Simultaneous determination of carbonyl compounds related to thermal treatment and oxidative stability of infant formulas by gas-diffusion microextraction and high-performance liquid chromatography with ultraviolet detection.

Infant formulae are the only possible alternative to breastfeeding during the first year of life, so it is crucial to assure their innocuousness. Infant formula undergoes heat treatments to ensure safety and shelf life. However, such processes impact health as they lead to the formation of malondialdehyde, acrolein, and α-dicarbonyl compounds, related to Maillard reaction. Thus, there is a need for improved analytical methods to ensure the safety, quality, and nutritional value of infant formulae, and also exploring the potential of specific compounds as indicators for quality control and monitoring purposes. We developed and validated a novel, efficient, and cost-effective method using gas-diffusion microextraction for the simultaneous quantification of carbonyl compounds in infant formula. Malondialdehyde, acrolein, glyoxal, methylglyoxal, and diacetyl were detected as o-phenylenediamine derivatives using HPLC with UV detection. Parameters influencing extraction efficiency were studied using an asymmetric screening design. The validated method has shown excellent linearity, sensitivity, accuracy, and precision. It was applied to analyze 26 infant formula samples, including starter, follow-up, and special formulated powdered infant formula. Methylglyoxal was found in all samples (0.201-3.153 µg mL-1), while malondialdehyde was present only in certain starter formulas (1.033-1.802 µg mL-1). Acrolein (0.510-3.246 µg mL-1), glyoxal (0.109-1.253 µg mL-1), and diacetyl (0.119-2.001 µg mL-1) were detected in various sample types. Principal components and hierarchical cluster analyses have showcased distinct sample clustering based on analyte contents. This study presents a novel methodology for the analysis of markers of thermal treatment and oxidative stability in infant formula. It contributes to the characterization of the products' composition and quality control of infant formulae, thereby enhancing their safety and nutritional adequacy. This study also presents the first reported quantification of acrolein in infant formula and introduces the application of the acrolein-o-phenylenediamine derivative for food analysis.

Fan Assisted Extraction of Volatile Carbonyl Compounds from Coffee Brews Based on the Full Evaporation Technique.

In this work, the fan assisted extraction approach is originally exploited to determine volatile compounds in liquid samples based on the full evaporation technique. The feasibility of this strategy was firstly evaluated using model solutions containing different volatile carbonyl compounds. Different media, volumes of sample, temperatures of extraction, and times of extraction were tested. Linear regressions presenting r > 0.999, intermediate precision values < 6%, and recoveries within 76-95% were attained using a period of extraction of 10 min, a volume of sample solution of 5 µL, and a temperature of extraction of 50 °C. Analyses of brewed coffees were performed. The slopes of the calibration curves obtained using aqueous model solutions and brewed coffee samples were not significantly different. These results revealed no matrix effect under the selected experimental conditions, enabling the use of the external calibration method for quantification purposes. Twenty-four volatile carbonyl compounds were identified in brewed coffee, which elucidates the sensitivity of this approach.

Fin ray branching is defined by TRAP+ osteolytic tubules in zebrafish.

The shaping of bone structures relies on various cell types and signaling pathways. Here, we use the zebrafish bifurcating fin rays during regeneration to investigate bone patterning. We found that the regenerating fin rays form via two mineralization fronts that undergo an osteoblast-dependent fusion/stitching until the branchpoint, and that bifurcation is not simply the splitting of one unit into two. We identified tartrate-resistant acid phosphatase-positive osteolytic tubular structures at the branchpoints, hereafter named osteolytic tubules (OLTs). Chemical inhibition of their bone-resorbing activity strongly impairs ray bifurcation, indicating that OLTs counteract the stitching process. Furthermore, by testing different osteoactive compounds, we show that the position of the branchpoint depends on the balance between bone mineralization and resorption activities. Overall, these findings provide a unique perspective on fin ray formation and bifurcation, and reveal a key role for OLTs in defining the proximo-distal position of the branchpoint.

Gas-diffusion microextraction coupled with spectrophotometry for the determination of formaldehyde in cork agglomerates.

In this work, a simple methodology was developed for the extraction and determination of free formaldehyde content in cork agglomerate samples. For the first time, gas-diffusion microextraction was used for the extraction of volatile formaldehyde directly from samples, with simultaneous derivatization with acetylacetone (Hantzsch reaction). The absorbance of the coloured solution was read in a spectrophotometer at 412 nm. Different extraction parameters were studied and optimized (extraction temperature, sample mass, volume of acceptor solution, extraction time and concentration of derivatization reagent) by means of an asymmetric screening. The developed methodology proved to be a reliable tool for the determination of formaldehyde in cork agglomerates with the following suitable method features: low LOD (0.14 mg kg-1) and LOQ (0.47 mg kg-1), r 2 = 0.9994, and intraday and interday precision of 3.5 and 4.9%, respectively. The developed methodology was applied to the determination of formaldehyde in different cork agglomerate samples, and contents between 1.9 and 9.4 mg kg-1 were found. Furthermore, formaldehyde was also determined by the standard method EN 717-3 for comparison purposes; no significant differences between the results of both methods were observed. Graphical abstract Representation of the GDME system and its main components.

An Insight on Salting-out Assisted Liquid-Liquid Extraction for Phytoanalysis.

INTRODUCTION: Salting-out assisted liquid-liquid extraction (SALLE) is a technique that, although simple and not requiring any complex equipment, is very powerful and versatile. It has obtained growing interest in bioanalysis particularly when combined with chromatographic techniques. OBJECTIVES: Herein, fennel seeds (Foeniculum vulgare Mill.) were used as a case-study to show the application of SALLE in phytochemical analysis. MATERIAL AND METHODS: SALLE combined with HPLC-UV-MS/MS and GC-MS. RESULTS: By HPLC-UV-MS/MS analysis of the organic extract it was possible to identify various phenolic compounds, including quercetin derivatives, caffeic acid, p-coumaric acid and chlorogenic acid. The main compounds identified by GC-MS were estragole, fenchone, anisaldehyde, anethole, benzaldehyde, camphor and apiole. CONCLUSION: HPLC and GC analysis of the extracts showed that it is possible to isolate, in only one step, a wide range of compounds with distinct properties, allowing a detailed phytochemical analysis. Copyright © 2017 John Wiley & Sons, Ltd.

Increased sensitivity of anodic stripping voltammetry at the hanging mercury drop electrode by ultracathodic deposition.

An improved approach to the anodic stripping voltammetric (ASV) determination of heavy metals, using the hanging mercury drop electrode (HMDE), is reported. It was discovered that using very cathodic accumulation potentials, at which the solvent reduction occurs (overpotential deposition), the voltammetric signals of zinc(II), cadmium(II), lead(II) and copper(II) increase. When compared with the classical methodology a 5 to 10-fold signal increase is obtained. This effect is likely due to both mercury drop oscillation at such cathodic potentials and added local convection at the mercury drop surface caused by the evolution of hydrogen bubbles.