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Impact of Alkalization on the Antioxidant and Flavanol Content of Commercial Cocoa Powders
Abstract
Cocoa is a food ingredient that is important for the contribution of flavor to foods but is also associated with potential health benefits. The chemistry thought to be responsible for its cardiovascular health benefits is the flavanol (flavan-3-ol) antioxidants. Evidence from the literature indicates that natural cocoas are high in flavanols, but when the cocoa is processed with alkali, also known as Dutch processing or Dutching, the flavanols are substantially reduced. This paper provides a survey of the physical and chemical composition of representative natural cocoas and lightly, medium, and heavily alkalized cocoas. As part of the survey, both brown/black and red/brown alkali-processed cocoas were measured. Natural cocoa powders have an extractable pH of 5.3−5.8. Alkalized cocoa powders were grouped into lightly treated (pH 6.50−7.20), medium-treated (pH 7.21−7.60), and heavily treated (pH 7.61 and higher). The natural, nonalkalized powders had the highest ORAC and total polyphenols and flavanols (including procyanidins). These chemical measurements showed a linear decrease as the extractable pH of the cocoa powder increased. Likewise, the flavanol monomers, oligomers, and polymers all showed a linear decrease with increasing pH of the final cocoa powder. When brown/black cocoa powders were compared to red cocoa powders, similar decreases in flavanols were observed with increased alkalization. The average total flavanol contents were 34.6 ± 6.8 mg/g for the natural cocoas, 13.8 ± 7.3 mg/g for the lightly processed cocoas, 7.8 ± 4.0 mg/g for the medium processed cocoas, and 3.9 ± 1.8 mg/g for the heavily processed cocoa powders. The observed linear and predictable impact of alkalization on flavanol content is discussed with respect to other reports in the literature as well as what implications it may have on diet and food manufacturing.Keywords: Alkalization; Dutching; flavanols; flavan-3-ols; procyanidins; antioxidants; cocoa powder; cacao
... Depending on the pH, the alkalized cocoa material can then be categorized as light-(pH 6-7.2), medium-(pH 7.2-7.6), or strong-alkalized cocoa (pH > 7.6) [19]. ...
... The obtained values allowed the classification of the different samples into different categories: light-alkalized (pH 6-7.2), mediumalkalized (pH 7.2-7.6), and strong-alkalized cocoa material (pH > 7.6) [19]. The pH of the alkalized CBS and commercial ...
... TPC changed from 24.02 to 14.27 mg GAE/g (40% reduction), TFC decreased from 22.51 to 16.20 mg GAE/g (28% reduction), and CTC decreased from 2.40 to 1.45 mg CE/g (40% reduction). This observation agrees with the results of several studies on alkalized cocoa powder where the employed alkalization process resulted in the reduction of polyphenols and flavonols of the samples [19,21,49,51]. ...
Cocoa bean shell (CBS) is a byproduct of cacao processing that is of high nutritional and functional value. However, its application in food is still limited due to some undesirable properties. The alkalization process can further broaden its use as a food ingredient by modifying its properties. This study investigated the physicochemical and prebiotic properties of variously alkalized CBS powders, and compared them with commercial alkalized cocoa powders. Samples were analyzed for pH, titratable acidity, water activity, color, proximate and bioactive composition, phenolic profile, antioxidant properties, and prebiotic potential. Findings revealed that the varying degrees of alkalization led to reduction in values of CBS properties including titratable acidity (23–88%), fiber (4–11%), total phenolic content (15–41%), and antioxidant activity (13–34%). Meanwhile, the prebiotic potential of the laboratory-produced CBS powder samples was confirmed by the computed positive prebiotic activity scores (0.75–1.05). Compared to commercial cocoa powders, alkalized CBS powders exhibited lower fat (7.43–7.98 g/100 g vs 10.16–12.18 g/100 g), and higher fiber (8.71–9.76 g/100 g vs 0.42–0.68 g/100 g) and total phenolic content (14.27–24.02 mg GAE/g vs 12.46–13.30 mg GAE/g). These results highlight the potential of alkalized CBS powder as a functional food ingredient. The varying levels of alkalization expand its potential applications across a range of food products.
... As expected, alkalization increased the pH of the cocoa powder (Table 2). According to the classification of alkalized cocoa powder [32], all of the investigated commercial samples fell into the medium-alkalized range (pH 6.5-7.2), whereas no samples were assigned into the highly alkalized range (pH > 7.6). ...
... The TPC values of the samples covered a quite broad interval of contents (Table 3), ranging from 3.63 to 140.89 mg GAE g −1 , giving an indication of the wide variability in the total content of phenolic compounds in cocoa powder, which, in turn, is related to the variability of the raw materials, as well as that of the processing conditions adopted. Such a wide range comprises the values reported in other studies [23,32,38]. ...
... As far as alkalization is concerned, it has been proven to strongly affect the content of phenolic compounds, generally causing a reduction, which is strictly related to the degree of alkalization when all the other conditions are equal. In fact, losses in the content of total polyphenols of around 27%, 54%, and 63% are reported for lightly, medium-, and heavily alkalinized cocoa powder, respectively [32]. In the samples under investigation in the present study, the reduction in both the TPC and flavanol (nSensor) values in the alkalized samples accounted, on average, for about 50% and 60%, respectively, when compared with the non-alkalized cocoa powders. ...
Cocoa (Theobroma cacao, L.) represents an important market that gained relevance and became an esteemed commodity thanks to cocoa powder, chocolate, and other related products. This work analyzed 59 cocoa powder samples from the European market. Three distinct subgroups were identified: organic or conventional, alkalized or not alkalized, and raw or roasted processing. The impact of the technological process on their pH, color, and compositional traits, as well as their content of biogenic amines and salsolinol, was evaluated. The phenolic fraction was also investigated through both common and emerging methods. The results depict that the influence of the agronomical practices (organic/conventional) did not significantly (p < 0.05) affect the composition of the cocoa powders; similarly, the roasting process was not a determinant of the compounds traced. On the other hand, the alkalinization process greatly impacted color and pH, no matter the cocoa’s provenience or obtention or other processes, also resulting in reducing the phenolic fraction of the treated samples. Principal component analysis confirmed that the alkali process acts on pH, color, and phenolic composition but not on the content of other bioactive molecules (biogenic amines and salsolinol). All the samples were safe, while the alkalized powders saw a great reduction in beneficial biocompounds. A novel strategy could be to emphasize on the label whether cocoa powder is non-alkalized to meet the demand for more beneficial products.
... Cocoa powder has been used as the primary raw material in a wide range of food products such as chocolate syrups and coatings, beverages, bakery products, icings, and dairy products in order to provide color and flavor to the end products (Miller et al., 2008). In addition to its flavor and color properties, cocoa powder gains more attraction from the industry every year due to its high polyphenol content, and its production and consumption are increasing. ...
... Alkalization or "Dutching" is applied since the 19th century in order to improve solubility and color properties and reduce astringent and bitter flavor and acidic volatile fractions by mixing cocoa products with alkali solutions under high pressure and temperature in the presence of oxygen. As a result, a reduction of up to 90% in the total flavanol content occurs depending on the processing parameters due to the Maillard and glycosylation reactions, degradation by polyphenol oxidase (PPO), and epimerization, isomerization, and polymerization reactions (Li et al., 2012;Miller et al., 2008). However, the conventional alkalization process has disadvantages such as high temperatures (60-130 • C), long processing times (5-180 min), difficulties in the control of color development, high concentrations of alkaline chemicals (up to 6%), large processing area requirements, complex process, high pressures (up to 12 atm), and the need for aeration (with rates up to 5 bar/min), which significantly increases the production cost. ...
... In the study of Gültekin-Özgüven et al. (2016), the TPC and TFC of cocoa liquor was decreased by 87% and 83% after heavy alkalization, respectively. Reductions up to 89% were also reported for the TFC of commercial cocoa powders by Miller et al. (2008). In parallel with these studies, percent losses of approximately up to 51% and 48% in the TPC and TFC have occurred following the alkalization, respectively (P < 0.05). ...
In the production of cocoa, a crucial process called “Alkalization” or “Dutching” has been used to reduce its acidity, bitterness and astringency as well as modify its solubility and color. It is a time- and energy-consuming process. It was investigated whether it is possible to replace the conventional alkalization with the cold plasma (CP) technique. We discover that atmospheric pressure plasma jet (APPJ) CP treatment is capable of reducing the lightness values, improving the solubility, and decreasing the acidic perception of natural cocoa powders as well as protecting bioactive compounds (total phenolic and flavonoid content) of natural cocoa powders, consuming ∼65% less time than the traditional method and without the need for external expenditures such as chemicals, high pressure, or aeration. Moreover, CP treatment did not increase the total ash content and thus water-holding capacity of powders unlike the conventional alkalization, which caused a 40% and 42% increase, respectively. The SEM micrographs demonstrated that CP treatment caused etching on the surface and removed the layer of protein-polyphenol-cell wall complex. FTIR spectra showed the incorporation of hydrophilic functional groups on the surface after CP treatment. CP treatment effectively reduced the acidic fractions of cocoa powder, but caused to the oxidation of cocoa butter and the formation of decomposition products of oleic and linoleic acid. Finally, this is a pioneering study for replacing an alkalization process step that has been used since the 19th century and has no alternative, and the results seem to be very promising for further detailed studies and pilot- and industrial-scale trials.
... Depending on the pH values, cacao powder is named dark natural (5-6 pH), light (6-7.2 pH), medium (7.2-7.6) and strong alkalized cocoa (higher than 7.6) (Miller et al., 2008). With this process, the acidic pH value of cocoa is shifted in the basic direction. ...
... This makes this process less expensive. As disadvantages, deficiencies in colour development and relative loss in aroma can be distinguished (Miller et al., 2008;Valverde García et al., 2020). The third method, chocolate liquor alkalization, is carried out by alkalizing cocoa beans after sorting, roasting and grinding. ...
... The disadvantages are that cocoa butter is alkalized and requires extra processing and is thus expensive. Colour development is limited and darker brown end product is formed (Miller et al., 2008;Moser, 2015). ...
... Several researchers have demonstrated the detrimental impact of alkalization on the phytochemical content of cocoa (Gu et al., 2006;Li et al., 2014;Miller et al., 2008;Payne et al., 2010;Quelal-Vásconez et al., 2020;Stanley et al., 2015;Todorovic et al., 2017;Valverde et al., 2020), whereas some others attempted to study the impact of alkalization conditions on the final cocoa flavor (Alasti et al., 2020;Huang & Barringer, 2010Li et al., 2012;Mohamadi Alasti et al., 2019;Serra Bonvehí & Ventura Coll, 2002). However, the minor flavonoids have not been investigated thus far and their presence in cocoa powder might affect its orosensory properties. ...
... According to the classification of alkalized cocoa powders, the powder treated with NaOH 1.17% w/w is assorted into the medium-alkalized range (pH 6.5-7.2), whereas the one treated with NaOH 2.34 % w/w is assorted into the highalkalized range (pH >7.6) (Miller et al., 2008). ...
... Apart from the epimerization, other processes must have taken place since the total level of procyanidin B1 and B2 also decreased when a more intense alkalization is applied. Several studies reported a similar reduction in total procyanidin content (monomers, dimers, trimers, up to oligomers and/or polymers) after alkalization (Andres-Lacueva et al., 2008;Gu et al., 2006;Miller et al., 2008;Stanley et al., 2015). However, in the current study, no higher procyanidin oligomers were quantified. ...
Alkalization is a process to improve color, dispersibility and flavor of cocoa powder but is likely to have a negative effect on the phytochemicals. Hereto, the impact of alkalization degree (none, medium and high) on the potential mood-enhancing compounds corresponding to the four levels of the mood pyramid model (flavanols, methylxanthines, biogenic amines and orosensory properties) was investigated. The phytochemical content, analyzed via UPLC-HRMS, showed reduction of specific potential mood-enhancing compounds upon alkalization, implying a decrease in bitterness and astringency. Moreover, volatile compounds analysis via HS-SPME-GC-MS indicated that alkalization reduced the levels of volatile compounds, responsible for acidity, fruity, floral and cocoa aromas. With respect to the orosensory properties, the cocoa powder palatability was suggested to be increased due to reduced acidity, bitterness, and astringency, while the desired volatile compounds were reduced. However, sensorial analysis is required to link the volatile results with the overall effect on the flavor perception.
... flavan-3-ols, anthocyanins and proanthocyanidins), and methylxanthines (i.e. theobromine, caffeine and theophylline) (Li et al., 2012;Miller et al., 2008). ...
... As expected, alkalization greatly darkened the color of cocoa powder and rapidly increased its pH (Table 1). All alkalized cocoa powders reached a pH above 8, meaning that they were in the range of heavily alkalized powders (Miller et al., 2008). Alkalization under constant alkali concentration of NaOH 2.34% w/w, altered the color since all alkalized powders had a ΔE value substantially above 1 when compared to the non-alkalized powder, which can be visually perceived darker from consumers, as the biggest differences were observed in the L* value (Stanley et al., 2015). ...
... Based on the classification of alkalized cocoa powders, the powders treated with NaOH 0.59 and 1.17% w/w fall into the lightly alkalized range (pH 6.5-7.2), while the ones treated with NaOH 2.34 and 3.59% w/w fall into the heavily alkalized range (pH > 7.6) irrespective of the alkalization time (Miller et al., 2008). Unlike the others, the pH values of powders treated with NaOH 0.59% w/w were below 7.2, which indicates that this alkali concentration was not sufficient to fully neutralize the acidity of the natural cocoa powder. ...
Alkalization is an important process in cocoa powder production that affects color and flavor. In this study, the impact of alkalization temperature (60, 70, 80, 90, 100 °C), NaOH concentration (0.59, 1.17, 2.34, 3.59% w/w of cocoa powder) and alkalization time (1 and 10 min) on the physicochemical properties (pH, color) and phytochemical profile (theobromine, caffeine, epicatechin, catechin) of cocoa powder were investigated, while the aroma was studied on the corresponding cocoa drinks. High-performance liquid chromatography coupled to an ultra-violet detector (HPLC-UV) was used for screening the non-volatiles and headspace solid - phase microextraction - gas chromatography - mass spectrometry (HS-SPME-GC-MS) for the aromatic compounds. Major changes of the cocoa properties occurred during the first minute of alkalization. Increase of temperature and alkali concentration generally reduced the levels of epicatechin and the lightness (L*), while the pH of the cocoa powder was affected by changing the alkali concentration. On the other hand, the reddish (a*) and yellowish (b*) color component values and theobromine levels were not significantly affected by varying temperature and alkali concentration. A higher temperature did not affect the concentration of the volatile compounds, while a decrease in certain chemical classes was observed by increasing the alkali concentration.
... These compounds are characterized by their high electrochemical activity and susceptibility to oxidative degradation (Cai et al., 2022). In particular, under neutral pH conditions, such as in the oral cavity or small intestine, they are known to immediately produce reactive oxygen species and decompose to produce decomposition products or oxides condensed with decomposition products (Friedman & Jürgens, 2000;Miller et al., 2008;Xue et al., 2024). FLs, a typical astringent substance, are abundant in cocoa, red wine, and berries. ...
... This process releases ROS in the neutral pH of the oral cavity and small intestine. It has been documented that this reaction yields lowmolecular-weight decomposition products and high-molecular-weight oxides, which are formed by condensation of the decomposition products (Friedman & Jürgens, 2000;Miller et al., 2008;Xue et al., 2024).In our previous study, the increase in skeletal muscle blood flow via hyperactivation of the SNS observed immediately after administration of epicatechin tetramer, a type of flavanol, to rodents was diminished by co-administration of the antioxidant N-acetylcysteine. In addition, this hemodynamic alteration of FL was marked suppressed by co-administration of a TRP-vanilid 1 or TRP-ankirin 1 antagonist . ...
Astringent flavanols (FLs) have shown enhanced cognitive function in a large intervention trial, but their mechanism remains unclear due to poor bioavailability. An oral dose of FLs increased spontaneous locomotion and memory, with activation of the sympathetic-adrenergic-medullary (SAM) and hypothalamic-pituitary-adrenal (HPA) axis, as shown by increased urinary catecholamine concentrations and corticotropin-releasing hormone (CRH) mRNA expression in the paraventricular nucleus (PVN) of mice. MS imaging showed high intensity of noradrenaline (NA) in the locus coeruleus (LC), which plays a key role in learning and memory, the hypothalamus lateral preoptic area, which affects sleep and arousal, and the brainstem as the origin of the sympathetic nervous system, immediately after FLs administration. Subsequent in situ hybridization (ISH) analysis showed that these NAs originated from LC. Astringent compounds like FLs influence brain function and physiological changes. Furthermore, the present series of results presents novel mechanisms by which food sensory properties maintain homeostasis.
Highlights
- A oral dose of astringent flavanols (FLs) immediately fires locus coeruleus-noradrenaline axis
- FLs enhance spontaneous locomotion and short-term memory in mice
- SAM and HPA axis are also activated by an oral dose of FLs
- FL’s astringency affects the brain and body, contributing to homeostasis.
... Principal component analysis (PCA) was conducted to summarize the relationships between the chocolate milk samples and sensory attributes [50]. In order to assess the relationship between the overall acceptability and the sensory characteristics, partial least squares regression (PLSR) was run on the mean overall liking scores and mean descriptive sensory scores [51]. Standardized regression coefficient figures were produced for overall acceptance and the sensory characteristics that show the "drivers of liking" or the sensory characteristics that correlate either positively or negatively with overall acceptance. ...
... This may be due to the inherent content of odor-active volatile compounds detected in a previous study in buffalo milk, such as octen-3-ol (mushroom), nonanal (grassy), indole (stable animals), and an unidentified compound characterized by a smoked cheese aroma [87]. A cursory inspection of the goodness of fit statistics of the PLS model shows that cumulative Q 2 = 0.80, indicating a high degree of stability in the model, and the difference between R 2 and Q 2 was below 0.3, indicating that the PLSR model had a high explanatory value [51,88]. Table 7 shows the purchase intention for buffalo chocolate milk with different types of cocoa powder. ...
Due to its nutritional quality and palatability, chocolate milk beverages are gaining popularity globally. Alkalized cocoa powder is mostly used in its production since it provides for more intense color and dispersibility, but it has a negative effect on the phytochemical content of cocoa powder. Studies have suggested that water buffalo milk is superior to other milk due to its higher protein content and superior emulsion properties. As such, this study investigated the physico-chemical characteristics, sensory profile, and consumer acceptability of commercial and prototype water buffalo chocolate milk incorporated with alkalized and natural cocoa powder. Based on four buffalo chocolate milk samples, consumer acceptance was assessed by 120 consumers, which was combined with descriptive sensory data using a trained panel (n = 8) to determine drivers of liking. Compositional proximate analysis of alkalized and natural cocoa powders showed a significant difference in pH, moisture content, ash content, and fat content. Descriptive analysis showed that 8 out of 13 attributes (color, visual sandiness, cocoa and vanilla aroma, smoothness, creaminess, vanilla taste, and chocolate aftertaste) were effective discriminators of sensory attributes. Overall, buffalo chocolate milk samples were equally liked, but hedonic ratings of the individual attributes revealed that the samples were statistically different for color, viscosity (mouthfeel), and chocolate flavor. Partial least square regression (PLSR) identified chocolate flavor, viscous appearance, viscous mouthfeel, and bitter aftertaste as positive “drivers of liking”. The darker color provided by alkalized cocoa powder did not increase consumer liking. The purchase intention was equal for all chocolate milk samples, whether alkalized or natural. Both cocoa powders showed comparable performance in the manufacture of buffalo chocolate milk. Using natural cocoa powder may be beneficial to local producers of cocoa powder and cocoa farmers since it is easier to produce, while it can provide a marketing advantage for dairy beverages in the global trend of going back to “organic” and “natural”.
... pH was used to classify samples into different categories according to Miller's scale (Miller et al., 2008). Those cocoas with a pH between 5 and 6 were considered natural cocoas, those with a pH between 6 and 7.2 were taken as lightly alkalized, between 7.2 and 7.6 were moderately alkalized, and those over 7.6 were strongly alkalized. ...
... Coef. used to classify cocoa into different categories (Miller et al., 2008). pH also conditions sample color because its increases the enzyme activity of polyphenol oxidase (Misnawi, Jamilah, & Nazamid, 2003;Rodríguez et al., 2009) and enhances several chemical reactions that darken cocoa (Germann, Stark, & Hofmann, 2019a, 2019b). ...
Traditional alkalization, essential for darkening color, modifying flavor and increasing cocoa powder solubility, is a discontinuous time-consuming technique that employs considerable energy. We herein propose extrusion as a promising alternative to improve and increase the sustainability of the traditional process. The aims of this work were twofold: on the one hand, to characterise the effects of extrusion on alkalised cocoa physico-chemical features; on the other hand, to determine if alkalized powders possess similar characteristics to those obtained by conventional treatment. The results showed that alkali was the main variable to increase pH and to diminish color. Compared to commercial samples, the developed cocoas had darker colors than, and similar sensory properties to, their reference commercial cocoas. These findings confirm that extrusion is suitable for producing high sensory acceptable alkalized products quickly, sustainably and continuously.
... Some manufacturers include an additional step of alkalization, also known as Dutching, which is applied to the cocoa beans, cocoa liquor or cocoa powder (Miller et al. 2008) to obtain the desirable dark brown color, reduce bitterness and astringency, and prevent the sinking of cocoa powder in cocoa-based drinks (Miller et al. 2008). When cocoa is alkalized, after heating in a closed mixing vessel, a warm alkali solution is added for a specific reaction time, and excess moisture is removed by heating or drying (Li et al. 2014). ...
... Some manufacturers include an additional step of alkalization, also known as Dutching, which is applied to the cocoa beans, cocoa liquor or cocoa powder (Miller et al. 2008) to obtain the desirable dark brown color, reduce bitterness and astringency, and prevent the sinking of cocoa powder in cocoa-based drinks (Miller et al. 2008). When cocoa is alkalized, after heating in a closed mixing vessel, a warm alkali solution is added for a specific reaction time, and excess moisture is removed by heating or drying (Li et al. 2014). ...
Cocoa beans, the seeds of the tree Theobroma cacao L., are the key raw material for chocolate production that implies an extensive post-harvest process. Chocolate properties can vary depending on cocoa origin, composition and manufacturing procedure, which will give unique sensory properties to the final product. On the other hand, the high global consumption of cocoa products, long recognized as a major source of dietary polyphenols with important health benefits, has increased interest in tracking the geographical origin of cocoa and authenticating chocolate to guarantee product quality and reveal possible commercial fraud. However, the sustainable production of high-quality cocoa is still far from reality, and the cocoa sector continues to face many challenges in this field. This review provides an update on the progress toward the authenticity, traceability and sustainability of cocoa products, issues that chocolate producers still need to resolve.
... Samples were classified into different alkalization levels by following the classification by Miller: natural (pH 5-6), slight (pH 6-7.2), medium (pH 7.2-7.6) and strong alkalized (pH > 7.6) (Miller et al., 2008). ...
... With NaOH, values lowered to 58% and 80% for catechin and epicatechin, respectively, when samples were treated with the strongest processing variables. These results agree with other authors in line with two facts: (1) cocoa alkalization leads to general polyphenols degradation (Gültekin-Özgüven et al., 2016;Miller et al., 2008;Gu et al., 2006;Jolić et al., 2011;Zhu et al., 2002); (2) (-)-epicatechin is more sensitive to alkalization than (+)-catechin (Gültekin-Özgüven et al., 2016;Andres-Lacueva et al., 2008). ...
Polyphenols, a group of secondary metabolites, have well-known relevant effects on human health. During traditional alkalization, this content dramatically lowers. We aimed to evaluate an alternative alkalization method based on extrusion on cocoa functional characteristics. The results showed that the antioxidant capacity and total phenolic values increased as alkali concentration and temperature did, and these values doubled under less extreme conditions. Comparing the functional properties between extruded and traditionally produced powders revealed that catechin, epicatechin and dimers B1 and B2 contents were 43%, 33%, 54% and 34% lower in the extruded samples, respectively. However, this reduction was partially balanced by increased clovamide content up to 50%. Thus the total phenol content and antioxidant capacity of the extruded samples were statistically above those of the commercial one. Hence extrusion alkalization should be considered a new processing alternative to avoid markedly reducing functional properties.
... These researchers reported that the previous characteristics reduced by 87%, 83%, and 50%. These losses were similar to those reported by Miller et al. (2008) in commercial cocoa powders, which were 89% for flavanols in highly alkalized cocoa, by Gu, House, Wu, Ou, and Prior (2006) in commercial cocoa powders, which were 51% for antioxidant activity and 78% for procyanidins, and by Jolić, Redovniković, Marković, Šipušić, and Delonga (2011) in commercially alkalized cocoa nibs, which were 64% for total phenolic content, 59% for total procyanidins, and 39% for antioxidant activity. In another work, Zhu et al. (2002) simulated the alkaline conditions of the lower gut and found an 85% loss in flavanols and procyanidins at pH 7.4 after 24 h, and a 100% loss at pH 9 after 4 hr. ...
... Andres-Lacueva et al., 2008;Rodríguez et al., 2009;Miller et al., 2008;Gültekin-Özgüven et al., 2016;Jolić et al., 2011;Zhu et al., 2002;Gu et al., 2006;Todorovic et al., 2017;Hurst et al., 2011;Kofink et al., 2007;Ortega et al., 2008;Stark and Hofmann, 2006; Peterson, 2005, 2007;Zhang et al., 2014;Germann et al., 2019a and2019b;Todorovic et al., 2017 Methylxanthines• Theobromine and caffeine are reduced Theobromine interacts with bases and forms saltsLi et al., 2012;Oduns and Longe, 1998 ...
Alkalization, also known as “Dutching,” is an optional, but very useful, step taken in the production chain of cocoa to darken its color, modify its taste, and increase natural cocoa solubility. Over the years, various attempts have been made to design new and more effective alkalization methods. Moreover, different authors have attempted to elucidate the impact of alkalization on the physicochemical, nutritional, functional, microbiological, and sensory characteristics of alkalized cocoa. The aim of this review is to provide a clear guide about not only the conditions that can be applied to alkalize cocoa, but also the reported effects of alkalization on the nutritional, functional, microbiological, and sensory characteristics of cocoa. The first part of this review describes different cocoa alkalization systems and how they can be tuned to induce specific changes in cocoa properties. The second part is a holistic analysis of the effects of the alkalization process on different cocoa features, performed by emphasizing the biochemistry behind all these transformations.
... Natrium bicarbonate which is also well-known as sodium bicarbonate is considerably cheap, easy to find and allowed to be used in food processing in the certain amount. However, it is also important to note that alkalization may affect the chemical properties of the cocoa powder particularly phenolic content and antioxidant activity (Miller et al., 2008;Li et al., 2012;Sioriki et al., 2022). Therefore, this research aimed to study the feasibility of a small-scale pressure vessel for cocoa powder alkalization. ...
Alkalisation is a vital process to strengthen the flavour or modify the colour of cocoa powder, prevent sedimentation, and reduce the acidity of cocoa powder. This study aims to determine the feasibility of a small-scale, environmentally friendly pressure vessel for cocoa powder for Alkalisation. The effect of sodium bicarbonate (NaHCO 3 ) concentration and Alkalisation time with pressurized vessels on cocoa powder’s physical and antioxidant characteristics was evaluated. This study was compiled using a Completely Randomized Factorial Design with variations in NaHCO3 concentration and Alkalisation time. The data were analyzed using a Two-way Analysis of Variance (ANOVA) and Duncan’s Multiple Range Test (DMRT). The result shows that the Alkalisation process significantly affects the physical and antioxidant properties of cocoa powder. The concentration of NaHCO3 and the duration of the Alkalisation decrease the sedimentation index and the powder’s lightness. However, these factors also decrease the cocoa powder’s total phenolic and anti-radical scavenging activity. This research opens a new opportunity for small-scale industries to alkalize cocoa using a commercially pressured vessel.
... The total polyphenol content (TPC) was determined by Folin-Ciocalteu method using gallic acid as a standard (Miller et al., 2008). Cocoa pulp (1 g) was extracted with a mixture of acetone, water, and acetic acid in a 70.0:29.5:0.5 volume ratio by sonication for 10 min, followed by centrifugation at 6000 ×g for 5 min. ...
The interaction and complex metabolism of microorganisms in cocoa pulp drive the fermentation process. To investigate this, four strains from spontaneous cocoa fermentation, including Hanseniaspora uvarum, Saccharomyces cerevisiae, Lactiplantibacillus plantarum, and Gluconobacter potus were combined to ferment cocoa pulp. Nineteen machine learning algorithms were run with the dataset of volatile compounds quantified by headspace solid-phase microextraction gas chromatography–mass spectrometry (HS-SPME-GC–MS) against integrated olfactory evaluation to reveal metabolite-sensory attribute relationships. The models showed high prediction accuracy, ranging from 0.85 for sourness by Gradient Boost Machine to 0.28 for sweetness by linear regression. Ethyl esters, specifically ethyl octanoate and ethyl 9-decenoate, were found positive for aroma development. Polynomial regression, neural network modeling and gradient boosting decision trees highlighted the high carbohydrate consumption rate of S. cerevisiae, the pectin degradation ability of H. uvarum, and the synergy of lactic acid bacteria with G. potus. This study offers new insights into cocoa flavor and the development of fermentation starter cocktails.
... The phenolic content measured in the non-treated samples was in the same range of data of commercial cocoa powders already reported in the literature (Miller et al., 2008). The decrease of the TPI observed in treated samples is ascribable to the high energy involved in the ball milling process where, almost the total of the energy involved in the process is dissipated as heat due to collisions and friction forces rather than for particle size reduction purposes (McCabe et al., 1993). ...
Ball milling (BM) was applied to cocoa powder with varying fat content to improve suitability for developing innovative beverages. Cocoa powder is widely used, but the limited water dispersibility and/or stabilizing ability of emulsified systems restricts its applications in food design. BM treatments applied differed in treatment time (10, 20, or 30 min) and rotation speed (450 or 550 rpm). After BM, particle size increased or decreased (39.7 and 22.3% respec-tively, on average) depending on cocoa composition and processing conditions. This corresponded to changes in microstructure, lipid structure, color, and bioactive content with promising results for novel ingredient development.
... Namun sayangnya, kakao Indonesia juga memiliki kelemahan yaitu keasamaan yang lebih tinggi, kualitas warna bubuk yang belum sebanding dengan produk impor, serta memiliki citarasa dan aroma yang beragam (Juliani et al. 2014;Khaerunnisa and Rejeki, 2019;Widayat, 2013). Untuk meningkatkan mutu serta memperbaiki warna dan citarasa bubuk kakao dapat dilakukan dengan proses tambahan pengolahan kakao yaitu proses alkalisasi (Miller et al. 2008;Purwanto et al. 2020). ...
The problem facing the industry of cocoa powder in Indonesia is that cocoa powder on the market has a high fat content, high acidity, a color quality that is not comparable with imported cocoa products, and a variety of flavors and aromas. Alkalization is a method that can handle these problems. Alkalization is a process to improve the quality and appearance of cocoa powder. Alkalization is carried out by adding potassium, magnesium, and others to cocoa. High potassium content can be found in cocoa pod husks. Cocoa pod husks are the main by-product from the cocoa industry, constituting 67 – 76% of the cocoa fruit weight. Cocoa pod husk contains potassium, fiber, and antioxidants that function as biomaterials for food and non-food products. The aims of the study were to determine and evaluate the quality of cocoa powder with the effect of alkalization treatments using cocoa pod husks. The study was carried out at The Indonesian Industrial and Beverage Crops Research Institute, Sukabumi, West Java, from January to June 2022. This study was designed in a factorial completely randomized design. The first factor was the alkaline material, which consisted of two levels (cocoa pod husk and baking soda). The second factor was the concentration, which consisted of 3 levels (1%, 2%, and 3%). The variables observed were the L*, a*, b*, moisture content, ash content, fineness, pH, fat content, protein, antioxidant activity, and organoleptic properties. The results showed that the alkalization process with alkaline material from cocoa pod husk and a concentration of 2% is the best quality characteristic of cocoa powder in accordance with SNI 01-3747-2013.
... The total levels of polyphenols in the present cocoa powders were assessed by a Folin-Ciocâlteu reagent calorimetric assay (as described in [68]). The individual monomer, procyanidin, and methylxanthine levels were confirmed by high-performance liquid chromatography (HPLC; as described in [69,70]). ...
The ingestion of dietary cocoa flavanols acutely alters functions of the cerebral endothelium, but whether the effects of flavanols permeate beyond this to alter other brain functions remains unclear. Based on converging evidence, this work tested the hypothesis that cocoa flavanols would alter brain excitability in young healthy adults. In a randomised, cross-over, double-blinded, placebo-controlled design, transcranial magnetic stimulation was used to assess corticospinal and intracortical excitability before as well as 1 and 2 h post-ingestion of a beverage containing either high (695 mg flavanols, 150 mg (−)-epicatechin) or low levels (5 mg flavanols, 0 mg (−)-epicatechin) of cocoa flavanols. In addition to this acute intervention, the effects of a short-term chronic intervention where the same cocoa flavanol doses were ingested once a day for 5 consecutive days were also investigated. For both the acute and chronic interventions, the results revealed no robust alteration in corticospinal or intracortical excitability. One possibility is that cocoa flavanols yield no net effect on brain excitability, but predominantly alter functions of the cerebral endothelium in young healthy adults. Future studies should increase intervention durations to maximize the acute and chronic accumulation of flavanols in the brain, and further investigate if cocoa flavanols would be more effective at altering brain excitability in older adults and clinical populations than in younger adults.
... Alkalized cocoa powder also affects the pH of chocolate beverages. The cocoa powder used in this study has a pH of 7.12, which, according to Miller et al. (2008) is classified as a light alkalized cocoa powder (pH 6-7.2). As reported by Valverde García et al. (2020), in chocolate beverages, cocoa powders with pH 5-6 (dark natural) and pH 6-7.2 (light) are generally used to obtain a strong chocolate beverage color, to reduce acidity and astringency, and to increase solubility. ...
Chocolate beverages made from cocoa powder contain phenolic compounds, especially flavonoids, as antioxidants, but these compounds are easily degraded. Incorporating clove bud extract is recommended to improve the quality of these beverages. However, encapsulation is necessary to protect bioactive compounds and reduce bitterness. This study investigated the total phenolic and flavonoid content, antioxidant activity, and characteristics of chocolate beverages formulated with encapsulated clove bud extract. Six formulations ranging from 0% to 10% encapsulated extract were evaluated. The results show that the incorporation of the encapsulated extract significantly improved several attributes as the percentage of clove extract increased. Phenolic and flavonoid content, antioxidant activity, hygroscopicity, lightness (L*), total color difference (∆E), viscosity, solubility, and soluble solids increased. In contrast, moisture content, red/green (a*) and blue/yellow (b*) values, sedimentation, pH, and dissolution time decreased. Panelists preferred beverages with up to 4% encapsulated clove extract, suggesting the potential for healthier ready-to-drink chocolates.
... One of the main ingredients in confectionery, bakery and pastry products used in food industry is cocoa powder. The cocoa beans are fermented, dried, deshelled, roasted, defatted and pulverized (Miller et al. 2008). Cocoa bean nibs that have been fermented, dried, roasted, are separated from their skins and ground into a paste which is melted to become the liquor. ...
Cocoa products namely cocoa powder (CP),
cocoa butter (CB) and cocoa mass (CM) were selected for
their utilization in soft dough biscuits. CP was blended with
the refined wheat flour (WF—0, 5, 10 and 15% levels) and
rheological and quality characteristics of biscuits were studied.
The spread ratio decreased (10.1–8.8), density (0.49–
0.52 g/cm3) and breaking strength values (1127–1369 g
force) increased gradually with increase in CP. Combination
of GMS and SSL at 0.25% each improved the quality of biscuits
at 10% incorporation of CP. Further the biscuit fat (BF)
was replaced with CB (0, 25, 50 and 75%). Later the biscuits
with CM were prepared by replacing the flour (15%) and BF
(0, 25, 50 and 75%). Acceptability of the CM based biscuits
was better when compared to CB based biscuits. The total
polyphenol content in control biscuits was 55.55 mg/100 g
and was in the range between 81.98 and 102.05 mg/100 g for
cocoa based biscuits. The protein content in cocoa based biscuits
was marginally higher than the control biscuit. Though
there was a wide variation in the fat content and different
fatty acids in raw materials, interestingly, the values varied
narrowly in biscuits
... The total polyphenol content (TPC) was determined using the Folin-Ciocalteu method using gallic acid as a standard (Miller et al., 2008). The quantification of total flavonoids followed the method described by Melo et al. (2021), using rutin as a standard. ...
The aim of this study was to investigate the dynamic profile of microorganisms and metabolites in Hainan
Trinitario cocoa during a six-day spontaneous box fermentation process. Shotgun metagenomic and metabolomic
approaches were employed for this investigation. The potential metabolic functions of microorganisms in cocoa
fermentation were revealed through a joint analysis of microbes, functional genes, and metabolites. During the
anaerobic fermentation phase, Hanseniaspora emerged as the most prevalent yeast genus, implicated in pectin
decomposition and potentially involved in glycolysis and starch and sucrose metabolism. Tatumella, possessing
potential for pyruvate kinase, and Fructobacillus with a preference for fructose, constituted the primary bacteria
during the pre-turning fermentation stage. Upon the introduction of oxygen into the fermentation mass, acetic
acid bacteria ascended to dominant within the microflora. The exponential proliferation of Acetobacter resulted
in a decline in taxonomic richness and abundance. Moreover, the identification of novel species within the
Komagataeibacter genus suggests that Hainan cocoa may serve as a valuable reservoir for the discovery of unique
cocoa fermentation bacteria. The KEGG annotation of metabolites and enzymes also highlighted the significant
involvement of phenylalanine metabolism in cocoa fermentation. This research will offer a new perspective for
the selection of starter strains and the formulation of mixed starter cultures.
... Previous authors reported that the total phenolic content of dark chocolate (578.64 ± 5.04 mg CAE/100 g chocolate) is higher than that of milk chocolate (160.46 ± 6.58 mg CAE/100 g chocolate). A similar finding by Miller et al. (2008) reported that the content of cocoa polyphenols, especially flavanols in dark chocolate, are five times higher than milk chocolate. This result has been linked to the amount of cocoa liquor used in the chocolate formulation. ...
Malaysian Cocoa J. 15 (2): 36-46 (2023) ABSTRACT-Ganache consists of cocoa butter, white chocolate and dairy cream that can be used as a chocolate filling. Nowadays, several plant seeds are incorporated into the ganache to improve the flavours, shelf life and nutritional composition. Sacha inchi (Plukenetia volubilis L.) is a seed that contains essential amino acids, polyunsaturated fatty acids, minerals, polyphenols and dietary fibre. In this study, ganache added with 10% sacha inchi was developed as a filling for milk and dark chocolates. The effect of sacha inchi ganache on the physico-chemical, total phenolic content, antioxidant activity and sensory acceptability of milk and dark chocolates was evaluated. Milk and dark chocolates filled with ganache (without sacha inchi) were used as control samples throughout the analysis. Incorporating sacha inchi ganache decreased significantly (p<0.05) the moisture and water activity of milk and dark chocolates compared to the control samples. Furthermore, the crude fibre content of milk and dark chocolates filled sacha inchi ganache were higher than the control samples. However, no significant differences (p>0.05) in hardness for all chocolate samples. Dark chocolate filled with sacha inchi ganache contains the highest total phenolic content and antioxidant activity compared to other chocolate samples. In terms of sensory evaluation, the mean scores for overall acceptability of the milk and dark chocolates filled with sacha inchi ganache corresponded to "like", which are similar (p>0.05) with control samples. Therefore, the addition of sacha inchi ganache improves the crude fibre, antioxidant activity and total phenolic content of milk and dark chocolates, which is well-accepted by consumers.
... Among the most important bioactive compounds found in cocoa powder are methylxanthines and flavonoids [1,2]. The alkalization process is optionally used to change the flavor and color of cocoa powder [3]. Cocoa powder has a specific and unique chemical composition of bioactive compounds and is therefore associated with various health benefits. ...
Plants are considered the major sources of biologically active compounds, which provide unlimited opportunities for their use either as medical treatments or as novel drug formulations. Cocoa powder is frequently used in nutrition and is known to have many benefits thanks to its wide range of biological activities. The presented study was focused on the evaluation of the anti-inflammatory potential of extracts obtained from cocoa powder. In vitro assays were employed to evaluate the level of inhibition of cyclooxygenases-1 and -2 activities (COX-1 and COX-2) by tested extracts. Molecular docking was used for in silico prediction of cyclooxygenase isoforms inhibition by selected cocoa powder constituents. The results showed that all tested extracts exerted much higher potential in inhibiting COX-2 activity and may be considered in use as selective inhibitors of COX-2 enzyme. On the other hand, in silico study shows quercetin and clovamide as the compounds with the highest potential to inhibit both COX-1 and COX-2.
... Chocolate spread was manufactured using different proportions of cocoa and date seed powder according to the proportions given in Table (1), according to the method described by [12,22], with some modifications, as the dry ingredients (cocoa, milk powder, sugar powder, salt, and vanilla) were mixed well until the mixture was completely homogeneous, and then placed in an electric mixer, then vegetable oil and lecithin were gradually added to it until the desired consistency of liquid chocolate was obtained. , and the absorbance was measured at a wavelength of 517 nm after 30 min, and the antioxidant activity was expressed by calculating the inhibition percentage of free radicals. ...
This research aimed to study the possibility of benefiting from date seed powder as a healthy substitute for cocoa powder in chocolate processing, by determining some chemical indicators of cocoa powder and date seed powder and studying the effect of replacing cocoa powder with date stone powder in different proportions in the content of total phenol, antioxidant activity and color indicators, and sensory properties of chocolate compared to the control. The cocoa powder sample showed a significant increase in moisture content and pH compared to the date seed powder sample. The date seed powder sample was characterized by higher fiber content (79.31%) on a dry weight basis than cocoa powder. Chocolate samples manufactured using 100% date seed powder showed a significant increase in ash and raw fiber content and a substantial decrease in moisture content, pH number, and total sugar content compared to the control sample. The addition of date seed powder led to a significant increase in the content of total phenol and antioxidant activity in the sample (100% date seed powder), a moral increase in the value of (L* and h) indicators, and a significant decrease in the (a*, b* and C)values compared with the other studied samples. The chocolate sample manufactured using 4% date seed powder was significantly superior in the degree of taste, aroma, and texture compared to the rest of the studied samples, while the control sample was significantly superior in color terms.
... Cocoa is the leading agricultural export product for several countries (Ecuador, Ivory Coast, Nigeria, etc), as these countries stand out in the global production of cocoa beans [11]. Cocoa beans are processed to obtain chocolate liquor, cocoa powder, and cocoa butter, which are the main ingredients of chocolate and a range of products like cocoa beverages, ice cream and bakery products [2,41]. Due to numerous health benefits and medicinal properties, cocoa products are becoming more and more popular worldwide [42,22]. ...
The fermented and dried cocoa beans are peeled, either before or after the roasting process, as peeled nibs are used for chocolate production, and shell content in cocoa powders may result from economically motivated adulteration (EMA), cross-contamination or misfits in equipment in the peeling process. The performance of this process is carefully evaluated, as values above 5% (w/w) of cocoa shell can directly affect the sensory quality of cocoa products. In this study chemometric methods were applied to near-infrared (NIR) spectra from a handheld (900-1700 nm) and a benchtop (400-1700 nm) spectrometers to predict cocoa shell content in cocoa powders. A total of 132 binary mixtures of cocoa powders with cocoa shell were prepared at several proportions (0 to 10% w/w). Partial least squares regression (PLSR) was used to develop the calibration models and different spectral preprocessing were investigated to improve the predictive performance of the models. The ensemble Monte Carlo variable selection (EMCVS) method was used to select the most informative spectral variables. Based on the results obtained with both benchtop (R2P = 0.939, RMSEP = 0.687% and RPDP = 4.14) and handheld (R2P = 0.876, RMSEP = 1.04% and RPDP = 2.82) spectrometers, NIR spectroscopy combined with the EMCVS method proved to be a highly accurate and reliable tool for predicting cocoa shell in cocoa powder. Even with a lower predictive performance than the benchtop spectrometer, the handheld spectrometer has potential to specify whether the amount of cocoa shell present in cocoa powders is in accordance with the Codex Alimentarius specifications.
... Undoubtedly, cocoa (Theobroma cacao L) remains one of the most distributed and well-known agricultural products worldwide. Remarkably, over 75% of global output comes from Africa (International Cocoa Organization, 2020) and serves as raw material for most beverage, biscuits, and pastry industries (Miller et al., 2008). In response to consumers' demand, the cocoa is sometimes processed into Dutch cocoa -a variant with the darker colour, less astringent, bitter and acidic notes, but more soluble (Puchol-Miquel et al., 2021). ...
... The main groups of polyphenols in cocoa and its derivatives (i.e., cocoa powder, chocolate bars, etc.) are proanthocyanidins (58% of total dry weight), catechins (37%), anthocyanins (4%), whose content and type may vary depending both on the cocoa cultivar or origin as well as processing of cocoa beans and chocolate manufacturing processes (i.e., fermentation, roasting, conching, alkalinisation, etc.) (Giacometti et al., 2015). In particular, it was well established that alkalinisation might cause a progressive reduction of polyphenols, as well as their antioxidant activity (Miller et al., 2008). The greatest losses have been observed for epicatechins and catechins content, thus highlighting a reduction of 98% and 80% respectively. ...
The green solvents and eco‐extraction methods are gaining increasing interest in chemical analysis for bioactive compounds in food matrices. Deep Eutectic Solvents (DES) developed as a greener and more sustainable alternative to organic solvents, owing to their non‐toxic, highly stable, and biodegradation‐friendly nature. DES application for polyphenols and antioxidant compounds extraction in dark chocolate samples has been evaluated in an integrated study for sustainability assessment, based on multivariate analysis and Life Cycle Assessment (LCA) methodology. A green extraction method based on DES was proposed testing different HBA:HBD pairs (ChCl:Fru, ChCl:Teg, Bet:Fru, and Bet:Teg). DES Bet:Fru resulted in the highest extraction yield in terms of both total polyphenols (0.34–3.37 g GAE/100 g) and flavonoids (1.13–8.32 g RUT/100 g), P < 0.05. Furthermore, the environmental performances of green and conventional solvents (MeOH:H2O, H2O, and MeOH) were evaluated by applying a comparative LCA (c‐LCA). The c‐LCA study highlighted that conventional extraction for polyphenols in dark chocolate was 60% more impactful than DES. DES pairs analysed quantitatively lowest impacted than conventional methods, considering the macro‐categories Human Health (9.99 × 10–8 ÷ 1.54 × 10–7 DALYs), Ecosystem (2.29 × 10–10 ÷ 3.57 × 10–10 species.yr), and Resources (6.57 × 10–3 ÷ 8.96 × 10–³ USD2013).
... According to Lee et al. [48], cocoa has a higher content of flavonoids per portion than tea or red wine. Powdered cocoa is one of the richest identified dietary sources of flavonoids so far, next to buckwheat hulls, sorghum, and cinnamon [49]. ...
The aim of this presented study was the sensory evaluation, the analysis of the nutritional composition, and the analysis of the content of health-promoting ingredients, i.e., the total phenolic compounds and the total flavonoids, in raw chocolate (made exclusively from unroasted cocoa beans, cane sugar, and cocoa butter) in comparison to classic commercial chocolates available in the consumer market. The research showed that raw chocolate, compared to commercial chocolates, contained less carbohydrates (39.6% in raw chocolate and 42.7% and 53.7% in commercial chocolate, respectively), was characterized by a higher content of total phenolic compounds (22.08 mg GAE/g in raw chocolate and 9.25 and 7.87 mg GAE/g in commercial chocolates, respectively), had a a higher content of total flavonoids (8.75 mg ECE/g in raw chocolate and 4.43 mg/g and 3.83 mg ECE/g in commercial chocolates, respectively), and also had a higher total antioxidant activity (172.16 μM TE/g in raw chocolate and 132.60 and 63.76 μM TE/g in commercial chocolates, respectively). In the sensory assessment, raw chocolate received lower ranks than commercial chocolates, especially in the case of the most important discriminant in the entire evaluation, i.e., taste, which was unquestionably related to the lower content of carbohydrates. However, currently, it is necessary to reduce the consumption of sugar, which, when excessively present in the diet, is the cause of many diseases. However, in the sensory evaluation for the criteria “external appearance—shape” and “external appearance—surface condition,” the raw chocolate received the highest marks.
... Type B proanthocyanidins are formed from (+)catechin and (-)-epicatechin, with the oxidative coupling occurring between the C 4 of the heterocycle and the C 6 or C 8 positions of the adjacent unit to create oligomers and polymers. Individual procyanidins that have been identified in cocoa include the B 1 , B 2 , B 4 and B 5 dimers, the C 1 trimer and tetramers such as cinnamtannin A 1 (Figure 7.2; Haslam 1998), although longer chain polymers comprising seven or more monomer units seemingly predominate (Haslam 1998;Hammerstone et al. 1999;Gu et al. 2006;Miller et al. 2008). Some dimeric epicatechin glycosides as the 3-O-arabinoside and the 3-O-galactoside conjugates of (+)-epicatechin-(2␣→7,4␣→8)-(+)-epicatechin (Figure 7.2) have also been reported in T. cacao (Buckingham 1994). ...
... According to Fig. 2, some MAC samples may have similar volatile profiles to LACs: these similarities could be attributed to the process stage in which alkalization was performed (Miller et al., 2008). During the alkalization process, volatile compounds can be better conserved depending on the process method, conditions (temperature and alkali levels), products (alkali types) and the presentation of the cocoa product to be alkalized: beans, cake or powder. ...
A total of 56 key volatile compounds present in natural and alkalized cocoa powders have been rapidly evaluated using a non-target approach using stir bar sorptive extraction gas chromatography mass spectrometry (SBSE-GC-MS) coupled to Parallel Factor Analysis 2 (PARAFAC2) automated in PARADISe. Principal component analysis (PCA) explained 80% of the variability of the concentration, in four PCs, which revealed specific groups of volatile characteristics. Partial least squares discriminant analysis (PLS-DA) helped to identify volatile compounds that were correlated to the different degrees of alkalization. Dynamics between compounds such as the acetophenone increasing and toluene and furfural decreasing in medium and strongly alkalized cocoas allowed its differentiation from natural cocoa samples. Thus, the proposed comprehensive analysis is a useful tool for understanding volatiles, e.g., for the quality control of cocoa powders with significant time and costs savings.
... improves the dispersibility of cocoa powder to be used, especially in beverages (Miller et al., 2008). However, alkalization is not applicable in this study. ...
There is an increase in cocoa utilisation as an alternative to espresso coffee due to its lower caffeine content (17% less) than coffee. The polyphenols, theobromine is a good source of antioxidant contributed to the flavor and aroma in cocoa products. Different fat content and grinding levels were evaluated in producing a concentrated cocoa drink with a close resemblance to espresso coffee. Concentrated cocoa drink made of cocoa bean with 20% fat, grind at level 50 showed better caffeine content (3.31 µg/mL), theobromine content (34.26 µg/mL), antioxidant capacity (1726.3 μM TE), and TPC (193.57 mg/mL GAE). Five different classes of volatile compounds were detected from fresh‐brewed concentrated cocoa drinks responsible for the unique aroma properties, including alcohols, aldehyde, ketones, esters, acids, and pyrazines. These findings are significant to the cocoa industries, where the concentrated cocoa drink may act as an alternative cocoa drink with improved nutritional content.
... Cocoa flavanols are present in good amounts in dark chocolate, with a content of catechin and epicatechin (estimated to be approximately 20 times higher than in tea [70]) that was reported to have some beneficial effects on glucose metabolism. Furthermore, a meta-analysis of 42 randomized controlled trials with acute or chronic consumption of chocolate or cocoa reported an improvement in insulin sensitivity associated with a decrease in serum insulin [71]. ...
Type 2 diabetes is an increasing health concern worldwide. Both genetic and environmental risk factors as improper dietary habits or physical inactivity are known to be crucial in the pathogenesis of type 2 diabetes. Polyphenols are a group of plant-derived compounds with anti-inflammatory and antioxidant properties that are associated with a low prevalence of metabolic conditions characterized by insulin resistance, including obesity, diabetes, and hypertension. Moreover, there is now full awareness that foods that are rich in phytochemicals and polyphenols could play an important role in preserving human cardiovascular health and substantial clinical evidence indicates that regular dietary consumption of such foods affects favorably carbohydrate metabolism. This review briefly summarizes the evidence relating dietary patterns rich in polyphenols with glucose metabolism and highlights the potential benefits of these compounds in the prevention of type 2 diabetes.
... Cocoa powder levels for flavanol monomers, procyanidin and methylxanthines (caffeine, theobromine) were measured by high-performance liquid chromatography (HPLC) as described previously [51,52]. Total levels of polyphenols were also assessed by a Folin-Ciocalteu reagent calorimetric assay as described previously [53]. The dose of flavanol monomers used in the present study is in line with previous studies, shown to be safe and effective in modifying human endothelial function in young healthy adults [33,34,54]. ...
Mental stress has been shown to induce cardiovascular events, likely due to its negative impact on vascular function. Flavanols, plant-derived polyphenolic compounds, improve endothelial function and blood pressure (BP) in humans, however their effects during stress are not known. This study examined the effects of acute intake of cocoa flavanols on stress-induced changes on vascular function. In a randomised, controlled, double-blind, cross-over intervention study, 30 healthy men ingested a cocoa flavanol beverage (high-flavanol: 150 mg vs. low-flavanol < 4 mg (−)-epicatechin) 1.5 h before an 8-min mental stress task). Forearm blood flow (FBF), BP, and cardiovascular activity were assessed pre- and post-intervention, both at rest and during stress. Endothelial function (brachial flow-mediated dilatation, FMD) and brachial BP were measured before the intervention and 30 and 90 min post-stress. FMD was impaired 30 min post-stress, yet high-flavanol cocoa attenuated this decline and remained significantly higher compared to low-flavanol cocoa at 90 min post-stress. High-flavanol cocoa increased FBF at rest and during stress. Stress-induced cardiovascular and BP responses were similar in both conditions. Flavanols are effective at counteracting mental stress-induced endothelial dysfunction and improving peripheral blood flow during stress. These findings suggest the use of flavanol-rich dietary strategies to protect vascular health during stress.
... Even though the processing with alkali in commercial cocoa powder manufacturing is known to reduce the phenolics substantially compared to unprocessed natural cocoa powder [59][60][61][62], there are some evidence that show about 40% of the natural level of flavanols is retained on average for lightly Dutched powders, and an average of 22% is retained in even moderately alkali processed cocoa powders [63]. Therefore, we thought to determine the TP, TF and the antioxidant activity of our cocoa powder as we attributed these beneficial effects of cocoa to cocoa polyphenols. ...
BACKGROUND
Cocoa, one of the richest dietary sources of polyphenols has been studied for its health promoting effects, but how long-term consumption of cocoa affects age-associated health and lifespan is not well defined.
OBJECTIVE
The objective of this study was to determine the effects of long-term cocoa consumption on age-associated health and lifespan in C. elegans
METHODS
The standard E. coli OP50 diet of wild type C. elegans was supplemented with cocoa powder starting from L1 stage until they die. Body length and area were measured as indicators of worm nutrition. Age associated health was determined at different stages of life as day 4, day 8 and day 12 using worm locomotion, thermotolerance, cognition and mitochondrial function. In addition, lifespan was evaluated.
RESULTS
Cocoa improved age-associated decline in neuromuscular function. Both mean and median lifespan were extended by cocoa supplementation. However, maximum lifespan was not affected. Cocoa showed beneficial effects on thermotolerance at all ages (more prominent effects at young (day 4) and middle (day 8) age). Further, consumption of cocoa improved age-related learning deficits, short-term memory loss and mitochondrial dysfunction.
CONCLUSIONS
Long-term cocoa consumption seemed to improve age-associated health and extends lifespan in C. elegans
... The benefits of cocoa and cocoa products depend on polyphenol content. Cocoa flavanols can be found in dark chocolate, with a content estimated to be five times higher than that in milk chocolate [16]; the content of catechin and epicatechin is approximately 20 times higher than in tea. ...
Obesity remains a major public health problem due to its increasing prevalence. Natural products have become common as adjunct therapeutic agents for treating obesity and preventing metabolic diseases. Cocoa and its products are commonly consumed worldwide. Dark chocolate, a rich source of polyphenols, has received attention lately for its beneficial role in the management of obesity; however, conflicting results are still being reported. This scoping review aims to provide a comprehensive understanding of the existing literature on the relationship and effects of cocoa and dark chocolate intake among obese adults. We searched multiple databases for research investigating the consumption of cocoa and/or dark chocolate in managing obesity among adults. This review includes epidemiological and human studies that were published in English over the last 10 years. Our review of the current literature indicates that epidemiological and human trials with obese adults have shown inconsistent results, which may be due to the different populations of subjects, and different types of cocoa products and doses used for intervention. Studies among obese adults are mainly focusing on obese individuals with comorbidities, as such more studies are needed to elucidate the role of cocoa polyphenols in weight control and preventing the risk of chronic diseases among obese individuals without comorbidities as well as healthy individuals. Careful adjustment of confounding factors would be required. The effects of cocoa and dark chocolate intake on obese adults were discussed, and further research is warranted to identify the gaps.
... A similar dose of (−)-epicatechin could be achieved through diet by consuming foods rich in flavanols, particularly apples, black grapes, blackberries, cherries, raspberries, pears, pulses, green tea and red wine 62 . Total levels of polyphenols in the powders were assessed by a Folin-Ciocalteu reagent calorimetric assay as described previously 63 . Individual monomer levels and procyanidin levels as well as levels of methylxanthines, were confirmed by HPLC as described previously 64,65 . ...
Cocoa flavanols protect humans against vascular disease, as evidenced by improvements in peripheral endothelial function, likely through nitric oxide signalling. Emerging evidence also suggests that flavanol-rich diets protect against cognitive aging, but mechanisms remain elusive. In a randomized double-blind within-subject acute study in healthy young adults, we link these two lines of research by showing, for the first time, that flavanol intake leads to faster and greater brain oxygenation responses to hypercapnia, as well as higher performance only when cognitive demand is high. Individual difference analyses further show that participants who benefit from flavanols intake during hypercapnia are also those who do so in the cognitive challenge. These data support the hypothesis that similar vascular mechanisms underlie both the peripheral and cerebral effects of flavanols. They further show the importance of studies combining physiological and graded cognitive challenges in young adults to investigate the actions of dietary flavanols on brain function.
... The beans are then broken to separate the nib from its shell and subsequently sterilized. This is followed by alkalization process by an alkali solution of potassium or sodium carbonate at a temperature of 80-100 Celsius [30]. Subsequently, the alkalized product is roasted and ground to reduce the nibs to liquor or pressed to separate the fat content from the powder and eventually to produce cocoa powder and butter [31]. ...
Cocoa and its products are rich sources of polyphenols such as flavanols. These compounds exert antioxidant and anti-inflammatory activities, accountable for cocoa health-promoting effects. However, cocoa polyphenols are poorly absorbed in the intestine, and most of them cannot reach the systemic circulation in their natural forms. Instead, their secondary bioactive metabolites are bioavailable, enter the circulation, reach the target organs, and exhibit their activities. In fact, once reaching the intestine, cocoa polyphenols interact bidirectionally with the gut microbiota. These compounds can modulate the composition of the gut microbiota exerting prebiotic mechanisms. They enhance the growth of beneficial gut bacteria, such as Lactobacillus and Bifidobacterium, while reducing the number of pathogenic ones, such as Clostridium perfringens. On the other hand, bioactive cocoa metabolites can enhance gut health, displaying anti-inflammatory activities, positively affecting immunity, and reducing the risk of various diseases. This review aims to summarize the available knowledge of the bidirectional interaction between cocoa polyphenols and gut microbiota with their various health outcomes.
Alkalization changes the physicochemical, bioactive, and powder flow properties of cocoa powders, so it is an essential factor affecting the quality of cocoa products. This study investigated the relationship of the alkalization process with physicochemical properties such as color, pH, and bioactive properties such as total phenolic, flavonoid, and antioxidant capacity of cocoa powders. For this purpose, natural cocoa powders were alkalized using sodium hydroxide (NaOH) or potassium carbonate (K2CO3), or potassium hydroxide (KOH) solutions at their different concentrations. The browning index, darkness, and pH values increased while the total phenolic content, flavonoid, and antioxidant capacity decreased depending on the type of alkali used. FTIR spectra revealed changes in the stretching vibrations in the molecular structure of alkalized cocoa powders. Even though the alkalization process did not affect the microstructure of cocoa particles visibly, treatment with different alkali agents altered the thermal behavior, compressibility and caused a decrease in the powder flowability.
Cocoa powder alkalization is an essential process in chocolate manufacturing, and traditionally, this process involves the use of alkaline agents, such as sodium hydroxide (NaOH), potassium hydroxide (KOH), and potassium carbonate (K2CO3). However, these methods involve harsh chemicals and energy-intensive procedures, raising significant environmental concerns. Water (H2O) has emerged as a promising alternative due to its safety, minimally harmful byproducts, and accessibility. Green chemistry principles have gained importance across industries, especially in food production, where sustainable practices are highly valued. This study aimed to develop a greener process by investigating the alkalization potential of H2O and comparing the results with those of NaOH. The particle size distribution, pH, color, antioxidant capacity, phenolic composition, and aroma profile of cocoa powders treated with H2O and NaOH were evaluated. The alkalization temperature significantly affected the color of the cocoa powders, and the alkali solution ratio influenced the L* values of H2O-treated powders. In industrial and commercial specifications, an ΔE value below 3 is considered standard for color measurements. Both H2O-treated and NaOH-treated natural cocoa powders had ΔE values exceeding 3 compared to the untreated powder, indicating that H2O treatment darkens the color in a similar way to that of traditional methods. While NaOH produced a darker color, process optimization allowed both H2O and NaOH treatments to achieve similar color attributes (ΔE < 3). Significant differences were observed in the antioxidant capacity and total phenolic content (TPC) between the H2O-treated and NaOH-treated cocoa powders. H2O treatment positively impacted the antioxidative properties of the cocoa powder. The antioxidant capacity, measured by the DPPH and CUPRAC methods, was significantly higher in H2O-treated samples (295.5–317.7 TEAC mg/100 g and 835–1542 TEAC mg/100 g, respectively) compared to NaOH-treated samples (256.6–306.2 TEAC mg/100 g and 171–849 TEAC mg/100 g, respectively). Additionally, the TPC of H2O-treated cocoa powder [281.3–321.6 gallic acid equivalent (GAE) mg/100 g] was significantly higher than that of NaOH-treated powder (100.0–298.6 GAE mg/100 g). The significant differences in the phenolic profiles suggested that the alkalization process affects individual phenolic compounds differently. Moreover, H2O-treated cocoa powders had significantly higher trimethylpyrazine/tetramethylpyrazine (TrMP/TMP) ratios than those of NaOH-treated samples, indicating notable differences in aroma profiles. This study suggests that H2O can replace NaOH in the alkalization process of the cocoa industry, particularly for lightly treated alkalized cocoa powders that maintain high antioxidant activity and TrMP/TMP ratios. This offers a more environmentally friendly, easily manageable, and sustainable process for cocoa powder alkalization.
Purpose
The purpose of this study was to development of a new chocolate-flavored powdered food supplement enriched with mesquite pod flour, oak extract and agave fructans, with proper sensory characteristics as well as its physicochemical and glycemic quality.
Design/methodology/approach
A powdered shake was formulated using experimental design (23) with mesquite (Prosopis laevigata) pod flour, oak (Quercus convallata) extracts, nonalkalinized cocoa, agave fructans, milk protein and xanthan gum. Sensory analysis (choice profile method, ranking test, focus group, quantitative descriptive analysis), moisture, ash, fiber, protein and lipids, pH, color, wettability, dispersibility and rheological tests were done. Phenolic profiling analysis to samples was done by ultraperformance liquid chromatography coupled to photodiode array detection and electrospray ionization tandem mass spectrometry, antioxidant activity was measured by 2,2’-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt radical cation, ferric reducing antioxidant power and oxygen radical absorbance capacity, glycemic index (GI) and glycemic load were evaluated.
Findings
The main sensory attributes in the powders were chocolate, bitter, astringent, grass/linseed flavors ( p < 0.05). The product has protein [66.9%], carbohydrates [22.0%], lipids [1.6%], ash [2.7%] and moisture [6.8%], with wettability (23 s), and dispersibility of 77.9%. Catechin, epicatechin, gallocatechin, procyanidin B2, chlorogenic, coumaric and ferulic acids were identified. GI and caloric load not show differences between men (73.3±2.4, 4.4±0.1) and women (67.0±2.1, 4.1±0.1) ( p > 0.05).
Originality/value
The use of mesquite pods, oak and agave fructans in powder food supplement is an alternative to obtain a product high in protein, with good sensory properties, antioxidant activity and moderate GI.
The cocoa bean is a component of the cocoa pod, which is frequently used as an ingredient in foods and drinks. Numerous healthy substances, such as polyphenols, which act as antioxidants, antiaging, anti-inflammatory, antidiabetic, and antihypertensive agents, are found in cocoa beans. The goal of this study is to create a useful instant beverage that acts as an antidiabetic. This study involved the creation of a combined instant chocolate powder and cocoa liquid. According to the findings, the Forastero variety processed cocoa powder had the highest total polyphenol content, namely 425.179 pm 0.01 mg GAE/g and the lowest polyphenol content was owned by Kalla cocoa, namely 172.768 pm 2.93 mg GAE/g. The formulation’s overall polyphenol content ranged from 3.125 pm 1.89 to 150.446 pm 17.04 mg GAE/g. The highest inhibition percentage with the lowest IC 50 value was found in the formulation A31 sample and the lowest inhibition percentage with the highest IC 50 value was in the formulation B32 sample. The higher the value of the total polyphenol content of the cocoa powder sample, the higher the percentage of inhibition of alpha-amylase activity. The physicochemical analysis is carried out by measuring the color. The color change in cocoa powder is due to changes in the structure of the cocoa anthocyanin-type polyphenols during the fermentation, drying and roasting processes. The sensory analysis of the ranking method showed the best formulations of B23 and B33, according to the panelists.
Background and aims: Tea polyphenols, such as green tea polyphenols, have been extensively studied as agents that ameliorate cardiovascular disease and blood pressure in vitro and in animal studies. However, epidemiological evidence for the association of green tea consumption with hypertension (HTN) is inconsistent. In addition, such an association has not been prospectively examined in the general adult population, particularly among young women. Therefore, we designed a cohort study to examine whether green tea consumption increases the risk of HTN in premenopausal women. Methods and results: This prospective cohort study investigated 6633 premenopausal female participants without hypertension, cardiovascular disease, and cancer at the baseline. Green tea consumption was measured at the baseline using a validated food frequency questionnaire. Hypertension was confirmed with the SBP ≥140 mm Hg-1 or with the DBP ≥90 mm Hg-1. Cox proportional hazards regression models were used to examine the association of green tea consumption with incident hypertension. A total of 488 first incident cases of hypertension occurred during 24 957 person-years of follow-up (median follow-up of 4.0 years). After adjustment for potential confounding variables, the multivariable hazard ratios (95% confidence intervals) for incident hypertension in premenopausal female participants with different green tea consumption frequencies were 1.00 (reference) for almost never, 0.84 (0.67, 1.07) for 1 cup per week, 1.02 (0.77, 1.35) for 2-6 cups per week, and 0.65 (0.44, 0.96) for ≥1 cup per day. Conclusions: The results from our prospective study indicate that the consumption of green tea is associated with a reduced risk of HTN in premenopausal women.
Dicarbonyl compounds (α‐DCs) are readily produced during the heating and storage of foods, mainly through the Maillard reaction, caramelization, lipid‐peroxidation, and enzymatic reaction. They contribute to both the organoleptic properties (i.e., aroma, taste, and color) and deterioration of foods and are potential indicators of food quality. α‐DCs are also important precursors to hazardous substances, such as acrylamide, furan, advanced lipoxidation end products, and advanced glycation end products, which are genotoxic, neurotoxic, and linked to several diseases. Recent studies have indicated that dietary α‐DCs can elevate plasma α‐DC levels and lead to “dicarbonyl stress.” To accurately assess their health risks, quantifying α‐DCs in food products is crucial. Considering their low volatility, inability to absorb ultraviolet light, and high reactivity, the analysis of α‐DCs in complex food systems is a challenge. In this review, we comprehensively cover the development of scientific approaches, from extraction, enrichment, and derivatization, to sophisticated detection techniques, which are necessary for quantifying α‐DCs in different foods. Exposure to α‐DCs is inevitable because they exist in most foods. Recently, novel strategies for reducing α‐DC levels in foods have become a hot research topic. These strategies include the use of new processing technologies, formula modification, and supplementation with α‐DC scavengers (e.g., phenolic compounds). For each strategy, it is important to consider the potential mechanisms underlying the formation and removal of process contaminants. Future studies are needed to develop techniques to control α‐DC formation during food processing, and standardized approaches are needed to quantify and compare α‐DCs in different foods.
This work is focused on the study of the metabolomic changes that occur in cocoa powder throughout the alkalization process by using an untargeted ultra high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-QTOF-MS) metabolomics approach. With this aim, cocoa powder samples submitted to different alkalization degrees (light, medium, and strong) were analyzed. Metabolite extraction was performed using 75% MeOH in water since it provided the highest number of molecular features. After data processing, non-supervised and supervised methods were applied to carry out the statistical data analysis. Thus, the most significant metabolites that allow establishing differences among the cocoa powder samples submitted to the alkalization processes were pointed out. Thus, 43 and 30 metabolites in positive and negative ionization modes, respectively, demonstrated to be relevant. Among them, 9 compounds were unequivocally identified and 22 tentatively identified. Most of them were amino acids, alkaloids, organic acids or polyphenols, among others.
Alkalization is a crucial process during cocoa processing to reduce its bitterness, improve solubility and develop color. Alkalization can be performed out at several points of the process (nib or cake), with different agents and at various intensities. All these variables may affect cocoa properties, but also physico-chemical and sensory properties of derived products (i.e. cakes). This work aims to evaluate the impact of alkalization type (nib vs. cake), alkalizing agent (K2CO3, NaHCO3 and KOH) and process intensity (mild and strong) on the physico-chemical and sensory properties of sponge cakes. For this aim, 8 different alkalized powders were industrially produced and used in the preparation of sponge cakes. Alkalizing conditions significantly affected cocoa properties (pH, color, sensory properties) and those of the corresponding cakes (cake doughs color and rheology, as well as baked cake color and texture). In general, doughs prepared with cocoas alkalized under strong conditions were a 55 % darker and a 15 % less elastic. After baking, the corresponding cakes were a 17 % darker (L*) and a 12 % harder in texture. Despite these differences, all the cakes were equally rated by consumers in sensory terms demonstrating that for this application, alkalization variables do not condition consumer acceptability.
Four cocoa powder varieties processed in different European countries (Germany, Poland, Romania and Bulgaria) were subjected to physicochemical, phytochemical and microbiological analysis. The cocoa powders were extensively characterized by recording their pH and titratable acidity, respectively, the polyphenols and also the methylxantine derivatives content (theobromine and caffeine). The cocoa powders pH ranged between 5.37 and 8.23, while the titratable acidity was 3.2–4.3 miliequivalent (100 g)−1 of cocoa powder. Their total polyphenols content ranged between 0.986 ÷ 2.003 g GAE/(100 g)−1. The methylxanthine derivatives (theobromine and caffeine) were analyzed by the HPLC method and ranges of 0.992–1.174% for theobromine and 0.096–0.369% for caffeine were obtained. Thermal analysis (TG–DTA) combined with mass spectrometry (MS) elucidated the decomposition processes and the volatile substances (CO, CO2, H2O, NO, theobromine, caffeine). The thermal analysis revealed transformations in the cocoa powders composition: drying and water loss; decomposition of pectic polysaccharides; lipids, amino acids and proteins, crystalline phase transformations and carbonizations. The microbiological analysis tested the degree of preservation of the cocoa powders across time, specifically immediately after unwrapping and after 14 days.
Cocoa and chocolate are widely consumed by humans, and habitual intake is associated with benefits to cardiovascular health, which has been attributed to its polyphenolic content. Classically, in the processing of cacao beans, a final brown color has been preferred over the natural red-violet hues present in raw beans as a marker of proper processing and the development of the characteristic chocolate aroma and flavors. Recently, the industry has shown a renewed interest in the purple-red hues of cacao since the introduction of ruby chocolate to the market. Here, we present a processing method to preserve the composition of flavan-3-ols and procyanidins and to retain pink-red hues in powders produced from unfermented cocoa beans, in which polyphenol-degrading enzymes were first inactivated at 95 °C followed by fast soaking in 1.5 M citric acid and immediate dehydration and grinding to obtain powders with nearly 150 mg/g flavan-3-ols and procyanidins and stable pink-red hues according to CIE L*a*b* color measurements. These procyanidin-rich cacao powders could be added to chocolate products to reach the desired health properties of eating polyphenol-rich chocolates in the new context of the preferred pink shades of the so-called fourth chocolate.
Background:
Small, short-term, intervention studies indicate that cocoa-containing foods improve endothelial function and reduce blood pressure. We studied whether habitual cocoa intake was cross-sectionally related to blood pressure and prospectively related with cardiovascular mortality.Methods:
Data used were of 470 elderly men participating in the Zutphen Elderly Study and free of chronic diseases at baseline. Blood pressure was measured at baseline and 5 years later, and causes of death were ascertained during 15 years of follow-up. Habitual food consumption was assessed by the cross-check dietary history method in 1985, 1990, and 1995. Cocoa intake was estimated from the consumption of cocoa-containing foods.Results:
One third of the men did not use cocoa at baseline. The median cocoa intake among users was 2.11 g/d. After adjustment, the mean systolic blood pressure in the highest tertile of cocoa intake was 3.7 mm Hg lower (95% confidence interval [CI], −7.1 to −0.3 mm Hg; P = .03 for trend) and the mean diastolic blood pressure was 2.1 mm Hg lower (95% CI, −4.0 to −0.2 mm Hg; P = .03 for trend) compared with the lowest tertile. During follow-up, 314 men died, 152 of cardiovascular diseases. Compared with the lowest tertile of cocoa intake, the adjusted relative risk for men in the highest tertile was 0.50 (95% CI, 0.32-0.78; P = .004 for trend) for cardiovascular mortality and 0.53 (95% CI, 0.39-0.72; P < .001) for all-cause mortality.Conclusion:
In a cohort of elderly men, cocoa intake is inversely associated with blood pressure and 15-year cardiovascular and all-cause mortality.
Monomeric and oligomeric procyanidins present in cocoa liquors and chocolates were separated and quantified in four different laboratories using a normal-phase high-performance liquid chromatography (HPLC) method with fluorescence detection. Procyanidin standards through decamers were obtained by extraction from cocoa beans, enrichment by Sephadex LH-20 gel permeation chromatography, and final purification by preparative normal-phase HPLC. The purity of each oligomeric fraction was assessed using HPLC coupled to mass spectrometry. A composite standard was then prepared, and calibration curves were generated for each oligomeric class using a quadratic fit of area sum versus concentration. Results obtained by each of the laboratories were in close agreement, which suggests this method is reliable and reproducible for quantification of procyanidins. Furthermore, the procyanidin content of the samples was correlated to the antioxidant capacity measured using the ORAC assay as an indicator for potential biological activity. Keywords: HPLC; procyanidins; cocoa; chocolate; quantification; antioxidant
Polyphenols have become an intense focus of research interest because of their perceived health-beneficial effects, such as anti-carcinogenic, anti-atherogenic, anti-inflammatory, anti-microbial, etc. Polyphenols in green and black tea, grape seeds, grapes and (red) wine have raised much attention but chocolate has not been investigated intensively up to now. This review is concerned with polyphenols in Theobroma cacao, the change in composition and quantity during fermentation, drying, and the manufacture of chocolate, as well as with analytical methods for isolation, characterisation and quantification. Cocoa beans are rich in polyphenols in particular catechins and proanthocyanidins. However, a sharp decrease in quantity occurs during fermentation and drying of cocoa beans and further retention has been reported during roasting. Characterisation and in particular quantification of polyphenols in chocolate has only been developed relatively recently. This work reviews further on the literature on the available methodology for analysis, quantification, isolation, purification, and structure elucidation of polyphenols in cocoa components and other commodities. Concerning the analytical methods main emphasis is put on HPLC as it is usually the method of choice due to its high resolution, high efficiency, high reproducibility and relatively short analysis time without restriction on sample volatility. Moreover, HPLC can be coupled to a variety of detectors such as UV–Vis, photodiode array (PDA), fluorescence, electrochemical (ECD), and mass spectrometry (MS). However, TLC as a screening method and capillary electrophoresis (CE) as a promising tool is taken into consideration as well. The characterisation and quantification of the polyphenol composition is amongst the first steps to be done to evaluate a putative contribution of chocolate to human health.
Epidemiologic studies have shown inverse associations between dietary polyphenols and mortality from coronary heart disease. However, the basis for this protective association is uncertain. Food polyphenols reportedly have antioxidant properties and decrease platelet function in vitro.
This study sought to evaluate whether consumption of a polyphenol-rich cocoa beverage modulates human platelet activation and primary hemostasis.
Peripheral blood was obtained from 30 healthy subjects before and 2 and 6 h after ingestion of a cocoa beverage (n = 10), a caffeine-containing control beverage (n = 10), or water (n = 10). Platelet activation was measured in terms of expression of activation-dependent platelet antigens and platelet microparticle formation by using fluorescent-labeled monoclonal antibodies and flow cytometry. Primary platelet-related hemostasis was measured with a platelet function analyzer.
Ex vivo epinephrine- or ADP-stimulated expression of the fibrinogen-binding conformation of glycoprotein IIb-IIIa was lower 2 and 6 h after consumption of cocoa than before consumption. Cocoa consumption also decreased ADP-stimulated P-selectin expression. In contrast, epinephrine-induced platelet glycoprotein IIb-IIIa expression increased after consumption of the caffeine-containing beverage but not after water consumption. Platelet microparticle formation decreased 2 and 6 h after cocoa consumption but increased after caffeine and water consumption. Primary hemostasis in response to epinephrine in vitro was inhibited 6 h after cocoa consumption. The caffeine-containing beverage inhibited ADP-induced primary hemostasis 2 and 6 h after consumption.
Cocoa consumption suppressed ADP- or epinephrine-stimulated platelet activation and platelet microparticle formation. Cocoa consumption had an aspirin-like effect on primary hemostasis.
Epidemiologic studies have linked flavonoid-rich foods with a reduced risk of cardiovascular mortality. Some cocoas are flavonoid-rich and contain the monomeric flavanols (-)-epicatechin and (+)-catechin and oligomeric procyanidins formed from these monomeric units. Both the monomers and the oligomers have shown potential in favorably influencing cardiovascular health in in vitro and preliminary clinical studies. Although previous investigations have shown increasing concentrations of (-)-epicatechin in human plasma after cocoa consumption, no information is available in the published literature regarding the presence of procyanidins in human plasma.
This study sought to determine whether procyanidins can be detected and quantified in human plasma after acute consumption of a flavanol-rich cocoa.
Peripheral blood was obtained from 5 healthy adult subjects before (baseline, 0 h) and 0.5, 2, and 6 h after consumption of 0.375 g cocoa/kg body wt as a beverage. Plasma samples were analyzed for monomers and procyanidins with the use of reversed-phase HPLC with coulometric electrochemical array detection and liquid chromatography-tandem mass spectrometry.
Procyanidin dimer, (-)-epicatechin, and (+)-catechin were detected in the plasma of human subjects as early as 0.5 h (16 +/- 5 nmol/L, 2.61 +/- 0.46 micro mol/L, and 0.13 +/- 0.03 micro mol/L, respectively) after acute cocoa consumption and reached maximal concentrations by 2 h (41 +/- 4 nmol/L, 5.92 +/- 0.60 micro mol/L, and 0.16 +/- 0.03 micro mol/L, respectively).
Dimeric procyanidins can be detected in human plasma as early as 30 min after the consumption of a flavanol-rich food such as cocoa.
The effects of chocolate on cardiovascular health are still a matter of debate. Chocolate may adversely affect cardiovascular risk because of its effects on glucose, lipids, and body weight or potentially favour cardiovascular health through antioxidative effects of chocolate ingredients, such as flavonoids (present in dark but not white chocolate).
Endothelial dysfunction and platelet activation are cornerstones in the pathogenesis of atherothrombosis, leading to vasoconstriction, thrombus formation, and inflammation. Smoking is a major cardiovascular risk factor. The mechanisms promoting atherothrombosis in smokers primarily include increased oxidative stress that enhances proatherogenic processes such as low density lipoprotein oxidation and inactivation of endothelium derived nitric oxide. Platelets contribute both to acute coronary syndromes and to the progression of atherothrombosis. Both active and passive cigarette smoking has consistently been shown to induce endothelial dysfunction. Therefore, smokers serve as an ideal model to study the beneficial vascular effects of antioxidant strategies such as dark chocolate.1
The goal of the present study was to investigate whether the beneficial antioxidant effect of polyphenol-rich dark chocolate can induce an improvement of endothelial and platelet function in healthy volunteers with known endothelial dysfunction and platelet hyperreactivity.
Twenty five male smokers were enrolled in the study after giving written informed consent. Women were excluded for known sex hormone induced differences in vascular tone and reactivity. All study participants did not take any medication, including vitamins or dietary supplements. The local institutional ethical review board approved the protocol.
To assess the effect of dark …
Small, short-term, intervention studies indicate that cocoa-containing foods improve endothelial function and reduce blood pressure. We studied whether habitual cocoa intake was cross-sectionally related to blood pressure and prospectively related with cardiovascular mortality.
Data used were of 470 elderly men participating in the Zutphen Elderly Study and free of chronic diseases at baseline. Blood pressure was measured at baseline and 5 years later, and causes of death were ascertained during 15 years of follow-up. Habitual food consumption was assessed by the cross-check dietary history method in 1985, 1990, and 1995. Cocoa intake was estimated from the consumption of cocoa-containing foods.
One third of the men did not use cocoa at baseline. The median cocoa intake among users was 2.11 g/d. After adjustment, the mean systolic blood pressure in the highest tertile of cocoa intake was 3.7 mm Hg lower (95% confidence interval [CI], -7.1 to -0.3 mm Hg; P = .03 for trend) and the mean diastolic blood pressure was 2.1 mm Hg lower (95% CI, -4.0 to -0.2 mm Hg; P = .03 for trend) compared with the lowest tertile. During follow-up, 314 men died, 152 of cardiovascular diseases. Compared with the lowest tertile of cocoa intake, the adjusted relative risk for men in the highest tertile was 0.50 (95% CI, 0.32-0.78; P = .004 for trend) for cardiovascular mortality and 0.53 (95% CI, 0.39-0.72; P < .001) for all-cause mortality.
In a cohort of elderly men, cocoa intake is inversely associated with blood pressure and 15-year cardiovascular and all-cause mortality.
Proanthocyanidins (PAs) have been shown to have potential health benefits. However, no data exist concerning their dietary intake. Therefore, PAs in common and infant foods from the U.S. were analyzed. On the bases of our data and those from the USDA's Continuing Survey of Food Intakes by Individuals (CSFII) of 1994-1996, the mean daily intake of PAs in the U.S. population (>2 y old) was estimated to be 57.7 mg/person. Monomers, dimers, trimers, and those above trimers contribute 7.1, 11.2, 7.8, and 73.9% of total PAs, respectively. The major sources of PAs in the American diet are apples (32.0%), followed by chocolate (17.9%) and grapes (17.8%). The 2- to 5-y-old age group (68.2 mg/person) and men >60 y old (70.8 mg/person) consume more PAs daily than other groups because they consume more fruit. The daily intake of PAs for 4- to 6-mo-old and 6- to 10-mo-old infants was estimated to be 1.3 mg and 26.9 mg, respectively, based on the recommendations of the American Academy of Pediatrics. This study supports the concept that PAs account for a major fraction of the total flavonoids ingested in Western diets.
Dietary flavonoids may have beneficial cardiovascular effects in human populations, but epidemiologic study results have not been conclusive.
We used flavonoid food composition data from 3 recently available US Department of Agriculture databases to improve estimates of dietary flavonoid intake and to evaluate the association between flavonoid intake and cardiovascular disease (CVD) mortality.
Study participants were 34 489 postmenopausal women in the Iowa Women's Health Study who were free of CVD and had complete food-frequency questionnaire information at baseline. Intakes of total flavonoids and 7 subclasses were categorized into quintiles, and food sources were grouped into frequency categories. Proportional hazards rate ratios (RR) were computed for CVD, coronary heart disease (CHD), stroke, and total mortality after 16 y of follow-up.
After multivariate adjustment, significant inverse associations were observed between anthocyanidins and CHD, CVD, and total mortality [RR (95% CI) for any versus no intake: 0.88 (0.78, 0.99), 0.91 (0.83, 0.99), and 0.90 (0.86, 0.95)]; between flavanones and CHD [RR for highest quintile versus lowest: 0.78 (0.65, 0.94)]; and between flavones and total mortality [RR for highest quintile versus lowest: 0.88 (0.82, 0.96)]. No association was found between flavonoid intake and stroke mortality. Individual flavonoid-rich foods associated with significant mortality reduction included bran (added to foods; associated with stroke and CVD); apples or pears or both and red wine (associated with CHD and CVD); grapefruit (associated with CHD); strawberries (associated with CVD); and chocolate (associated with CVD).
Dietary intakes of flavanones, anthocyanidins, and certain foods rich in flavonoids were associated with reduced risk of death due to CHD, CVD, and all causes.
Regular intake of cocoa-containing foods is linked to lower cardiovascular mortality in observational studies. Short-term interventions of at most 2 weeks indicate that high doses of cocoa can improve endothelial function and reduce blood pressure (BP) due to the action of the cocoa polyphenols, but the clinical effect of low habitual cocoa intake on BP and the underlying BP-lowering mechanisms are unclear.
To determine effects of low doses of polyphenol-rich dark chocolate on BP.
Randomized, controlled, investigator-blinded, parallel-group trial involving 44 adults aged 56 through 73 years (24 women, 20 men) with untreated upper-range prehypertension or stage 1 hypertension without concomitant risk factors. The trial was conducted at a primary care clinic in Germany between January 2005 and December 2006.
Participants were randomly assigned to receive for 18 weeks either 6.3 g (30 kcal) per day of dark chocolate containing 30 mg of polyphenols or matching polyphenol-free white chocolate.
Primary outcome measure was the change in BP after 18 weeks. Secondary outcome measures were changes in plasma markers of vasodilative nitric oxide (S-nitrosoglutathione) and oxidative stress (8-isoprostane), and bioavailability of cocoa polyphenols.
From baseline to 18 weeks, dark chocolate intake reduced mean (SD) systolic BP by -2.9 (1.6) mm Hg (P < .001) and diastolic BP by -1.9 (1.0) mm Hg (P < .001) without changes in body weight, plasma levels of lipids, glucose, and 8-isoprostane. Hypertension prevalence declined from 86% to 68%. The BP decrease was accompanied by a sustained increase of S-nitrosoglutathione by 0.23 (0.12) nmol/L (P < .001), and a dark chocolate dose resulted in the appearance of cocoa phenols in plasma. White chocolate intake caused no changes in BP or plasma biomarkers.
Data in this relatively small sample of otherwise healthy individuals with above-optimal BP indicate that inclusion of small amounts of polyphenol-rich dark chocolate as part of a usual diet efficiently reduced BP and improved formation of vasodilative nitric oxide.
clinicaltrials.gov Identifier: NCT00421499.
Die im internationalen Sprachgebrauch verwendeten Worte „Kakao und Schokolade“ leiten sich aus der Aztekensprache ab. (H. Fincke 1932, W. T. Clarke 1953). „Kakao“ entstammt der aztekischen Bezeichnung für Kakaokern „kakauatl“, Schokolade aus den Bezeichnungen „xococ“ -sauer, herbwürzig- „atl“ -wasser-, zusammengesetzt zu „xocoatl“.
Three polyphenols of chocolate were separated by chemical fractionation and paper chromatography after different steps in the manufacturing process. These polyphenols were characterized by color tests and by ultraviolet and infrared spectra. One was identified as (-)-epicatechin; the other two are apparently similar compounds. Roasting diminished the concentration of (-)-epicatechin, and alkalizing or conching caused stereochemical changes in its structure. The other two compounds also underwent stereochemical changes during roasting; no further change occurred with alkalization, but conching reversed the change caused by roasting.
An improved method of oxygen radical absorbance capacity (ORAC) assay has been developed and validated using fluorescein (3',6'-dihydroxyspiro[isobenzofuran-1[3H],9'[9H]-xanthen]-3-one) as the fluorescent probe. Our results demonstrate that fluorescein (FL) is superior to B-phycoerythrin. The oxidized FL products induced by peroxyl radical were identified by LC/MS, and the reaction mechanism was determined to follow a classic hydrogen atom transfer mechanism. In addition, methodological and mechanistic comparison of ORAC(FL) with other widely used methods was discussed. It is concluded that, unlike other popular methods, the improved ORAC(FL) assay provides a direct measure of hydrophilic chain-breaking antioxidant capacity against peroxyl radical.
Cocoa flavanols and procyanidins possess wide-ranging biological activities. The present study investigated the stability of the cocoa monomers, (-)-epicatechin and (+)-catechin, and the dimers, epicatechin-(4beta-8)-epicatechin (Dimer B2) and epicatechin-(4beta- 6)-epicatechin (Dimer B5), in simulated gastric and intestinal juice and at different pH values. The dimers were less stable than the monomers at both acidic and alkaline pH. Incubation of Dimer B2 and Dimer B5 in simulated gastric juice (pH 1.8) or acidic pH resulted in degradation to epicatechin and isomerization to Dimer B5 and Dimer B2, respectively. When incubated in simulated intestinal juice or at alkaline pH, all four compounds degraded almost completely within several hours. These results suggest that the amount, and type, of flavanols and procyanidins in the gastrointestinal tract following the consumption of cocoa can be influenced by the stability of these compounds in both acidic and alkaline environments.
We recently reported the improved oxygen radical absorbance capacity (ORAC) assay using fluorescein (FL) as the fluorescent probe. The current ORAC(FL) assay is limited in hydrophilic antioxidant due to the aqueous environment of the assay. Lipophilic antioxidants mainly include the vitamin E family and carotenoids, which play a critical role in biological defense systems. In this paper, we expanded the current ORAC(FL) assay to lipophilic antioxidants. Randomly methylated beta-cyclodextrin (RMCD) was introduced as the water solubility enhancer for lipophilic antioxidants. Seven percent RMCD (w/v) in a 50% acetone-H(2)O mixture was found to sufficiently solubilize vitamin E compounds and other lipophilic phenolic antioxidants in 75 mM phosphate buffer (pH 7.4). This newly developed ORAC assay (abbbreviated ORAC(FL-LIPO)) was validated through linearity, precision, accuracy, and ruggedness. The validation results demonstrate that the ORAC(FL-LIPO) assay is reliable and robust. For the first time, by using 6-hydroxy-2,5,7,8-tetramethyl-2-carboxylic acid as a standard (1.0), the ORAC values of alpha-tocopherol, (+)-gamma-tocopherol, (+)-delta-tocopherol, alpha-tocopherol acetate, tocotrienols, 2,6-di-tert-butyl-4-methylphenol, and gamma-oryzanol were determined to be 0.5 +/- 0.02, 0.74 +/- 0.03, 1.36 +/- 0.14, 0.00, 0.91 +/- 0.04, 0.16 +/- 0.01, and 3.00 +/- 0.26, respectively. The structural information of oxidized alpha-tocopherol obtained by liquid chromatography/mass spectrometry reveals that the mechanism for the reaction between the vitamin E and the peroxyl radical follows the hydrogen atom transfer mechanism, which is in agreement with the notion that vitamin E is the chain-breaking antioxidant.
Purpose of review:
Cardiovascular benefits for cocoa are being claimed in the scientific literature with growing intensity. To date, excitement over the potential health benefits of flavonoids has been driven mostly by epidemiological studies of tea and red wine, but raw cocoa contains specific flavonoids in concentrations far exceeding those from most other sources. Early evidence supports cocoa's enhancement of endothelial function via improvement of nitric oxide synthesis. However, many new studies have brought more confusion than clarity to the enterprise. This review provides guidelines for legitimate research in this promising field.
Topics of discussion:
Evidence generated from epidemiological studies, linking an increase in flavonoid ingestion to a reduction in cardiovascular events, is less convincing than data from controlled clinical trials. Whereas a few trials have shown evidence for an enhancement of endothelial function, inhibition of platelet adhesion and low-density lipoprotein oxidation, many studies have ignored scientific principles. Tremendous variability in cocoa processing, flavonoid content, measurement and dosing threatens the field. Valid research depends upon the precise identification and measurement of compounds of interest, which are probably the flavanols catechin and epicatechin, their oligomers and metabolites. These measures depend upon reliable methods of separation and quantification. Whether the monomers, dimers or larger flavanol oligomers, or their metabolites, are responsible for biological efficacy remains to be determined. Final questions surround bioavailability and dosing frequency.
Conclusions:
Evidence is mounting to support cardiovascular health benefits from the consumption of flavanol-rich cocoa. This review hopes to illuminate sound scientific principles by which future research in the field can be guided.
In the United States, commercially available foods, including cocoa and chocolate, are being marketed with statements referring to the level of antioxidant activity and polyphenols. For cocoa-containing foods, there has been no comprehensive survey of the content of these and other chemistries. A survey of cocoa and chocolate-containing products marketed in the United States was conducted to determine antioxidant activity and polyphenol and procyanidin contents. Commercially available samples consisted of the top market share products in each of the following six categories: natural cocoa, unsweetened baking chocolate, dark chocolate, semisweet baking chips, milk chocolate, and chocolate syrup. Composite samples were characterized using four different methods: oxygen radical absorbance capacity (ORAC), vitamin C equivalence antioxidant capacity (VCEAC), total polyphenols, and procyanidins. All composite lots were further characterized for percent nonfat cocoa solids (NFCS) and percent fat. Natural cocoas had the highest levels of antioxidant activities, total polyphenols, and procyanidins followed by baking chocolates, dark chocolates and baking chips, and finally milk chocolate and syrups. The results showed a strong linear correlation between NFCS and ORAC (R (2) = 0.9849), total polyphenols (R (2) = 0.9793), and procyanidins (R (2) = 0.946), respectively. On the basis of principal component analysis, 81.4% of the sample set was associated with NFCS, antioxidant activity, total polyphenols, and procyanidins. The results indicated that, regardless of the product category, NFCS were the primary factor contributing to the level of cocoa antioxidants in the products tested. Results further suggested that differences in cocoa bean blends and processing, with the possible exception of Dutching, are minor factors in determining the level of antioxidants in commercially available cocoa-containing products in the United States.
Cocoa and chocolate products from major brands were analyzed blind for total antioxidant capacity (AOC) (lipophilic and hydrophilic ORAC(FL)), catechins, and procyanidins (monomer through polymers). Accuracy of analyses was ascertained by comparing analyses on a NIST standard reference chocolate with NIST certified values. Procyanidin (PC) content was related to the nonfat cocoa solid (NFCS) content. The natural cocoa powders (average 87% of NFCS) contained the highest levels of AOC (826 +/- 103 micromol of TE/g) and PCs (40.8 +/- 8.3 mg/g). Alkalized cocoa (Dutched powders, average 80% NFCS) contained lower AOC (402 +/- 6 micromol of TE /g) and PCs (8.9 +/- 2.7 mg/g). Unsweetened chocolates or chocolate liquor (50% NFCS) contained 496 +/- 40 micromol of TE /g of AOC and 22.3 +/- 2.9 mg/g of PCs. Milk chocolates, which contain the least amount of NFCS (7.1%), had the lowest concentrations of AOC (80 +/- 10 micromol of TE /g) and PCs (2.7 +/- 0.5 mg/g). One serving of cocoa (5 g) or chocolate (15 or 40 g, depending upon the type of chocolate) provides 2000-9100 micromol of TE of AOC and 45-517 mg of PCs, amounts that exceed the amount in a serving of the majority of foods consumed in America. The monomers through trimers, which are thought to be directly bioavailable, contributed 30% of the total PCs in chocolates. Hydrophilic antioxidant capacity contributed >90% of AOC in all products. The correlation coefficient between AOC and PCs in chocolates was 0.92, suggesting that PCs are the dominant antioxidants in cocoa and chocolates. These results indicate that NFCS is correlated with AOC and PC in cocoa and chocolate products. Alkalizing dramatically decreased both the procyanidin content and antioxidant capacity, although not to the same extent.
Dark chocolate has potent antioxidant properties. Coronary atherosclerosis is promoted by impaired endothelial function and increased platelet activation. Traditional risk factors, high oxidative stress, and reduced antioxidant defenses play a crucial role in the pathogenesis of atherosclerosis, particularly in transplanted hearts. Thus, flavonoid-rich dark chocolate holds the potential to have a beneficial impact on graft atherosclerosis.
We assessed the effect of flavonoid-rich dark chocolate compared with cocoa-free control chocolate on coronary vascular and platelet function in 22 heart transplant recipients in a double-blind, randomized study. Coronary vasomotion was assessed with quantitative coronary angiography and cold pressor testing before and 2 hours after ingestion of 40 g of dark (70% cocoa) chocolate or control chocolate, respectively. Two hours after ingestion of flavonoid-rich dark chocolate, coronary artery diameter was increased significantly (from 2.36+/-0.51 to 2.51+/-0.59 mm, P<0.01), whereas it remained unchanged after control chocolate. Endothelium-dependent coronary vasomotion improved significantly after dark chocolate (4.5+/-11.4% versus -4.3+/-11.7% in the placebo group, P=0.01). Platelet adhesion decreased from 4.9+/-1.1% to 3.8+/-0.8% (P=0.04) in the dark chocolate group but remained unchanged in the control group.
Dark chocolate induces coronary vasodilation, improves coronary vascular function, and decreases platelet adhesion 2 hours after consumption. These immediate beneficial effects were paralleled by a significant reduction of serum oxidative stress and were positively correlated with changes in serum epicatechin concentration.
Major brands of cocoa powder products present in the Spanish market were analyzed for monomeric flavanols [(+)-catechin and (-)-epicatechin] and flavonols [quercetin-3-glucuronide, quercetin-3-glucoside (isoquercitrin), quercetin-3-arabinoside, and quercetin]. In addition, the influence of the manufacturing process of cocoa powder products, in particular, the alkalinization treatment ( Dutching), on the original content of these flavonoids has been studied. (-)-Epicatechin was in the range of 116.02-730.26 microg/g, whereas (+)-catechin was in the range of 81.40-447.62 microg/g in the commercial cocoa products studied. Among flavonols, quercetin-3-arabinoside and isoquercitrin were the major flavonols in the cocoa powder products studied, ranging from 2.10 to 40.33 microg/g and from 3.97 to 42.74 microg/g, respectively, followed by quercetin-3-glucuronide (0.13-9.88 microg/g) and quercetin aglycone (0.28-3.25 microg/g). To our knowledge, these results are the first quantitative data in relation to the content of individualized flavonol derivatives in commercial cocoa powder products. The alkalinization treatment resulted in 60% loss of the mean total flavonoid content. Among flavanols, (-)-epicatechin presented a larger decline (67%, as a mean percentage difference) than (+)-catechin (38%), probably because of its epimerization into (-)-catechin, a less bioavailable form of catechin. A decline was also confirmed for di-, tri-, and tetrameric procyanidins. In the case of flavonols, quercetin presented the highest loss (86%), whereas quercetin-3-glucuronide, quercetin-3-arabinoside, and isoquercitrin showed a similar decrease (58, 62, and 61%, respectively). It is concluded that the large decrease found in the flavonoid content of natural cocoa powder, together with the observed change in the monomeric flavanol profile that results from the alkalinization treatment, could affect the antioxidant properties and the polyphenol biovailability of cocoa powder products.
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