The aim of this work was to study the extraction behavior of the main coffee antioxidants (caffeoylquinic acids, melanoidins and caffeine) and the antioxidant capacity, during brewing time in the most widely consumed coffee brew methods (filter and espresso) in coffee. Antioxidant capacity by colorimetric assays (Folin–Ciocalteau, ABTS and DPPH) and electron spin resonance spectroscopy techniques (Fremy's salt and TEMPO) were analyzed. In espresso coffee, more than 70% of the antioxidants (except dicaffeoylquinic acids, diCQA) of a coffee brew were extracted during the first 8s. In filter coffee, a U-shape antioxidants extraction profile was observed, starting later (after 75s) in Vietnam coffee than in Guatemala one, probably due to different wettability. Other technological parameters, such as turbulences and a longer contact time between water and ground coffee in filter coffeemaker, increased extraction efficiency, mainly in less polar antioxidant compounds as diCQA. In conclusion, these technological factors should be considered to optimize coffee antioxidants extraction that can be used as ingredients for functional foods.

The main hydrophilic antioxidant compounds (3-, 4-, and 5-monocaffeoylquinic and 3,4-, 3,5-, and 4,5-dicaffeoylquinic acids, caffeine, and browned compounds, including melanoidins) and the antioxidant capacity (Folin-Ciocalteu, ABTS, DPPH, Fremy's salt, and TEMPO) were evaluated in Arabica and Robusta spent coffee obtained from the preparation of coffee brews with the most common coffeemakers (filter, espresso, plunger, and mocha). All spent coffee grounds, with the exception of those from the mocha coffeemaker, had relevant amounts of total caffeoylquinic acids (6.22-13.24 mg/g of spent coffee), mainly dicaffeoylquinic acids (3.31-5.79 mg/g of spent coffee), which were 4-7-fold higher than in their respective coffee brews. Caffeine ranged from 3.59 to 8.09 mg/g of spent coffee. The antioxidant capacities of the aqueous spent coffee extracts were 46.0-102.3% (filter), 59.2-85.6% (espresso), and <42% (plunger) in comparison to their respective coffee brews. This study obtained spent coffee extracts with antioxidant properties that can be used as a good source of hydrophilic bioactive compounds.

The antioxidant capacity of coffee brews prepared with different coffeemakers (filter, plunger, mocha, and espresso) was measured by colorimetric (total phenolic compounds and ABTS) and electron spin resonance (ESR) spectroscopy techniques (Fremy's salt and TEMPO). The mocha coffeemaker had the highest yield in coffee antioxidant extraction per gram of ground roasted coffee, but espresso coffee was richest in terms of antioxidant intake (per milliliter of coffee brew) followed by mocha, plunger, and filter. Both Folin-Ciocalteu (total phenolic compounds) and ABTS assays reacted with standard solutions of chlorogenic acids (CGA) and melanoidins (MO-Ala and MO-Gly). However, Fremy's salt was mainly scavenged by chlorogenic acids, whereas the stabilized radical TEMPO was effectively scavenged by melanoidins, but not by chlorogenic acids. Thus, ESR spectroscopy allows distinguishing between phenolic and nonphenolic antioxidants. Moreover, the addition of pH-regulator agents to coffee, such as sodium carbonate (75 ppm) and bicarbonate (75 ppm), to extend its shelf life, slightly increases the pH, modifying the antioxidant capacity in those coffee brews with the highest capacity (mocha and espresso).

AbstractJe niedriger die antioxidative Aktivität von Erdnüssen ist, desto schneller verderben sie. Die Elektronenspinresonanzspektroskopie erfasst den Gehalt von antioxidativen Substanzen eines Lebensmittels und sagt so die Lagerfähigkeit der Produkte voraus.

Changes in the oxidative status of peanuts and linseeds during storage were investigated by the ESR spin trapping technique with N-tert. butyl-α-phenylnitrone. It has proven to be a suitable method for the determination of the radical generating reactions in the very early stage of fat spoilage and deterioration reactions can still be detected, before changes in sensory properties are noticeable. Primarily, due to oxidative reactions of lipids, shelf life of peanuts and linseeds as well as their sensory quality decreases with storage time. Roasting has a controversial influence on the stability of linseeds and peanuts, respectively. Roasted linseeds became rancid more rapidly than fresh seeds. With increasing roasting temperature and time the oxidative stability of peanuts was improved and shelf life prolonged. This can be attributed to the formation of antioxidant Maillard reaction products. A correlation was found between the amount of deoxyosones as reactive Maillard reaction intermediates and shelf life of roasted nuts.

During the roasting of cocoa beans chemical reactions lead to the formation of Maillard reaction (MR) products and to the degradation of catechin-containing compounds, which are very abundant in these seeds. To study the modifications occurring during thermal treatment of fat and antioxidant rich foods, such as cocoa, a dry model system was set up and roasted at 180 degrees C for different times. The role played in the formation of MR products and in the antioxidant activity of the system by proteins, catechin, and cocoa butter was investigated by varying the model system formulation. Results showed that the antioxidant activity decreased during roasting, paralleling catechin concentration, thus suggesting that this compound is mainly responsible for the antioxidant activity of roasted cocoa beans. Model system browning was significantly higher in the presence of catechin, which contributed to the formation of water-insoluble melanoidins, which are mainly responsible for browning. HMF concentration was higher in casein-containing systems, and its formation was strongly inhibited in the presence of catechin. No effects related to the degree of lipid oxidation could be observed. Data from model systems obtained by replacing fat with water showed a much lower rate of MR development and catechin degradation but the same inhibitory effect of catechin on HMF formation.

The antioxidative properties of coffee brew fractions were studied using electron spin resonance spectroscopy using 2,2,6,6-tetramethyl-1-piperidin-1-oxyl (TEMPO) and Fremy's salt (nitrosodisulfonate) as stabilized radicals. TEMPO was scavenged by antioxidants formed during roasting and not by chlorogenic acid, whereas Fremy's salt was scavenged by all antioxidants tested including chlorogenic acid. The stabilized radical TEMPO allowed the exclusive measurement of roasting-induced antioxidants. The roasting-induced antioxidant activity of coffee brews increased with increasing degree of roast, and most of these antioxidants were formed during the initial roasting stage. The majority of these roasting-induced antioxidants were present in the high molecular weight fractions, indicating that the formation of these antioxidants preferably occurs at specific high molecular weight structures, likely being arabinogalactan and/or protein moieties which might be part of the melanoidin complex. It was found that chlorogenic acids most probably do not lose their antioxidant activity and phenolic characteristics upon incorporation in coffee melanoidins. The parameter fast reacting antioxidants (FRA) was introduced as an alternative for the antioxidative potential. FRA levels showed that coffee fractions rich in roasting-induced antioxidants exposed their antioxidant activity relatively slowly, which must be a consequence of its complex structure. Finally, the melanoidin content and the roasting-induced antioxidant activity showed a positive and linear correlation for the coffee brew fractions, showing that roasting-induced antioxidants are present within melanoidins. This is the first time that the formation of roasting-induced antioxidants could be directly correlated with the extent of Maillard reaction and melanoidin formation in a complex product such as coffee.

Raw, pre-roasted and roasted Cocoa samples were separated into four different molecular weight fractions (> 30, 30-10, 10-5 and < 5 kDa) with ultrafiltration and tested for their antibacterial, mutagenic, as well as their radical-scavenging effects. Radical-scavenging effects were tested with electro paramagnetic resonance spectroscopy, anti-mutagenicity in the Salmonella microsome assay (with and without metabolic activation), and antibacterial effects by incubating the fractions with several strains of Bifidobacteria, Enterobacter and Escherichia, and observing their growth. The radical-scavenging activity and reducing substance concentrations increased, particularly in the 5-10-kDa roasted fraction. Chromaticity testing elucidated that the 10-5-kDa fraction was one of the darkest fractions. The Salmonella microsome assay showed neither mutagenic nor anti-mutagenic effects in any of the samples at any of the different concentrations applied when using TA98, TA100 and TA102. All fractions reduced the growth of pathogenic bacteria, in particular at the highest concentration of 100 microg/mL; however, the same trends were also observed for Bifidobacteria.

During the early stage of the Maillard reaction pyrazinium radical cations were detected by ESR within the reaction system d-glucose/glycine. The spectra were characterized by completely resolved hyperfine structure. The partial pressure of oxygen and the radical concentrations were measured directly in the reaction mixture by ESR using solutions of the spin probe TEMPOL and of DPPH, respectively. There are quantitative and qualitative relations of the actual concentration of the radical ions to the partial pressure of oxygen, the temperature-time regime and the mechanical mixing of the reaction system. These macroscopic parameters significantly affect both the induction period and the velocity of the time-dependent formation of free radicals. From in situ variations of p(O2) and p(Ar) including the connected mixing effects caused by the passing the gases through the reaction mixture, steric and chemical effects of the stabilization of the radical ions were established. The determination of suitable and relevant conditions for stabilization and subsequent radical reactions contributes to the elucidation of the macroscopically known antioxidant activity of Maillard products.