Valorization of cocoa pod side streams improves nutritional and sustainability aspects of chocolate.

Chocolate production faces nutritional, environmental and socio-economic challenges present in the conventional cocoa value chain. Here we developed an approach that addresses these challenges by repurposing the often-discarded pectin-rich cocoa pod endocarp and converting it into a gel. This is done using cocoa pulp juice concentrate to replace traditional sugar from sugar beets. Although swelling of fibres, proteins and starches can limit gel incorporation, our proposed chocolate formulation contains up to 20 wt% gel. It also has comparable sweet taste as traditional chocolate while offering improved nutritional value with higher fibre and reduced saturated fatty acid content. A cradle-to-factory life cycle assessment shows that large-scale production of this chocolate could reduce land use and global warming potential compared with average European dark chocolate production. The process also provides opportunities for diversification of farmers' income and technology transfer, offering potential socio-economic benefits for cocoa-producing regions.

Occurrence of heavy metals coupled with elevated levels of essential elements in chocolates: Health risk assessment.

The presence of contaminants in cacao-derived products, especially in chocolates, has raised concerns regarding food safety and human health. The study assessed the concentration variation of 16 elements in 155 chocolate samples from the US market by cacao content and country of geographic origin. The study further examined the potential health risks posed by toxic metals and determined the contribution of essential elements to the Daily Recommended Intake (DRI), estimated based on an ounce (∼28.4 g) of daily chocolate consumption. Dark chocolates with ≥50 % cacao exhibited consecutively increasing mean levels from 1.2 to 391 µg/kg for U, Tl, Th, As, Pb, Se, Cd, and Co. Similarly, Ni, Sr, Cu, Mn, Zn, Fe, Ca, and Mg had mean concentrations from 4.0 to 1890 mg/kg. Dark chocolates sourced from Central and South America exhibited the highest mean levels of Cd, and South America samples also contained elevated Pb, whereas those from West Africa and Asia had low Cd and Pb, respectively. Cacao contents showed increasingly strong association with Cd, Co, Mn, Sr, Ni, Cu, Zn, and Mg (r = 0.60-0.84), and moderately with Se, Fe, As, and Tl (r = 0.35-0.49), indicating these elements are primarily derived from cacao beans. Weak association of cacao contents with Pb, Th, and U levels (r < 0.25), indicates post-harvest contaminations. Hazard Quotient (HQ) > 1 was found only for Cd in 4 dark chocolates, and Hazard Index (HI) > 1 for cumulative risk of Cd, Pb, Ni, As, and U was found in 33 dark chocolates, indicating potential non-carcinogenic risks for 15 kg children but none for 70 kg adults. Dark chocolate also substantially contributed to 47-95 % of the DRI of Cu for children and 50 % for adults. Dark chocolates also provided notable Fe, Mn, Mg, and Zn contributions to the DRI. These essential elements are recognized to reduce the bioavailability of toxic metals such as Cd, Pb, or Ni, thereby potentially lowering associated health risks. This study informs consumers, food industries, and regulatory agencies to target cacao origins or chocolate brands with lower toxic metal contents for food safety and minimizing adverse health effects.

Influence of process conditions of alkalization on quality of cocoa powder.

In this study, the effects of independent variables such as alkaline (NaOH) salt concentration (3.0-6.0 g/100 mL), alkalization temperature (60-90 °C), and time (20-40 min) on cocoa powder (low-fat) properties were investigated by using Central Composite Design. The physicochemical and color properties of samples, powder characteristics, volatile component profile, total polyphenol content (TPC), as well as antioxidant activity potentials using different methods (DPPH and ABTS) were determined. Significant models were identified for the effects on major alkalization indicators (L*, a*/b*, pH), as well as TPC and antioxidant activity potential (DPPH), which are the main motivators for the preference and consumption of cocoa products (p < 0.05). The established model was validated, and their predicted values were found to be very close to real results. It was determined that the alkali concentration had a more significant effect on dependent variables, especially on alkalization indicators, compared to the other independent variables. Furthermore, strong correlations were determined between TPC and antioxidant activity potential and color properties (L*, a*, b*, and a*/b*). Optimum concentration, temperature and time were found to be 5.3 %, 84 °C and 35.7 min for maximizing a*/b* value. The establishment of such models lead to optimizing process conditions of alkalization with minimum effort and labor force for obtaining cocoa powder with desired quality depending on the usage purpose.

Sensory attributes of fine flavor cocoa beans and chocolate: A systematic literature review.

Fine flavor cocoa (FFC) is known for its unique flavor and aroma characteristics, which vary by region. However, a comprehensive overview of the common sensory attributes used to describe FFC beans and chocolate is lacking. Therefore, a systematic review was conducted to analyze existing literature and identify the most commonly used sensory attributes to describe FFC beans and chocolate. A systematic search of the Web of Science and Scopus databases was conducted in May 2023, and Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines were followed to ensure transparency and reproducibility. This review summarizes the origins of cocoa and explores their unique flavor profiles, encompassing caramel, fruity, floral, malty, nutty, and spicy notes. Although some origins may exhibit similar unique flavors, they are often described using more specific terms. Another main finding is that although differences in sensory attributes are anticipated at each production stage, discrepancies also arise between liquor and chocolate. Interestingly, fine chocolate as the final product does not consistently retain the distinctive flavors found in the liquor. These findings emphasize the need for precise descriptors in sensory evaluation to capture flavor profiles of each origin. As such, the exploration of attributes from bean to bar holds the potential to empower FFC farmers and chocolate producers to effectively maintain quality control.

Trace elements in bean-to-bar chocolates from Brazil and Ecuador.

BACKGROUND: The high quality and unique flavor and aroma of bean-to-bar chocolates have resulted in an increase in the consumption of these products. Nevertheless, cocoa beans may present inorganic contaminants from environmental and anthropogenic sources which can contribute to contamination of the chocolates, despite the fewer processing steps and few ingredients used in bean-to-bar manufacturing process compared to the industrial one. Therefore, this study aimed to evaluate the content of trace elements (As, Cd, Co, Cu, Hg, Pb, Se) in bean-to-bar chocolates and traceable cocoa beans from Brazil and Ecuador. METHODS: Bean-to-bar chocolate samples were acquired in Brazil (n=65) and Ecuador (n=10), considering the main products available: white, milk, semisweet and dark chocolate. Cocoa samples from dedicated farms (n=23) were analyzed for trace elements and inorganic contaminants regulated by Brazil and European agencies. Samples were mineralized using acid digestion (nitric acid and hydrogen peroxide) in a closed microwave-assisted system. Quantification of trace elements was performed using Inductively coupled plasma mass spectroscopy (ICP-MS) and Inductively coupled plasma optical emission spectroscopy (ICP OES) in optimized conditions. The analytical control was performed with certified reference materials (ERM BD512 - Dark Chocolate, Tort-2 and Tort-3 - Lobster Hepatopancreas and SRM 1547 - Peach leaves) and recoveries ranged between 84% and 105% for all elements. RESULTS: The trace element levels in the bean-to-bar chocolates were (mg/kg): As (<0.022-0.023), Cd (<0.002-0.74), Cu (0.11-21.2), Co (<0.003-1.88), Hg (<0.010-<0.010), Pb (<0.007-0.22), and Se (<0.029-0.35). The exposure assessment from inorganic contaminants in chocolates revealed up to 93% of provisional tolerable monthly intake (PTMI) for Cd and 123% of tolerable upper intake level (UL) for Co for children. Inorganic contaminants were also analyzed in cocoa beans from dedicated farms and Cd and Pb levels were found above the thresholds established by Brazil health agency. CONCLUSION: The results observed for both bean-to-bar chocolates and raw materials (cocoa beans from dedicated farms) indicated a need for monitoring these trace elements.

Determination of the process effect on cocoa butter crystallization by rheometer: Kinetic modeling by Gompertz equation.

In this study, the effects of temperature (22, 24, 26, 28, and 30°C) and strain (0.1%, 1%, and 5%) on cocoa butter (CB) crystallization were investigated by oscillatory test, and the four-parameter Gompertz model was used to interpret the effect of parameters on pre-crystallization, nucleation, and crystal growth stages of CB. Lag time and growth rate were calculated using the Gompertz model using time-dependent storage modulus (G') data. According to the results, CB crystallization at 26°C with a 1% strain value had the highest growth rate value, the shortest lag time, and the formation of ßv polymorph type. Followingly, polymorphic types of the CB crystals were determined based on the melting points of polymorphs via the temperature ramp step, and the results obtained were correlated with a polarized light microscope. In conclusion, using a rheometer in both the observation of the pre-crystallization process and the determination of polymorph types is very important for research and development studies in the chocolate industry for process and formulation optimization. PRACTICAL APPLICATION: This study demonstrates the feasibility of a novel approach for investigating crystallization and oscillatory shear of CB using a rheometer, both for observing crystallization kinetics and determining polymorph type, accompanied by the Gompertz equation to model the crystallization kinetics. According to the results, the effect of process parameters (temperature and shear) on the crystallization behavior of CB can be observed by rheometer, which can provide a detailed perspective for chocolate manufacturers and researchers in research and development studies.

Phenolic composition and sensory dynamic profile of chocolate samples enriched with red wine and blueberry powders.

Cabernet Sauvignon (CS) and a combination of Cabernet Sauvignon with blueberry extract (CS + B), were spray dried (using maltodextrin DE10, 13.5% w/w as a carrier) to obtain two types of phenolic-rich powders. The addition of blueberry to CS increased phenolic compounds content by 16%. Eight chocolate formulations were obtained by modifying concentrations of cocoa solids, cocoa butter, and sugar. Six of the samples were added with 10% w/w of phenolic-rich powder, while two of them remained as powder-free controls. The anthocyanin and flavan-3-ol profiles of chocolates were determined by HPLC-DAD-MS and HPLC-MS, respectively. In addition, the sensory dynamic profile of samples was assessed by Temporal Dominance of Sensations with a consumer panel. Results showed that the addition of phenolic-rich powders produced a significant increase in the anthocyanin composition obtaining the highest anthocyanin content in the white chocolate added with CS + B powder. On the other hand, adding 10% of CS powder to dark chocolate (55% cocoa pellets) did not result in a significant increase in phenolic compounds. The addition of phenolic-rich powders to chocolates influenced visual color, texture, and taste, leading to new products with distinctive characteristics and increasing the possibility of using phenolic-rich powders as innovative and healthy ingredients.

Chocolates, compounds and spreads: A review on the use of oleogels, hydrogels and hybrid gels to reduce saturated fat content.

This study is a bibliometric analysis and literature review on the use of oleogels (OGs), hydrogels (HGs) and hybrid gels (HYGs) in chocolate, compounds and spreads with the aim of reducing the saturated fat in these products. The articles were selected by analyzing titles, keywords and abstracts in the Web of Science (WoS), Scopus and Google Scholar databases. Supplementary documents were obtained from government sources, including patent registrations. The theoretical and practical aspects were critically analyzed, highlighting the main points of agreement and disagreement between the authors. The results revealed a lack of regulations and official guidelines that widely allow the use of OGs, HGs and HYGs in chocolate confectionery products. The type and characteristics of raw materials affect the properties of products. Replacing cocoa butter (CB) with OGs, HGs or HYGs also affects texture, melting point and behavior, and nutritional aspects. These substitutions can result in products with better sensory acceptance and health benefits, such as reducing saturated fat and promoting cardiovascular health. However, it is important to find the ideal combination and proportions of components to obtain the desired properties in the final products.

Determination of Acrylamide in Coffee, Cereals, Baby Food, Cocoa, Dry Pet Food, Potato Products, Vegetable Crisps, Biscuits, Tea, Nuts, and Spices by LC-MS/MS in a Single-Laboratory Validation: First Action 2023.01.

BACKGROUND: Acrylamide (AA) is a process contaminant naturally formed during the cooking of starchy food at high temperatures. Considering existing risks of misquantification inherent to the analysis of AA, an AOAC initiative raised the need for a consensus standard to determine AA in a broad variety of food. OBJECTIVE: A quantitative LC-MS/MS method for AA determination in food was validated in a single-laboratory study. Targeted performance requirements in terms of target matrixes, limit of quantification, recovery, and precision were as defined per Standard Method Performance Requirement (SMPR®) 2022.006. METHOD: The proposed method derives from EN 16618:2015 standard pending modifications brought to the (1) sample preparation (simplified, potentially automated); (2) scope of application (significantly extended); and (3) LC conditions (improved selectivity). Confirmatory detection of AA is conducted by LC-MS/MS in the Selected Reaction Monitoring mode (SRM), and isotopic dilution was applied for quantification approach using either 2,3,3-d3-acrylamide (d3-AA), or 13C3-2,3,3-d3-acrylamide (13C3-d3-AA) as labeled internal standard. RESULTS: A total of 16 laboratory samples from nine matrix categories were included in the validation process. A full validation was conducted on coffee (instant, roast), infant cereal, cocoa powder, pet food (croquettes), tea (green tea), spices (black pepper), and nuts (roasted almonds) with satisfactory performances both in terms of recovery (97-108%) and precision (RSDr and RSDiR <12%). The method applicability was further demonstrated through the analysis of quality control materials and reference materials including French fries, potato crisps, vegetable crisps, instant coffee, infant food, and biscuits (cookies), with accuracy values determined within a 94-107% range. CONCLUSIONS: The performances of the presented method are in agreement with the acceptance criteria stipulated in SMPR 2022.006. HIGHLIGHTS: The Expert Review Panel for acrylamide approved the present method as AOAC Official First Action 2023.01.

In-house validation of an LC-MS method for the multiplexed quantitative determination of total allergenic food in chocolate.

Mass spectrometry has been widely accepted as a confirmatory tool for the sensitive detection of undeclared presence of allergenic ingredients. Multiple methods have been developed so far, achieving different levels of sensitivity and robustness, still lacking harmonization of the analytical validation and impairing comparability of results. In this investigation, a quantitative method has been validated in-house for the determination of six allergenic ingredients (cow's milk, hen's egg, peanut, soybean, hazelnut, and almond) in a chocolate-based matrix. The latter has been produced in a food pilot plant to provide a real and well-characterized matrix for proper assessment of method performance characteristics according to official guidelines. In particular, recent considerations issued by the European Committee for Standardization have been followed to guide a rigorous single-laboratory validation and to feature the main method performance, such as selectivity, linearity, and sensitivity. Synthetic surrogates of the peptide markers have been used both in native and labelled forms in matrix-matched calibration curves as external calibrants and internal standards, respectively. A two-order of magnitude range was investigated, focusing on the low concentration range for proper assessment of the detection and quantification limits (LOD and LOQ) by rigorous calibration approach. Conversion factors for all six allergenic ingredients have been determined for the first time to report the final quantitative information as fraction of total allergenic food protein (TAFP) per mass of food (µgTAFP/gfood), since such a reporting unit is exploitable in allergenic risk assessment plans. The method achieved good sensitivity with LOD values ranging between 0.08 and 0.2 µgTAFP/gfood, for all ingredients besides egg and soybean, whose quantitative markers reported a slightly higher limit (1.1 and 1.2 µgTAFP/gfood, respectively). Different samples of chocolate bar incurred at four defined concentration levels close to the currently available threshold doses have been analyzed to test the quantitative performance of the analytical method, with a proper estimate of the measurement uncertainty from different sources of variability. The sensitivity achieved resulted in compliance with the various threshold doses issued or recommended worldwide.

Toward Unified Flavor Quantitation in Cocoa-Based Products.

Because food flavor is perceived through a combination of odor and taste, an analytical method that covers both dimensions would be very beneficial for mapping the consistent product quality over the entirety of a manufacturing process. Such a method, so-called "unified flavor quantitation", has been successfully applied to several different food products in recent years. The simultaneous detection of aroma and taste compounds by means of ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) enables the analysis and quantification of an enormously large number of compounds in a single run. To evaluate the limits of this method, chocolate, a high-fat, complex matrix, was selected. In 38 distinct commercial chocolate samples, 20 flavor-active acids, aldehydes, and sugars were analyzed after a simple, rapid extraction step followed by derivatization with 3-nitrophenylhydrazine using a single UHPLC-MS/MS method. The results obtained highlight the great potential of the "unified flavor quantitation" approach and demonstrate the possibility of high-throughput quantitation of key aroma- and taste-active molecules in a single assay.

Honey contamination from plant protection products approved for cocoa (Theobroma cacao) cultivation: A systematic review of existing research and methods.

The main component of chocolate, cocoa (Theobroma cacao), is a significant commercial agricultural plant that directly sustains the livelihoods of an estimated forty to fifty million people. The economies of many cocoa producing nations, particularly those in the developing world, are supported by cocoa export revenue. To ensure satisfactory yields, however, the plant is usually intensely treated with pesticides because it is vulnerable to disease and pest attacks. Even though pesticides help protect the cocoa plant, unintended environmental contamination is also likely. Honey, produced from nectar obtained by honeybees from flowers while foraging, can serve as a good indicator for the level of pesticide residues and environmental pesticide build-up in landscapes. Here, we use a systematic literature review to quantify the extent of research on residues of pesticides used in cocoa cultivation in honey. In 81% of the 104 studies examined for this analysis, 169 distinct compounds were detected. Imidacloprid was the most frequently detected pesticide, making neonicotinoids the most frequently found class of pesticides overall. However, in cocoa producing countries, organophosphates, organochlorines, and pyrethroids were the most frequently detected pesticides. Interestingly, only 19% of studies were carried out in cocoa producing countries. We recommend prioritizing more research in the countries that produce cocoa to help to understand the potential impact of pesticide residues linked with cocoa cultivation in honey and the environment more generally to inform better pesticide usage, human health, and environmental policies.

Identification of Important Aroma Components and Sensory Profiles of Minimally Processed (Unroasted) and Conventionally Roasted Dark Chocolates.

Roasting is an important unit operation for the development of characteristic chocolate aroma during manufacturing. However, there is an increase in interest in minimally processed chocolate products due to their potential positive health benefits. The odor-important compounds and sensory characteristics of minimally processed (unroasted) and conventionally roasted dark chocolates were determined by gas chromatography-olfactometry, aroma extract dilution analysis (AEDA), and stable isotope dilution analysis (SIDA). Except for acetic acid, all odorants had higher odor-activity values (OAVs) in roasted chocolate. Acetic acid, developed during fermentation and drying, had the highest OAV in both chocolates but was better preserved in unroasted chocolate. Compounds making a greater aroma impact on roasted chocolate compared with unroasted chocolate included dimethyl trisulfide, 2-ethyl-3,5-dimethylpyrazine, and 3-methylbutanal. Nine significant sensory attributes in unroasted and roasted chocolates were identified. Vinegar (aroma) and roasted (aroma and aroma by mouth), sweet (taste), and hardness (texture) attributes differed between unroasted and roasted chocolates. The results of this study enforce the embracement of low thermal processes to showcase the inherent flavor potential of cacao beans but also to support the concept of chocolate "terroir" by potentially preserving important aroma compounds developed during fermentation.

Link between Flavor Perception and Volatile Compound Composition of Dark Chocolates Derived from Trinitario Cocoa Beans from Dominican Republic.

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.

Impact of the pre-drying process on the volatile profile of on-farm processed Ecuadorian bulk and fine-flavour cocoa varieties.

Aiming to improve the quality of cocoa, preconditioning of cocoa after harvesting and before fermentation has become an on-farm processing step of great interest in recent times. The present work aimed to evaluate the influence of a pre-drying process on the volatile composition of Ecuadorian bulk (Forastero and CCN-51) and fine-flavour (ETT103 and LR14) cocoa at the end of primary processing. A total of 63 volatile compounds including aldehydes, alcohols, acids, ketones, esters, terpenes, lactones and other miscellaneous compounds were identified in cocoa samples by HS-SPME-GC-MS. The use of a pre-drying step revealed a varietal homogenization and a reduction in the fermentation time, making this preconditioning step an inexpensive and attractive option for farmers. Moreover, different varietal behaviour was observed after pre-drying, the fine-flavour varieties obtaining a clear improvement in aromatic quality with higher levels of compounds imparting positive notes.

Aspectos de calidad de un chocolate oscuro elaborado con formulación óptima / Quality aspects of a dark chocolate made with optimal formulation

Introducción: Los chocolates son procesados en fábricasde alta, mediana y pequeña escala, donde el cacao pasa pordiferentes operaciones unitarias que brindan el valor agregado esperado; sin embargo, es importante controlar los ingredientes de la formulación: azucares totales y grasa saturada, que afecta el sobrepeso del consumidor de chocolates. Objetivo: Evaluar aspectos de calidad de un chocolate oscuro al 70% de cacao a partir de una fórmula optimizada (CO-70) en cuanto a aspectos energéticos, componentes antioxidantes, de inocuidad y sensoriales. Materiales y métodos: Se analizó valores nutricionales, componentes antioxidantes y alcaloides, valores microbiológicos y toxicológicos, así como la aceptabilidad sensorial conconsumidores de 20 a 40 años, utilizando métodos analíticos. Resultados y discusiones: Los resultados muestran aun CO-70 reducido en calorías con 555,9 ± 0,1 kcal; un nivel de azúcar de 35,45 g; un nivel de grasa de 35,12 g; contenido de ácidos grasos insaturados de 13,05 ± 0,03 g; uncontenido de proteínas de 11,88 g; una cantidad importantede polifenoles de 2,20 ± 0,15 g EAG en 100 g chocolate; libre de microorganismos patógenos y compuestos tóxicos;con una aceptabilidad sensorial de 70,80 % en consumidores peruanos. Conclusiones: Con el adecuado diseño y desarrollo deproductos se pueden obtener chocolates con calidad sensoria nutricional cada vez mejores, en beneficio de la salud del consumidor.(AU)

Introduction: The chocolates are processed in factoriesof high, medium, and small scale, where the cacao beansgo through different unit operations that provide the exected added value; however, it is important to control theingredients of the formulation: total sugars and saturatedfatty acids, which affects the overweight of the chocolateconsumer. Aim: To evaluate quality aspects of a dark chocolate 70 %cacao made from an optimized formula (CO-70) in terms ofenergy aspects, antioxidants components, safety and sensory. Materials and methods: The following were analyses nutritional values, antioxidant, and alkaloid components, microiological and toxicological, as well as sensory acceptabilitywith 20–40-year-old consumers, using analytical methods. Results and discussions: The CO-70 reduced in calorieswith 555.9 ± 0.1 kcal; a sugar level of 35.45 g; a fat level of35.12 g; unsaturated fatty acid content of 13.05 ± 0.03 g; aprotein content of 11.88 g; a significant number of polyphenols of 2.20 ± 0.15 g GAE in 100 g chocolate; free of pathogenic microorganisms and toxic compounds; with a sensoryacceptability of 70.80% in peruvian eaters. Conclusions: With the adequate design and developmentof products, chocolates with sensory and nutritional quality that are increasingly better for the health of the consumer canbe obtained.(AU)

Screening for pesticide residues in cocoa (Theobroma cacao L.) by portable infrared spectroscopy.

Rapid assessment of pesticide residues ensures cocoa bean quality and marketability. In this study, a portable FTIR instrument equipped with a triple reflection attenuated total reflectance (ATR) accessory was used to screen cocoa beans for pesticide residues. Cocoa beans (n = 75) were obtained from major cocoa growing regions of Peru and were quantified for pesticides by gas chromatography (GC) or liquid chromatography (LC) coupled with mass spectrometry (MS). The FTIR spectra were used to detect the presence of pesticides in cocoa beans or lipid fraction (butter) by using a pattern recognition (Soft Independent Modeling by Class Analogy, SIMCA) algorithm, which produced a significant discrimination for cocoa nibs (free or with pesticides). The variables related to the class grouping were assigned to the aliphatic (3200-2800 cm-1) region with an interclass distance (ICD) of 3.3. Subsequently, the concentration of pesticides in cocoa beans was predicted using a partial least squares regression analysis (PLSR), using an internal validation of the PLRS model, the cross-validation correlation coefficient (Rval = 0.954) and the cross-validation standard error (SECV = 14.9 mg/kg) were obtained. Additionally, an external validation was performed, obtaining the prediction correlation coefficient (Rpre = 0.940) and the standard error of prediction (SEP = 16.0 µg/kg) with high statistical performances, which demonstrates the excellent predictability of the PLSR model in a similar real application. The developed FTIR method presented limits of detection and quantification (LOD = 9.8 µg/kg; LOQ = 23.1 µg/kg) with four optimum factors (PC). Mid-infrared spectroscopy (MIR) offered a viable alternative for field screening of cocoa.

Physical characterization of chocolates prepared with various soybean and milk powders.

The physical characterization of chocolate products is vital in manufacturing, and the chocolate's processing time and composition directly influence physical properties, such as rheology and melting. The objective of this study was to investigate the effects of processing time and the ingredient types on the physical properties of milk chocolates containing soy milk powder and soy protein isolate. Characteristics of skimmed milk chocolate (SMC) and whole milk chocolate (WMC) were compared to soy milk chocolate and soy protein chocolate (SPC). Rheological data of chocolate products were fitted to Casson, Herschel-Bulkley, and Bingham models. The highest viscosity was observed for SPC samples, whereas yield stress was the highest for SMC samples after 2 hr of processing. The increase in milk and soy fats in the formulation softened the texture and decreased the whiteness index significantly (p < .05). PSD results show that SPC had the highest D90 (40.1 µm) and the lowest specific surface area (893 m2 /kg) after 6 hr of processing. SPC samples had the narrowest particle size distribution observed by the span values. X-ray diffraction analysis showed that all the samples had the desired Form V, crystal form. The differential scanning calorimetry thermogram was used to determine phase transitions and melting behaviors. At the end of processing, melting enthalpies (ΔHmelt ) were significantly lower (p < .05) in milk chocolates.

New trends of new psychoactive substances (NPS)-infused chocolate: Identification and quantification of trace level of NPS in complex matrix by GC-MS and NMR.

For the first time, the identification and quantification of trace level of new psychoactive substances (NPS) in a complex chocolate matrix have been reported. Since the beginning of 2022, suspected NPS-infused chocolate samples confiscated in inbound packages have been continuously sent to our laboratory for analysis. The qualitative gas chromatography-mass spectrometry (GC-MS) results were verified by 1H nuclear magnetic resonance (1H NMR) and 19F NMR to distinguish between potential aromatic isomers. A total of 11 NPS including deoxymethoxetamine, 3-OH-PCP, 6-APB, 4-APB, 4-OH-MiPT, 3-FEA, 2-FEA, 3-MMC, bromazolam, 2-FDCK, and ADB-BUTINACA were detected in 65 seized chocolate samples. A general 1H quantitative NMR (1H qNMR) method for quantification of 297 types of NPS in complex chocolate matrixes was devised for the first time after rigorous analysis of various critical features of merit, including suitable deuterated solvent, internal standard, quantitative peaks, and instrument acquisition parameters. Validation of the method using six different types of NPS afforded limits of detection of 0.05-0.1 mg/mL, limits of quantification of 0.01-0.03 mg/mL, repeatability and reproducibility lower than 0.5% and 3.6%, recoveries of 91.7%∼104.4%, and absence of matrix effect. The quantitative analysis of 65 seized chocolate samples by 1H qNMR and 19F qNMR showed that the content of NPS was in the range of 0.5 mg/g∼44.1 mg/g. Generally, the developed qNMR method was simple, fast, precise, and can be performed without reference materials of NPS. Since the type and content of NPS are relatively random, chocolate consumers will face huge health risks. Therefore, this new trend of NPS-infused chocolate deserves and requires more attention from national NPS monitoring departments as well as forensic laboratories.

Chemical Characterization of Quality-Related Compounds in Cocoa Matrices: An Overview of Analytical Methods Applied for Their Analysis.

Cocoa currently faces differentiation processes toward niches of specialty products, leading to greater competitiveness for producers who must compete with products differentiated by their integral quality regarding their organoleptic characteristics, such as fine-flavor cocoa and their functional characteristics. Quality is influenced by the genetic variety of the cultivars on the one hand, and the correct postharvest processing operations of cocoa seeds, on the other. During the transformation operations, the native chemical compounds of the seeds, especially proteins, carbohydrates, and polyphenols, are transformed and generate other compounds called flavor precursors, which are responsible for defining the product quality. In this sense, the analysis of the most relevant chemical compounds in cocoa is essential to guarantee higher overall quality. Similarly, understanding the fundamental aspects that affect fine-flavor cocoa production is crucial for improving transformation processes. Therefore, reliable and robust analytical techniques are required to detect and quantify these chemical compounds. This review highlights the main techniques used to analyze essential cocoa metabolites and derived products throughout all postharvest transformation stages: from cocoa seeds to chocolate bar, offering an overview of the sample preparation methods and the analytical and imaging methodologies often employed to characterize qualifying cocoa products.