Potravinarstvo Slovak Journal of Food Sciences
Volume 14 202 2020
Potravinarstvo Slovak Journal of Food Sciences
vol. 14, 2020, p. 202-207
https://doi.org/10.5219/1299
Received: 3 February 2020. Accepted: 2 April 2020.
Available online: 28 April 2020 at www.potravinarstvo.com
© 2020 Potravinarstvo Slovak Journal of Food Sciences, License: CC BY 3.0
ISSN 1337-0960 (online)
EXTRACTIVE STRIPPING VOLTAMMETRY AT A GLASSY CARBON PASTE
ELECTRODE FOR ANALYSIS OF COW'S MILK AND CREAM
Granit Jashari, Michaela Frühbauerová, Milan Sýs, Libor Červenka
ABSTRACT
In this paper, a procedure based on extractive accumulation of milk fat globules (MFGs) into a pasting liquid (lipophilic
binder) of glassy carbon paste electrode (GCPE) with subsequent electrochemical detection by square-wave voltammetry
(SWV) in 0.1 mol L
-1
Britton-Robinson buffer of pH 4.0 has been tested to find out whether it can be utilized as a simple
screening analytical method for cow's milk and cream nutrition control. Since there is assumption that the necessary
alkaline hydrolysis of cow's milk and subsequent extraction of lipophilic vitamins into an organic solvent could be avoided,
several GCPEs differing in type (atactic polypropylene, paraffin oil, paraffin wax, silicone oil, and vaseline) and content
(5, 10, 15, 20, and 25%; w/w) of pasting liquid used were tested as part of complex optimization. The obtained results show
that MFGs contain predominantly vitamin A (carotenoids and retinoids), especially all-trans-retinol, which could serve as
significant marker of the fat content. However, their individual forms were not possible to distinguish due to the
considerable anodic peak broadening (overlapping).
Keywords: carbon paste electrode; cow's milk; extraction; milk fortification; nutrition control; voltammetry
INTRODUCTION
In the mammary glands, milk fat globules (MFGs),
ranging in size from 0.1 to 15 µm in diameter (Logan et
al., 2014), originate as fat droplets composed largely
(>98%) of triacylglycerols (TCGs). These fat droplets are
evenly emulsified throughout the volume and contain
lipophilic (fat-soluble) vitamins dissolved in them (Heid
and Keenan, 2005). Losses of naturally occurring
lipophilic vitamins are significant after mechanical
separating the milk fat (cream) from the raw milk.
Obtained skimmed milk is then homogenized that is a
process of breaking down the large fat droplets under high
pressure so that they stay together and do not separate as
cream. To improve the nutritional values, the homogenized
milk is usually fortified by extra vitamins (retinyl
palmitate and cholecalciferol) and minerals that are not
naturally found in milk in significant amounts (Trinidad
et al., 2015).
The cow's milk and products made from it are considered
as very complex sample matrixes and their analysis is
often complicated and time-consuming (Trenerry et al.,
2011). Valid reference analytical methods used for
lipophilic vitamins determination in foodstuffs in
laboratories of the Czech Agriculture and Food Inspection
Authority 211/2004 Coll4. utilize a HPLC with UV
detection, known as standard: ČSN EN 12823 (vitamin A),
ČSN EN 12821 (vitamin D), ČSN EN 12822 (vitamin E)
and ČSN EN 14148 (vitamin K). In addition, a gravimetric
method (EN 1211) is used to determine milk fat content.
Evaluation of the lipophilic vitamins content in milk
(also dairy produce) has its substantiation, especially in
case of human nutrition which deals on provision of
essential nutrients in food necessary to support human life
and health (Haug et al., 2007). Moreover, analytical
methods for simultaneous determination of lipophilic
vitamins and their provitamins in milk using microcolumn
(Gomis et al., 2000), narrow-bore column (Blanco et al.,
2000) and two-dimensional liquid chromatography
(Zhang et al., 2015) have been developed.
Time-consuming sample preparation is the most
challenging step in the analysis as it involves several steps
(alkaline hydrolysis, liquid-liquid extraction, filtration and
evaporation of organic solvent) in which the analytes may
be lost (Trenerry et al., 2011). To avoid degradation of
analytes, the alkaline hydrolysis shoud be carried out in
presence of an antioxidant, under an inert atmosphere, and
in absence of light.
A simple semiquantitative method for the determination
of vitamin D in skim milk is worth mentioning (Michlová
et al., 2012) when a sample is diluted with water, ethanol,
and an aqueous ammonia solution. Vitamin D is
subsequently extracted with a mixture of ether and hexane