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The aim of this study was to obtain drinking yogurts enriched with ACTICOA cocoa powder (ACTICOA), its extract (EACTICOA) and pure phenolics, as well as their inclusion complexes with cyclodextrins and alginate–chitosan (A-Ch) capsules, and to evaluate the effects of these additives on the viability of lactic acid bacteria (LAB) and antioxidant properties of fresh yogurts and yogurts stored for 14 days at 4 °C. The application of cocoa phenolic compounds in free form and in the form of EACTICOA to yogurts resulted in the greatest increase in the concentration of phenolic compounds and a significant improvement in the antioxidant properties of the fortified products. The highest TPC was found in yogurts enriched with free quercetin (107.98 mg CE/g). Yogurt fortified with free gallic acid showed the highest ability to neutralize free radicals (EC50 = 2.74 mg/mg DPPH, EC50 = 5.40 mg/mg ABTS) and reduce ferric ions (183.48 µM Trolox/g). The enrichment of yogurts with the tested phenolic compounds preparations, especially in the form of encapsulates, did not affect the viability of LAB during storage. [ABSTRACT FROM AUTHOR]

The aim of this study was to obtain drinking yogurts enriched with ACTICOA cocoa powder (ACTICOA), its extract (EACTICOA) and pure phenolics, as well as their inclusion complexes with cyclodextrins and alginate–chitosan (A-Ch) capsules, and to evaluate the effects of these additives on the viability of lactic acid bacteria (LAB) and antioxidant properties of fresh yogurts and yogurts stored for 14 days at 4 °C. The application of cocoa phenolic compounds in free form and in the form of EACTICOA to yogurts resulted in the greatest increase in the concentration of phenolic compounds and a significant improvement in the antioxidant properties of the fortified products. The highest TPC was found in yogurts enriched with free quercetin (107.98 mg CE/g). Yogurt fortified with free gallic acid showed the highest ability to neutralize free radicals (EC50 = 2.74 mg/mg DPPH, EC50 = 5.40 mg/mg ABTS) and reduce ferric ions (183.48 µM Trolox/g). The enrichment of yogurts with the tested phenolic compounds preparations, especially in the form of encapsulates, did not affect the viability of LAB during storage.

The following investigations describe the potential of handheld NIR spectroscopy and Raman imaging measurements for the identification and authentication of food products. On the one hand, during the last decade, handheld NIR spectroscopy has made the greatest progress among vibrational spectroscopic methods in terms of miniaturization and price/performance ratio, and on the other hand, the Raman spectroscopic imaging method can achieve the best lateral resolution when examining the heterogeneous composition of samples. The utilization of both methods is further enhanced via the combination with chemometric evaluation methods with respect to the detection, identification, and discrimination of illegal counterfeiting of food products. To demonstrate the solution to practical problems with these two spectroscopic techniques, the results of our recent investigations obtained for various industrial processes and customer-relevant product examples have been discussed in this article. Specifically, the monitoring of food extraction processes (e.g., ethanol extraction of clove and water extraction of wolfberry) and the identification of food quality (e.g., differentiation of cocoa nibs and cocoa beans) via handheld NIR spectroscopy, and the detection and quantification of adulterations in powdered dairy products via Raman imaging were outlined in some detail. Although the present work only demonstrates exemplary product and process examples, the applications provide a balanced overview of materials with different physical properties and manufacturing processes in order to be able to derive modified applications for other products or production processes. [ABSTRACT FROM AUTHOR]

The chemical composition of dark chocolate has a significant impact on its complex flavor profile. This study aims to investigate the relationship between the volatile chemical composition and perceived flavor of 54 dark chocolate samples made from Trinitario cocoa beans from the Dominican Republic. The samples were evaluated by a trained panel and analyzed using gas chromatography-mass spectrometry (GC-MS) to identify and quantify the volatile compounds. Predictive models based on a partial least squares regression (PLS) allowed the identification of key compounds for predicting individual sensory attributes. The models were most successful in classifying samples based on the intensity of bitterness and astringency, even though these attributes are mostly linked to non-volatile compounds. Acetaldehyde, dimethyl sulfide, and 2,3-butanediol were found to be key predictors for various sensory attributes, while propylene glycol diacetate was identified as a possible marker for red fruit aroma. The study highlights the potential of using volatile compounds to accurately predict chocolate flavor potential. [ABSTRACT FROM AUTHOR]

Ecuador is one of the major cocoa producers worldwide, but its productivity has lately been affected by diseases. Endophytic biocontrol agents have been used to minimize pathogenic effects; however, compounds produced by endophytes are minimally understood. This work presents the chemical characterization of the Trichoderma species extracts that proved inhibition against cocoa pathogens. Solid–liquid extraction was performed as a partitioning method using medium with the fungal mycelia of Trichoderma reesei (C2A), Trichoderma sp. (C3A), Trichoderma harzianum (C4A), and Trichoderma spirale (C10) in ethyl acetate individually. The extract of T. spirale (C10) exhibited the growth inhibition (32.97–47.02%) of Moniliophthora perniciosa at 10 µg/mL, while a slight stimulation of Moniliophthora roreri was shown by the extracts of T. reesei (C2A) and T. harzianum (C4A) at higher concentrations. The inhibitory activity could be related to alkaloids, lactones, quinones, flavonoids, triterpenes, and sterols, as indicated by chemical screening and antifungal compounds, such as widdrol, β-caryophyllene, tyrosol, butyl isobutyrate, sorbic acid, palmitic acid, palmitelaidic acid, linoleic acid, and oleic acid, which were identified by gas chromatography–mass spectrometry (GC-MS). The results showed that the extracts, particularly T. spirale (C10), have the potential as biocontrol agents against witches' broom disease; however, further studies are needed to confirm their effectiveness. [ABSTRACT FROM AUTHOR]

Fine-grade cocoa beans are characterized by their great organoleptic quality. Brazilian cocoa producers increasingly privilege organoleptic quality over yield. Catongo and FL89, fine Brazilian cocoa genotypes from Bahia, are characterized by particular flavors (respectively, kerosene and whisky). The beans IMC67, PA121, and P7 from the state of Pará are genotypes that have high resistance to diseases. Solvent-assisted flavor evaporation (SAFE) aroma extraction was used here to identify and quantify the volatile compounds discriminating these genotypes. The results show that the kerosene aroma of Catongo is likely due to the presence, at high levels, of ethyl acetate and isobutyl acetate. On the other hand, ethyl benzoate, heptanoate, and octanoate, trans-2-nonenal, 1-octen-3-ol, and 3-methylbutanol could play a key role in the whisky notes of FL89. Heptan-2-ol, heptan-2-one, nonan-2-one, linalool (although still more concentrated in IMC67 from Pará state), benzaldehyde, and phenylacetaldehyde also discriminate these beans. Other compounds, although not discriminating, appear important in determining their aromatic quality. The PCA showed that cocoa from Pará state formed a cluster due to similar aromas, while FL89 was the most distinct among the genotypes. Beans from Brazil show great potential and diversity for the fine cocoa market. [ABSTRACT FROM AUTHOR]

Arabica-coffee and Theobroma-cocoa agroindustrial wastes were treated with NaOH and characterized to efficiently remove Pb(II) from the aqueous media. The maximum Pb(II) adsorption capacities, qmax, of Arabica-coffee (WCAM) and Theobroma-cocoa (WCTM) biosorbents (qmax = 303.0 and 223.1 mg·g−1, respectively) were almost twice that of the corresponding untreated wastes and were higher than those of other similar agro-industrial biosorbents reported in the literature. Structural, chemical, and morphological characterization were performed by FT-IR, SEM/EDX, and point of zero charge (pHPZC) measurements. Both the WCAM and WCTM biosorbents showed typical uneven and rough cracked surfaces including the OH, C=O, COH, and C-O-C functional adsorbing groups. The optimal Pb(II) adsorption, reaching a high removal efficiency %R (>90%), occurred at a pH between 4 and 5 with a biosorbent dose of 2 g·L−1. The experimental data for Pb(II) adsorption on WACM and WCTM were well fitted with the Langmuir-isotherm and pseudo-second order kinetic models. These indicated that Pb(II) adsorption is a chemisorption process with the presence of a monolayer mechanism. In addition, the deduced thermodynamic parameters showed the endothermic (ΔH0 > 0), feasible, and spontaneous (ΔG0 < 0) nature of the adsorption processes studied. [ABSTRACT FROM AUTHOR]

The following investigations describe the potential of handheld NIR spectroscopy and Raman imaging measurements for the identification and authentication of food products. On the one hand, during the last decade, handheld NIR spectroscopy has made the greatest progress among vibrational spectroscopic methods in terms of miniaturization and price/performance ratio, and on the other hand, the Raman spectroscopic imaging method can achieve the best lateral resolution when examining the heterogeneous composition of samples. The utilization of both methods is further enhanced via the combination with chemometric evaluation methods with respect to the detection, identification, and discrimination of illegal counterfeiting of food products. To demonstrate the solution to practical problems with these two spectroscopic techniques, the results of our recent investigations obtained for various industrial processes and customer-relevant product examples have been discussed in this article. Specifically, the monitoring of food extraction processes (e.g., ethanol extraction of clove and water extraction of wolfberry) and the identification of food quality (e.g., differentiation of cocoa nibs and cocoa beans) via handheld NIR spectroscopy, and the detection and quantification of adulterations in powdered dairy products via Raman imaging were outlined in some detail. Although the present work only demonstrates exemplary product and process examples, the applications provide a balanced overview of materials with different physical properties and manufacturing processes in order to be able to derive modified applications for other products or production processes.

Optimization of pectin extraction from cocoa pod husk was carried out to examine independent variables that affect the quality of pectin obtained and determine the best conditions for the extraction process. In this study, three independent variables thought to contribute to microwave-assisted pectin extraction were used, namely, extraction time (20, 25, and 30 min), microwave power (180, 300, and 450 W), and citric acid concentration (2.5%, 5%, and 10%). Response surface methodology was applied using central composite design (CCD) to examine the effect of independent variables on the parameter measured. Among the seven parameters measured, namely, yield, temperature, moisture content, ash content, equivalent weight, methoxyl content, and galacturonic acid content, the statistical analysis test showed that the model equations that were suitable for predicting response values were temperature, moisture content, and ash content. Therefore, the optimization of conditions was only reviewed for these three parameters. Optimization results concluded that the factors that had the most significant effect on temperature, moisture content, and ash content were extraction time and microwave power. Optimal conditions for pectin extraction were at 30 min extraction time, 450 W microwave power, and 10% solvent concentration, resulting in a temperature of 104 °C, moisture content of 6%, and ash content of 8%. Other parameter values measured under these conditions were a yield of 21.10%, equivalent weight of 602.40 mg/mol, methoxyl content of 6.07%, and galacturonic acid content of 72.86%. Pectin extracted from cocoa pod husk using this method has the potential to be further applied, especially in the food and pharmaceutical industries. [ABSTRACT FROM AUTHOR]

The chemical composition of dark chocolate has a significant impact on its complex flavor profile. This study aims to investigate the relationship between the volatile chemical composition and perceived flavor of 54 dark chocolate samples made from Trinitario cocoa beans from the Dominican Republic. The samples were evaluated by a trained panel and analyzed using gas chromatography-mass spectrometry (GC-MS) to identify and quantify the volatile compounds. Predictive models based on a partial least squares regression (PLS) allowed the identification of key compounds for predicting individual sensory attributes. The models were most successful in classifying samples based on the intensity of bitterness and astringency, even though these attributes are mostly linked to non-volatile compounds. Acetaldehyde, dimethyl sulfide, and 2,3-butanediol were found to be key predictors for various sensory attributes, while propylene glycol diacetate was identified as a possible marker for red fruit aroma. The study highlights the potential of using volatile compounds to accurately predict chocolate flavor potential.

Fine-grade cocoa beans are characterized by their great organoleptic quality. Brazilian cocoa producers increasingly privilege organoleptic quality over yield. Catongo and FL89, fine Brazilian cocoa genotypes from Bahia, are characterized by particular flavors (respectively, kerosene and whisky). The beans IMC67, PA121, and P7 from the state of Pará are genotypes that have high resistance to diseases. Solvent-assisted flavor evaporation (SAFE) aroma extraction was used here to identify and quantify the volatile compounds discriminating these genotypes. The results show that the kerosene aroma of Catongo is likely due to the presence, at high levels, of ethyl acetate and isobutyl acetate. On the other hand, ethyl benzoate, heptanoate, and octanoate, trans-2-nonenal, 1-octen-3-ol, and 3-methylbutanol could play a key role in the whisky notes of FL89. Heptan-2-ol, heptan-2-one, nonan-2-one, linalool (although still more concentrated in IMC67 from Pará state), benzaldehyde, and phenylacetaldehyde also discriminate these beans. Other compounds, although not discriminating, appear important in determining their aromatic quality. The PCA showed that cocoa from Pará state formed a cluster due to similar aromas, while FL89 was the most distinct among the genotypes. Beans from Brazil show great potential and diversity for the fine cocoa market.

The aim of this study was to estimate the contamination of grain coffee, roasted coffee, instant coffee, and cocoa purchased in local markets with ochratoxin A (OTA) and its isomerization product 2′R-ochratoxin A (2′R-OTA), and to assess risk of dietary exposure to the mycotoxins. OTA and 2′R-OTA content was determined using the HPLC chromatography with immunoaffinity columns dedicated to OTA. OTA levels found in all the tested samples were below the maximum limits specified in the European Commission Regulation EC 1881/2006. Average OTA concentrations calculated for positive samples of grain coffee/roasted coffee/instant coffee/cocoa were 0.94/0.79/3.00/0.95 µg/kg, with the concentration ranges: 0.57–1.97/0.44–2.29/0.40–5.15/0.48–1.97 µg/kg, respectively. Average 2′R-OTA concentrations calculated for positive samples of roasted coffee/instant coffee were 0.90/1.48 µg/kg, with concentration ranges: 0.40–1.26/1.00–2.12 µg/kg, respectively. In turn, diastereomer was not found in any of the tested cocoa samples. Daily intake of both mycotoxins with coffee/cocoa would be below the TDI value even if the consumed coffee/cocoa were contaminated with OTA/2′R-OTA at the highest levels found in this study. Up to now only a few papers on both OTA and 2′R-OTA in roasted food products are available in the literature, and this is the first study in Poland.

Increasing production of cocoa (Theobroma cacao L.) leads to a higher environmental burden due to its solid waste generation. Cocoa pod husk, one of the major solid wastes of cocoa production, contains rich bioactive compounds unveiling its valorization potential. With that in mind, our research aimed to explore the biological and antioxidant activities of aqueous extracts from cocoa pod husks. In this present work, cocoa pod husk was extracted using water and subsequentially partitioned using n-hexane, ethyl acetate, and methanol. The antimicrobial investigation revealed that the ethyl acetate solubles were active against the Staphylococcus aureus, Escherichia coli, and Candida albicans, where at a 20% w/v concentration, the inhibition diameters were 6.62 ± 0.10, 6.52 ± 0.02, and 11.72 ± 0.36 mm, respectively. The extracts were found non-toxic proven by brine shrimp lethality tests against Artemia salina with LC50 scores ranging from 74.1 to 19,054.6 μg/mL. The total phenolic content and total flavonoid content were obtained in the range of 47.44 to 570.44 mg/g GAE and 1.96 to 4.34 mg/g QE, respectively. Antioxidant activities of the obtained extracts were revealed by 2,2-diphenyl-1-picryl-hydrazyl-hydrate (DPPH) assay with EC50 reached as low as 9.61 μg/mL by the ethyl acetate soluble. Phytochemical screening based on gas chromatography—mass spectroscopy analysis on the sample with the highest antioxidant activities revealed the dominant presence of three phytosterols, namely gamma-sitosterol, stigmasterol, and campesterol.

Peru is one of the main areas where there are large cocoa crops with special relevance to the economy of this country. In fact, cocoa is a major, economically important, international crop which has been linked to several benefits, such as anti-allergenic, anti-atherogenic, anti-inflammatory, anti-microbial, anti-oxidant, anti-thrombotic, cardioprotective and vasodilatory properties, relating to its bioactive compound content. However, in cocoa industrial processing, several residues or wastes, which are commonly discarded generating a negative impact on the environment, are produced in large amounts. Some of the cocoa by-products, which go underutilized, could be a good source of bioactive compounds with high utility for the development of innovative products in nutraceutical, medical or pharmaceutical industries. For this reason, the aim of this study is to qualitatively determine the phytochemical composition of husk and bean extracts from different cocoa-growing areas and processes from Peru by high performance liquid chromatography coupled to mass spectrometry. Furthermore, we aim to evaluate their phenolic and flavan-3-ol contents and antioxidant capacities for the purpose of highlighting the potential of cocoa by-products from these cultivars as functional ingredients. In total, 49 chemical compounds were detected in the analyzed extracts. Comparing both husks and beans, bean extracts were characterized by high content in flavonoids whereas husk extracts had a higher content of phenolic acids. The presence of these compounds together with the bioactivity results suggest that these matrices may be further studied for their revaluation in the development of high added-value products in nutraceutical, medical, and pharmaceutical industries.

Chocolate production suffered a vast impact with the emergence of the "witches' broom" disease in cocoa plants. To recover cocoa production, many disease-resistant hybrid plants have been developed. However, some different cocoa hybrids produce cocoa beans that generate chocolate with variable quality. Fermentation of cocoa beans is a microbiological process that can be applied for the production of chocolate flavor precursors, leading to overcoming the problem of variable chocolate quality. The aim of this work was to use a cocktail of microorganisms as a starter culture on the fermentation of the ripe cocoa pods from PH15 cocoa hybrid, and evaluate its influence on the microbial communities present on the fermentative process on the compounds involved during the fermentation, and to perform the chocolate sensorial characterization. According to the results obtained, different volatile compounds were identified in fermented beans and in the chocolate produced. Bitterness was the dominant taste found in non-inoculated chocolate, while chocolate made with inoculated beans showed bitter, sweet, and cocoa tastes. 2,3-Butanediol and 2,3-dimethylpyrazine were considered as volatile compounds making the difference on the flavor of both chocolates. Saccharomyces cerevisiae UFLA CCMA 0200, Lactobacillus plantarum CCMA 0238, and Acetobacter pasteurianus CCMA 0241 are proposed as starter cultures for cocoa fermentation. [ABSTRACT FROM AUTHOR]

This report describes the characterization of a series of commercially available procyanidin standards ranging from dimers DP = 2 to decamers DP = 10 for the determination of procyanidins from cocoa and chocolate. Using a combination of HPLC with fluorescence detection and MALDI-TOF mass spectrometry, the purity of each standard was determined and these data were used to determine relative response factors. These response factors were compared with other response factors obtained from published methods. Data comparing the procyanidin analysis of a commercially available US dark chocolate calculated using each of the calibration methods indicates divergent results and demonstrate that previous methods may significantly underreport the procyanidins in cocoa-containing products. These results have far reaching implications because the previous calibration methods have been used to develop data for a variety of scientific reports, including food databases and clinical studies.

Cocoa and cocoa products have received much attention due to their significant polyphenol contents. Cocoa and cocoa products, namely cocoa liquor, cocoa powder and chocolates (milk and dark chocolates) may present varied polyphenol contents and possess different levels of antioxidant potentials. For the past ten years, at least 28 human studies have been conducted utilizing one of these cocoa products. However, questions arise on which of these products would deliver the best polyphenol contents and antioxidant effects. Moreover, the presence of methylxanthines, peptides, and minerals could synergistically enhance or reduce antioxidant properties of cocoa and cocoa products. To a greater extent, cocoa beans from different countries of origins and the methods of preparation (primary and secondary) could also partially influence the antioxidant polyphenols of cocoa products. Hence, comprehensive studies on the aforementioned factors could provide the understanding of health-promoting activities of cocoa or cocoa products components.

Cocoa contains high levels of different flavonoids. In the present study, the enantioseparation of catechin and epicatechin in cocoa and cocoa products by chiral capillary electrophoresis (CCE) was performed. A baseline separation of the catechin and epicatechin enantiomers was achieved by using 0.1 mol·L−1 borate buffer (pH 8.5) with 12 mmol·L-1 (2-hydroxypropyl)-γ-cyclodextrin as chiral selector, a fused-silica capillary with 50 cm effective length (75 μm I.D.), +18 kV applied voltage, a temperature of 20°C and direct UV detection at 280 nm. To avoid comigration or coelution of other similar substances, the flavan-3-ols were isolated and purified using polyamide-solid-phase-extraction and LC-MS analysis. As expected, we found (-)-epicatechin and (+)-catechin inunfermented, dried, unroasted cocoa beans. In contrast, roasted cocoa beans and cocoa products additionally contained the atypical flavan-3-ol (-)-catechin. This is generally formed during the manufacturing process by an epimerization which converts (-)-epicatechin to its epimer (-)-catechin. High temperatures during the cocoa bean roasting process and particularly the alkalization of the cocoa powder are the main factors inducing the epimerization reaction. In addition to the analysis of cocoa and cocoa products, peak ratios were calculated for a better differentiation of the cocoa products.

The annual production of cocoa is approximately 4.7 million tons of cocoa beans, of which only 10% corresponds to the cocoa bean and the remaining value corresponds to a high number of residues, cocoa bean shell, pulp and husk. These by-products are a source of nutrients and compounds of notable interest in the food industry as possible ingredients, or even additives. The assessment of such by-products is relevant to the circular economy at both environmental and economic levels. Investigations carried out with these by-products have shown that cocoa husk can be used for the production of useful chemicals such as ketones, carboxylic acids, aldehydes, furans, heterocyclic aromatics, alkylbenzenes, phenols and benzenediols, as well as being efficient for the removal of lead from acidic solutions, without decay in the process due to the other metals in this matrix. The fibre present in the cocoa bean shell has a considerable capacity to adsorb a large amount of oil and cholesterol, thus reducing its bioavailability during the digestion process, as well as preventing lipid oxidation in meats, with better results compared to synthetic antioxidants (butylated hydroxytoluene and β-tocopherol). Finally, cocoa pulp can be used to generate a sweet and sour juice with a natural flavour. Thus, this review aimed to compile information on these by-products, focusing mainly on their chemical and nutritional composition, simultaneously, the various uses proposed in the literature based on a bibliographic review of articles, books and theses published between 2000 and 2021, using databases such as Scopus, Web of Science, ScieLO, PubMed and ResearchGate. [ABSTRACT FROM AUTHOR]

The aim of this study was to estimate the contamination of grain coffee, roasted coffee, instant coffee, and cocoa purchased in local markets with ochratoxin A (OTA) and its isomerization product 2′R-ochratoxin A (2′R-OTA), and to assess risk of dietary exposure to the mycotoxins. OTA and 2′R-OTA content was determined using the HPLC chromatography with immunoaffinity columns dedicated to OTA. OTA levels found in all the tested samples were below the maximum limits specified in the European Commission Regulation EC 1881/2006. Average OTA concentrations calculated for positive samples of grain coffee/roasted coffee/instant coffee/cocoa were 0.94/0.79/3.00/0.95 µg/kg, with the concentration ranges: 0.57–1.97/0.44–2.29/0.40–5.15/0.48–1.97 µg/kg, respectively. Average 2′R-OTA concentrations calculated for positive samples of roasted coffee/instant coffee were 0.90/1.48 µg/kg, with concentration ranges: 0.40–1.26/1.00–2.12 µg/kg, respectively. In turn, diastereomer was not found in any of the tested cocoa samples. Daily intake of both mycotoxins with coffee/cocoa would be below the TDI value even if the consumed coffee/cocoa were contaminated with OTA/2′R-OTA at the highest levels found in this study. Up to now only a few papers on both OTA and 2′R-OTA in roasted food products are available in the literature, and this is the first study in Poland. [ABSTRACT FROM AUTHOR]

This report describes the characterization of a series of commercially available procyanidin standards ranging from dimers DP = 2 to decamers DP = 10 for the determination of procyanidins from cocoa and chocolate. Using a combination of HPLC with fluorescence detection and MALDI-TOF mass spectrometry, the purity of each standard was determined and these data were used to determine relative response factors. These response factors were compared with other response factors obtained from published methods. Data comparing the procyanidin analysis of a commercially available US dark chocolate calculated using each of the calibration methods indicates divergent results and demonstrate that previous methods may significantly underreport the procyanidins in cocoa-containing products. These results have far reaching implications because the previous calibration methods have been used to develop data for a variety of scientific reports, including food databases and clinical studies. [ABSTRACT FROM AUTHOR]

Cocoa pulp occurs as a by-product of cocoa bean production and can be repurposed to different food applications, such as jams, fruit preparations and beverages, improving the sustainability of cocoa production, as well as the livelihoods of cocoa farmers. In this work, aroma-active compounds of fresh cocoa fruit pulps from different origins were investigated by applying aroma extract dilution analyses in combination with gas chromatography-mass spectrometry/olfactometry for identification. In total, 65 aroma-active compounds were determined in four different pulps originating from Indonesia, Vietnam, Cameroon, and Nicaragua. Vietnamese pulp showed the highest number of aroma-active regions, while Cameroonian pulp accounted for the lowest. Moreover, Cameroonian cocoa pulp showed the lowest FD factors. Overall, the odorants with the highest FD factors were trans-4,5-epoxy-(E)-decenal, 2- and 3-methylbutanoic acid, 3-(methylthio)propanal, 2-isobutyl-3-methoxypyrazine, (E,E)-2,4-nonadienal, (E,E)-2,4-decadienal, 4-vinyl-2-methoxyphenol, δ-decalactone, 3-hydroxy-4,5-dimethylfuran-2(5H)-one, dodecanoic acid, and linalool. This study provides insights into the aroma composition of fresh cocoa pulp from different origins for future food applications. [ABSTRACT FROM AUTHOR]

Methylxanthines and polyphenols from cocoa byproducts should be considered for their application in the development of functional ingredients for food, cosmetic and pharmaceutical formulations. Different cocoa byproducts were analyzed for their chemical contents, and skincare properties were measured by antioxidant assays and anti-skin aging activity. Musty cocoa beans (MC) and second-quality cocoa beans (SQ) extracts showed the highest polyphenol contents and antioxidant capacities. In the collagenase and elastase inhibition study, the highest effect was observed for the SQ extract with 86 inhibition and 36% inhibition, respectively. Among cocoa byproducts, the contents of catechin and epicatechin were higher in the SQ extract, with 18.15 mg/100 g of sample and 229.8 mg/100 g of sample, respectively. Cocoa bean shells (BS) constitute the main byproduct due to their methylxanthine content (1085 mg of theobromine and 267 mg of caffeine/100 g of sample). Using BS, various influencing factors in the extraction process were investigated by response surface methodology (RSM), before scaling up separations. The extraction process developed under optimized conditions allows us to obtain almost 2 g/min and 0.2 g/min of total methylxanthines and epicatechin, respectively. In this way, this work contributes to the sustainability and valorization of the cocoa production chain. [ABSTRACT FROM AUTHOR]

Ochratoxin A (OTA) is a highly toxic mycotoxin and poses great threat to human health. Due to its serious toxicity and widespread contamination, great efforts have been made to evaluate its human exposure. This review focuses on the OTA occurrence and contamination level in nine plant and animal derived food commodities: cereal, wine, coffee, beer, cocoa, dried fruit, spice, meat, and milk. The occurrence and contamination level varied greatly in food commodities and were affected by many factors, including spices, geography, climate, and storage conditions. Therefore, risk monitoring must be routinely implemented to ensure minimal OTA intake and food safety. [ABSTRACT FROM AUTHOR]

Increasing production of cocoa (Theobroma cacao L.) leads to a higher environmental burden due to its solid waste generation. Cocoa pod husk, one of the major solid wastes of cocoa production, contains rich bioactive compounds unveiling its valorization potential. With that in mind, our research aimed to explore the biological and antioxidant activities of aqueous extracts from cocoa pod husks. In this present work, cocoa pod husk was extracted using water and subsequentially partitioned using n-hexane, ethyl acetate, and methanol. The antimicrobial investigation revealed that the ethyl acetate solubles were active against the Staphylococcus aureus, Escherichia coli, and Candida albicans, where at a 20% w/v concentration, the inhibition diameters were 6.62 ± 0.10, 6.52 ± 0.02, and 11.72 ± 0.36 mm, respectively. The extracts were found non-toxic proven by brine shrimp lethality tests against Artemia salina with LC50 scores ranging from 74.1 to 19,054.6 μg/mL. The total phenolic content and total flavonoid content were obtained in the range of 47.44 to 570.44 mg/g GAE and 1.96 to 4.34 mg/g QE, respectively. Antioxidant activities of the obtained extracts were revealed by 2,2-diphenyl-1-picryl-hydrazyl-hydrate (DPPH) assay with EC50 reached as low as 9.61 μg/mL by the ethyl acetate soluble. Phytochemical screening based on gas chromatography—mass spectroscopy analysis on the sample with the highest antioxidant activities revealed the dominant presence of three phytosterols, namely gamma-sitosterol, stigmasterol, and campesterol. [ABSTRACT FROM AUTHOR]

In this study, the antifungal potential of chemical constituents from Piper pesaresanum and some synthesized derivatives was determined against three phytopathogenic fungi associated with the cocoa crop. The methodology included the phytochemical study on the aerial part of P. pesaresanum, the synthesis of some derivatives and the evaluation of the antifungal activity against the fungi Moniliophthora roreri, Fusarium solani and Phytophthora sp. The chemical study allowed the isolation of three benzoic acid derivatives (1–3), one dihydrochalcone (4) and a mixture of sterols (5–7). Seven derivatives (8–14) were synthesized from the main constituents, of which compounds 9, 10, 12 and 14 are reported for the first time. Benzoic acid derivatives showed strong antifungal activity against M. roreri, of which 11 (3.0 ± 0.8 µM) was the most active compound with an IC50 lower compared with positive control Mancozeb® (4.9 ± 0.4 µM). Dihydrochalcones and acid derivatives were active against F. solani and Phytophthora sp., of which 3 (32.5 ± 3.3 µM) and 4 (26.7 ± 5.3 µM) were the most active compounds, respectively. The preliminary structure–activity relationship allowed us to establish that prenylated chains and the carboxyl group are important in the antifungal activity of benzoic acid derivatives. Likewise, a positive influence of the carbonyl group on the antifungal activity for dihydrochalcones was deduced. [ABSTRACT FROM AUTHOR]

According to the World Health Organization, cardiovascular diseases are responsible for 31% of global deaths. A reduction in mortality can be achieved by promoting a healthy lifestyle, developing prevention strategies, and developing new therapies. Polyphenols are present in food and drinks such as tea, cocoa, fruits, berries, and vegetables. These compounds have strong antioxidative properties, which might have a cardioprotective effect. The aim of this paper is to examine the potential of polyphenols in cardioprotective use based on in vitro human and rat cardiomyocytes as well as fibroblast research. Based on the papers discussed in this review, polyphenols have the potential for cardioprotective use due to their multilevel points of action which include, among others, anti-inflammatory, antioxidant, antithrombotic, and vasodilatory. Polyphenols may have potential use in new and effective preventions or therapies for cardiovascular diseases, yet more clinical studies are needed. [ABSTRACT FROM AUTHOR]

Chocolate is considered as both caloric and functional food. Its nutritional properties may be improved by addition of fiber; however, this may reduce polyphenols content. The aim of this research was to determine the influence of cocoa shell addition (as a source of fiber) and its combination with different ingredients (cocoa butter equivalents (CBE), emulsifiers, dairy ingredients) on polyphenols of dark and milk chocolates. Total polyphenol (TPC) and total flavonoid (TFC) contents were determined spectrophotometrically, identification and quantification of individual compounds by high pressure liquid chromatography and antioxidant capacity by ferric reducing antioxidant power (FRAP) assay. Results showed that even though addition of cocoa shell to chocolate results in reduced contents of TPC, TFC, and individual compounds, it is not significant compared to ones reported by other authors for commercial chocolates. Other ingredients influence determined values for all investigated parameters; however, additional research is needed to reveal exact mechanisms and implications. [ABSTRACT FROM AUTHOR]

The biological activity of chocolates gains more and more attention of consumers. Its antioxidant properties depend, among other factors, mainly on the origin of cocoa and the characteristics that this origin gives to the final product. Therefore, the aim of the study was to measure and compare the total content of polyphenols, antioxidant activity, and key odorants of commercial chocolates made from blend cocoa with single-origin ones. The highest content of polyphenols was found in 90% blend cocoa chocolate and single-origin samples, while the lowest content was exhibited by 100% chocolate from blend cocoa mass. The highest antioxidant activity measured by 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and ferric reducing antioxidant power (FRAP) assays was observed in the sample of chocolate with 90% cocoa solids from blend mass, followed by single-origin chocolates. A high positive correlation between ABTS assay and the total polyphenol and phenolic acids' content, as well as among the total content of polyphenols, flavonoids, and phenolic acids was found. Mineral composition analysis showed that dark chocolate is a valuable source of some elements, especially Mg, Fe, and Zn. Potentially toxic elements were not detected or below permitted limits. Moreover, it was noticed that the main volatile compound in all tested samples was acetic acid, but pyrazines were considered the most important group of chocolate odorants. [ABSTRACT FROM AUTHOR]

Peru is one of the main areas where there are large cocoa crops with special relevance to the economy of this country. In fact, cocoa is a major, economically important, international crop which has been linked to several benefits, such as anti-allergenic, anti-atherogenic, anti-inflammatory, anti-microbial, anti-oxidant, anti-thrombotic, cardioprotective and vasodilatory properties, relating to its bioactive compound content. However, in cocoa industrial processing, several residues or wastes, which are commonly discarded generating a negative impact on the environment, are produced in large amounts. Some of the cocoa by-products, which go underutilized, could be a good source of bioactive compounds with high utility for the development of innovative products in nutraceutical, medical or pharmaceutical industries. For this reason, the aim of this study is to qualitatively determine the phytochemical composition of husk and bean extracts from different cocoa-growing areas and processes from Peru by high performance liquid chromatography coupled to mass spectrometry. Furthermore, we aim to evaluate their phenolic and flavan-3-ol contents and antioxidant capacities for the purpose of highlighting the potential of cocoa by-products from these cultivars as functional ingredients. In total, 49 chemical compounds were detected in the analyzed extracts. Comparing both husks and beans, bean extracts were characterized by high content in flavonoids whereas husk extracts had a higher content of phenolic acids. The presence of these compounds together with the bioactivity results suggest that these matrices may be further studied for their revaluation in the development of high added-value products in nutraceutical, medical, and pharmaceutical industries. [ABSTRACT FROM AUTHOR]

To provide further insight into the antioxidant potential of procyanidins (PCs) from cocoa beans, PC extract was fractionated by several methodologies, including solid phase extraction, Sephadex LH-20 gel permeation, and preparative HPLC using C18 and diol stationary phases. All the isolated fractions were analyzed by UHPLC-QTOF-MS to determine their relative composition. According to our results, classical techniques allowed good separation of alkaloids, catechins, dimers, and trimers, but were inefficient for oligomeric PCs. Preparative C18-HPLC method allowed the attainment of high relative composition of fractions enriched with alkaloids, catechins, and PCs with degree of polymerization (DP) < 4. However, the best results were obtained by preparative diol-HPLC, providing a separation according to the increasing DP. According to the mass spectrometry fragmentation pattern, the nine isolated fractions (Fractions II–X) consisted of exclusively individual PCs and their corresponding isomers (same DP). In summary, an efficient, robust, and fast method using a preparative diol column for the isolation of PCs is proposed. Regarding DPPH• and ABTS•+ scavenging activity, it increases according to the DP; therefore, the highest activity was for cocoa extract > PCs > monomers. Thereby, cocoa procyanidins might be of interest to be used as alternative antioxidants. [ABSTRACT FROM AUTHOR]

The antioxidant activity and polyphenols content of beer associated with its low alcohol content are relevant factors for an evaluation of the nutritional quality of beer. To investigate the effect of adding foods on the nutritional quality of beer, seven special beers that were commercially available and produced adding natural foods (walnut, chestnut, cocoa, honey, green tea, coffee, and licorice) during the fermentation process were analyzed for their polyphenols and flavonoids contents, phenolics profile, and antioxidant activity. The results obtained showed that most of the special beers under study possessed antioxidant activity, as well as total polyphenols and flavonoids contents notably higher as compared with the five conventional beers analyzed. The highest polyphenols and flavonoids contents were exhibited in cocoa, walnut, chestnut, and licorice beers, followed by coffee, honey, and green tea beers. Antioxidant activity decreased in the order walnut, cocoa, chestnut, licorice, coffee, honey, and green tea. Most special beers were enriched in catechin, epicatechin, rutin, myricetin, quercetin, and resveratrol. The content of phenolic acids, especially ferulic, p-coumaric, syringic, and sinapic acids was generally higher in special beers as compared with conventional beers. Our findings showed that the addition of natural foods during the fermentation process remarkably increased antioxidant activity of beer and qualitatively and quantitatively improved its phenolics profile. [ABSTRACT FROM AUTHOR]

The present study addressed the protective effects against oxidative stress (OS) of a cocoa powder extract (CPEX) on the protein expression profile of S. cerevisiae. A proteomic analysis was performed after culture preincubation with CPEX either without stress (−OS) or under stress conditions (+OS) (5 mM of H2O2). LC-MS/MS identified 33 differentially expressed proteins (–OS: 14, +OS: 19) that were included By Gene Ontology analysis in biological processes: biosynthesis of amino acids, carbohydrate metabolism and reactive oxygen species metabolic process. In a gene-knockout strains study, eight proteins were identified as putative candidates for being involved in the protective mechanism of cocoa polyphenols against OS induced by H2O2. CPEX was able to exert its antioxidant activity in yeast mainly through the regulation of: (a) amino acids metabolism proteins by modulating the production of molecules with known antioxidant roles; (b) stress-responsive protein Yhb1, but we were unable to fully understand its down-regulation; (c) protein Prb1, which can act by clipping Histone H3 N-terminal tails that are related to cellular resistance to DNA damaging agents. [ABSTRACT FROM AUTHOR]

Natural methylxanthines, caffeine, theophylline and theobromine, are widespread biologically active alkaloids in human nutrition, found mainly in beverages (coffee, tea, cocoa, energy drinks, etc.). Their detection is thus of extreme importance, and many studies are devoted to this topic. During the last decade, graphene oxide (GO) and reduced graphene oxide (RGO) gained popularity as constituents of sensors (chemical, electrochemical and biosensors) for methylxanthines. The main advantages of GO and RGO with respect to graphene are the easiness and cheapness of synthesis, the notable higher solubility in polar solvents (water, among others), and the higher reactivity towards these targets (mainly due to π–π interactions); one of the main disadvantages is the lower electrical conductivity, especially when using them in electrochemical sensors. Nonetheless, their use in sensors is becoming more and more common, with the obtainment of very good results in terms of selectivity and sensitivity (up to 5.4 × 10−10 mol L−1 and 1.8 × 10−9 mol L−1 for caffeine and theophylline, respectively). Moreover, the ability of GO to protect DNA and RNA from enzymatic digestion renders it one of the best candidates for biosensors based on these nucleic acids. This is an up-to-date review of the use of GO and RGO in sensors. [ABSTRACT FROM AUTHOR]

Due to its polyphenol content, cocoa's potential health effects are attracting much attention, showing, among other things, cardioprotective, anti-inflammatory, anti-obesity, and neuroprotective actions. However, there is very limited information regarding the effect of cocoa on human immunity. This study aimed to establish the relationship between cocoa consumption and health status, focusing on physical activity habits and allergy prevalence in young people. For this, a sample of 270 university students was recruited to complete a food frequency questionnaire, the International Physical Activity Questionnaire (IPAQ), and a lifestyle and health status questionnaire. The results were analysed by classifying the participants into tertiles defined according to their cocoa consumption: low (LC), moderate (MC), and high (HC) consumers. The consumption of cocoa inversely correlated with physical activity and the MC group had significantly less chronic disease frequency than the LC group. The percentage of allergic people in the MC and HC groups was lower than that in the LC group and, moreover, the cocoa intake, especially moderate consumption, was also associated with a lower presence of allergic symptoms. Thus, from these results a positive effect of cocoa intake on allergy can be suggested in the young population. [ABSTRACT FROM AUTHOR]

This study investigates the ultrasound-assisted extraction of flavonoids from Malaysian cocoa shell extracts, and optimization using response surface methodology. There are three variables involved in this study, namely: ethanol concentration (70–90 v/v %), temperature (45–65 °C), and ultrasound irradiation time (30–60 min). All of the data were collected and analyzed for variance (ANOVA). The coefficient of determination (R2) and the model was significant in interaction between all variables (98% and p < 0.0001, respectively). In addition, the lack of fit test for the model was not of significance, with p > 0.0684. The ethanol concentration, temperature, and ultrasound irradiation time that yielded the maximum value of the total flavonoid content (TFC; 7.47 mg RE/g dried weight (DW)) was 80%, 55 °C, and 45 min, respectively. The optimum value from the validation of the experimental TFC was 7.23 ± 0.15 mg of rutin, equivalent per gram of extract with ethanol concentration, temperature, and ultrasound irradiation time values of 74.20%, 49.99 °C, and 42.82 min, respectively. While the modelled equation fits the data, the T-test is not significant, suggesting that the experimental values agree with those predicted by the response surface methodology models. [ABSTRACT FROM AUTHOR]

Large amounts of residues are produced in the food industries. The waste shells from cocoa processing are usually burnt for fuel or used as a mulch in gardens to add nutrients to soil and to suppress weeds. The objectives of this work were: (a) to separate valuable compounds from cocoa shell by applying sustainable green separation process—subcritical water extraction (SWE); (b) identification and quantification of active compounds, sugars and sugar degradation products in obtained extracts using HPLC; (c) characterization of the antioxidant activity of extracts; (d) optimization of separation process using response surface methodology (RSM). Depending on applied extraction conditions, different concentration of theobromine, caffeine, theophylline, epicatechin, catechin, chlorogenic acid and gallic acid were determined in the extracts obtained by subcritical water. Furthermore, mannose, glucose, xylose, arabinose, rhamnose and fucose were detected as well as their important degradation products such as 5-hydroxymethylfurfural (5-HMF), furfural, levulinic acid, lactic acid and formic acid. [ABSTRACT FROM AUTHOR]

Solving the problem of large quantities of organic waste, which represents an enormous ecological and financial burden for all aspects of the process industry, is a necessity. Therefore, there is an emerged need to find specific solutions to utilize raw materials as efficiently as possible in the production process. The cocoa shell is a valuable by-product obtained from the chocolate industry. It is rich in protein, dietary fiber, and ash, as well as in some other valuable bioactive compounds, such as methylxanthines and phenolics. This paper gives an overview of published results related to the cocoa shell, mostly on important bioactive compounds and possible applications of the cocoa shell in different areas. The cocoa shell, due to its nutritional value and high-value bioactive compounds, could become a desirable raw material in a large spectrum of functional, pharmaceutical, or cosmetic products, as well as in the production of energy or biofuels in the near future. [ABSTRACT FROM AUTHOR]