Analysis of potential and free furfural compounds in milk-based formulae by high-performance liquid chromatography. Evolution during storage

A simple and reproducible HPLC-diode array detection method for the qualitative and quantitative analysis of potential and free furfural compounds (5-hydroxymethyl-2-furaldehyde, HMF; 2-furaldehyde, F; 2-furyl methyl ketone, FMC; and 5-methyl-2-furaldehyde, MF) in milk-based formulae was developed and validated. The method showed good linearity with determination coefficients over 0.999. The limits of detection and quantification were acceptable for all furfurals. The relative standard deviations (RSDs) for repeatability and reproducibility were <4.28. Recoveries in all furfurals were between 94.5 and 98.7%. In addition, we report the evolution over shelf life of furfural compound levels in an experimental powder formula for pregnant women stored at 25 and 37 degrees C from production until 15 months.     

HPLC determination of 2-furaldehyde and 5-hydroxymethyl-2-furaldehyde in alcoholic beverages

A method for the determination of 2-furaldehyde (F) and 5-hydroxymethyl-2-furaldehyde (HMF) in alcoholic beverages by high performance liquid chromatography (HPLC) is described. A C-18 column and an acetonitrile-water mobile phase with isocratic elution were used. UV detection at 280 nm was carried out. The method was validated according to the EURACHEM guidelines. The procedure offers a high specificity and detection limits of the order of 0.005 μg mL^− 1. Recoveries of 94-103% were obtained from spiked samples at different levels with both analytes. Intermediate precision calculated for a period of 2 months was + 0.8% for HMF and + 0.4% for F. The method was applied to the analysis of alcoholic beverages like bourbon, rum, brandy, liquors and aperitif wines.     

Trace zinc determination by synchronous derivative fluorimetry

A sensitive and selective synchronous-scanning derivative spectrofluorimetric determination of zinc based on the formation of a fluorescent chelate with 2-furaldehyde 2-pyridylhydrazone (FAPH) is described, and its analytical performance compared with that of the ordinary fluorimetric method. The detection limits lie in the ng ml range and the coefficient of variation is below 2% in both cases. The methods have been applied to the trace determination of zinc in pig liver tissue and environmental fume samples.     

A direct RP-HPLC method for the determination of furanic aldehydes and acids in honey

In this study 5-hydroxymethyl-2-furaldehyde (HMF), 2-furaldehyde, 3-furaldehyde, 2-furoic acid and 3-furoic acid are contemporarily determined in honey using a swift and direct RP-HPLC approach. The validation protocol was performed in terms of detection and quantification limits, precision (by repeatability and reproducibility), linearity and accuracy (by recovery tests); the acceptability of the precision and accuracy results was positively verified using Horwitz's model and AOAC guidelines, respectively. The method was tested on 18 honey samples of different ages, and botanical and geographical origin. HMF and 2-furaldehyde correlated highly with the age of the samples, whereas no correlation was observed with regards to 2-furaldehyde and 2-furoic acid. Hypotheses relating to the formation of minority furanic compounds are also proposed.     

High-performance liquid chromatographic determination of 2-furaldehyde in spirits

Official methods for the determination of 2-furaldehyde in spirits involve for a spectrophotometric evaluation, which is characterized by poor specificity. Gas chromatographic evaluations have also been proposed, which offer a much higher sensitivity, particularly when capillary columns are used. In this paper a high-performance liquid chromatographic (HPLC) method based on the formation of the 2,4-dinitrophenylhydrazones of carbonyl compounds and subsequent reversed-phase separation of these derivatives is described. Derivatization is carried out by utilizing an acidic solution of 2,4-dinitrophenylhydrazine in acetonitrile. Precipitation of the derivatives is avoided, and direct injection of the sample into the HPLC system is allowed. The determination ofrers a high specificity and a detection limit of the order of 10⁻⁸ mol/1. Accuracy and reproducibility data are presented.     

High-performance liquid chromatographic determination of furfural and hydroxymethylfurfural in apple juices and concentrates

Summary A rapid and sensitive method for determining 2-furaldehyde (FUR) and 5-hydroxymethyl-2-furaldehyde (HMF) in apple juices and juice concentrates has been developed. The method for FUR and HMF involves the solid-liquid extraction of the juice by using a C-18 cartridge prior to reversed-phase separation with detection at 280 nm. The mobile phase was acetonitrile-water (8/92, v/v) at a flow rate of 1.0 ml/min. Recoveries from apple juices and juice concentrates spiked at different levels ranged from 94.1 to 104.0 (FUR) and 94.5 to 100.5 (HMF). The quantification limit for both, FUR and HMF, was 5 ppb.     

Rapid determination of banned Sudan I in foodstuffs using a mesoporous SiO2 modified electrode

Rapid determination of Sudan I in foodstuffs is very important because it was found to be a carcinogen and its use in the food industry was banned. A rapid, sensitive, and convenient electrochemical method was developed for the determination of Sudan I based on the distinctive properties of mesoporous SiO2. The electrochemical responses of Sudan I were investigated. A sensitive oxidation peak was observed for Sudan I, and the peak currents greatly increased at the mesoporous SiO2-modified electrode, which can be attributed to its large surface area and high accumulation efficiency. The effects of pH, amount of mesoporous SiO2, scan rate, accumulation potential, and time were examined on the oxidation signals of Sudan I. The linear range was from 4.00 x 10(-8) to 2.00 x 10(-5) M, and the LOD was 7.50 x 10(-9) M. The newly developed method was successfully used to detect and quantify Sudan I in hot chili powder and juice samples.     

Photometric determination of cobalt by means of photochemically generated anti-2-furaldehyde 2-pyridylhydrazone

The photochemical syn-anti isomerization of 2-furaldehyde 2-pyridylhydrazone (FAPH) in ethanolic solutions has been investigated. A study of the infrared, visible and ultraviolet, and n.m.r. spectra of the two isomers was made. The syn-anti ratio at the photostationary state was determined. syn-FAPH scarcely reacts with metal ions but the anti-FAPH formed by irradiation gives sensitive reactions with several metal ions to form stable chelates. A photometric method for the determination of cobalt (0.025-1.0 microg/ml ) in aqueous ethanolic medium (50% v/v ) at pH 9.7 is described. A detection limit of 0.007 microg/ml and relative standard deviation of 0.5% were found. By consideration of the syn-anti ratio at the photostationary state, the stoichiometry of the chelate was determined. An application of this technique to determination of cobalt in environmental fume samples is also described.     

Molecular mapping of the acid catalysed dehydration of fructose

Several intermediates and different reaction paths were identified for the acid catalysed conversion of fructose to 5-(hydroxymethyl)-2-furaldehyde (HMF) in different solvents. The structural information combined with results of isotopic-labelling experiments allowed the determination of the irreversibility of the three steps from the fructofuranosyl oxocarbenium ion to HMF as well as the analogous pyranose route.     

Rapid method for the determination of organochlorine pesticides and PCBs in fish muscle samples by microwave-assisted extraction and analysis of extracts by GC-ECD

A procedure for the multiresidue determination of organochlorine pesticides and polychlorinated biphenyls in fish muscle samples has been developed. The method is based on the microwave-assisted extraction (MAE) of food samples from an acetonitrile-water (95 + 5, v/v) mixture followed by SPE cleanup of the extracts and analysis by GC with an electron capture detector. MAE operational parameters, such as the extraction solvent, temperature, and time, were optimized with respect to the extraction efficiency of the target compounds from food samples with 10-13% fat content. The chosen extraction technique allows reduction of the solvent consumption and extraction time when compared with methods already used. Acetonitrile is a good extraction solvent for low-fat matrixes (2-20% fat content), such as fish samples, because it does not significantly dissolve the highly polar proteins, salts, and sugars commonly found in food and gives high recoveries of a wide polarity range of analytes. For purification, SPE using LC-Florisil was shown to be sufficient for the removal of coextracted substances. Recoveries > 78% with RSD values < 15% were obtained for all compounds under the selected conditions. Method quantification limits were in the 5-10 microg/kg range. The method was applied to the analysis of samples of herring (Clupea harengus) purchased at the local fish market. The method is rapid and reliable for the determination of organochlorine analytes in fish muscle.     

Electrochemical Determination of the “Furanic Index” in Honey

5-(hydroxymethyl)furan-2-carbaldehyde, better known as hydroxymethylfurfural (HMF), is a well-known freshness parameter of honey: although mostly absent in fresh samples, its concentration tends to increase naturally with aging. However, high quantities of HMF are also found in fresh but adulterated samples or honey subjected to thermal or photochemical stresses. In addition, HMF deserves further consideration due to its potential toxic effects on human health. The processes at the origin of HMF formation in honey and in other foods, containing saccharides and proteins—mainly non-enzymatic browning reactions—can also produce other furanic compounds. Among others, 2-furaldehyde (2F) and 2-furoic acid (2FA) are the most abundant in honey, but also their isomers (i.e., 3-furaldehyde, 3F, and 3-furoic acid, 3FA) have been found in it, although in small quantities. A preliminary characterization of HMF, 2F, 2FA, 3F, and 3FA by cyclic voltammetry (CV) led to hypothesizing the possibility of a comprehensive quantitative determination of all these compounds using a simple and accurate square wave voltammetry (SWV) method. Therefore, a new parameter able to provide indications on quality of honey, named “Furanic Index” (FI), was proposed in this contribution, which is based on the simultaneous reduction of all analytes on an Hg electrode to ca. −1.50 V vs. Saturated Calomel Electrode (SCE). The proposed method, validated, and tested on 10 samples of honeys of different botanical origin and age, is fast and accurate, and, in the case of strawberry tree honey (Arbutus unedo), it highlighted the contribution to the FI of the homogentisic acid (HA), i.e., the chemical marker of the floral origin of this honey, which was quantitatively reduced in the working conditions. Excellent agreement between the SWV and Reverse-Phase High-Performance Liquid Chromatography (RP-HPLC) data was observed in all samples considered.     

Rapid determination of 1,1-dimethylhydrazine transformation products in soil by accelerated solvent extraction coupled with gas chromatography–tandem mass spectrometry

A method for the analytical extraction of mobile species of eightmain transformation products of 1,1-dimethylhydrazine (formaldehyde dimethylhydrazone, acetaldehyde dimethylhydrazone, 2-furaldehyde dimethylhydrazone, 1,1,4,4-tetramethyl-2-tetrazene, N,N-dimethylformamide, N-nitrosodimethylamine, 1-methyl-1H-1,2,4-triazole, and 1-formyl-2,2-dimethylhydrazine) from soils using subcritical acetonitrile at a pressure of 100 bar is proposed. The effects of temperature, number of extraction cycles, and the moisture content of soil samples on the recovery of analytes were studied. It was found that, for soils with high concentrations of lignin humic substances, efficient extraction can be attained with an addition of significant amounts of alkali to the soil (2.5 g/g). Under the optimum conditions, the recovery of analytes was higher than 70% at the extraction time no more than 30 min. A combination of the proposed sample preparation approach with analysis by gas chromatography–tandem mass spectrometry (GC-MS/MS) ensures the determination of the products of unsymmetrical dimethylhydrazine (UDMH) transformation in complex matrixes, such as soils with high concentrations of organic substance with detection limits from 1.8 to 15 µg kg^–1 using the direct injection of the extract into the chromatography system. The error of determination at a confidential probability of 0.95 was not worse than 15% even for analyte concentrations close to lower limit of quantitation (LLOQ) values. The method developed is a significant improvement compared to the highly efficient methods previously reported in literature differing from them with simple sample preparation, rapidity, low consumption of reagents, the possibility of simultaneous determination of eight compounds and 1–2 orders of higher sensitivity. It was successfully used for the analysis of real samples of peaty soil from the place of impact of the first step of a carrier rocket.     

Polarographic Study of Reactions in the System 2-Furaldehyde-Hydrogen Peroxide-NaVO3

The oxidation of 2-furaldehyde to -formylacrylic acid in 0.1 N HClO₄ containing hydrogen peroxide and sodium vanadate was studied by polarography using a dropping mercury electrode. The conversion of 2-furaldehyde and the yield of the products were found to depend on the reactant ratio. A mechanism was proposed which includes preliminary complex formation between the reactants.     

Spectrophotometric determination of hydrazine,methylhydrazine, and 1,1-dimethylhydrazine with preliminary derivatization by 5-nitro-2-furaldehyde

5-Nitro-2-furaldehyde, a new derivatizing agent for the spectrophotometric determination of hydrazine, methylhydrazine, and 1,1-dimethylhydrazine is proposed. It is characterized by high solubility in water and by a substantial difference in the positions of absorption bands of the formed colored derivatives. The kinetics of the reaction of analyte derivatization is studied, and reaction conditions (pH 5, concentration of derivatizing agent 2 mM, 60° C, duration 40 min) are optimized. The limits of detection are 5, 3, and 1.5 μg/L for hydrazine, methylhydrazine, and 1,1-dimetlhydrazine, respectively. A possibility of the spectrophotometric determination of analytes in their simultaneous presence using the Firordt method is shown. The developed approach is successfully applied to the analysis of polluted peat bog soil selected at a place of impact of the first step of a carrier rocket.     

Ultra-performance liquid chromatography-tandem mass spectrometry for the analysis of heterocyclic amines in food

A new ultra-performance liquid chromatography-electrospray tandem mass spectrometry (UPLC-ESI-MS/MS) method was developed to perform the determination of 16 mutagenic heterocyclic amines (HAs) in complex food samples in less than 2 min. The UPLC separation was carried out using an Acquity BEH C18 column (50 mm x 2.1 mm i.d., 1.7 microm particle size) that provided high efficiency and resolution in combination with high linear velocities. The UPLC system was coupled to the triple quadrupole Waters Micromass Quattro Premier. This system permits high-speed data acquisition without peak intensity degradation which is required to monitor the narrow chromatographic peaks (1-2 s) of HAs. The determination was performed in selected reaction monitoring (SRM) mode. The quality parameters of the developed method were established, obtaining instrumental LODs lower than 0.23 pg injected and a repeatability at low concentration level lower than 9.1% CV (n = 6). To evaluate the performance of the method in high throughput analysis of complex samples, the UPLC-MS/MS method was applied to the analysis of HAs in two meat extracts.     

超高效液相色谱-串联质谱法同时测定食品接触材料及制品中9种抗氧化剂迁移量

为了评估食品接触材料及制品中抗氧化剂的迁移风险,采用超高效液相色谱-串联质谱法(UPLC-MS/MS)建立了同时测定食品接触材料及制品中9种抗氧化剂迁移量的方法。采用C18色谱柱对迁移实验后的食品模拟物中9种抗氧化剂进行分离,1 mmol/L氟化铵和甲醇为流动相洗脱,采用电喷雾离子源(ESI),多反应监测(MRM)正负离子模式进行扫描。结果表明,9种抗氧化剂的色谱分离效果良好,并在0.3~6 mg/L质量浓度范围内与其峰面积均呈良好的线性关系,检出限为0.1 mg/L。加标回收率为93.9%~106%,相对标准偏差(RSD)为0.80%~9.3%。该方法快速高效、线性范围好,适用于塑料食品接触材料及制品中9种抗氧化剂迁移量的检测。     

Purification of polar compounds from Radix isatidis using conventional C18 column coupled with polar-copolymerized C18 column

Regarding hydrophilic interaction chromatography and normal phase liquid chromatography, RPLC is another choice used to separate polar compounds with the improvement of polar-modified C18 stationary phase. In this study, a method using conventional C18 column coupled with polar-copolymerized C18 column was successfully developed for the separation and purification of polar compounds from Radix isatidis, which is one of the most commonly used traditional Chinese medicines (TCMs). An XTerra MS C18 column was used to fractionate the extract of R. isatidis and a homemade polar-copolymerized C18 column was utilized for the final purification due to its good separation selectivity and high resolution for polar compounds. The established purification system demonstrated good orthogonality for the polar compounds. As a result, ten compounds were purified and three of them were identified as 3-methyl-5-vinyloxazolidin-2-one (compound A), 5-hydroxymethyl-2-furaldehyde (compound B) and 3-methylfuran-2-carboxylic acid (compound G) based on the MS, IR and extensive NMR data, respectively. It was demonstrated to be a feasible and powerful technique for the purification of polar compounds under RPLC mode and more chemical information of TCMs will be obtained to interpret the efficiency of TCMs.     

Determination of vitamin B5 in a range of fortified food products by reversed-phase liquid chromatography-mass spectrometry with electrospray ionisation

Methods for Vitamin B5 determination in food products remain limited by their low sensitivity and poor selectivity. Here, we have developed a liquid chromatography-mass spectrometry (LC-MS) method for Vitamin B5 determination in wide range of fortified food products. Vitamin B5 was extracted from food samples by heat treatment and analysed by LC-MS in the positive mode using electrospray ionisation (ESI). Vitamin B5 was quantified using hopantenic acid (HOPA) as internal standard after their separation on a C18 narrow-bore column with a gradient of mobile phase made of water/acetonitrile and trifluoroacetic acid (TFA) 0.025%. MS with single ion monitoring mode at mass m/z 220 was used for Vitamin B5 quantification. Calibration curve between 0.5 and 10 microg/ml of Vitamin B5 was linear (r2=0.9993) and the detection limit was determined to be 800 pg. The overall quantitative efficiency of the method was evaluated using Nestle reference sample (infant formula). The intra-assay RSD was 4.8% (n=8), the inter-assay RSD 6.4% (n=4) and the recoveries of the spiked samples were above 95%. Application of the LC-MS method to Vitamin B5 determination in wide range of fortified food products including three US National Institute of Standards and Technology (NIST) reference samples (RM 8435, RM 8415 and SRM 1546) shows consistent results with those obtained by microbiology and recoveries of Vitamin B5 between 93 and 104% for the spiked samples.     

Electromembrane extraction of tartrazine from food samples: Effects of nano‐sorbents on membrane performance

In the present study, for the first time electromembrane extraction followed by high‐performance liquid chromatography coupled with ultraviolet detection was developed and validated for the determination of tartrazine in some food samples. The parameters influencing electromembrane extraction were evaluated and optimized. The membrane consists of 1‐octanol immobilized in the pores of a hollow fiber. As a driving force, a 30 V electrical field was applied to make the analyte migrate from sample solution with pH 3, through the supported liquid membrane into an acceptor solution with pH 10. Best preconcentration (enrichment factor >21) was obtained in extraction duration of 15 min. Effects of some solid nano‐sorbents like carbon nanotubes and molecularly imprinted polymers on membrane performance and electromembrane extraction efficiency were evaluated. The method provided the linearity in the range 25–1000 ng/mL for tartrazine (R² > 0.9996) with repeatability range (RSD) between 3.8 and 8.5% (n = 3). The limits of detection and quantitation were 7.5 and 25 ng/mL, respectively. Finally, the method was applied to the determination and quantification of tartrazine from some food samples with relative recoveries in the range between 90 and 98%.     

抑制褪色光度法测定油炸面制食品中痕量铝

建立抑制褪色光度法快速测定食品中痕量铝的方法。在硫酸介质中,一定量的铝离子对溴酸钾氧化罗丹明B褪色有抑制作用,据此建立了抑制褪色光度法快速测定食品中痕量铝的新体系,最大吸收波长为550 nm。在1 mol/L硫酸介质中,铝含量在0.07~0.4μg/mL范围内与吸光度具有良好的线性关系,相关系数r=0.9995,检出限为0.02μg/mL。用该方法测定油炸面制食品中痕量铝,测定结果的相对标准偏差为1.3%~3.1%(n=11),加标回收率为99.3%~103.5%。该方法测定结果准确可靠,可用于食品中痕量铝的测定。