Polyphenolic Compounds from Indigenous Malus Species: A Novel Approach to Improve Ice Cream’s Thermodynamic Properties
Abstract
1. Introduction
- The polyphenolic profile of apples, with emphasis on indigenous varieties;
- Extraction methodologies for apple polyphenols, evaluating efficiency, yield, and compound preservation;
- Mechanisms by which polyphenols interact with ice cream components to enhance stability;
- Sensory implications and consumer acceptance considerations;
- Potential health benefits of apple polyphenols as a value-added aspect;
- Technical challenges and future research directions.
2. Polyphenolic Profile of Apples
2.1. Classification and Distribution of Apple Polyphenols
- Flavanols (Flavan-3-ols): Constituting 60–65% of total phenolic content, this group includes catechins, epicatechins, and procyanidins (oligomeric forms). Flavanols represent the predominant class of polyphenols in most apple varieties [15].
- Phenolic Acids: Accounting for 30–35% of total phenolics, this group is primarily represented by hydroxycinnamic acids, with chlorogenic acid being the most abundant. Other phenolic acids include caffeic acid, p-coumaric acid, ferulic acid, and neochlorogenic acid [15].
- Dihydrochalcones: Contributing 5–10% of total phenolic content, this group includes phloridzin and its derivatives, which are relatively unique to apples and closely related species [15].
- Flavonols: These compounds, particularly quercetin glycosides, are present primarily in apple peel tissues and contribute to the antioxidant capacity of apples.
- Anthocyanins: Found exclusively in red-skinned varieties, anthocyanins contribute to the red coloration and represent approximately 1% of total polyphenols in colored varieties.
2.2. Varietal Differences in Polyphenolic Composition
2.3. Environmental and Postharvest Factors Affecting Polyphenolic Content
- Light exposure: Light intensity and quality affect the synthesis of certain phenolic compounds, particularly anthocyanins and flavonols, in apple peels. Higher sun exposure typically results in increased phenolic content, especially in the peel tissue [15].
- Temperature stress: Both cold and heat stress can trigger increased polyphenol production as part of the plant’s adaptive response to environmental challenges. Apples grown in regions with greater temperature fluctuations may develop higher polyphenol concentrations.
- Soil composition: Mineral availability in the soil impacts enzyme activity involved in the phenylpropanoid pathway, which is responsible for polyphenol synthesis. Soil composition therefore affects both the quantity and profile of polyphenols [15].
- Water availability: Water stress typically increases polyphenol production in apples, though extreme drought conditions may ultimately reduce overall biosynthetic capacity.
- Maturity at harvest: Polyphenol content generally decreases during apple ripening, though the changes are compound-specific. Procyanidins and flavanols tend to decrease more substantially than phenolic acids during maturation.
- Storage conditions: Postharvest storage affects polyphenol stability, with different classes showing varied degradation rates. Low-temperature storage generally preserves polyphenols better, though some compounds, particularly flavanols, still show significant decreases during long-term storage [19].
- Processing methods: Common processing techniques can significantly impact polyphenol content. Pressing for juice extraction removes a substantial portion of polyphenols with the pomace, while thermal processing can lead to the degradation of heat-sensitive compounds.
3. Extraction Methods for Apple Polyphenols
3.1. Conventional Extraction Techniques
3.1.1. Maceration
3.1.2. Percolation
- Particle size distribution and uniformity;
- Bed height-to-diameter ratio (typically from 3:1 to 5:1);
- Flow rate control;
- Solvent selection and concentration.
3.2. Non-Conventional Extraction Techniques
3.2.1. Ultrasound-Assisted Extraction (UAE)
- The physical disruption of cell walls through microjet formation;
- Improved solvent penetration into the plant matrix;
- Enhanced mass transfer rates due to turbulent mixing;
- Localized heating that increases the solubility of target compounds.
- Frequency (typically 20–40 kHz for optimal cavitation effects);
- Power density (10–100 W/cm2, with higher values increasing extraction efficiency but potentially causing degradation);
- Temperature (30–60 °C, as higher temperatures reduce cavitation intensity);
- Processing time (10–60 min, with diminishing returns beyond this range);
- Solvent composition (ethanol–water mixtures of 50–80% typically yield best results).
3.2.2. Microwave-Assisted Extraction (MAE)
- Significantly reduced extraction times (1–30 min versus hours for conventional methods);
- Lower solvent consumption;
- Higher extraction yields for certain compound classes;
- Rapid heating that disrupts cell structures through internal pressure generation.
- Power level (typically 400–800 W, with higher power accelerating extraction but potentially causing degradation);
- Temperature (50–150 °C, with optimal conditions depending on target compounds);
- Solvent selection (water–ethanol mixtures are particularly effective due to their high dielectric constants);
- Solid-to-liquid ratio (typically 1:10 to 1:20).
3.2.3. Enzyme-Assisted Extraction (EAE)
- Sample preparation (often without drying to preserve enzyme activity);
- pH adjustment for optimal enzymatic activity (usually 4.0–6.0);
- The addition of enzymes (0.5–5% w/w);
- Incubation at the optimal temperature (30–50 °C for 1–24 h);
- Enzyme inactivation (by heating or pH adjustment);
- Extraction with the appropriate solvent.
3.3. Comparison of Extraction Methods
3.4. Extraction from Apple Processing By-Products
4. Mechanisms of Ice Cream Stabilization by Polyphenols
4.1. Thermodynamic Properties of Ice Cream
- Freezing point depression: The freezing point of an ice cream mix varies with its composition; it is primarily influenced by sugars, while milk solids and whey solids play a minor role. Typically, the initial freezing point ranges from −2.2 °C to −2.8 °C, with freezing occurring progressively as temperature decreases [28].
- Ice crystal formation: During freezing, ice crystals form when the temperature drops below the freezing point of the mix. The initial nucleation temperature typically ranges from −5 °C to −8 °C, with optimal crystal sizes ranging from 20–50 μm for a smooth texture [28]. Temperature fluctuations during storage cause recrystallization, with smaller crystals melting and water refreezing onto larger crystals, leading to perceived textural deterioration.
- Melting behavior: Melting starts on the outside and progresses inward as heat penetrates. The melting rate is influenced by several factors, with fat destabilization having the greatest impact because it forms clumps and chains that support air cells, resulting in a fat network that increases resistance to serum phase flow when ice melts [29].
- Viscosity of unfrozen phase: The consistency coefficient of the unfrozen serum phase significantly affects melting behavior. Higher viscosity indicates greater resistance to flow, resulting in slower melting rates and improved shape retention [29].
- Air cell structure and stability: Overrun, or incorporated air, affects ice cream’s texture and melting behavior. Products with larger overruns typically melt more slowly due to reduced heat transfer efficiency [30].
4.2. Polyphenol Interactions with Ice Cream Components
4.2.1. Protein Interactions
- Hydrogen bonding: The numerous hydroxyl groups in polyphenols form hydrogen bonds with protein amino acid residues, creating protein–polyphenol complexes.
- Hydrophobic associations: Aromatic rings in polyphenols interact with hydrophobic protein regions, further stabilizing the complexes.
- Covalent binding: Under certain conditions, polyphenols can form covalent bonds with protein nucleophilic sites, particularly those containing thiol or amino groups.
4.2.2. Fat Structuring
4.2.3. Viscosity Modification
4.2.4. Water Binding Effects
- Reduce ice crystal growth rates by ≥25% compared to untreated controls;
- Enhance melting resistance equivalent to or exceeding commercial stabilizers (carrageenan, guar gum);
- Provide dual functionality as both stabilizers and bioactive compounds;
- Offer sustainable alternatives derived from agricultural waste streams.
4.2.5. Quantitative Performance Metrics
- Concentration–Effect Relationships:
- 0.5% polyphenols: Minimal melting resistance improvement (~10–15%);
- 1.0–2.5% polyphenols: Significant melting resistance (25–40% improvement);
- >3.0% polyphenols: Maximum effect but potential sensory issues.
4.3. Evidence of Stabilization in Frozen Desserts
- Apple peel polyphenol extract (APPE): Ahmad et al. [30] reported that APPE in yogurt ice cream increased acidity, lowered melting rate, and improved overrun. The fortified samples exhibited greater hardness compared to controls and demonstrated enhanced sensory properties.
- Strawberry polyphenols: Researchers at Japan’s Biotherapy Development Research Center developed melt-resistant ice cream using strawberry polyphenol extract. This ice cream could maintain its shape and remain stable at room temperature, likely due to interactions between phenolic compounds and milk proteins [12].
- Barberry anthocyanins: Dara et al. [11] studied the impact of copigmented and unpigmented barberry anthocyanins on ice cream properties. Higher anthocyanin levels improved firmness, consistency, and melting resistance by stabilizing milk protein networks. Ice cream with 5% copigmented anthocyanins exhibited better melting stability, with melting start times increasing from 18.30 min in the control to 30.52 min.
- Peer-reviewed articles (2015–2025);
- Studies on polyphenol–ice cream interactions;
- Quantitative melting/stability data;
- Temperature range: −20 °C to +25 °C;
- English-language publications.
- Conference abstracts only;
- Studies without quantitative data;
- Non-dairy frozen desserts only;
- Studies focusing solely on color/flavor.
5. Potential Health Benefits of Apple Polyphenols
5.1. Antioxidant Activity
- Free radical scavenging: Apple polyphenols readily donate hydrogen atoms to neutralize free radicals, with the resulting polyphenol radicals stabilized through resonance delocalization.
- Metal chelation: Compounds like quercetin glycosides and chlorogenic acid can chelate transition metals such as iron and copper, preventing their participation in Fenton reactions that generate hydroxyl radicals.
- Enzyme modulation: Apple polyphenols can inhibit enzymes involved in ROS generation, including xanthine oxidase and NADPH oxidase.
5.2. Cardiovascular Protection
- Cholesterol modulation: Apple polyphenols, particularly procyanidins and phloridzin, may reduce total and LDL cholesterol while increasing HDL cholesterol through the inhibition of HMG-CoA reductase and the modulation of reverse cholesterol transport.
- Anti-inflammatory effects: Apple polyphenols demonstrate anti-inflammatory activity through the inhibition of NF-κB signaling and the reduced expression of inflammatory cytokines including TNF-α, IL−6, and IL-1β.
- Endothelial function improvement: Clinical studies have demonstrated improved flow-mediated dilation following apple polyphenol consumption, suggesting enhanced nitric oxide bioavailability and vascular function.
- Platelet aggregation inhibition: Certain apple polyphenols, particularly flavanols, inhibit platelet activation and aggregation, potentially reducing thrombosis risk.
5.3. Glycemic Control and Metabolic Effects
- Carbohydrate digestion modulation: Polyphenols, particularly procyanidins, can inhibit digestive enzymes, including α-amylase and α-glucosidase, slowing carbohydrate digestion and reducing postprandial glucose spikes.
- Glucose transport inhibition: Phloridzin and its derivatives competitively inhibit sodium-glucose transport proteins (SGLTs), reducing intestinal glucose absorption and potentially decreasing postprandial glycemia.
- Insulin signaling enhancement: Certain apple polyphenols may improve insulin sensitivity by activating insulin receptor substrates and downstream signaling pathways, particularly in skeletal muscle and adipose tissue.
5.4. Gastrointestinal Effects
- Prebiotic effects: Unabsorbed apple polyphenols, particularly high molecular weight procyanidins, reach the colon, where they can selectively stimulate beneficial bacteria, including the Bifidobacterium and Lactobacillus species.
- Microbial metabolism: Gut microbes transform apple polyphenols into metabolites with distinct biological activities. For example, chlorogenic acid is converted to caffeic acid and quinic acid, while flavanols undergo C-ring cleavage to produce phenylvaleric acids.
- Anti-pathogenic activity: Several apple polyphenols demonstrate direct antimicrobial effects against gastrointestinal pathogens, including Helicobacter pylori and Escherichia coli O157:H7.
5.5. Implications for Functional Ice Cream
- Bioactive concentration: The concentration of polyphenols required for stabilization effects (typically 0.5–3%) likely exceeds levels needed for potential health benefits, potentially enabling dual functionality.
- Matrix effects: The dairy matrix of ice cream may influence polyphenol bioavailability. Milk proteins can bind polyphenols, potentially reducing immediate absorption but providing a controlled release mechanism in the digestive tract.
- Thermal stability: Many apple polyphenols maintain bioactivity following the pasteurization and freezing processes used in ice cream production. Procyanidins and chlorogenic acid derivatives demonstrate good stability under these conditions.
- Target consumer segments: Functional ice cream containing apple polyphenols could appeal to health-conscious consumers seeking indulgent treats with added benefits.
6. Sensory Considerations and Consumer Acceptance
6.1. Impact of Polyphenols on Sensory Properties
6.2. Strategies for Sensory Optimization
- Variety Selection
- 2.
- Extraction Optimization
- 3.
- Complementary Flavoring
- 4.
- Sweetness Modulation
- 5.
- pH Adjustment
6.3. Consumer Acceptance Considerations
7. Conclusions
- Apple polyphenols represent a complex and diverse group of compounds whose composition and concentration vary significantly across different varieties and tissues. Indigenous varieties often contain elevated polyphenol concentrations compared to commercial cultivars, offering promising sources for extraction.
- Advanced extraction methodologies, particularly ultrasound-assisted extraction (UAE), demonstrate superior efficiency and yield compared to conventional methods while maintaining compound integrity. These techniques can be systematically optimized through the design of experimental approaches to maximize extraction efficiency.
- Polyphenols interact with ice cream components, particularly proteins and fats, through multiple mechanisms, including hydrogen bonding, hydrophobic associations, and potential covalent interactions. These interactions modify the structure and behavior of the frozen dessert matrix, enhancing stability and resistance to melting.
- Studies with various plant polyphenols have demonstrated significant improvements in ice cream stability, including reduced melting rates, enhanced shape retention, and improved textural properties. These findings suggest that indigenous apple polyphenols could provide similar benefits.
- Beyond their functional properties, apple polyphenols offer potential health benefits including antioxidant activity, cardiovascular protection, and glycemic control, potentially adding value to fortified ice cream products.
- Sensory considerations require careful management to balance functional benefits against potential impacts on flavor, astringency, and color. Several strategies including variety selection, flavor complementation, and formulation optimization can address these challenges.
- Significant knowledge gaps remain, particularly regarding compound-specific effects, structure–function relationships, and the specific properties of indigenous Lebanese apple varieties. These gaps present opportunities for future research.
- Current industry context includes these factors:
- Cold chain resilience: Enhanced stability could reduce product losses due to temperature fluctuations, particularly relevant in regions with inconsistent electrical supply.
- Clean label formulation: Natural stabilizers align with consumer preferences for recognizable, plant-derived ingredients.
- Agricultural waste valorization: Utilizing apple processing by-products transforms an environmental challenge into a value-added opportunity, supporting circular economy principles.
- Health benefits: The inherent bioactive properties of polyphenols may provide complementary nutritional advantages beyond technological functionality.
- Local resource utilization: For countries with significant apple production like Lebanon, developing value-added applications for indigenous varieties could support local agricultural practices and reduce dependence on imported stabilizers.
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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Phenolic Compound | Quantity (μg/g) |
---|---|
Chlorogenic acid | 2388 |
Epicatechin | 2036 |
Rutin | 980 |
Protocatechuic acid | 89.9 |
Criteria | Ultrasound-Assisted Extraction (UAE) | Microwave-Assisted Extraction (MAE) | Enzyme-Assisted Extraction (EAE) | Maceration | Percolation |
---|---|---|---|---|---|
Cost | 3 | 3 | 2 | 5 | 4 |
Environmental impact | 4 | 4 | 5 | 2 | 2 |
Safety | 4 | 3 | 5 | 4 | 4 |
Reproducibility | 5 | 5 | 3 | 2 | 2 |
Feasibility | 4 | 3 | 3 | 4 | 3 |
Total score | 20 | 18 | 18 | 17 | 15 |
Parameter | Synthetic Stabilizers | Apple Polyphenols | Technological Gap Addressed | References |
---|---|---|---|---|
Mechanism | Physical thickening, water binding | Protein–fat network formation, hydrogen bonding | Multifunctional approach vs. single-mode action | [1,3,10,30] |
Stability range | −18 °C to −12 °C optimal | Potentially effective −8 °C to −2 °C | Enhanced temperature abuse tolerance | [2,5,8] |
Melting resistance | Moderate (varies by type) | Up to 31% improvement demonstrated | Superior performance under stress conditions | [1,3,12,13] |
Health benefits | None/minimal | Antioxidant, cardiovascular protection | Added nutritional value | [11,34,35] |
Clean label appeal | Low (E-numbers) | High (natural origin) | Consumer preference alignment | [10,26,36] |
Cost | $2–5/kg | Estimated $8–15/kg * | Value justified by multifunctionality | [16,25] |
Sustainability | Petroleum/synthetic origin | Agricultural waste valorization | Circular economy integration | [16,26,37] |
Regulatory status | Established (E407, E412) | GRAS potential ** | Natural ingredient advantage | [10,38] |
Polyphenol Source | Concentration | Quantitative Effect | Measurement Condition | References |
---|---|---|---|---|
Temperature Effects | ||||
General ice cream | Storage at −18 °C | Ice crystal size: 40.3 μm → 100.1 μm (52 weeks) | Commercial storage conditions | [2] |
General ice cream | Storage at −50 °C | Ice crystal size: limited to 57–58 μm (52 weeks) | Controlled storage conditions | [2] |
Viscosity and Stabilization | ||||
General serum phase | 10% viscosity increase | 23% reduction in ice crystal coarsening rates | At −15 °C | [4] |
Apple pomace extract | 0.5615 ± 0.007 g/100 g FW | Total polyphenol content in commercial pomace | 80–20% ethanol–water extraction | [16] |
Apple pomace extract | Not specified | 31% reduction in ice crystal growth rates | Through hydrogen bonding mechanism | [1,3] |
Fat destabilization | N/A | Contributes 68% of variance in yield stress (σY) | In melted ice cream at 0 °C | [5] |
Specific Polyphenol Concentrations | ||||
Tannic acid | 0.75% (w/w) | Progressive increase in complex viscosity | In cream system | [10,30] |
Tannic acid | 1.5% (w/w) | Gelation effects observed | Above protein isoelectric point | [10,30] |
Tannic acid | 3.0% (w/w) | Maximum gelation and viscosity | Concentrated system | [10,30] |
Melting Resistance | ||||
Barberry anthocyanins (copigmented) | 5.0% | Melting start time: 18.30 → 30.52 min | Room temperature conditions | [12] |
Strawberry polyphenols | Not specified | Two-fold increase in consistency index (K) | Compared to control samples | [13] |
Apple peel polyphenol extract | Variable | Enhanced hardness and reduced melting rate | In yogurt ice cream | [39] |
Tissue-Specific Polyphenol Content | ||||
Apple peel | N/A | 401.6–952.9 μg/g fresh weight | Various apple varieties | [16] |
Apple flesh | N/A | 202.5–423.5 μg/g fresh weight | Various apple varieties | [16] |
Apple core | N/A | 368.6–684.0 μg/g fresh weight | Various apple varieties | [16] |
Individual Compound Concentrations | ||||
Chlorogenic acid (core) | Variable | 21.49–389.68 μg/g FW (3.08–45.46% total phenolics) | Different apple varieties | [16] |
Chlorogenic acid (pulp) | Variable | 25.37–215.06 μg/g FW (14.86–75.47% total phenolics) | Different apple varieties | [16] |
Quercetin-3-O-galactoside (core) | Variable | 71.48–202.44 μg/g FW (9.90–22.19% total phenolics) | Different apple varieties | [16] |
Extraction Optimization | ||||
UAE vs. conventional | N/A | 20–35% increase in polyphenol yields | 70–90% reduction in extraction time | [22,24] |
MAE vs. conventional | N/A | Similar or higher yields | 90–95% reduction in extraction time | [24] |
Enzyme-assisted (pectinase) | 0.5–5% w/w | 24–32% increase in polyphenol yields | From apple pomace | [25] |
Study | Polyphenol Source | Concentration | Key Findings | Melting Improvement | Limitations |
---|---|---|---|---|---|
[31] | Apple peel extract | 0.5–2% | ↓ melting rate, ↑ overrun | 15–25% | Limited temperature range |
[11] | Barberry anthocyanins | 1–5% | ↑ firmness, ↑ melting resistance | 67% (at 5%) | High astringency |
[12] | Strawberry polyphenols | 1–3% | 2× viscosity ↑ | 30–40% | Color interference |
[26] | Tannic acid (model) | 0.5–3% | Protein–fat netweork formation | 20–35% | Model compound study |
[40] | Persimmom puree | 5–15% | Natural stabilization | 25% | High sugar content |
Metric Category | Parameter | Measurement Method | Target Range | Reference Standard | Validation Studies |
---|---|---|---|---|---|
Melting Resistance | |||||
Melting rate coefficient | g/min at 22 °C, 50% RH | Weight loss measurement every 5 min for 60 min | 0.10–0.25 g/min (control: 0.30–0.45 g/min) | ASTM D3418 modified | [11,12,31,43] |
Melting start time | Minutes to first drip | Visual observation at standardized conditions | 15–35 min (control: 8–15 min) | Based on [11] methodology | [11] |
Shape Retention | |||||
Shape retention index | % original shape after 30 min | Digital image analysis | 60–85% (control: 30–45%) | Comparative visual scoring | [12,31] |
Structural integrity | Time to 50% collapse | Video analysis | 25–45 min (control: 10–20 min) | Modified from [35] | [35] |
Rheological Properties | |||||
Viscosity enhancement ratio | Fold increase vs. control | Rheometer at 4 °C | 1.5–3.0× (control: 1.0×) | Consistency index (K) measurement | [12,30] |
Yield stress | Pa at 4 °C | Controlled stress rheometry | 25–50 Pa (control: 15–25 Pa) | Based on [4] methodology | [4] |
Microstructural Analysis | |||||
Ice crystal size | μm average diameter | Polarized light microscopy | 25–45 μm (control: 35–55 μm) | Image Tool 3.0; UTHSCSA, San Antonio, TX, USA Avizo 2019.4 | [2,3] |
Fat globule size | μm average diameter | Confocal microscopy | 3–8 μm (control: 2–5 μm) | Particle size analyzer | [2,26] |
Sensory Thresholds | |||||
Astringency detection | Intensity scale 1–9 | Trained sensory panel | <3 for acceptability | Triangle test methodology | [26,35] |
Bitterness threshold | mg/L equivalent | Chemical analysis + sensory | <150 mg/L tannic acid equiv. | Based on [26] data | [26] |
Chemical Composition | |||||
Total polyphenol content | mg GAE/100 g product | Folin–Ciocalteu method | 50–300 mg GAE/100 g | Standard GAE curve | [10,15] |
Individual compounds | μg/g product | HPLC–DAD analysis | Variable by compound | Authentic standards | [15] |
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Nehme, L.; El Rayess, Y.; Semaan, M.; Nawfal, E.; Riachy, P. Polyphenolic Compounds from Indigenous Malus Species: A Novel Approach to Improve Ice Cream’s Thermodynamic Properties. Processes 2025, 13, 2019. https://doi.org/10.3390/pr13072019
Nehme L, El Rayess Y, Semaan M, Nawfal E, Riachy P. Polyphenolic Compounds from Indigenous Malus Species: A Novel Approach to Improve Ice Cream’s Thermodynamic Properties. Processes. 2025; 13(7):2019. https://doi.org/10.3390/pr13072019
Chicago/Turabian StyleNehme, Lea, Youssef El Rayess, Maribelle Semaan, Elsa Nawfal, and Philip Riachy. 2025. "Polyphenolic Compounds from Indigenous Malus Species: A Novel Approach to Improve Ice Cream’s Thermodynamic Properties" Processes 13, no. 7: 2019. https://doi.org/10.3390/pr13072019
APA StyleNehme, L., El Rayess, Y., Semaan, M., Nawfal, E., & Riachy, P. (2025). Polyphenolic Compounds from Indigenous Malus Species: A Novel Approach to Improve Ice Cream’s Thermodynamic Properties. Processes, 13(7), 2019. https://doi.org/10.3390/pr13072019