Cocoa byproduct inclusion in dairy sheep diet: Effects on sensory, volatile, and antioxidant properties of cheese.

The possibility of inclusion of agro-industrial byproducts in the diet of small ruminants represents both an economic and an environmental strategy for reducing waste management by industries and costs of feeding as well as the impact of livestock farming. Large amounts of wastes from the cocoa industry are produced annually, with a considerable part represented by cocoa bean shells, considered a suitable ingredient to be included in the diet of ruminants within the limits established by European legislation. The aim of this study was to assess the effect of including cocoa bean shells in the diet of dairy sheep on the sensory, volatile, and antioxidant properties of cheese. To this purpose, 20 lactating Comisana ewes were randomly assigned to 2 experimental groups: control (CTRL) and cocoa bean shells (CBS), and received alfalfa hay ad libitum and 800 g of conventional (CTRL) or experimental (CBS) concentrate containing 11.7% CBS to partially replace corn and barley of the CTRL concentrate. Bulk milk collected from each group was used to produce a total of 15 cheeses per group, obtained in 5 different days of cheesemaking (3 cheeses a day per group). After 60 d of aging, each cheese of each experimental group was sampled for the analyses. The results on chemical composition revealed a greater content of monounsaturated fatty acids and an increase in the nutritional indices, suggesting a favorable role of cocoa bean shell dietary inclusion on the nutritive value of cheese. The cheese sensory profile was affected by the cocoa bean shell inclusion, with more pronounced appearance, odor, aroma, and taste attributes in the product. The volatile profile showed only a few significant differences, mainly related to the cheese ripening process, and no differences were found in α-tocopherol contents in cheese fat between the 2 groups. Therefore, the inclusion of coca bean shells in the diet of dairy sheep allowed us to obtain a good-quality cheese, without altering the characteristics associated with the typical profiles of sheep cheese. Furthermore, the use of this byproduct could contribute to decreasing feed costs and waste management, representing a good practice for increasing the sustainability of dairy products.

Improving the Composition and Bioactivity of Cocoa (Theobroma cacao L.) Bean Shell Extract by Choline Chloride-Lactic Acid Natural Deep Eutectic Solvent Extraction Assisted by Pulsed Electric Field Pre-Treatment.

An environmentally friendly method for the release of cocoa bean shell (CBS) extracts is proposed in this paper. This work aims to investigate the effect of pulsed electric field (PEF) pre-treatment on subsequent solid-liquid extraction (SLE) of metabolites with choline chloride-lactic acid natural deep eutectic solvent (NaDES) and bioactivity of cocoa bean shell (CBS) extract. Two different media for PEF application were evaluated: water and chlorine chloride-lactic acid. Total polyphenols (TPC), total flavonoids (TFC), individual major compounds, and antioxidant and antibacterial activity of CBS extracts were assessed. The performance of PEF-assisted extraction was compared with SLE and ultrasound-assisted extraction (UAE). The proposed method improved the release of TPC up to 45% and TFC up to 48% compared with the conventional extraction. The CBS extract showed medium growth inhibition of Escherichia coli and high growth inhibition of Salmonella sp, Listeria monocytogenes, and Staphylococcus aureus. Thus, an extract with enhanced antioxidant and antibacterial properties was obtained.

Cocoa bean shells: a review into the chemical profile, the bioactivity and the biotransformation to enhance their potential applications in foods.

During processing, cocoa bean shells (CBS) are de-hulled from the bean and discarded as waste. Undermined by its chemical and bioactive composition, CBS is abundant in dietary fiber and phenolic compounds that may serve the valorization purpose of this by-product material into prebiotic and functional ingredients. In addition, the cell-wall components of CBS can be combined through enzymatic feruloylation to obtain feruloylated oligo- and polysaccharides (FOs), further enhancing the techno-functional properties. FOs have attracted scientific attention due to their prebiotic, antimicrobial, anti-inflammatory and antioxidant functions inherent to their structural features. This review covers the chemical and bioactive compositions of CBS as well as their modifications upon cocoa processing. Physical, chemical, and enzymatic approaches to extract and bio-transform bioactive components from the cell wall matrix of CBS were also discussed. Although nonspecific to CBS, studies were compiled to investigate efforts done to extract and produce feruloylated oligo- and polysaccharides from the cell wall materials.

Effect of choline chloride-based deep eutectic solvents on polyphenols extraction from cocoa (Theobroma cacao L.) bean shells and antioxidant activity of extracts.

The effective extraction of natural compounds from cocoa bean shells using deep eutectic solvents could contribute to the sustainable valorization of this waste material. The objective of this study was to: (1) analyze the extraction kinetics of polyphenols released from cocoa (Theobroma cacao L.) bean shells (CBS) by the solid-liquid extraction method using choline chloride-based deep eutectic solvents (ChCl-DES) and their aqueous solutions; (2) investigate the effect of choline chloride-based deep eutectic solvents (ChCl-DES) aqueous solutions on in-vitro antioxidant capacity and the main individual compounds of the extracts. ChCl-DES were prepared with lactic acid, glycerol, and ethylene glycol in a 1:2 ratio. Aqueous solutions (30%, 40%, and 50% water) to obtain solvents with different physicochemical properties were performed. The total phenolic content (TPC) was determined by the Folin-Ciocalteu method. The solution of Fick's law model for plate geometry particles was applied to fit the experimental data and calculate the effective diffusivity coefficient (De). The antioxidant capacity of the extracts was analyzed by a combination of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl (DPPH) free radical scavenging capacity and ferric-reducing antioxidant power (FRAP) assays. The main bioactive compounds were quantified by high-performance liquid chromatography. The results showed that the type of hydrogen bond donor influences the total phenolic content, antioxidant activity and the main individual compounds in the extracts. Moreover, the washing/diffusion mechanism adequately depicts the extraction kinetics data for total phenolic content. However, the influence of an additional mechanism that enhanced the extraction capacity of deep eutectic solvents compared with organic solvent was confirmed.

Cocoa Bean Shell: A By-Product with High Potential for Nutritional and Biotechnological Applications.

Cocoa bean shell (CBS) is one of the main solid wastes derived from the chocolate industry. This residual biomass could be an interesting source of nutrients and bioactive compounds due to its high content in dietary fibres, polyphenols and methylxanthines. Specifically, CBS can be employed as a raw material for the recovery of, for example, antioxidants, antivirals and/or antimicrobials. Additionally, it can be used as a substrate to obtain biofuels (bioethanol or biomethane), as an additive in food processing, as an adsorbent and, even, as a corrosion-inhibiting agent. Together with the research on obtaining and characterising different compounds of interest from CBS, some works have focused on the employment of novel sustainable extraction methods and others on the possible use of the whole CBS or some derived products. This review provides insight into the different alternatives of CBS valorisation, including the most recent innovations, trends and challenges for the biotechnological application of this interesting and underused by-product.

Development and Characterization of a 3D Printed Cocoa Bean Shell Filled Recycled Polypropylene for Sustainable Composites.

Natural filler-based composites are an environmentally friendly and potentially sustainable alternative to synthetic or plastic counterparts. Recycling polymers and using agro-industrial wastes are measures that help to achieve a circular economy. Thus, this work presents the development and characterization of a 3D printing filament based on recycled polypropylene and cocoa bean shells, which has not been explored yet. The obtained composites were thermally and physically characterized. In addition, the warping effect, mechanical, and morphological analyses were performed on 3D printed specimens. Thermal analysis exhibited decreased thermal stability when cacao bean shell (CBS) particles were added due to their lignocellulosic content. A reduction in both melting enthalpy and crystallinity percentage was identified. This is caused by the increase in the amorphous structures present in the hemicellulose and lignin of the CBS. Mechanical tests showed high dependence of the mechanical properties on the 3D printing raster angle. Tensile strength increased when a raster angle of 0° was used, compared to specimens printed at 90°, due to the load direction. Tensile strength and fracture strain were improved with CBS addition in specimens printed at 90°, and better bonding between adjacent layers was achieved. Electron microscope images identified particle fracture, filler-matrix debonding, and matrix breakage as the central failure mechanisms. These failure mechanisms are attributed to the poor interfacial bonding between the CBS particles and the matrix, which reduced the tensile properties of specimens printed at 0°. On the other hand, the printing process showed that cocoa bean shell particles reduced by 67% the characteristic warping effect of recycled polypropylene during 3D printing, which is advantageous for 3D printing applications of the rPP. Thereby, potential sustainable natural filler composite filaments for 3D printing applications with low density and low cost can be developed, adding value to agro-industrial and plastic wastes.

Cocoa Coproducts-Based and Walnut Oil Gelled Emulsion as Animal Fat Replacer and Healthy Bioactive Source in Beef Burgers.

The aim of this work was to evaluate the effects on the chemical, physic-chemical, technological, and sensory properties of beef burger when replacing different quantities of fat (50 and 100%) with different levels of oil-in-water-gelled emulsion elaborated with walnut oil and cocoa bean shell flour (GECW). The chemical composition of the samples was affected by the fat replacement. The reformulation increased the moisture and ash content while the fat and protein content decreased with respect to the control sample. The linolenic and linolenic acid content of the beef burgers increased as the GECW replacement was augmented. The polyunsaturated fatty/saturated fatty acid ratio increased in both raw and cooked burgers, whereas the atherogenicity index and thrombogenicity index were reduced in both raw and cooked burgers with respect to the control sample. The use of GECW as a fat replacer was found to be effective in improving the cooking loss. Similarly, there were positive effects on reductions in the diameter and the increases in the thickness of the beef burgers. Regarding lipid stability, in both the raw and cooked burgers, the reformulation increased the 2-thiobarbituric acid reactive substance (TBARs) values with respect to the control sample. In both types of reformulated burgers, three bound polyphenols (mainly catechin and epicatechin) and two free polyphenols were identified, as were methylxanthines theobromine and caffeine. The sensory properties for the control and partial pork backfat replacement treatments were similar, while the sample with the total pork backfat replacement treatment showed the lowest scores. The blend of cocoa bean shell flour and walnut oil could be used as new ingredients for the development of beef burgers with a healthier nutritional profile without demeriting their sensory or cooking characteristics and physic-chemical properties.

Bioactive Poly(lactic acid)-Cocoa Bean Shell Composites for Biomaterial Formulation: Preparation and Preliminary In Vitro Characterization.

The unique lignocellulosic and solvent-extractive chemical constituents of most natural fibers are rich in natural polymers and bioactive molecules that can be exploited for biomaterial formulation. However, although natural fibers' main constituents have been already incorporated as material reinforcement and improve surface bioactivity of polymeric materials, the use of the whole natural fibers as bioactive fillers remains largely unexplored. Thus, we put forward the formulation of natural fiber filling and functionalization of biomaterials by studying the chemical composition of cocoa bean shells (CBS) and proposing the fabrication and characterization of polylactic acid (PLA) and CBS-based composite by solvent-casting. As was expected from previous studies of agro-industrial wastes, the main components of CBS were to cellulose (42.23 wt.%), lignin (22.68 wt.%), hemicellulose (14.73 wt.%), and solvent extractives (14.42 wt.%). Structural analysis (FTIR) confirms the absence of covalent bonding between materials. Thermal degradation profiles (DSC and TGA) showed similar mass losses and thermal-reaction profiles for lignocellulosic-fibers-based composites. The mechanical behavior of the PLA/CBS composite shows a stiffer material behavior than the pristine material. The cell viability of Vero cells in the presence of the composites was above 94%, and the hemolytic tendency was below 5%, while platelet aggregation increased up to 40%. Antioxidant activity was confirmed with comparable 2,2-diphe-277 nyl-1-picryl-hydrazyl-hydrate (DPPH) free-radical scavenging than Vitamin C even for PLA/CBS composite. Therefore, the present study elucidates the significant promise of CBS for bioactive functionalization in biomaterial-engineering, as the tested composite exhibited high biocompatibility and strong antioxidant activity and might induce angiogenic factors' release. Moreover, we present an eco-friendly alternative to taking advantage of chocolate-industry by-products.

Evaluation of Cocoa Beans Shell Powder as a Bioadsorbent of Congo Red Dye Aqueous Solutions.

The use of synthetic dyes in the textile, leather, and paper industries is a source of groundwater pollution around the world. There are different methods for the treatment of wastewater that has been contaminated with dyes, among which adsorption with agro-industrial wastes is gaining relevance. In the present study, the adsorption capacity of cocoa bean shell powder was evaluated when it was used as a bioadsorbent for Congo red dye in an aqueous medium. A 24 central factorial design with central and axial points was proposed to determine the adsorption capacity. The factors that were studied were the adsorbent (0.06-0.15 g), Congo red (40-120 mg L-1), pH (3-11), and time (4-36 h). The bioadsorbent was characterized through scanning electron microscopy and Fourier-transform infrared spectroscopy. The effects of the factors on the adsorption capacity for Congo red using cocoa bean shell were nonlinear, and they were modeled with a second-order polynomial (p < 0.05) and with an R2 of 0.84. The bioadsorbent obtained a maximum adsorption of 89.96% in runs. The process of optimization by using the surface response allowed the maximization of the adsorption, and the validation showed that 95.79% adsorption of the dye was obtained.

Inclusion of cocoa by-product in the diet of dairy sheep: Effect on the fatty acid profile of ruminal content and on the composition of milk and cheese.

In this study, we hypothesized that dietary cocoa bean shell (CBS) as a partial replacer of human edible cereal grains in the diet of lactating ewes may affect performance and milk and cheese composition. Twenty Comisana lactating ewes allotted into control (CTRL; n = 10) or cocoa (CBS; n = 10) group received alfalfa hay ad libitum and 800 g of conventional (CTRL) or experimental (CBS) concentrate containing 11.7% CBS to partially replace corn and barley of the CTRL concentrate. Milk yield and composition did not differ between groups, and only urea concentration was lower in CBS milk. Dietary CBS increased cheese fat and reduced protein percentage in CBS group. Fatty acid composition of rumen content partially reflected that of the ingested diet, with total saturated fatty acids (SFA), total monounsaturated fatty acids (MUFA), 16:0, 18:0 and 18:1c9 greater in the CBS group. Moreover, all the identified trans- and cis-18:1 isomers were greater in CBS rumen content. Milk and cheese showed a similar fatty acid composition. Total MUFAs were greater in milk and cheese of CBS, mainly due to the proportion of 18:1c9, and conversely, total polyunsaturated fatty acids (PUFA), PUFAn-6 and PUFAn-6-to-PUFAn-3 ratio was greater in CTRL group. Concluding, the inclusion of CBS in the diet of lactating ewes within the limit imposed by the current legislation did not cause detrimental effects on animal performance and milk composition. Interestingly, dietary CBS reduced milk urea concentration probably due to the phenols contained in CBS concentrate. However, our results support that biohydrogenation was weakly impaired by dietary CBS. Finally, CBS negatively affected cheese nutritional characteristics due to lower protein and greater fat content, but improved fat health indexes in milk and cheese.

Characterization and Classification of Cocoa Bean Shells from Different Regions of Venezuela Using HPLC-PDA-MS/MS and Spectrophotometric Techniques Coupled to Chemometric Analysis.

The cocoa bean shell (CBS) is one of the main cocoa byproducts with a prospective to be used as a functional food ingredient due to its nutritional and sensory properties. This study aims to define the chemical fingerprint of CBSs obtained from cocoa beans of diverse cultivars and collected in different geographical areas of Venezuela assessed using high-performance liquid chromatography coupled to photodiodes array and mass spectrometry (HPLC-PDA-MS/MS) and spectrophotometric assays combined with multivariate analysis for classification purposes. The study provides a comprehensive fingerprint and quantitative data for 39 compounds, including methylxanthines and several polyphenols, such as flavan-3-ols, procyanidins, and N-phenylpropenoyl amino acids. Several key cocoa markers, such as theobromine, epicatechin, quercetin-3-O-glucoside, procyanidin_A pentoside_3, and N-coumaroyl-l-aspartate_2, were found suitable for the classification of CBS according to their cultivar and origin. Despite the screening methods required a previous purification of the sample, both methodologies appear to be suitable for the classification of CBS with a high correlation between datasets. Finally, preliminary findings on the identification of potential contributors for the radical scavenging activity of CBS were also accomplished to support the valorization of this byproduct as a bioactive ingredient in the production of functional foods.

Chemometric Classification of Cocoa Bean Shells Based on Their Polyphenolic Profile Determined by RP-HPLC-PDA Analysis and Spectrophotometric Assays.

The cocoa bean shell (CBS), a byproduct from the cocoa industry, was recently proposed as a functional and low-cost ingredient, mainly because of its content in polyphenols. However, vegetal food products could significantly differ in their chemical composition depending on different factors such as their geographical provenience. This work is aimed to determine the polyphenolic and methylxanthine profile of different CBS samples and utilize it for achieving their differentiation according to their geographical origin and variety. RP-HPLC-PDA was used to determine the CBS polyphenolic profile. Spectrophotometric assays were used to obtain the total phenolic, flavonoid, and tannin contents, as well as to evaluate their radical scavenging activity. The results obtained from both methods were then compared and used for the CBS differentiation according to their origin and varieties through chemometric analysis. RP-HPLC-PDA allowed to determine 25 polyphenolic compounds, as well as the methylxanthines theobromine and caffeine. Polyphenolic profile results highlighted significant differences among the analyzed samples, allowing for their differentiation based on their geographical provenience. Similar results were achieved with the results of the spectrophotometric assays, considered as screening methods. Differentiation based on CBS variety was instead obtained based on the HPLC-determined methylxanthine profile.

Pectin-Based Films with Cocoa Bean Shell Waste Extract and ZnO/Zn-NPs with Enhanced Oxygen Barrier, Ultraviolet Screen and Photocatalytic Properties.

In this work, pectin-based active films with a cocoa bean shell extract, obtained after waste valorisation of residues coming from the chocolate production process, and zinc oxide/zinc nanoparticles (ZnO/Zn-NPs) at different concentrations, were obtained by casting. The effect of the active additive incorporation on the thermal, barrier, structural, morphological and optical properties was investigated. Moreover, the photocatalytic properties of the obtained films based on the decomposition of methylene blue (MB) in aqueous solution at room temperature were also studied. A significant increase in thermal and oxidative stability was obtained with the incorporation of 3 wt% of ZnO/Zn-NPs compared to the control film. The addition of 5 wt% cocoa bean shell extract to pectin significantly affected the oxygen barrier properties due to a plasticizing effect. In contrast, the addition of ZnO/Zn-NPs at 1 wt% to pectin caused a decrease in oxygen transmission rate per film thickness (OTR.e) values of approximately 50% compared to the control film, resulting in an enhanced protection against oxidation for food preservation. The optical properties were highly influenced by the incorporation of the natural extract but this effect was mitigated when nanoparticles were also incorporated into pectin-based films. The addition of the extract and nanoparticles resulted in a clear improvement (by 98%) in UV barrier properties, which could be important for packaged food sensitive to UV radiation. Finally, the photocatalytic activity of the developed films containing nanoparticles was demonstrated, showing photodegradation efficiency values of nearly 90% after 60 min at 3 wt% of ZnO/Zn-NPs loading. In conclusion, the obtained pectin-based bionanocomposites with cocoa bean shell waste extract and zinc oxide/zinc nanoparticles showed great potential to be used as active packaging for food preservation.

Green Extraction Methods for Active Compounds from Food Waste-Cocoa Bean Shell.

This is the first report on the extraction of cocoa bean shell (CBS) using deep eutectic solvents (DESs). Screening results with 16 different choline chloride-based DESs showed how choline chloride:oxalic acid DES was the most suitable solvent for the extraction of the bioactive compounds from CBS and that concentrations varied greatly depending on the used solvent. The DES extraction was compared to the DESs coupled with microwave extraction (MAE), and the yields of the extracted compounds were higher for DES/MAE. For theobromine, the obtained yields for DES extraction were 2.145-4.682 mg/g, and for caffeine, were 0.681-1.524 mg/g, whereas for DES/MAE, the same compounds were obtained in 2.502-5.004 mg/g and 0.778-1.599 mg/g. Antioxidant activity was also determined, using DPPH method, obtaining 24.027-74.805% activity for DES extraction and 11.751-55.444% for DES/MAE. Water content significantly influenced the extraction of targeted active compounds from CBS, whereas extraction time and temperature did not show statistically significant influence. The extraction temperature only influenced antioxidant activity. The study demonstrated how extraction using DES and microwaves could be of a great importance in the future trends of green chemistry for the production of CBS extracts rich in bioactive compounds.

Physical Properties and Consumer Evaluation of Cocoa Bean Shell-Functionalized Biscuits Adapted for Diabetic Consumers by the Replacement of Sucrose with Tagatose.

The cocoa bean shell (CBS), a by-product of the cocoa industry, has been reported to be rich in fiber and polyphenols, which could contribute to reducing the metabolism of sugars and glucose adsorption. The production of CBS-based biscuits in which sucrose is replaced with tagatose (a low-glycemic sugar with prebiotic properties), benefiting diabetic consumers, is proposed. Six prototype biscuits were produced using sucrose, tagatose, and CBS powder at 0%, 10%, and 20% as a wheat flour replacement. Biscuits were studied in terms of fiber content, and those with 10% and 20% CBS showed to contain 5.66% and 8.70-8.71% of total dietary fiber, respectively. Moreover, the physicochemical and structural properties of the biscuits were studied to evaluate their differences due to the use of sucrose and tagatose combined with CBS. Significant effects mainly caused by the reducing nature and lower solubility of tagatose with respect to sugar, and the water retention capacities of CBS were observed. Finally, the biscuits were evaluated by performing a consumer acceptance evaluation, and their perceptible sensorial differences were studied by performing a Napping® sensory characterization. CBS-based biscuits represent an interesting possibility for cocoa by-product revalorization, although an optimized recipe is recommended, especially when employing tagatose.

Polyphenolic and Methylxanthine Bioaccessibility of Cocoa Bean Shell Functional Biscuits: Metabolomics Approach and Intestinal Permeability through Caco-2 Cell Models.

Cocoa bean shell (CBS), a by-product with considerable concentrations of bioactive compounds and proven biofunctional potential, has been demonstrated to be a suitable ingredient for high-fiber functional biscuits adapted to diabetic consumers. In this work, the in vitro bioaccessibility and intestinal absorption of polyphenols and methylxanthines contained in these biscuits were evaluated, and the effect of the food matrix was studied. Biscuits containing CBS and the CBS alone underwent in vitro digestion followed by an intestinal permeability study. The results confirmed that compounds were less bioavailable in the presence of a food matrix, although the digestion contributed to their release from this matrix, increasing the concentrations available at the intestinal level and making them capable of promoting antioxidant and antidiabetic activities. After digestion, CBS biscuits were shown to possess α-glucosidase inhibition capacity comparable to that of acarbose. Moreover, the presence of the food matrix improved the stability of polyphenols throughout the digestion process. Intestinal absorption of flavan-3-ols seemed to be limited to a maximum threshold and was therefore independent of the sample, while procyanidin was not absorbed. Methylxanthine absorption was high and was boosted by the presence of the food matrix. The results confirmed the biofunctional potential of CBS-based biscuits.

In Vitro Bioaccessibility and Functional Properties of Phenolic Compounds from Enriched Beverages Based on Cocoa Bean Shell.

The cocoa bean shell (CBS), a cocoa by-product, contains a significant number of bioactive compounds with functional properties, such as polyphenols and methylxanthines, and is used as an ingredient in beverages and foods. In this work, the bioaccessibility of polyphenols and methylxanthines after In Vitro digestion was evaluated in new flavoured beverages for at-home consumption (capsules and tea bags). In addition, the polyphenolic composition, functional properties (antiradical and α-glucosidase inhibition capacities) and consumer acceptability of these beverages were evaluated. In both capsule and tea bag beverages, the bioaccessibility of methylxanthines was 100% while that of total polyphenols exceeded 50%. The main polyphenols determined using reverse-phase liquid chromatography were type B procyanidins and epicatechin. The antiradical activity in capsule and tea bag beverages was 1.75 and 1.88 mM of Trolox equivalents, respectively, of which 59.50% and 57.09% were recovered after simulated digestion. The percentage of α-glucosidase inhibition before In Vitro digestion (51.64% and 53.82% for capsules and tea bags, respectively) was comparable to that of acarbose at 0.5 mM. All the beverages obtained a high consumer acceptability. Therefore, these results highlight that CBSs can be used as a valid source of bioactive compounds in the preparation of beverages with homemade techniques.

A Dietary Mixture of Oxysterols Induces In Vitro Intestinal Inflammation through TLR2/4 Activation: The Protective Effect of Cocoa Bean Shells.

BACKGROUND: Exaggerated Toll-like receptor (TLR)-mediated immune and inflammatory responses play a role in inflammatory bowel diseases. This report deals with the ability of a mixture of oxysterols widely present in cholesterol-rich foods to induce in vitro intestinal inflammation through TLR up-regulation. The anti-inflammatory action of four cocoa bean shell (CBS) extracts with different polyphenol content, was tested. METHODS: Differentiated intestinal CaCo-2 cells were treated with a dietary oxysterol mixture (Oxy-mix) (60 µM). The expression and activation of TLR2 and TLR4, as well as the production of their downstream signaling effectors IL-8, IFNß and TNFα were analyzed in the presence or absence of TLR antibodies. Honduras CBS extracts were characterized for their polyphenol contents; their anti-inflammatory action was analyzed in CaCo-2 cells treated with Oxy-mix. RESULTS: Oxysterol-dependent TLR-2 and TLR4 over-expression and activation together with cytokine induction were abolished by blocking TLRs with specific antibodies. Polyphenol-rich CBS extracts consisting of high quantities of (-)-epicatechin and tannins also prevented TLR induction. CONCLUSIONS: TLR2 and TLR4 mainly contribute to inducing oxysterol-dependent intestinal inflammation. The fractionation method of CBS allowed the recovery of fractions rich in (-)-epicatechin and tannins able to counteract oxysterol-induced inflammation, thus highlighting the beneficial biological potential of specific CBS extracts.

Authentication of cocoa bean shells by near- and mid-infrared spectroscopy and inductively coupled plasma-optical emission spectroscopy.

The aim of this study was to evaluate the efficacy of a multi-analytical approach for origin authentication of cocoa bean shells (CBS). The overall chemical profiles of CBS from different origins were characterized using diffuse reflectance near-infrared spectroscopy (NIRS) and attenuated total reflectance mid-infrared spectroscopy (ATR-FT-IR) for molecular composition identification, as well as inductively coupled plasma-optical emission spectroscopy (ICP-OES) for elemental composition identification. Exploratory chemometric techniques based on Principal Component Analysis (PCA) were applied to each single technique for the identification of systematic patterns related to the geographical origin of samples. A combination of the three techniques proved to be the most promising approach to establish classification models. Partial Least Squares-Discriminant Analysis modelling of fused PCA scores of three independent models was used and compared with single technique models. Improved classification of CBS samples was obtained using the fused model. Satisfactory classification rates were obtained for Central African samples with an accuracy of 0.84.

Analytical dataset on volatile compounds of cocoa bean shells from different cultivars and geographical origins.

This data article describes the analysis of volatile organic compounds (VOCs) in 44 samples of cocoa bean shells (CBS) obtained from cocoa beans of diverse cultivars and collected in different geographical origins. The volatile compounds were extracted by headspace solid-phase microextraction (HS-SPME) method and then analyzed by gas chromatography coupled to a quadrupole mass spectrometry GC-qMS. The retention times, identification and semi-quantification of 101 VOCs are reported. Data collected on the volatile profile of CBS samples using E-nose analysis are also available. Additional data related to physicochemical characteristics and color analysis for CBS samples are reported. Further interpretation and discussion on these datasets can be found in the related article entitled "Assessment of volatile fingerprint by HS-SPME/GC-qMS and E-nose for the classification of cocoa bean shells using chemometrics" (Barbosa-Pereira et al., 2019).