Proanthocyanidins (OPACs) are the second largest class of plant metabolites after lignans. Although knowledge of their 3D conformations would add greatly to our understanding of their biological properties, very little has been published on the conformations of OPACs with a degree of polymerization (DP) above 4. We investigated the conformations of the linear epicatechin oligomers, prominent representatives of OPACs prevalent in apples and cocoa, where the epicatechin units are interconnected through the 4β-8 bonds. For DP-2 to DP-10 oligomers, conformational preferences reflected in the arrangement of consecutive flavan-3-ol units, are characterized by the φ torsion. For dimers, there are two energy wells corresponding to two preferred φ torsions, designated as compact and extended form. This behaviour is preserved in OPACs with higher DPs, but the most energetically favoured conformations are a combination of both, with compact-only or extended-only conformations being very unlikely. Thus, oligomers with DP ≥ 7 tend to assume an overall conformation approximating a spherical shape. This shape has a significant influence on the polarity of the OPAC oligomers expressed as 3D polar surface area, calculated using Spartan software for geometry-optimized 3D models, and possibly on other physicochemical properties. The results of polarity calculations provide a molecular-level rationale for the polarity-based chromatographic separation of the cocoa B-type procyanidins with DP range 4 to 10. In our experiments, using centrifugal partition chromatography (CPC) (a solvent system consisting of EtOAc-EtOH-water (6:1:5) v/v/v with aqueous phase stationary and upper phase mobile) we found that an enriched mixture of proanthocyanidins eluted first DP-1 (epicatechin) followed by consecutive elution of the DP-2 to DP-10 in the linear 4β-8 form. We demonstrated that such separation would not be possible if compact-only or extended-only conformations were present in solution. However, for the energy-favoured, spherically shaped conformations, the observed CPC elution order is fully justified.

Cocoa bean shells (CBSs) are a byproduct of the chocolate production process, representing the external layer of the cocoa bean. CBSs exhibit many interesting chemical and nutritional characteristics resulting in a very rich content of dietary fiber (DF) and antioxidant compounds such as phenolic acids and flavan-3-ols. The DF fraction of CBSs is notably rich in soluble dietary fibers (SDFs), which may be associated with fermentability and prebiotic properties. The objective of this study was the valorization of CBSs through enzymatic treatments, thereby increasing the solubility of DF and potentially augmenting fermentability. CBSs were treated both raw and defatted. Three sets of carbohydrases were used in order to impact the dietary fiber profile. Cellulase, xylanase, pectinase and their combinations were used to perform enzymatic treatments. The application of cellulase, xylanase and a combination of both enzymes proved effective in achieving a high SDF destructuring of the insoluble dietary fiber (IDF) fraction in both defatted and raw CBSs. Notably, the SDF/IDF ratio was significantly elevated in the enzymatically hydrolyzed samples (1.13-1.33) compared to the untreated CBSs (0.33). Furthermore, the various treatments did not affect the antioxidant activity or the content of the main bioactive compounds. These results provide a foundation for new opportunities in the biovalorization of CBSs through green techniques for a range of potential industrial applications in the food and nutraceutical sectors.

Cocoa can undergo an alkalization process to enhance its color and solubility. It reduces astringency and alters its composition, particularly in the phenolic compound content, which is related to cocoa health benefits. This study aimed to investigate the impact of alkalization on the composition of seven commercial cocoa powders. A liquid chromatography-based metabolomic approach was employed to assess the metabolic differences between alkalized and non-alkalized cocoa powders. Supervised orthogonal partial least squares discriminant analysis (OPLS-DA) was used to identify the most discriminating variables between groups. A feature-based molecular network (FBMN) was used to explore the chemical space. Three hundred forty-seven metabolites were obtained as the most discriminant, among which 60 were tentatively annotated. Phenolic compounds, lysophosphatidylethanolamines, amino acids, and their derivatives were significantly reduced in alkalized cocoas. In contrast, fatty acids and their derivatives significantly increased with alkalization. Despite the variability among commercial cocoas, chemometrics allowed the elucidation of alterations induced specifically by alkalization in their composition.

UNASSIGNED: Contamination of cocoa containing products, such as dark chocolate, with heavy metals including lead, cadmium and arsenic has been reported in the US. However, a formal exploration into the significance of this contamination, nor multi-year trends in the degree or scope remain unresolved.
UNASSIGNED: From 2014 to 2022, 72 consumer cocoa-containing products were purchased and analyzed for heavy metal contamination with lead (Pb), cadmium (Cd), and arsenic (As) in 4 distinct cohorts (2014, 2016, 2019, 2022). The thresholds used to assess heavy metal contamination were set to Prop 65 maximum allowable dose levels (MADLs) of 0.5 mcg/day, 4.1 mcg/day, 10 mcg/day for Pb, Cd, and As, respectively.
UNASSIGNED: Our analysis reports that 43, 35, and 0% of the products tested exceed Prop 65 MADLs for heavy metal concentrations, respectively, of Pb, Cd, and As, while 97.2% (70 of 72) fall below US FDA IRL limits established for Pb. Median concentrations of each metal tested were lower than even the conservative Prop 65 MADLs, indicating a potentially large effect of product outliers. This indicates that heavy metal contamination-in more than half of products tested-may not pose any appreciable risk for the average person when consumed as a single serving; however, consuming some of the products tested, or more than one serving per day in combination with non-cocoa derived sources heavy metals, may add up to exposure that would exceed the Prop 65 MADLs. Notably, \"organic\" products were significantly more likely to demonstrate higher levels of both Cd and Pb.

Optimizing sustainability among smallholder farms poses challenges due to inherent trade-offs. In the study of organic and conventional cocoa smallholder farming in Ghana, 398 farms are assessed using the Food and Agriculture Organsation of the United Nations (FAO) Sustainability Assessment of Food and Agriculture systems (SAFA) Guidelines and Sustainability Monitoring and Assessment Routine (SMART)-Farm Tool. Organic farming exhibited synergies in environmental aspects (e.g., soil quality, energy efficiency) and between biodiversity conservation and risk management. Conventional farming showed potential vulnerabilities, including trade-offs with long-range investments (e.g., chemical inputs) and species diversity. Both systems demand tailored approaches for short-term economic and environmental sustainability, aligning with community-wide long-term goals. To mitigate trade-offs in conventional farming, smallholders should adopt practices like material reuse, recycling, and recovery within their operations.

The cacao fruit is a rich source of polyphenols, including flavonoids and phenolic acids, which possess significant health benefits. The accurate identification and quantification of these bioactive compounds extracted from different parts of the cacao fruit, such as pods, beans, nibs, and cacao shells, require specific treatment conditions and analytical techniques. This review presents a comprehensive comparison of extraction processes and analytical techniques used to identify and quantify polyphenols from various parts of the cacao fruit. Additionally, it highlights the environmental impact of these methods, exploring the challenges and opportunities in selecting and utilizing extraction, analytical, and impact assessment techniques, while considering polyphenols\' yield. The review aims to provide a thorough overview of the current knowledge that can guide future decisions for those seeking to obtain polyphenols from different parts of the cacao fruit.

Mesoamerica is the center of origin of a great number of food crops that nowadays are part of a healthy diet. Pre-Columbian civilizations utilized more than 90% of these foods as ingredient or in main dishes, as well as for remedies and religious ceremonies. Since several years ago, Mesoamerican foods have been recognized by their outstanding concentration of bioactive compounds, including, phenolic compounds, pigments, essential fatty acids, amino acids, peptides, carbohydrates and vitamins, which provide a great number of health benefits. As a result of their unique composition, these ancient crops have several positive effects, such as hypoglycemic, antioxidant, anti-obesity, anti-inflammatory, anti-ageing, neuroprotective, anti-diarrheal, and anti-hypercholesterolemic capacity. Hence, this review is focused mainly in the anti-obesity and antioxidant potential of some of the most cultivated, harvested, as well as commercialized and consumed, food crops native of Mesoamerica, like, nopal and its fruit (Opuntia ficus indica spp.), chia (Salvia hispanica L.), pumpkin (Cucurbita spp.) and cacao (Theobroma cacao).

Indonesia is the world\'s third largest cocoa producer, but production is decreasing since 2011. We revisited cocoa farmers for an environmental assessment in Luwu Timur, Sulawesi, 7 months after a socio-economic survey on cocoa certification outcomes and observed many cocoa plantations being converted into oil palm and maize. Including our field data as well as secondary data on commodity prices and yields, we outline reasons for cocoa conversion, potential consequences for biodiversity, and assess the future outlook for the Indonesian cocoa sector. Low cocoa productivity, volatile cocoa prices and higher revenue for oil palm, among others, drive land-use change. If shade trees are cut during cocoa conversion, it may have negative implications for biodiversity. Solutions to low soil fertility, omnipresent pests and diseases, and stable producer prices are needed to increase profitability of cocoa and prevent conversion of cocoa agroforests to oil palm monocultures.

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.

Cocoa extract (CE) offers several health benefits, such as anti-obesity and improved glucose intolerance. However, the mechanisms remain unclear. Adipose tissue includes white adipose tissue (WAT) and brown adipose tissue. Brown adipose tissue leads to body fat reduction by metabolizing lipids to heat via uncoupling protein 1 (UCP1). The conversion of white adipocytes into brown-like adipocytes (beige adipocytes) is called browning, and it contributes to the anti-obesity effect and improved glucose tolerance. This study aimed to evaluate the effect of CE on glucose tolerance in terms of browning. We found that dietary supplementation with CE improved glucose intolerance in mice fed a high-fat diet, and it increased the expression levels of Ucp1 and browning-associated gene in inguinal WAT. Furthermore, in primary adipocytes of mice, CE induced Ucp1 expression through β3-adrenergic receptor stimulation. These results suggest that dietary CE improves glucose intolerance by inducing browning in WAT.