiPF₆), sodium hexafluorophosphate (NaPF₆) and potassium hexafluorophosphate (KPF₆) were prepared and stored for different times. Ion chromatography (IC) with UV as well as non-suppressed and suppressed conductivity detection was used for the analysis of the reaction products. For the detection and identification of the formed decomposition products, an IC method using IonPac AS14A 250 mm × 4.0 mm i.d. column and 2.5 mM KHCO₃–2.5 mM K₂CO₃ eluent was established. Besides hexafluorophosphate, four other anionic species were detected in fresh and matured aqueous solutions. The hydrolysis products fluoride (F⁻), monofluorophosphate (HPO₃F⁻), phosphate (HPO₄²⁻) and difluorophosphate (PO₂F₂⁻) were found and were unambiguously identified by means of standards or electrospray ionization mass spectrometry (ESI-MS). It was shown that stability of hexafluorophosphate solutions depends on the nature of the counter ion and decreases in the order potassium > sodium > lithium.     

High-performance liquid chromatographic separation and detection methods for anabolic compounds.

The role of high-performance liquid chromatography (HPLC) in methods of analysis for anabolic compounds in biological samples is reviewed. Special attention is given to both the separation and detection of anabolic compounds. A distinction is made between on-line detection systems, such as ultraviolet detection and diode-array detection, and off-line detection methods with special emphasis on immunochemical detection methods using non-isotopic labels. A number of applications are given to elucidate the possibilities of HPLC in the analysis of anabolic compounds.     

Ion chromatographic identification and quantification of glycol degradation products

In water-based heat transfer systems, frequently glycols are added to the water to obtain freeze protection. For this purpose, ethylene glycol (EG) is the most common substance used. When heated, the glycol will slowly degrade and the pH of the glycol-water mixture will decrease, leading to corrosion and foaming problems. Carboxylic acids were identified as the main degradation products. Quantification of the carboxylic acids is of importance to monitor the degradation reactions in order to identify hot spots or overheating, caused by severe heat exchanger scaling, where pH measurements will not be sufficient due to buffer substances added for corrosion protection. In this work, ion chromatographic methods havebeen developed to identify the main degradation products of EG in heat transfer systems and to monitor the degradation process. Possible acidic reaction products of EG are glycolic acid, glyoxylic acid, oxalic acid, acetic acid and formic acid. Separations with a Dionex AS9-HC column with Na2CO3 eluents of differing concentrations showed that only trace amounts of carboxylic acids are present in aged heat transfer media. Oxalic acid can be quantified simultaneously to nitrite or molybdate which are added as corrosion inhibitors. A Dionex AS10 separation column with Na2B4O7 eluent enabled base line separation of glycolic acid, acetic acid and formic acid. Heat transfer media, which are operated in different heat transfer systems under different conditions, were analysed. A system was identified, where severe overheating due to fluid maldistribution in the heat exchanger took place.     

Synergy between liquid chromatographic-pulsed amperometric detection and capillary-gas chromatographic methods for the detection of juice adulteration.

The use of liquid chromatography linked with pulsed amperometric detection, and capillary-gas chromatography to detect the adulteration of fruit juices is discussed. These are 2 complementary approaches which can be used to detect the addition of sugar syrups to juices at low levels.     

Ion chromatographic determination of inositol in infant formulae and clinical products for enteral feeding

An ion chromatographic method is described for the determination of inositol in infant formula and products for enteral feeding. A two-step procedure for hydrolysis and extraction of total inositol has been developed, involving alkaline hydrolysis with 3 M potassium hydroxide and enzymatic dephosphorylation. Substances having a long chromatographic retention time were removed with an ion-exchange resin. Inositol was separated on a high-resolution ion-exchange column and detected by pulsed amperometric detection. Phytic acid interferes only slightly in the analysis. This method can be used for determination of total inositol in infant formulae, and enteral feeding products. The analytical method gave an average recovery of 94% from infant formula samples spiked with inositol and a recovery of 86+/-3% from products spiked with lecithin.     

Ion chromatographic separation of alkylsulphonic acids with conductivity detection

Summary An ion chromatographic (IC) method has been developed for the separation of alkylsulphonic acid. Two different stationary phases, silica-based and polymer-based ion-exchange resins, were studied using pure ion exchange and/or hydrophobic interaction mechanisms. Correlations between analyte hydrophobicity and eluent polarity were made in order to investigate the possibility of changing the dominant separation mechanism by varying the eluent composition. The alkyl chain lengths of the sulphonic acids analysed ranged from C₁ to C₉. Detection limits in the submicromolar range were obtained by suppressed conductivity detection.     

Ion chromatographic separation of alkylsulphonic acids with conductivity detection

Summary An ion chromatographic (IC) method has been developed for the separation of alkylsulphonic acid. Two different stationary phases, silica-based and polymer-based ion-exchange resins, were studied using pure ion exchange and/or hydrophobic interaction mechanisms. Correlations between analyte hydrophobicity and eluent polarity were made in order to investigate the possibility of changing the dominant separation mechanism by varying the eluent composition. The alkyl chain lengths of the sulphonic acids analysed ranged from C₁ to C₉. Detection limits in the submicromolar range were obtained by suppressed conductivity detection.     

Reactive desorption electrospray ionization for selective detection of the hydrolysis products of phosphonate esters

Reactive desorption electrospray ionization (reactive DESI) is demonstrated to be a rapid and sensitive method for the direct detection of alkyl methylphosphonic acids, the hydrolysis products and metabolites of the chemical warfare (CW) agents VX (S-2-diisopropylaminoethyl-O-ethyl methylphosphonothiolate) and GB (sarin, isopropylmethyl phosphonofluoridate). Rapid and sensitive detection of these compounds is readily achieved by performing DESI from a solid surface; detection specificity is enhanced by implementation of a heterogeneous ion/molecule reaction using boric acid in the spray solvent. The reagent ion H(2)BO(3) (-) generated in the spray readily reacts with condensed-phase alkyl MPA to form anionic adducts. The specificity of this chemical reaction, together with the characteristic fragmentation patterns of the reaction products, supplies a highly discriminatory detection method for methylphosphonic acid (MPA), ethylphosphonic acid (EMPA) and isopropyl methylphosphonic acid (IMPA) in complex matrices.     

Application of a simple high-performance liquid chromatographic method for the determination of melphalan in the presence of its hydrolysis products

A procedure for the separation and quantitation of melphalan (L-PAM) and its hydrolysis products by high-performance liquid chromatography is described. The hydrolysis of L-PAM at 25 +/- 0.1 degrees and 41 +/- 0.1 degrees was studied between pH 3.0 and 9.0. The pattern of hydrolysis suggested that L-PAM decomposes via two consecutive pseudo first-order reactions. Pseudo first-order rate constants (k1) were determined for the disappearance of L-PAM at various pH values in buffered solutions and in a formulated product. At both temperatures L-PAM solutions were found to be most stable at low pH. Chloride ion was found to reduce the rate of hydrolysis.     

Determination of glyphosate and its biodegradation products by chromatographic methods

Conditions were selected for the separation of the herbicide glyphosate (N-(phosphonomethyl)glycine) and products of its microbiological utilization as N-acylated derivatives by ion-exchange liquid chromatography. The order of the elution of compounds on a Repro-Gel H column with UV detection correlates with their structures. The detection limits of the derivatives (wavelength 210 nm) are as follows (ng): glyphosate, 30; glycine and sarcosine, 20 and 43, respectively; aminomethylphosphonic acid, 45. The detection limit of methylphosphonic acid is 14 μg. Glyphosate and its biodegradation products were separated by thin-layer chromatography on plates with silica gel in the system isopropanol-5% aqueous ammonia solution (1: 1).     

Ion mobility detection of polydimethylsilicone oligomers following supercritical fluid chromatographic separation

A mixture of polydimethylsilicones (Dow Corning 200), average molecular weight 2000 a.m.u., was separated by simultaneous density and temperature-programmed supercritical fluid chromatography and detected by ion mobility detection. Ion mobility spectra were captured by Fourier transform ion mobility spectrometry. Using information from these spectra it was possible to selectively detect a single compound in the complex mixture. A detector temperature investigation demonstrated that, for the efficient transfer of high-molecular-weight compounds from the column to the detector, the interface to the detector must be heated. Using a 50 microns I.D. column, a Guthrie-type restrictor and a detection temperature of 250 degrees C, as many as 70 oligomers were separated and detected.     

Comparison of high-performance liquid chromatographic detection methods for thyronine and tyrosine residues in toxicological studies of the thyroid.

Four high-performance liquid chromatographic methods for the detection of thyroid hormones (iodinated thyronines) and precursors (iodinated tyrosines) have been developed and evaluated. Two methods consist of direct determination of the parent compounds with detection at ultraviolet wavelength (230 nm) and with electrochemical detection. The two other methods consist of a pre-column derivatization (with fluorenylmethyl chloroformate and dabsyl chloride) prior to high-performance liquid chromatographic analysis. The various methods were evaluated based on their practical use and sensitivity. The method with direct ultraviolet detection turned out to be the most practical method. With this method analyses of thyroid homogenates have been performed from rats from a toxicological experiment.     

Evaluation of two different extraction methods for chromatographic determination of bioactive amines in tomato products

Bioactive amines are organic bases originating from corresponding amino acid which have undergone decarboxylation by putrefactive bacteria or lactic acid bacteria. When formed by microbial enzymatic decarboxylation of amino acids, they are called “ biogenic” and can produce detrimental effects on human health. Many techniques have been developed for extraction and/or clean up of bioactive amines in food, including acidic or organic extraction as well as solid phase extraction. This study deals with the comparison of two different extraction methods, homogenizing and matrix solid phase dispersion, for the chromatographic determination of eight non-volatile bioactive amines in tomato-based products (mashed tomato, biological mashed tomato, concentrated tomato pasta and ketchup) very popular in Italian alimentary habits. In both cases, perchloric acid has been used for analytes extraction and the influence of different parameters affecting amine recoveries have been evaluated. After a derivatization step with dansyl-chloride, samples were analyzed for amines quantitative determination using 1,7-diaminoheptane as internal standard on a C₁₈-RP-HPLC-UV system. Method performances were tested and good results of linearity, repeatability and recovery were obtained for all the considered amines. The collected data have shown that ketchup contains the highest levels of amines followed by concentrated tomato pasta, biological mashed tomato and common mashed tomato. Moreover, it has been found that in all samples, putrescine is the most abundant amine followed by tyramine, spermidine and tryptamine.     

Ion chromatographic method for the simultaneous determination of nitrite and nitrate by post-column indirect fluorescence detection

This short paper highlights the suitability of ion chromatography with post-column indirect fluorescence detection to determine simultaneously nitrite and nitrate based on the quenching of tryptophan native fluorescence. The method uses an enhanced fluorescence mobile phase containing tryptophan and detects the suppression of fluorescence of the mobile phase due to the elution of the target ions. The phenomenon of fluorescence quenching of tryptophan is highly induced by the presence of phosphate ions. The quenched fluorescence intensity exhibits concentration dependence in the range 1-25 mg/l and 3-65 mg/l for nitrite and nitrate, respectively. The relative standard deviation for five replicates of a standard solution containing a mixture of 5 mg/l of nitrite and 10 mg/l of nitrate lies around 2.8%. This simple coupling technique results in a relatively sensitive, fast, and accurate method, allowing for both qualitative and quantitative analysis of nitrite and nitrate. The method can easily be implemented to real samples such as foodstuffs, fertilizers and soils and is proven to be precise and accurate when compared with reference methods.     

Two ion-exchange chromatographic methods for the isolation of antibacterial peptides from lactoferrin. In situ enzymatic hydrolysis on an ion-exchange membrane

Two ion-exchange chromatographic methods are reported for the rapid isolation of antibacterial peptides from lactoferrin (LF). Using the first method, a pepsin hydrolysate of LF was fractionated by bead-based cation-exchange chromatography. After removal of weakly bound material by washing with ammonia, highly purified lactoferricin-B (LFcin-B) was obtained in a single step by elution with 2 M NaCl. Some other cationic peptides, copurified as minor components, were also characterised by N-terminal sequencing, mass spectrometry and antibacterial activity determination. With the second method, cheese whey was filtered through a cation-exchange membrane, and the selectively bound LF was directly hydrolysed in situ with pepsin. Inactive LF fragments were washed off the membrane with ammonia, and a fraction enriched in LFcin-B was obtained by further elution with 2 M NaCl. The membrane method is more rapid and offers several economic advantages.     

Determination of preservatives in cosmetic products. I. Thin-layer chromatographic procedure for the identification of preservatives in cosmetic products

A thin-layer chromatographic procedure is presented for the separation and identification of preservatives that are listed in the current EEC Council Directive on cosmetic products or have been permitted in the past. The method consists of an extraction of acidified cosmetics with methanol, separation of the extracts by thin-layer chromatography on aluminium oxide and silica gel-coated plates using one developing solvent, and visualization of the preservatives on the plates using short-wavelength UV light and six detection reagents. The retention behaviour and the detectability of 88 preservatives were investigated, of which 74 were characterized by this method. The preservatives in fourteen commercial cosmetic products were tentatively identified by the procedure described. In general this method will permit the routine detection of preservatives in cosmetics in an approximate concentration of 0.1% (w/w).     

Ion chromatographic determination of traces of some oxoanions with direct spectrophotometric detection

Investigation of the use of a single analytical procedure using the non-suppressed ion chromatographic method with direct spectrophotometric detection capable of determining eight oxoanions simultaneously is presented in this paper. Potassium phosphate was found to be the most suitable eluent for UV absorbance detection at 205 nm. Oxoanions AsO³⁻₃, SeO²⁻₃, AsO³⁻₄, VO⁻₃, SeO²⁻₄, WO²⁻₄, MoO²⁻₄ and CrO²⁻₄ were detected at ng ml⁻¹ levels with well separated peaks at retention time < 25 min. The working range is in the range ng ml⁻¹ to 50 μg ml⁻¹. The method is sufficiently sensitive to determine As (V), V(V), Mo(VI) and Cr(VI) anions (and NO⁻₃) directly in a river water sample. The accuracy of these results was established by comparison with conventional atomic absorption methods.