Search

Per- and polyfluoroalkyl substances (PFASs) are man-made chemicals that have been identified as global pollutants. Their widespread occurrence, including in food, is a potential concern for consumers. This work focuses on the application of a simple and reliable analytical method for the simultaneous determination of ten perfluoroalkyl acids in highly complex fatty matrices (fats and oils). The perfluoroalkyl substances were extracted by the QuEChERS method, based on the dispersive-Solid Phase Extraction using styrene–divinylbenzene bulk sorbent, and quantitatively analysed by micro-high performance liquid chromatography tandem mass spectrometry. Recoveries ranged from 72 to 104% with an acceptable relative standard deviation below 10%. Limits of quantification were within the range 0.002–0.075 ng/g depending on the perfluoroalkyl compound. The most predominant compound in fat and oil food samples was perfluorooctanoic acid (PFOA) with a detection frequency of 100%, and the highest levels were found for perfluorobutanoic acid (PFBA). The estimated exposure to PFOA, which was 46% and 19% of the existing TWI for the EU and Polish population, respectively, is relatively high and indicates a potential risk to human health.

A highly sensitive and simple method for determining cryptotanshinone (Cry), tanshinone I (Tan I), and tanshinone IIA (Tan IIA) in Salvia miltiorrhiza was developed using micro HPLC with electrochemical detection (µHPLC-ED). The tanshinones were extracted using an ultrasonic method, with methanol as the extractant. The separation was carried out on a C18 (150 mm × 1.0 mm i.d., 3 µm particle size) analytical column. The mobile phase was acetonitrile-water-formic acid mixture (52:48:0.6, v/v/v) solution. The flow rate and the temperature of the column were set at 30 µL/min and 35°C. The applied potential was set at −0.4 V vs. Ag/AgCl. The peak heights for Cry, Tan I, and Tan IIA were found to be linearly related to the amounts injected, ranging from 0.145 µmol/L to 3.88 µmol/L, 0.226 µmol/L to 3.01 µmol/L, and 0.149 µmol/L to 3.98 µmol/L, respectively. The RSD values of intra-day precision and repeatability were not more than 3.0%, and the recovery of three analytes were ranged from 96.7% to 97.5%. The resu...

A simple, fast, sensitive, and environmental friendly micro-method is described for the determination of desmosterol and cholesterol in milk samples using isocratic normal phase high performance liquid chromatography and diode array detection. After sample micro-saponification, the chromatographic separation is achieved in 10 min, further reduced to 6 min when only cholesterol is expected to be present. The method is accurate, presenting cholesterol and desmosterol recoveries >96% and inter-day RSD lower than 3%. Quantification limits were clearly below the requirements for any milk sample, with 40 and 20 μg/100 mL for cholesterol and desmosterol, respectively. Several raw and UHT commercial milk samples, infant powder formulas, and human breast milks were analyzed, with cholesterol and desmosterol (present only in the latter) contents within reported amounts. The proposed method proved to be simple and feasible for determination of a large number of samples, requiring less solvent consumption (9–13 mL of hexane for all saponification/extraction/chromatographic steps) and simpler equipment than most ones reported, and a further possibility of partial solvent recycling due to the isocratic chromatographic mode.

Objectives: the development of a simple, rapid, sensitive, and accurate HPLC-UV method for the simultaneous determination of retinol and α-tocopherol in human plasma, suitable for the evaluation of these vitamins in pregnant women suffering from intrahepatic cholestasis of pregnancy (ICP). (b) Design and methods: chromatographic separation of vitamins was achieved with a microcolumn BDS HYPERSIL C18 (100 mm × 2.1 mm, 2.4 μm) using a C18 guard column. The developed and validated HPLC method proposed in this study was applied in the assessment of plasma concentrations of retinol and α-tocopherol in normal pregnancy (n = 37) and in pregnancy complicated with ICP (n = 19). (c) Results: the validation of the method showed excellent linearity for retinol and α-tocopherol (r2: 0.998 and 0.997), high sensitivity (LOD: 0.02 and 0.11 μM, LOQ: 0.07 and 0.36 μM), and high recovery (96.0–104.0% and 99.3–102.0%), respectively. The method requires a low sample volume and all procedures of sample preparation and analytical determination take less than 20 min to be completed. The evaluation of the results in ICP patients showed that α-tocopherol significantly diminished compared to normal pregnant women (13.1 ± 2.9 vs. 22.4 ± 2.2 μM, p < 0.05) whereas retinol remains unchanged (1.27 ± 0.21 vs. 1.25 ± 0.10 μM). (d) Conclusions: a simple, accurate, reliable, selective, highly sensitive and cost effective method suitable for routine determination of retinol and α-tocopherol in biological samples is proposed. It was possible to determine the decrease of α-tocopherol in ICP patients by this method. Fil: Martinefski, Manuela Romina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Analítica y Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Scioscia, Silvia. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Tecnología Farmacéutica; Argentina Fil: Contin, Mario Daniel. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Analítica y Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Samassa, Paula. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Analítica y Fisicoquímica; Argentina Fil: Lucangioli, Silvia Edith. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Tecnología Farmacéutica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Tripodi, Valeria Paula. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Tecnología Farmacéutica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

The main difficulty in micro-HPLC separation is the manipulation with the composition of the mobile phase (degassing of solvents and a slow establishment of equilibrium) but the problem of elution can be solved by temperature optimalization. The effect of temperature in micro-HPLC separation of the 16 polycyclic aromatic hydrocarbons (PAHs) (mixture SRM 1647 of the US EPA) has been studied using conventional C18 and new developed AP phase (an amide group localized in the hydrophobic ligands). All the investigations have been performed under isocratic conditions (binary hydroorganic mobile phase: acetonitrile/water). The results have shown that, in the case of AP phase, application of temperature gradient (from 298 to 303 K), enabled the attainment of complete 16 PAHs separation (especially of the first 4 solutes).

A micro high-performance liquid chromatography (HPLC) method has been developed for the determination of the anti-coccidial drug nicarbazin in chicken tissues, eggs, poultry feeds and litter. The 4,4′-dinitrocarbanilide (DNC) component of nicarbazin was extracted from foods, feeds and litter with acetonitrile. The extracts were purified by liquid-liquid partitioning, evaporated to dryness and taken up in methanol-acetonitrile-water (50:30:20, v/v). Micro HPLC of the 4,4′-dinitrocarbanilide (DNC) portion of nicarbazin is performed isocratically using a small bore column (1 mm I.D.) packed with reversed-phase and a UV detector set at 340 nm. The average recoveries of nicarbazin added to muscle, liver and egg were 92.8, 84.3 and 85.2%, respectively, 95.9% in poultry feed and 76.8–95.9% in different litters. The limit of detection was 25 pg, based on a detector signal-to-noise ratio of 3. These results were achieved with a simplified step extraction without the solid-phase extraction used by various researchers. This method offers a sensitive, selective, rapid, and less expensive alternative to conventional HPLC for such evaluations.

Organic-silica hybrid monolithic columns have drawn more and more attention due to the ease of preparation and good mechanical stability in recent years. Many synthetic approaches have been developed and a variety of hybrid monolithic capillary columns have been prepared. The sol-gel process is well recognized in the fabrication of hybrid monolithic columns, which can be mainly classified as one-step, acid/base two-step procedures. The new approaches such as the " one-pot'' and nano-scaled inorganic-organic hybrid reagent of polyhedral oligomeric silsesquioxane used as a cross-linker have also emerged for the preparation of hybrid monolithic columns. The applications of the organic-silica hybrid monolithic capillary columns for capillary electrochromatography, micro high-performance liquid chromatography, solid-phase microextraction and enzymatic reactor etc. are included in this review.

This work deals with the application of stereoselective antibodies against L-T3 as a tailor-made chiral selector in micro-HPLC. The separations were performed in microbore columns using commercially available anti-L-T3 antibodies chemically bonded to 5 microm silica gel. The enantiomers of T3 were baseline separated under mild continuous isocratic elution conditions using 10 mM phosphate buffer, pH 7.4. The D-enantiomer eluted with the void volume, while the L-enantiomer was retained by the antibody phase and eluted second. An indirect competitive and non-competitive enzyme linked immunosorbent assay (ELISA) was used for testing the stereoselectivity of anti-L-T3 antibodies.

Anthocyanins of red orange juices were analyzed by micro-HPLC coupled on-line with an MS detector equipped with an ESI source. The use of microcolumn HPLC greatly enhanced detection performance, allowing direct identification of the anthocyanins present in the orange juices. The use of a soft ionization technique allows detection of the molecular ions of the aglycons. Eight components were identified, five of them for the first time in red orange juice. Three additional anthocyanins were detected, of which only the aglycon was identified.

A dry-packing method has been developed which enables the preparation of packed capillary columns for micro HPLC from 250 μm i.d. tubing and 5 μm packing materials. Pressurized gases, such as hydrogen and argon, were used to transport the packing media, and ethanol or methanol were used as discharge agents. By changing the gas pressure, the packing density could be easily adjusted. It was found that, within experimental limits, the higher the packing density, the greater the column efficiency. Comparison between dry- and slurrypacked columns showed that the former had greatly improved stability; the efficiency of dry-packed columns was about the same as, or even better than, that obtained by slurry-packing.

The retention and selectivity behaviour of some antiepileptic drugs were studied by micro high-performance liquid chromatography on nine types of phenyl-modified glasses, prepared with xylene solution containing phenyldimethylchlorosilane (P), diphenylmethylchlorosilane (D) or triphenylchlorosilane (T), using three types of glass with various mean pore diameters and/or specific surface areas. From elemental analysis data for carbon, the maximum number of accessible phenyl surface groups per 100A2 of glass (mean pore diameter: 335A, specific surface area: 69m2/g) in P, D and T gel was calculated to be 2.38, 1.58 and 0.76, respectively. Using various CH3CN−0.01 M KH2PO4 mixtures as eluents, the antiepileptic drugs were separated on all the glasses studied, but with different degrees of resolution. With an increase in the specific surface area, the k′ values of some antiepileptic drugs also increased.

Microcolumn techniques involving pre-column concentration and post-column derivatization make good use of micro-scale high-performance liquid chromatography. The efficient use of microcolumns is illustrated by some applications to the analysis of amino acids, bile acids and catecholamines. The potential of new detector techniques based on the multichannel photodiode array detector, and on immobilized enzyme post-column reaction systems with fluorimetric detection, is also discussed.

Infrared monitoring was accomplished in reversed phase HPLC on using deuterated solvents. The end of a micro HPLC column was flattend and used as a flow cell for on-column IR detection. Detection of alkylbenzenes and oil-soluble vitamins which were separeted on ODS packing with CD3CN/D2O and CD3OD, respectively, was performed at 2940 cm−1.

The chromatographic performance of deuterated solvents, heavy water and deuteriobenzene, has been investigated in reversed phase and normal phase micro-HPLC. The performance of heavy water in separation was comparable or superior to that of light water in reversed phase mode. A slight improvement was also observed in catecholamines separation with heavy water. The performance of deuteriobenzene was observed as complicated in metal complexes separation, but a little difference was present. From those results, the combinations of micro HPLC and IR via flow-cell technique, proton-NMR, and ICP could be accomplished free from absorption or signals from mobile phase solvents.

A simple scheme was developed by utilization of a micro-HPLC technique in order to monitor synthetic reactions in-situ. The application of this system for the organic reaction of bromination of toluene was successfully presented.

Phenol-formaldehyde resins of the Novolak and Resol type were chromatographed on a reverse-phase micro-column packed with octadecylsilane on silica gel. A good separation of most components was achieved by the use of gradient elution with methanol-water; the contents of methanol in the mobile phase increased continually from 10 to 90%. The gradient was generated in a simple tubular mixer with an internal volume of 1.5 ml. Samples were applied to the column in a non-eluting solvent, using a six-port injection value with a 10 μl sample loop. The method, which shows a good reproducibility, is suitable for the characterization of phenol-formaldehyde resins. Phenol-Formaldehyd-Harze vom Novolak- und Resol-Typ wurden durch Chromatographie an einer mit Octadecylsilan auf Kieselgel bepackten Umkehrphasen-Mikro-Saule getrennt. Eine gute Auftrennung der meisten Komponenten wurde durch die Verwenndung der Gradientelution mit Methanol und Wasser erzielt. Der Gradient wurde in einer Rohr-Mischkammer (Volumen 1,5 ml) erzeugt; der Anteil von Methanol in der mobilen Phase wurde im Verlauf der Analyse von 10 auf 90% kontinuierlich gesteigert. Die Probenaufgabe erfolgte mit Hilfe eines Dosierventils und einer Probenschleife (Volumen 10 μl). Das Verfahren ergab reproduzierbare Ergebnisse; es erwies sich als gut geeignet zur Charakterisierung von Phenol-Formaldehyd-Harzen.

Application de la methode du titre a l'analyse des hydrocarbures paraffiniques et aromatiques d'une fraction essence

The exclusion properties of ten commercially available silica gels have been determined and their relative merits for use as stationary phases in exclusion chromatography discussed. Examples are given of the use of three selected silica gels in the separation of synthetic mixtures of high-molecular-weight standards. The effect of the exclusion properties of silica gel on retention data is considered and a modified retention volume equation that takes into account these exclusion properties is given. The validity of the equation is tested against retention data determined for three different solutes chromatographed on three silica gels of widely different porosities. The use of silica gel as an exclusion medium in conjunction with a column having 250,000 theoretical plates is also demonstrated.

The application of micro HPLC to the determination of amygdalin in Semen pruni armeniacae and Semen pruni persicae is described. Amygdalin is separated at ambient temperature on a reversed phase column of U-Finepak SIL C18(150 x 0.5 mm) with methanol + water (25:75 v/v) as the mobile phase at a flow rate of 10 microL/min. The results are calculated by the internal standard method. The linear range is 1-7 micrograms. The CV and recovery of pure amygdalin are 1.47% (n = 10) and 98.13%, respectively. The results of analysis are lower than those obtained by TLC, but microHPLC is much simpler, faster, and more sensitive and reproducible than TLC.