Ilyes Dammak

Cocoa prices are expected to continue rising due to strong demand and unstable crop yields, increasing the need for plant‐based alternatives in chocolate spread formulations. This study aimed to investigate the effects of replacing cocoa powder with carob powder (0–100%) on the physicochemical, nutritional, textural, structural, and sensory properties of chocolate spreads. Cocoa and carob powders were first comparatively characterized, and six spread formulations containing 0, 20, 35, 50, 75, and 100% carob substitution were produced under standardized conditions. Color, nutritional composition, texture, oil syneresis, and sensory properties were evaluated, and Partial Least Squares (PLS) regression was used to identify the main predictors of sensory perception. Increasing carob substitution increased lightness and soluble sugars while reducing protein, lipid, and polyphenol contents. Hardness increased progressively, whereas spreadability decreased markedly, particularly between 35 and 50% substitution. Oil syneresis was highest in the intermediate formulations (5.8–7.5%) and lowest in the extreme formulations (3.0–3.8%). Sensory profiling revealed that cocoa aromatic identity was maintained up to 50% substitution, while texture descriptors did not significantly discriminate among formulations despite instrumental differences. PLS regression identified hue angle, soluble sugars, and lightness as major predictors of visual chocolate identity. Overall, the results indicate that 35–50% cocoa replacement with carob represents a promising reformulation range, offering nutritional benefits while maintaining structural stability and sensory quality.

Comprehensive component‐resolved mass balances of enzyme‐assisted apple juice production remain scarce, particularly for sequential dual‐enzyme strategies employing non‐commercial GRAS‐certified preparations. This study established a detailed mass balance across all unit operations of pilot‐scale clarified apple juice production, evaluating the individual and combined contributions of two enzymatic treatments to yield, bioactive retention, and juice quality. Gala apples (33 kg batches, Sbiba, Tunisia) were processed on a Pignat pilot line using a 2 × 2 factorial design ( n = 3 independent batches per condition): cellulolytic/hemicellulolytic POL6 ( Penicillium occitanis Pol6) for maceration ± pectin methylesterase/esterase‐rich LIP2 ( Yarrowia lipolytica ) for clarification. Fourteen compositional parameters were tracked from raw apple through pasteurized juice. The full enzyme treatment achieved 65.0% ± 1.5% overall yield versus 52.3% ± 2.1% for the no‐enzyme control ( p < 0.001, η ² p = 0.88), with a significant maceration × clarification interaction for polyphenol retention ( p = 0.019). Sugar extraction reached 59.0% ± 3.2% and polyphenol retention 71.7% ± 2.5%. LIP2‐mediated clarification liberated matrix‐bound polyphenols, increasing free polyphenols by 52.8% with a concurrent 54.8% decrease in bound polyphenols, as validated by bound/free fractionation. Pasteurization (72°C, 2 min) induced 30.4% ± 2.3% ascorbic acid loss and 21.1% ± 1.8% polyphenol degradation. Apple pomace (27.1% of initial mass) contained 13.3% insoluble fibers and 2.3% pectin on a dry‐matter basis. The sequential dual‐enzyme strategy significantly outperformed single‐enzyme and no‐enzyme controls through a synergistic mechanism, and the component‐resolved mass balance identifies filtration and pasteurization as priority optimization targets for enhanced bioactive retention and circular economy integration.

Solid–liquid equilibrium (SLE) data were measured for gallic acid (model polyphenol) and raffinose (model saccharide) in ethanol–water mixtures at temperatures from 278.15 to 303.15 K. The solubility of raffinose decreased 400-fold with increasing ethanol content, while gallic acid solubility increased 29-fold under identical conditions, demonstrating divergent solubility behavior consistent with the thermodynamic requirements for selective drowning-out crystallization. The modified Universal Quasi-Chemical (UNIQUAC) model with Larsen’s combinatorial term successfully correlated the experimental data (average absolute deviations < 5%). UNIQUAC Functional-group Activity Coefficients (UNIFAC) group contributions, including specialized saccharide groups (pyranose, furanose, OH _ring ), were used to calculate molecular parameters. Thermodynamic properties of dissolution (Δ _sol H °, Δ _sol G °, Δ _sol S °) were derived from van’t Hoff analysis. Favorable separation conditions were identified at ethanol mass fractions of 0.70–0.80 and temperatures of 283.15–293.15 K, achieving selectivity factors of 70–180. The thermodynamic framework provides a quantitative foundation for process design of polyphenol recovery from olive mill wastewater via drowning-out crystallization, as confirmed by preliminary separation experiments achieving 92.5% raffinose recovery at 96.3% purity.