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Starch gelatinization

Starch gelatinization is an order-to-disorder phase transition in which native starch granules, composed primarily of amylose and amylopectin, absorb water and swell irreversibly upon heating, leading to the disruption of their semi-crystalline structure, leaching of amylose molecules, and formation of a viscous paste or gel.^[1] This process fundamentally alters the physicochemical properties of starch, transforming insoluble granules into a soluble, hydrated matrix that influences texture, viscosity, and digestibility in food systems.^[1] Starch, a major carbohydrate reserve in plants such as cereals, tubers, and legumes, typically consists of amylose (15–25% by weight), a linear polymer of α-D-glucose linked by α-1,4 glycosidic bonds, and amylopectin (75–85%), a highly branched polymer with additional α-1,6 linkages. The gelatinization temperature range varies by starch source and granule composition, generally occurring between 50–80°C for most botanical starches, with amylopectin branching providing thermal stability and amylose content affecting the enthalpy of the transition. Mechanistically, heating promotes water penetration into the amorphous regions of granules, breaking intra- and intermolecular hydrogen bonds within double helices formed by amylopectin chains, which facilitates granule swelling and eventual rupture.^[2] Key factors influencing gelatinization include water availability, with excess moisture (>65%) yielding a single endothermic peak in differential scanning calorimetry, while limited water (35–60%) results in multiple peaks due to sequential melting of amylopectin-amylose complexes.^[1] Additives such as salts, sugars, lipids, and proteins can either promote or inhibit the process by altering water mobility, granule stability, or molecular interactions—for instance, lipids form inclusion complexes with amylose, raising gelatinization temperatures.^[1] In food applications, controlled gelatinization is essential for achieving desired rheological properties in products like sauces, baked goods, and extruded snacks, while incomplete gelatinization can reduce digestibility and enhance resistant starch formation for nutritional benefits.^[3]

Introduction and Fundamentals

Definition and Overview

Starch gelatinization is the process in which native starch granules absorb water and heat, leading to irreversible swelling, disruption of their crystalline structure, and a marked increase in viscosity as the granules rupture and release amylose and amylopectin into solution.^[4] This transition transforms the ordered, insoluble starch into a disordered, soluble form, fundamentally altering its physical properties.^[5] The process has been integral to cooking practices for centuries, enabling the softening and thickening of foods like grains, tubers, and pasta to achieve desirable textures.^[6] Scientific investigation of starch gelatinization began in the 19th century, with early researchers using microscopy to observe granule swelling and proposing initial theories on the structural changes involved.^[7] In modern applications, starch gelatinization is essential to food processing, where it underpins the functionality of thickening agents in products such as sauces, puddings, and baked goods, influencing texture, stability, and mouthfeel.^[8] Beyond food, it supports industrial uses like adhesives, where the viscous paste formed provides strong binding capabilities in paper, textiles, and wood products.^[9] The ultimate outcome of complete gelatinization is the production of a thick, viscous paste or gel from native starch, which serves as a versatile base for further formulation in both culinary and manufacturing contexts.^[10]

Starch Molecular Structure

Starch is primarily composed of two polysaccharides: amylose and amylopectin. Amylose constitutes approximately 20-30% of native starch and consists of linear chains of α-D-glucose units linked primarily by α-1,4 glycosidic bonds, forming a helical structure with occasional branches via α-1,6 linkages in some variants.^[11] Amylopectin, making up 70-80% of starch, is a highly branched polymer with α-1,4-linked glucose chains forming the backbone and α-1,6 linkages at branch points every 24-30 glucose units, resulting in a clustered, tree-like molecular architecture.^[11]^[12] Starch granules exhibit a semi-crystalline organization, characterized by alternating amorphous and crystalline regions arranged in a radial pattern from a central hilum. The amorphous regions, rich in amylose and branch points of amylopectin, alternate with crystalline lamellae formed by short amylopectin chains in double-helical conformations, creating growth rings visible under microscopy.^[11] This layered structure varies by botanical origin; for instance, potato starch granules display large, lenticular shapes with prominent radial channels, while corn starch features smaller, polyhedral granules with more compact radial arrangements.^[11] Key properties of starch granules stem from this molecular organization. Under polarized light microscopy, native granules show birefringence, manifesting as a characteristic "Maltese cross" pattern, which indicates the radial orientation of crystalline helices.^[11] Granules have a high water absorption capacity, primarily in amorphous regions, influenced by their size range of 5-100 μm, which affects surface area and hydration potential.^[12]^[11] The amylose-to-amylopectin ratio varies significantly across botanical sources, influencing granule properties. Cereal starches, such as those from corn, wheat, and rice, typically contain 20-30% amylose, leading to more balanced semi-crystalline structures. Tubers like potato have around 20% amylose with higher amylopectin content, resulting in larger granules and greater swelling potential. Legume starches, including pea and lentil, often exhibit higher amylose levels of 30-40%, contributing to denser packing and altered hydration behaviors.^[12]^[13]

Gelatinization Process

Mechanism

Starch gelatinization at the molecular level begins with the disruption of hydrogen bonds that stabilize the interactions between amylose and amylopectin chains within the starch granule. When heated in the presence of water, these bonds weaken, allowing water molecules to penetrate and hydrate the amorphous regions of the granule. This hydration initiates swelling and expansion of the granule structure, as the polymer chains absorb water and increase in volume.^[14]^[15] The process progresses to the melting of crystallites in the ordered lamellae, where double helices formed by amylopectin side chains lose their structural integrity. Swelling in the amorphous domains generates mechanical stress on these crystalline regions, leading to their dissociation and an overall loss of molecular order. This phase transition is endothermic and entropy-driven, with the increase in disorder (positive \Delta S) favoring the shift from a crystalline to an amorphous state under elevated temperatures.^[16]^[17] The energy associated with crystallite melting is captured as the gelatinization enthalpy (\Delta H), determined by differential scanning calorimetry (DSC), which typically ranges from 5 to 20 J/g for various starches, reflecting the heat required to overcome intermolecular forces.^[18]^[19] Concurrently, viscoelastic changes occur as amylose leaches selectively into the aqueous phase, enhancing solution viscosity without complete granule dissolution, thereby forming a paste-like matrix.^[14]^[15]

Stages

The gelatinization of starch occurs in distinct sequential stages as granules are heated in the presence of water, typically under excess moisture conditions. The initial stage begins at the onset temperature (To), generally ranging from 50 to 70°C depending on the starch source, where granules absorb water primarily in their amorphous regions, leading to initial swelling without significant morphological disruption.^[20] This water uptake destabilizes the crystalline structure, initiating a gradual loss of birefringence observable under polarized light microscopy, as the Maltese cross pattern begins to fade.^[16] For example, in corn starch, this stage starts around 62-65°C, with granules remaining intact but undergoing subtle expansion.^[19] In the intermediate stage, at the peak temperature (Tp), swelling intensifies, reaching maximum granule volume—often up to 100 times the original for many cereal starches—and viscosity peaks as the suspension thickens due to entangled swollen granules.^[21] Birefringence is fully lost, indicating the melting of crystallites, and some larger granules begin to rupture, leaching amylose into the surrounding medium. Microscopic observations reveal deformed and expanded granules, with scanning electron microscopy showing surface irregularities and internal disruption.^[22] For corn starch, Tp occurs around 70°C, within an overall range of 62-72°C, where swelling is most pronounced before partial breakdown.^[20] The final stage concludes at the conclusion temperature (Tc), where remaining granules rupture completely, forming a viscous paste as amylopectin and amylose fully disperse, eliminating any residual crystallinity.^[16] Under standard heating conditions (e.g., excess water at a rate of 5-12°C/min), the entire process typically takes 10-30 minutes, with full gelatinization achieved by 75-85°C for corn starch.^[19] Light microscopy at this point shows no intact granules, only a homogeneous amylose-amylopectin matrix.^[23]

Factors Influencing Gelatinization

Intrinsic Factors

Intrinsic factors refer to the inherent properties of starch granules that govern their gelatinization behavior, independent of external conditions such as temperature or additives. These properties arise from the starch's molecular composition and supramolecular organization, influencing key parameters like onset temperature (To), peak temperature (Tp), conclusion temperature (Tc), gelatinization enthalpy (ΔH), and swelling capacity. Variations in these intrinsic characteristics determine how readily starch undergoes the disruption of its crystalline structure during heating in the presence of water.^[19] Botanical source significantly affects gelatinization due to differences in granule architecture and composition across plant origins. Cereal starches, such as those from wheat, exhibit lower onset temperatures around 58°C, reflecting their A-type crystallinity and relatively compact structure. In contrast, tuber starches like potato display higher swelling capacities during gelatinization owing to their larger granules and B-type crystallinity, which allows greater hydration despite similar temperature ranges of 58-68°C. These variations stem from evolutionary adaptations in starch storage, with cereal starches optimized for rapid energy mobilization and tuber starches for long-term reserve. For instance, maize starch gelatinizes between 64.3 and 77.2°C, higher than rice at 58.9-72.4°C, highlighting intra-cereal differences.^[19]^[24]^[18]^[18] The amylose-to-amylopectin ratio profoundly influences gelatinization dynamics, as amylose acts as a linear, less branched molecule that restricts granule expansion compared to the highly branched amylopectin. High-amylose starches (e.g., 25-30% amylose in normal maize) require higher gelatinization temperatures (up to 70-80°C) and exhibit reduced swelling due to amylose's tendency to form tighter helices that stabilize the granule structure. Conversely, low-amylose or waxy starches (nearly 100% amylopectin) gelatinize at lower temperatures (around 60-65°C) with greater swelling, as amylopectin's branching facilitates easier crystalline melting and water uptake. This ratio directly correlates with ΔH, where higher amylopectin content elevates enthalpy by increasing the energy needed to disrupt more extensive crystalline domains.^[25]^[19]^[24] Granule size and morphology further modulate gelatinization by affecting surface area, water accessibility, and internal organization. Larger granules, typical of potato starch (20-100 μm), absorb more water and swell extensively, leading to higher viscosity but potentially broader gelatinization ranges as outer layers disrupt before inner cores. Smaller granules, such as those in rice (2-8 μm), gelatinize more uniformly and at slightly lower temperatures due to their higher surface-to-volume ratio, which enhances heat transfer and hydration efficiency. Morphology plays a key role: A-type polymorphs in cereals (polygonal, dense) confer thermal stability and higher To compared to B-type in tubers (spherical, less ordered), which promote rapid swelling but lower overall ΔH. These traits arise from the concentric growth of alternating amorphous and crystalline lamellae within granules.^[26]^[19]^[27] Genetic and varietal differences amplify these effects through mutations altering biosynthesis pathways, impacting gelatinization enthalpy and temperature profiles. For example, waxy maize varieties (0% amylose) show lower ΔH (12.0-13.8 J/g) and onset temperatures (65.6-70.7°C) compared to normal maize (20-25% amylose), due to reduced crystalline stability from pure amylopectin composition, resulting in easier melting but higher retrogradation potential. In contrast, high-amylose mutants exhibit elevated ΔH and To, reflecting stronger intermolecular associations. Varietal selections in cereals like rice demonstrate ΔH variations from 5-15 J/g across genotypes, driven by differences in amylopectin chain length and granule crystallinity. These genetic traits enable tailored starch functionality in breeding programs.^[28]^[19]^[24]

Extrinsic Factors

Extrinsic factors play a crucial role in modulating the starch gelatinization process by altering the conditions under which starch granules absorb water, swell, and lose their crystalline structure. Temperature is a primary driver, with gelatinization typically occurring between 60°C and 80°C for most cereal starches such as maize and rice, where the onset temperature (To) for maize starch ranges from 64.3°C to 77.2°C and for rice from 58.9°C to 72.4°C under excess water conditions.^[19] The heating rate influences the breadth of the gelatinization temperature range; higher rates, such as increasing from 1.6°C/min to 10.1°C/min, shift exothermic peaks to higher temperatures and narrow the overall transition range by accelerating granule disruption and reducing the time for partial melting.^[29] This effect is particularly pronounced at intermediate moisture levels, where slower heating allows more gradual swelling.^[30] Water content is essential for initiating gelatinization, requiring a minimum of approximately 25-30% moisture to enable sufficient hydration and granule swelling, as levels below 25% hinder complete disruption even at elevated temperatures.^[31] Excess water (typically >60-70% moisture content) promotes full cooperative melting of crystallites but can dilute the system, leading to reduced viscosity without proportional increases in swelling beyond a starch-to-water ratio of 1:2.^[32] At limited water availability, such as 20% moisture during heat-moisture treatment, gelatinization is restricted, resulting in higher resistant starch content up to 68% in sweet potato starch.^[33] pH and ionic environment further tune the process; acidic conditions lower the onset temperature (To) by hydrolyzing amorphous regions, reducing peak temperature (Tp) and enthalpy (ΔH) up to threefold in treated starches.^[19] Salts like NaCl compete for water and stabilize granule structure at low concentrations (below 7-9%), increasing To and Tp while decreasing ΔH, though higher levels may promote peripheral gelatinization due to ion exclusion from granule interiors.^[34]^[35] This dual effect arises from electrostatic interactions that limit water penetration.^[36] Additives such as sugars elevate To by reducing free water availability and stabilizing crystalline junctions through hydrogen bonding; for instance, sucrose increases Tgel more than monosaccharides like glucose or fructose at concentrations above 40% w/w.^[37] Lipids form inclusion complexes primarily with amylose, inhibiting granule swelling and lowering ΔH, as seen in high-lipid rice starches where complexation restricts hydration during heating.^[19]^[38] These complexes, often enhanced by saturated fatty acids, delay full gelatinization and reduce digestibility.^[33] Processing conditions like shear and pressure accelerate gelatinization in applications such as extrusion, where combined high shear and pressure (e.g., 500 MPa) promote granule breakdown and increase the extent of disruption compared to heat alone, yielding up to 20% resistant starch in corn starch extrudates.^[39]^[33] Shear stress facilitates molecular degradation and mixing, while pressure resists swelling without shear but enhances it when paired, leading to faster transition through the standard stages of hydration and melting.^[40]

Measurement and Characterization

Key Parameters

Starch gelatinization is characterized by several key thermal and rheological parameters that quantify the transition from ordered crystalline structure to a disordered, viscous state. These metrics, primarily determined through techniques like differential scanning calorimetry (DSC) for thermal properties and rapid visco analysis (RVA) for pasting behavior, enable standardized comparisons across starch sources and processing conditions.^[18] The primary temperature parameters include the onset temperature (To), which marks the initial melting of crystalline regions; the peak temperature (Tp), corresponding to the maximum rate of gelatinization; and the conclusion temperature (Tc), indicating the completion of the process. These values typically range from 57°C to 77°C for To, 62°C to 83°C for Tp, and 67°C to 95°C for Tc, depending on the botanical origin of the starch. The gelatinization temperature range, defined as ΔT = Tc - To, generally spans 5–20°C and reflects the breadth of thermal energy required for complete granule disruption. For example, normal corn starch exhibits To ≈ 64°C, Tp ≈ 69°C, Tc ≈ 75°C, and ΔT ≈ 11°C.^[18]^[5] The enthalpy of gelatinization (ΔH) measures the heat absorbed during the melting of starch crystallites, serving as an indicator of the degree of molecular order and crystallinity in native granules. Higher ΔH values correlate with greater crystalline content, as more energy is needed to disrupt hydrogen bonds and helical structures. Typical ΔH for cereal starches ranges from 7 to 18 J/g; for instance, normal corn starch shows ΔH ≈ 12 J/g, underscoring its moderate crystallinity compared to tuber starches.^[18]^[5] Pasting properties, assessed via RVA, describe the viscosity changes during heating and cooling of starch suspensions, providing insights into granule swelling and network formation. Peak viscosity represents the maximum consistency achieved upon granule rupture and amylose leaching, typically 800–1200 cP (or 70–100 RVU) for corn starch at standard 8–12% concentrations. Breakdown viscosity quantifies the decline in viscosity under shear and heat (e.g., 200–400 cP for corn), reflecting granule stability, while setback viscosity measures the increase during cooling (e.g., 100–300 cP for corn), indicating amylopectin recrystallization tendencies. These parameters, expressed in centipoise (cP) or rapid visco units (RVU, where 1 RVU ≈ 12 cP), are crucial for predicting product texture in applications like sauces and batters.^[41]^[42] Swelling power and solubility further characterize water interactions during gelatinization, with swelling power denoting the mass of sedimented starch per gram of dry sample (g/g) after hydration and centrifugation, typically 14–21 g/g for corn starch at 90°C, indicative of granule expansion capacity. Solubility, expressed as the percentage of leached amylose and low-molecular-weight components, averages 9–11% for corn starch under similar conditions, highlighting limited initial solubilization before full disruption. These metrics underscore the balance between hydration-driven swelling and partial dissolution essential for viscous paste formation.^[41]

Analytical Techniques

Differential scanning calorimetry (DSC) is a widely used thermal analysis technique to quantify starch gelatinization by measuring the onset temperature (To), peak temperature (Tp), conclusion temperature (Tc), and enthalpy change (ΔH) associated with the endothermic transition during granule disruption.^[43] In this method, a small sample of starch (typically 3-5 mg) is mixed with excess water at a ratio of approximately 1:3 (starch:water by weight) to ensure hydration without water limitation, then sealed in a pan and heated at a controlled rate (e.g., 5-10°C/min) from 20°C to 100°C under an inert atmosphere.^[44] The resulting thermogram provides precise thermodynamic data, with ΔH reflecting the energy required to melt crystalline regions, typically ranging from 5-20 J/g for native starches depending on botanical origin.^[43] The Rapid Visco Analyzer (RVA) assesses gelatinization through pasting behavior by monitoring viscosity changes in a starch-water suspension (e.g., 3 g starch in 25 mL water) subjected to programmed heating, holding, and cooling under shear.^[45] This instrument profiles key pasting parameters such as peak viscosity (indicating maximum granule swelling), breakdown (viscosity loss due to shear and heat), and setback (viscosity increase upon cooling from amylose alignment), with gelatinization onset often observed around 60-70°C for cereal starches.^[45] RVA is particularly valuable for simulating industrial processes like cooking, providing insights into functional properties under dynamic conditions.^[46] Microscopy techniques visualize structural transformations during gelatinization, with polarized light microscopy detecting the loss of Maltese cross birefringence as crystalline order disrupts.^[47] Native starch granules exhibit strong birefringence under crossed polarizers due to radial arrangement of amylopectin helices, which fades progressively above 50-60°C as hydration swells the granules.^[47] Scanning electron microscopy (SEM) complements this by revealing morphological changes, such as surface roughening, cracking, and eventual rupture of granules upon heating in water, often showing a honeycomb-like internal structure post-gelatinization.^[48] Samples for SEM are typically dehydrated and gold-coated to enhance resolution of these alterations.^[48] X-ray diffraction (XRD) quantifies the loss of crystallinity during gelatinization by tracking the diminution of characteristic peaks in the diffraction pattern, shifting from A- or B-type crystalline structures to an amorphous profile.^[49] Native starches show relative crystallinity of 15-40%, which decreases sharply as heating exceeds Tp, confirming the melting of crystallites.^[49] Nuclear magnetic resonance (NMR), particularly low-field proton NMR, probes molecular mobility by measuring transverse relaxation times (T2), where increased water proton mobility signals enhanced granule hydration and chain disentanglement during gelatinization.^[50] This technique distinguishes rigid (crystalline) from mobile (amorphous) domains, with T2 values rising from ~10 ms in native starch to over 100 ms post-gelatinization.^[50] Recent advances incorporate in-situ synchrotron radiation techniques, such as time-resolved small- and wide-angle X-ray scattering (SAXS/WAXS), to capture real-time dynamics of lamellar and crystalline disruptions during heating at rates mimicking DSC.^[51] These methods, developed post-2010, reveal heterogeneous gelatinization mechanisms, including initial melting of defective crystallites followed by ordered disassembly, offering higher temporal and spatial resolution than conventional lab-based XRD.^[52]

Post-Gelatinization Phenomena

Retrogradation

Retrogradation is the process by which gelatinized starch molecules, specifically the linear amylose and branched amylopectin chains, reassociate into more ordered, crystalline structures during cooling and storage, reversing aspects of the initial gelatinization. This re-association begins immediately after the disruption of native granule order during heating, leading to the formation of double helices and B-type crystallites that contribute to structural reorganization.^[53]^[54] The kinetics of retrogradation differ markedly between amylose and amylopectin due to their molecular architectures. Amylose retrogrades rapidly, often within hours, forming short-range ordered structures through quick nucleation and propagation of double helices, while amylopectin retrogrades more slowly over days, involving the alignment of its branched chains into crystalline domains via intra- and intermolecular interactions. This two-phase process follows models like the consecutive reaction (CR) model, where nucleation serves as the rate-limiting step.^[53]^[55] The enthalpy of retrogradation (ΔH_r), measured by differential scanning calorimetry (DSC) through re-scanning of stored gels, is typically lower than the gelatinization enthalpy (ΔH_g), often around half or less depending on starch type and conditions; for instance, rice starch stored at 4°C may exhibit ΔH_r values of 3.9–7.0 J/g compared to ΔH_g of 2.6–14.4 J/g at moderate water contents. Specific factors accelerate this process, including higher starch concentration, which promotes chain proximity for association, and temperature cycling (e.g., 4/30°C fluctuations), which enhances crystallite stability over constant low temperatures. Storage at 4°C notably speeds amylopectin crystallization by favoring molecular mobility near the glass transition temperature.^[56]^[53]^[55] Microstructurally, retrogradation results in the aggregation of helices into a firm gel network, increasing the overall order and leading to texture firming through enhanced intermolecular forces and reduced water mobility within the matrix. This network formation is evident in the transition from a viscous paste to a more rigid, opaque structure, particularly driven by amylose's rapid gelation backbone.^[53]^[55]

Gel Stability Issues

One major stability issue in starch gels is syneresis, the expulsion of water from the gel network due to contraction and reorganization of starch molecules, particularly amylose chains, which reduces the gel's water-holding capacity.^[57] This phenomenon is more pronounced in high-amylose starches, such as corn starch with approximately 22% amylose content, where syneresis can reach 17-20% after storage at 4°C, compared to lower levels of 10-13% in tapioca starch with 16% amylose.^[57] Syneresis often stems from retrogradation, where aligned starch helices form a denser structure that squeezes out bound water.^[58] Texture degradation in starch-based products, such as firming and staling in baked goods like bread, arises from both physical and enzymatic mechanisms. Physically, retrogradation leads to crumb firming by increasing starch crystallinity and reducing water mobility, resulting in a drier, tougher texture over time.^[59] Enzymatically, endogenous or added amylases can hydrolyze starch chains, either accelerating breakdown for softer initial textures or, in controlled applications, mitigating long-term firming by limiting amylopectin recrystallization.^[59] Freeze-thaw instability further compromises gel integrity, as ice crystal formation during frozen storage concentrates solutes in the unfrozen phase, promoting starch aggregation and exacerbating retrogradation upon thawing.^[60] This leads to significant syneresis, with some starches like sweet potato exhibiting up to 2.9% water loss after four cycles, while others show higher expulsion due to disrupted gel networks.^[60] These stability issues directly impact shelf life in products like puddings and sauces, where syneresis causes visible water separation and reduced viscosity.^[61] In desserts, this results in phase separation and textural deterioration, limiting commercial viability.^[61] Non-chemical mitigation strategies include adding hydrocolloids, such as xanthan gum or konjac glucomannan, which enhance water retention and stabilize the gel matrix against syneresis without altering starch structure.^[62]

Applications and Modifications

Food Industry Uses

Starch gelatinization plays a pivotal role in the food industry for thickening and stabilizing various products, particularly sauces, soups, and instant puddings. When heated in the presence of water, starch granules swell and rupture, releasing amylose and amylopectin molecules that form a viscous gel network, enhancing mouthfeel and preventing separation.^[63] In sauces and soups, native starches like potato or corn provide a smooth texture at concentrations of 2-5%, with combinations such as potato starch and xanthan gum maintaining stability for up to three months under storage.^[63] For instant puddings, pre-gelatinized native starches enable rapid hydration and thickening in cold liquids, eliminating the need for cooking and ensuring quick preparation.^[19] In baking and extrusion processes, gelatinization is essential for developing structure and texture. During bread baking, partial gelatinization of wheat starch in dough creates an elastic network that traps carbon dioxide, contributing to loaf volume and softness; higher degrees of gelatinization from pregelatinized starch additions can increase specific volume while reducing hardness.^[64] In extrusion cooking for puffed snacks, high shear forces and temperatures of 100-150°C promote complete gelatinization of cereal starches, leading to moisture flash-off, expansion, and a crispy, low-density product with improved solubility.^[65] This process, often applied to corn or rice, achieves high degrees of gelatinization, typically 90-100%, under controlled moisture (12-22%), enhancing digestibility without chemical additives.^[66] Gelatinization also influences texture in dairy and confectionery applications. In ice cream production, controlled starch gelatinization stabilizes the emulsion by increasing viscosity and preventing ice crystal formation, resulting in a smoother mouthfeel during freezing and storage.^[67] For gummy candies, native or lightly processed starches, such as corn starch, contribute to gel formation alongside sugars, where gelatinization temperature is modulated by high sucrose levels to achieve a chewy consistency without syneresis.^[68] From a nutritional perspective, gelatinization enhances starch digestibility in food products by disrupting crystalline structures, allowing faster enzymatic breakdown and glucose release in the small intestine, which is desirable for energy provision in items like baked goods and cereals.^[69] This process reduces the formation of resistant starch, which resists digestion and acts as a fiber; thus, full gelatinization in processed foods helps avoid unintended resistant starch content that could lower glycemic availability.^[70] Recent trends in the food industry emphasize clean-label approaches using native starches, often processed via physical methods like extrusion cooking to mimic modified starch functionality without chemicals. These starches provide natural thickening and stabilization in ready-to-eat cereals and snacks, aligning with consumer demands for transparency while maintaining product quality under high-temperature processing.^[71]

Types of Modified Starches

Modified starches are altered through various processes to enhance their gelatinization properties, such as solubility, viscosity, thermal stability, and resistance to retrogradation, making them suitable for specific industrial applications. These modifications can be physical, chemical, or enzymatic, each targeting different aspects of starch structure to control the onset temperature (To), peak temperature (Tp), enthalpy change (ΔH), and gelatinization range (ΔT).^[72] Pregelatinized starch undergoes pre-swelling through methods like drum-drying or extrusion, where starch slurries are heated and dried to disrupt granule structure partially. This results in instant solubility in cold water without requiring heat for gelatinization, as the process eliminates the need for the typical endothermic transition observed in native starch. Such starches exhibit high cold paste viscosity and are commonly used in infant foods for easy preparation and thickening.^[73]^[74]^[75] Chemical modifications involve introducing functional groups or linkages to starch molecules, significantly altering gelatinization behavior. Cross-linking, often using sodium trimetaphosphate (STMP), forms intra- and inter-molecular bonds that raise To and Tp while maintaining ΔH, enhancing shear resistance and stability under high temperatures or acidic conditions. Acetylation and hydroxypropylation, which substitute hydroxyl groups with acetyl or hydroxypropyl groups, lower the gelatinization temperature, increase paste clarity and viscosity, and reduce retrogradation by disrupting crystalline order. These changes improve freeze-thaw stability, making them ideal for processed foods.^[76]^[77]^[72]^[78] Physical modifications rely on heat and moisture without chemical agents to reorganize starch structure. Annealing involves pre-heating starch in excess water at temperatures below To, which narrows ΔT by promoting uniform crystalline perfection and increasing thermal stability. Heat-moisture treatment (HMT), conducted at limited moisture (10-30%) and temperatures of 90-120°C, elevates To and Tp, reduces swelling and solubility, and enhances paste stability against shear and acid. Both methods minimize retrogradation without altering molecular weight.^[72]^[79] Enzymatic modifications use specific enzymes to hydrolyze starch chains, tailoring functional properties. α-Amylase hydrolysis cleaves α-(1,4) glycosidic bonds, reducing molecular weight and viscosity while increasing solubility and lowering the gelatinization temperature. Dual enzymatic modifications, combining α-amylase with branching enzymes like pullulanase, further improve freeze-thaw resistance by creating shorter chains with more branch points, reducing syneresis in gels. These approaches are valued for their specificity and clean-label appeal.^[72]^[80] As of 2025, advances in starch modification include genetic engineering to produce starches with enhanced solubility and water absorption, as well as emerging physical techniques like ultrasonication and high hydrostatic pressure, which improve functional properties for sustainable food applications without chemical additives.^[81]^[82] Overall, these modifications preserve or adjust key gelatinization parameters; for instance, cross-linked starches show unchanged ΔH but higher Tp, ensuring structural integrity during processing. Post-2000 advances, including dual chemical-physical combinations, have expanded applications in frozen foods by enhancing gel stability and reducing water separation after thaw cycles.^[83]^[84]

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Swelling and deformation of the starch granules observed in the scanning electron microscope correlated with the loss of birefringence in the light microscope.
[23]
Light Microscopy as a Tool to Evaluate the Functionality of Starch in ...
As oxidation increased, not only swelling but also disintegration of starch granules was observed at the temperature of 65 °C (Figure 6C,E). At the temperature ...
[24]
The Principles of Starch Gelatinization and Retrogradation
We review the structure-function relationship of polysaccharides and starch on the view point of rheological aspects and discuss their gelation, gelatinization ...
[25]
The influence of the amylose content and gelatinization method
Gelatinization and retrogradation, influenced by amylose and amylopectin ratio, are important characteristics for starch hydrogels elaboration.
[26]
Starch granule size: Does it matter?
### Summary: Starch Granule Size and Gelatinization Behavior
[27]
Physical and chemical properties of corn, cassava, and potato starchs
This implied that the granule size of starch affected gelatinization temperature. The larger the granule size, the more easily the starch to be gelatinized.
[28]
Comparison of the physicochemical properties of starches from ...
Waxy maize starch had higher breakdown viscosity and retrogradation percentage, and lower setback viscosity and gelatinization enthalpy than the sweet-waxy ...
[29]
Thermal Characterization of the Gelatinization of Corn Starch ... - NIH
DSC analysis showed the gelatinization endotherm, the melting endotherm of starch−lipid complexes, and an exotherm attributable to the alkali-decomposition of ...
[30]
Effect of heating rate at different moisture contents on starch ...
Sep 15, 2010 · A significant interaction was observed between moisture content and heating rate. The results suggest that the gelatinization process is ...
[31]
evaluation of conditioning time and temperature on gelatinized ...
True starch gelatinization is thought to occur at temperatures above 70°C and moisture above. 25% (Lund, 1984). Although the temperatures evalu- ated in the ...
[32]
Rapid Estimation of Parameters for Gelatinization of Waxy Corn Starch
These parameters were found to be ≥65 wt.% water, 75–85 °C, and 10 min, respectively. The estimation of the minimum gelatinization temperature was determined ...
[33]
(PDF) Effects of processing and additives on starch physicochemical ...
Modifying the physicochemical properties of starch using some processing technologies or additives such as sugars, hydrocolloids, proteins, lipids, and other ...Missing: paper | Show results with:paper
[34]
Effect of sodium chloride on the gelatinization of starch - PubMed
These two effects conflict with one another and result in complex effect patterns depending on the concentration of the salts.
[35]
Effect of sodium chloride on the gelatinization of starch: A ...
Dec 12, 2001 · Indeed, Wooton and Bamunuarachchi4 reported that NaCl, up to 9% caused an increase in the gelatinization temperature (To = onset, and Tp = peak ...Missing: NaCl | Show results with:NaCl
[36]
The mechanism of salt effects on starch gelatinization from a ...
Salt ions therefore have less access to starch molecules within the granule and promote gelatinization from the periphery. This peripheral gelatinization has ...
[37]
Effects of Sugars and Sugar Alcohols on the Gelatinization ... - NIH
Jun 8, 2020 · The gelatinization temperature (Tgel) of starch increases in the presence of sweeteners due to sweetener-starch intermolecular interactions ...
[38]
Starch–lipid and starch–lipid–protein complexes: A comprehensive ...
Mar 6, 2020 · When only water is used as the solvent, the starch is gelatinized by heating and the complexes are formed during cooling stage (Figure 6c). The ...INTRODUCTION · METHODS USED TO STUDY... · FACTORS INFLUENCING...
[39]
Effect of pressure with shear stress on gelatinization of starches with ...
The results showed that without shear stress, pressure could resist the gelatinization process due to weak swelling of starch granules and lower quantity of ...
[40]
Effects of Extrusion on Starch Molecular Degradation, Order ... - NIH
Aug 22, 2022 · Starch molecular structures are thus the driving factors in determining the starch digestibility in both gelatinized and retrograded states, as ...
[41]
Some properties of corn starches II: Physicochemical, gelatinization ...
The range for peak viscosity among different varieties was between 804 and 1252 cP. The hardness of starch gels ranged from 21.5 to 32.3 g. African Tall and ...
[42]
Physicochemical and morphological properties of starch from fresh ...
Granule size distribution showed a two population of starch granules with peak values ranged from 0.8 to 1.1 μm (small) and 9.0 to 12.2 μm (large). Genotypes ...
[43]
STARCH GELATINIZATION PHENOMENA STUDIED BY ...
Differential Scanning Calorimetry (DSC) was used to study gelatinization phenomena of corn, potato, acid-modified corn and smooth pea, and various legume ...
[44]
A study of starch gelatinization using differential scanning ...
The order-disorder transition that occurs on heating an aqueous suspension of starch granules has been investigated using differential scanning calorimetry ...
[45]
[PDF] Rapid Visco Analyser (RVA) as a Tool for Measuring Starch-Related ...
Oct 1, 2019 · During an RVA test, the process of pasting is observed in a starch/flour and water slurry subjected to stirring and heat, i.e. the formation of.
[46]
Rapid Visco Analyzer (RVA) - PerkinElmer
The Rapid Visco Analyzer (RVA) is a cooking, stirring viscometer optimized for testing the viscous properties of starch, grain, dairy products and other.Missing: gelatinization | Show results with:gelatinization
[47]
[PDF] Determination of Starch Gelatinization Temperatures by Means of ...
The analyses of initial gelatinization temperatures measured by DSC and the polarized light detector showed a linear relationships for potato and tapioca ...
[48]
Scanning Electron Microscope Study on Gelatinization of Starch ...
A honeycomb-like structure was observed within the granules at the gelatinization temperature. It was believed that formation of this structure caused the ...
[49]
[PDF] Starch Gelatinization: An X-ray Diffraction Study'
Starch gelatinization was defined as the melting of starch crystallites, as granule fatty acids. Formation of these complexes partly explains.
[50]
[PDF] Starch Gelatinization Measured By Pulsed Nuclear Magnetic ...
The objective of this work was to study the possibility of using pulsed-proton NMR to measure the degree of gelatinization. Simul- taneously, the kinetics of ...
[51]
Recent advances in structural characterization of ... - PubMed Central
Nov 17, 2022 · Kuang et al. investigated the lamellar structure change of waxy corn starch during gelatinization and reveal the gelatinization mechanism by TR- ...
[52]
Changes of multi-scale structure during mimicked DSC heating ...
Jun 20, 2016 · Here we reveal the molecular mechanism of starch gelatinization by differential scanning calorimetry (DSC) in conjunction with a protocol using ...
[53]
Full article: Unraveling the Complexities of Starch Retrogradation
Apr 30, 2024 · This review for the first time summarized recent understandings on starch retrogradation property, especially from the kinetics and molecular perspectives.
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https://ift.onlinelibrary.wiley.com/doi/full/10.1111/1541-4337.12143
[55]
[PDF] Starch Retrogradation: Role of Food Ingredients and Extrinsic Factors
Jul 10, 2023 · Several approaches have been applied to study starch retrogradation and elucidate the mechanism and effect of different factors at the ...
[56]
Retrogradation enthalpy does not always reflect the ... - Nature
Feb 10, 2016 · Gelatinization of starch causes loss of molecular order in both the amylose and amylopectin components. Subsequent retrogradation is the process ...<|control11|><|separator|>
[57]
The Properties of Different Starches under the Influence of Glucono ...
Apr 25, 2023 · Starch gel syneresis happens when starch molecules interact and expel liquid from their network. Figure 2 displays the percentages of syneresis ...
[58]
Storage retrogradation behavior of sorghum, maize and rice starch ...
Starch gel syneresis. Over the course of. Conclusions. The rate and degree of starch retrogradation varied substantially among sorghum, maize, and rice ...
[59]
Influence of Amylase Addition on Bread Quality and Bread Staling
All those chemical and physical changes that occur during bread storage are regarded as bread staling. ... amylase (G4 amylase) are used to mitigate bread staling ...
[60]
Insights into the effects of frozen storage on the rheology, texture ...
Based on the above results, it could be speculated that starch retrogradation caused by ice crystals recrystallization was the critical reason for the changes ...
[61]
Freeze‐thaw Stability of Gels Prepared from Starches of Non ...
Mar 28, 2007 · The sweet potato starch gel was stable until the second cycle, but presented low syneresis until the fourth freeze-thaw cycle (2.9%). During ...
[62]
Ohmic pasteurization of probiotic chocolate dairy desserts and its ...
... storage of the samples. During cold storage of desserts formulated with gelatinized starch, syneresis may occur due to the reorganization of the ...Missing: pudding holding
[63]
Effect of mulberry leaf polysaccharides on the physicochemical ...
... starch gel syneresis (Charoenrein, Tatirat, Rengsutthi, & Thongngam, 2011). Besides, digestibility is one of the main indexes for starch-based food quality ...
[64]
Hydrocolloids as thickening and gelling agents in food
In dessert sauces like strawberry sauce, starch-xanthan combination is found to be suitable as a thickener. It provides stable sensory and textural properties ...Thickening Agents · Gels And Gelling Agents · Rheology Of Thickeners And...
[65]
Recent advances in the impact of gelatinization degree on starch
Sep 15, 2024 · Starch gelatinization involves diffusion of water through the granules, absorption of water by amorphous regions, swelling of starch granules, ...
[66]
Extrusion puffing pretreated cereals for rapid production of high ...
Oct 30, 2022 · The puffed extrudates exhibited lower bulk density, higher water solubility and gelatinization as compared to untreated cereals. The FTIR-ATR ...
[67]
Clean label starch: production, physicochemical characteristics, and ...
Notably, high temperature–short time extrusion cooking is used by many food industries to produce expanded snack foods, ready-to-eat cereals, and pet foods ( ...
[68]
Formulation of functional gummy candies containing natural ...
Jun 15, 2024 · Modified starch is widely used, alone or in combination with other gelling agents, for making gummy candies due to their good gelling properties ...
[69]
Impact of Starch Gelatinization on Digestibility and Human Health
Jan 30, 2023 · Native starches resist digestion or release glucose slowly in the small intestine. Ungelatinized starch may be beneficial to health.
[70]
Starch gelatinization implications for nutrient digestibility and ...
Starch gelatinization from 83% to 87% was enough to optimize digestibility. Crude protein apparent digestibility is the most impacted by gelatinization.
[71]
Customizing Starch Properties: A Review of Starch Modifications ...
Aug 21, 2023 · In principle two types of starch exist, storage starch and transitory starch. The latter is synthesized in chloroplasts of leaves and followed a ...
[72]
Research progress on properties of pre-gelatinized starch and its ...
Extruded and drum-dried pre-gelatinized starch showed serious structure destruction, significant increases in cold water solubility and cold paste viscosity.
[73]
Particle Agglomeration and Properties of Pregelatinized Potato ... - NIH
In general, pregelatinized starch is produced through spray drying, drum drying, and extrusion processes. Among these procedures, drum drying is the most ...Missing: infant | Show results with:infant
[74]
[PDF] Effect of blending and pregelatinizing order on properties of ...
Aug 20, 2019 · Pregelatinized starch is applied as a food thickening agent in infant foods and salad dressings (William, 2009) and in other non-thermally ...
[75]
Recent advancements in cross-linked starches for food applications
Cross-linking of starch granules increases its resistance to high temperatures, acidity, and shear forces, rendering it exceptionally useful in processed foods.
[76]
Preparation and characterization of starch crosslinked with sodium ...
The results showed that the porous starch which was crosslinked with 6% (w/w) STMP (ScPS-6) possessed remarkable superiority in terms of thermal and shear ...
[77]
Influence of hydroxypropylation on retrogradation properties of ...
Hydroxypropylation decreased the rate and extent of increase in turbidity during storage of native, defatted and heat-moisture treated starches.
[78]
Influence of heat–moisture treatment and annealing on functional ...
Annealing is the treatment of starch in excess water (40–60% w/w) at temperatures below the gelatinization temperature whereas heat–moisture treatment is done ...
[79]
(PDF) Physicochemical Properties of Enzymatically Modified Starch
Aug 6, 2025 · Common enzymes used in starch modification include α-amylase, β-amylase, glucoamylase, isoamylase, and pullulanase.
[80]
Effect of Crosslinking on Thermal and Microscopic Transitions of ...
Crosslinking delayed the gelatinization process (without decreasing total enthalpy) by restricting swelling and reducing the hydration of starch. No evidence of ...
[81]
Development of Freeze-Thaw Stable Starch through Enzymatic ...
Sep 25, 2021 · The use of unmodified starch in frozen foods can cause extremely undesirable textural changes after the freeze-thaw process.