Compositions comprising oleogels and methods of producing compositions comprising oleogels

Abstract

A composition is disclosed herein. The composition may comprise a mixture comprising an oleogel and a filler wherein the oleogel comprises a liquid or semi-solid fat composition and optionally a gelling agent. The filler may be in the form of solid particles.

Description

Technical Field

[0001] The present disclosure relates to a composition, a method of producing the composition, a food product, and uses of the composition.

[0002] Background

[0003] It is well known that saturated fats and hydrogenated fats, if consumed in large amounts, can lead to cardiovascular diseases, and thus people are looking for alternatives to saturated fats and hydrogenated fats for various food products. However, in certain food categories such as puff pastry, saturated fats such as butter are not necessarily easy to replace.

[0004] Oleogels are a very promising material for replacing saturated fats and hydrogenated fats, but due to their mechanical properties, they are generally not suitable for lamination during the preparation of dough for puff pastry.

[0005] Summary

[0006] This summary is provided to introduce some concepts in a simplified form that will be further described in the detailed description below. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0007] A composition is disclosed. The composition can comprise a mixture that includes an oleogel and a filler. The oleogel can comprise a liquid or semi-solid fat composition and optionally a gelling agent. The filler can be in the form of solid particles.

[0008] Brief Description of the Drawings

[0009] The drawings are included to assist in further understanding of the embodiments and form a part of this specification, which illustrate the embodiments and, together with the description, help to explain the principles. In the drawings:

[0010] Figure 1 . Visual appearance of oleogels containing increasing concentrations (2.5%, 5%, 10%, 20%, 30%, 40% and 50%) of cellulose crystals (Arbocel, Vivapur and DS-CNC). A plain oleogel (0% cellulose) is shown for reference.

[0011] Figure 2 . Micrographs of composite oleogels containing increasing concentrations (2.5%, 5%, 10%, 20% and 30%) of cellulose fillers (Arbocel, Vivapur and DS-CNC). A plain oleogel (0% cellulose) and cellulose dispersed in oil are shown for reference. White arrows indicate the presence of crystalline spherulites.

[0012] Figure 3 A, 3B, 3C, and 3D. Stress–strain curves of oleogels and dispersions containing cellulose (A) Arbocel, (B) Vivapur, and (C) DS-CNC. (D) Critical strain calculated from the stress–strain curves as a function of the cellulose amount.

[0013] Figure 4 A and 4B. (A) Recovery ratio as a function of cellulose concentration calculated from the complex modulus (G*) of composite oleogels using cellulose Arbocel, Vivapur, and DS-CNC. The rate constant (k) fitted according to the single correlation model (Equation 2) is shown in the table, and a statistical analysis of the estimated value (k) was performed (inset in Figure A). The data points in parentheses in Figure A were excluded from the regression analysis. (B) G* of the composite oleogels as a function of cellulose concentration. G* was calculated as the average of the initial four points except the first two points in the LVR. Inset in Figure B: Hyperbolic function fitting for the scaled cellulose concentration.

[0014] Figure 5 . Oil release relative to the oil weight of composite oleogels of cellulose Arbocel, Vivapur, and DS-CNC as a function of cellulose concentration compared to pure oleogels.

[0015] Figure 6 . Macroscopic appearance of croissants obtained using a laminating agent (top) 30% Vivapur composite oleogel, (middle) a mixture of 30% Vivapur composite oleogel and butter (ratio 2:1), and (bottom) butter.

[0016] Detailed Description

[0017] A composition is disclosed.

[0018] The composition can comprise a mixture that includes an oleogel and a filler. The oleogel can comprise a liquid or semi-solid fat composition and an optional gelling agent. The filler can be in the form of solid particles.

[0019] The composition can be considered a composite oleogel.

[0020] The composition can be used to replace a fat component, such as butter, margarine, or shortening, in the preparation of laminated puff pastries or other foods that typically may contain a large amount of saturated fat.

[0021] For example, compared to various oleogel compositions, the composition can have improved mechanical properties and can provide an improved structure to the foods in which it is used.

[0022] Compared to butter or other fat components that can be partially or fully replaced by the composition, the composition can also help provide a better nutritional profile for the food. For example, the composition and the resulting food can include more monounsaturated and polyunsaturated fats. Additionally, the filler can act as a source of fiber, such that the food can have an increased fiber content. Thus, the composition can result in an increased fiber content without adding other fibers to the dough (which may affect the taste of the food).

[0023] Meanwhile, the composition and the resulting food can have a desirable texture and / or taste.

[0024] The filler can be in the form of solid particles. In other words, the filler can be particulate filler. For example, the filler can be in the form of a powder or added to the composition in powder form. The filler can comprise or be, for example, fiber or in the form of fiber. The solid particles of the filler can be considered volume filling particles. However, the filler disclosed in this specification can also act as a reinforcing filler material.

[0025] The filler may not dissolve in the composition, i.e., it may be insoluble in the composition. Specifically, at least in some embodiments, even when the composition is heated, the filler may not dissolve in the composition. Thus, the solid particles can be inert particles that do not change, such as undergo a phase change, during the formation of the composition (i.e., when the liquid or semi-solid fat composition, gelling agent, and filler are mixed at a temperature above the melting point of the gelling agent). Additionally, at least in some embodiments, the solid particles can be such that they do not change, such as undergo a phase change or dissolve, when the composition and / or the food containing the composition (e.g., dough) are heated during food preparation.

[0026] The filler can be a bio-based filler.

[0027] The filler (e.g., polymers that can form the filler) can comprise or can be: cellulose, such as crystalline cellulose; resistant modified starch; xylan nanocrystals; chitin nanocrystals; starch, such as resistant starch; β-glucan; or any mixture or combination thereof.

[0028] The filler can be crystalline cellulose. Crystalline cellulose can comprise or can be cellulose microcrystals and / or nanocrystals. In other words, crystalline cellulose can comprise or can be microcrystalline cellulose and / or nanocrystalline cellulose. Crystalline cellulose is very suitable as a filler due to its strength, biodegradability, and abundance. It can also have adjustable surface chemistry and a large surface area, which can improve interfacial interactions.

[0029] The composition may contain from about 10 to about 50% (w / w), or 20% to 45% (w / w), or 30% to 40% (w / w) of a filler. However, certain fillers, such as certain fibers, may be included in the composition in lower amounts such that the composition may contain, for example, 0.5 to 1% (w / w) of the filler.

[0030] Generally, increasing the proportion and / or concentration of the filler can increase the stiffness and mechanical strength of the composition. Thus, it can increase the resistance to large deformations and / or shear forces and reduce the release of oil from the composition. This can make the composition well-suited for applications where large deformations are applied, such as lamination during puff pastry dough production. However, at high concentrations, the filler may make the composition brittle. The optimal proportion and / or concentration of the filler may also depend on the filler (e.g., surface composition, shape, particle size, and / or other considerations of the filler). A person skilled in the art is capable of selecting an appropriate filler concentration.

[0031] Gelling agents, such as monoglycerides, can form crystals. These crystals together with the filler form a microstructure. Without being bound by theory, the gelling agent crystals and the solid particles of the filler may interact in a complex manner, such as the filler affecting the organization of the gelling agent crystals in the composition. The solid particles can provide a solid matrix for the growth of the gelling agent crystals. Then, the gelling agent crystals can (at least partially) acquire the morphology of spherulites. Fillers, such as in the form of fibers, can serve as nucleation points for the growth of crystals of a gelling agent (such as monoglyceride) to start during the cooling process. The gelling agent crystals can continue to grow until they are interconnected. Thus, the gelling agent crystals can form a crystalline network in which the filler (such as fibers) is embedded.

[0032] The morphology of the composite network formed by the gelling agent crystals and the filler may depend on the filler concentration and / or shape. However, it can be observed using a microscope that at low filler concentrations, the gelling agent may form both spherulites and platelet-like crystals. At high filler concentrations, the network may be more crowded and blocked. In such a network, the gelling agent can have the role of connecting the filler particles in addition to gelling the oil.

[0033] Without a gelling agent, the system may be less stable. When the filler content is high enough (e.g., 20 - 40% (w / w)) and the composition is stored for a long enough time (e.g., 2 - 3 days or longer), the filler may precipitate and the oil may leak out of the composition. At low filler concentrations, the composition can be in a liquid state (similar to oil).

[0034] The composition may comprise from about 90 to about 50% (w / w) of an organogel. The proportion of the organogel may naturally depend, for example, on the proportion of the filler. Thus, the composition may comprise from about 80 to about 55% (w / w) of an organogel, or from about 60 to about 70% (w / w) of an organogel. The proportions of each and / or all of the components in the composition may be selected such that they add up to 100% (w / w). Of course, the composition may also comprise other components and / or additives.

[0035] The filler may be blended with the organogel.

[0036] There is no particular limitation on the shape and / or size of the solid particles. However, solid particles having a specific size may impart specific properties to the composition. For example, solid particles having an elongated shape may provide better composition performance than solid particles having a spherical shape.

[0037] The solid particles of the filler may have a specific shape. They may be produced to have a specific shape. For example, such solid particles of the filler may be formed from a polymer (e.g., any of the polymers described below) dissolved in water or a suitable solvent. They may be spray-dried or anti-solvent precipitated to obtain spherical / elongated particles. In the case of anti-solvent precipitation, they may subsequently be dried.

[0038] The average particle size of the solid particles may be in the range of 100 nm to 150 μm, or in the range of 10 to 100 μm.

[0039] The solid particles may have the shape of spheres and / or rods. Alternatively or additionally, the solid particles may be (at least substantially) in the shape of ellipsoids, cylinders, grain-shaped, granules, flakes and / or platelets. The solid particles may be in the form of various different shapes, i.e., a mixture of different shapes. The aspect ratio of the solid particles may be in the range of 1:1000000 to 1:1. At least in one embodiment, the aspect ratio may be considered as the ratio of the diameter (e.g., average diameter) of the solid particles to the length. In embodiments where the filler comprises fibers or is in the form of fibers, the aspect ratio of the fibers may be in the range of 1:1000000 to 1:1.

[0040] The average particle size, diameter and / or average diameter may be measured, for example, by sieve analysis (i.e., by using sieves), laser diffraction or microscopy. The average particle size and / or average diameter may be measured, for example, by standard ISO 13320:2009.

[0041] Therefore, the particle size of the filler can be selected or adjusted to be suitable. Before producing the composition, the filler can also be crushed, for example, ground. In this way, a filler with a certain size and / or average particle size can be obtained.

[0042] The filler can be dried before producing the composition. Drying can remove residual moisture and may have an impact on the structure and / or mechanical properties of the composition.

[0043] The liquid or semi-solid fat composition can comprise or can be: vegetable oils such as rapeseed oil, canola oil and / or palm oil; long-chain triacylglycerols; medium-chain triacylglycerols; short-chain triacylglycerols; or any combination or mixture thereof. However, other liquid or semi-solid fat compositions can also be considered.

[0044] The gelling agent can comprise or can be: monoglycerides, waxes, fatty acids, fatty alcohols, ethyl cellulose, or any mixture or combination thereof. For example, monoglycerides are very suitable as gelling agents. Specifically, a composition with desired properties can be obtained using crystalline cellulose as the filler and monoglycerides as the gelling agent. The term "monoglyceride" or "a monoglyceride" can be understood to refer to at least one monoglyceride, that is, it can also refer to a mixture of different monoglyceride molecules.

[0045] The oil gel and / or composition can comprise, for example, 50 to 99.5% (w / w) or 60 to 95% (w / w) of a liquid or semi-solid fat composition such as oil. The oil gel and / or composition can comprise, for example, 0.1 to 20% (w / w) or 2.5 to 15% (w / w) of a gelling agent.

[0046] The composition can be a semi-solid or solid composition. Therefore, the structure of the composition can be in such a form that although the fat in the composition can itself be included as a liquid or semi-solid fat composition, the composition can be in a semi-solid or solid form. For example, the composition can have a solidity similar to butter or margarine.

[0047] The composition can be stable or in the form of a stable gel. If no oil leakage is observed in the composition during storage for a period of time (e.g., at least one month) at, for example, room temperature or 4 °C, the composition can be considered stable.

[0048] The composition can have a complex modulus in the range of 0.1 - 1.1 MPa and / or a yield stress in the range of 0.07 - 6 kPa. The yield stress can be the yield stress measured during an oscillatory amplitude sweep at an angular frequency of 2 rad / s at room temperature. The yield stress can be measured, for example, as described in the examples. For comparison, a similar composition without filler (oil gel) can have a complex modulus of about 0.04 MPa and a yield stress of about 0.08 kPa.

[0049] A method of producing a composition according to one or more embodiments disclosed in this specification is disclosed. The method can include mixing a liquid or semi - solid fat composition, a gelling agent, and a filler at a temperature above the melting point of the gelling agent; and cooling the mixture to obtain the composition.

[0050] The filler can be added or mixed into the mixture of the liquid or semi - solid fat composition and the gelling agent before heating, during heating, or during the period when the mixture is maintained (and further stirred or otherwise mixed) at a temperature above the melting point of the gelling agent. In other words, in embodiments where the liquid or semi - solid fat composition and the gelling agent form an oil gel, the filler can be added when the mixture (oil gel) is molten or during its cooling. Thus, the filler can be added before and / or during the formation of the crystal structure of the oil gel. In other words, the filler can be added before the crystal structure of the oil gel is fully formed.

[0051] Oil gels are generally produced by mixing a gelling agent and a liquid or semi - solid fat composition at a temperature above the melting point of the gelling agent, and cooling the mixture to obtain the composition. In the method of the present invention, a filler can be included in the mixture. However, the filler does not melt or dissolve in the mixture but remains as solid particles.

[0052] Also disclosed is a composition obtainable by a method of producing a composition according to one or more embodiments disclosed in this specification.

[0053] However, there may be other methods of producing the composition and the oil gel.

[0054] Also disclosed herein are foods containing a composition according to one or more embodiments disclosed in this specification or prepared using the composition. The composition can contain the composition as a fat component or be used as a fat component to prepare the food. For example, in a food where butter can be used as a fat component, the butter can be at least partially or completely replaced by a composition according to one or more embodiments disclosed in this specification.

[0055] The food product can be a baked product such as a croissant, puff pastry or Danish pastry; a dough such as a laminated dough; a spread; ice cream; chocolate; or a meat or dairy analogue such as a cheese analogue.

[0056] A food product, such as a croissant, can contain up to 20% (w / w) or up to 15% (w / w) fat. It can contain up to 10% (w / w) or up to 5% (w / w) saturated fat. It can contain at least 5% (w / w) fibre.

[0057] For example, a typical croissant made with butter as the fat component can contain 21% (w / w) fat; 12% (w / w) saturated fat (57% of the total fat content); and 1.3% (w / w) fibre.

[0058] For example, a comparative croissant made using the composition described in this specification (which contains 30% (w / w) fibre as a filler) as a 100% replacement for butter can contain 14.5% (w / w) fat; 2% (w / w) saturated fat (16% (w / w) of the total fat); and 7.5% (w / w) fibre.

[0059] A comparative croissant using the composition described in this specification (which contains 40% (w / w) fibre as a filler) 100% replacing butter can contain 12% (w / w) fat; 2% (w / w) saturated fat (15% of the total fat content); and 9.6% (w / w) fibre.

[0060] The use of a composition according to one or more embodiments disclosed in this specification in dough lamination is also disclosed.

[0061] The use of a composition according to one or more embodiments disclosed in this specification in the preparation of a food product according to one or more embodiments disclosed in this specification is also disclosed.

[0062] A method of preparing a laminated dough is also disclosed. The method can include providing a dough and a composition according to one or more embodiments disclosed in this specification; disposing the composition on the dough so as to form a layered composition, the layered composition including a layer of the composition on a layer of the dough; and folding the layered composition on itself one or more times to form a laminated dough.

[0063] Methods of preparing laminated dough using, for example, butter rather than a composition according to one or more embodiments disclosed in this specification are well known in the art. Examples

[0064] Various embodiments will now be mentioned in detail, examples of which are shown in the accompanying drawings.

[0065] The following description discloses some embodiments in detail, such that those skilled in the art can utilize these embodiments based on the present disclosure. Not all steps or features of the embodiments are discussed in detail because many steps or features will be apparent to those skilled in the art based on this specification.

[0066] Example 1 - Size-Dependent Filling Effect of Crystalline Cellulose in the Structural Engineering of Composite Oleogels

[0067] Composite oleogels based on monoglycerides and filled with crystalline cellulose were developed. The function of the filler in the composite material matrix depends on the particle size, particle loading, and particle-matrix interfacial interactions. To study this effect, three types of cellulose crystals ranging from microscale to nanoscale were used as fillers in monoglyceride-based oleogels. The effect of gradually adding crystalline cellulose on the mechanical properties under small-amplitude and large-amplitude oscillatory strains was investigated. To understand the filler-matrix interaction, the microstructure and nanostructure of the composite oleogel network were studied using microscopy, synchrotron X-ray diffraction, and small-angle X-ray scattering techniques. Finally, the melting properties and oil-holding capacity of the composite oleogels were investigated.

[0068] The results showed that crystalline cellulose of different sizes can be used to design the structure of oleogels, thereby achieving tunable mechanical properties. Novel lipid-based functional composites with better mechanical properties can be obtained through cellulose microcrystals and nanocrystals in oleogels. Such materials can be used in applications such as fat substitutes, resulting in foods with a higher fiber content and richer nutrition.

[0069] Materials

[0070] The dry microcrystalline celluloses Arbocel M80 (bulk density 0.20 - 0.24) and Vivapur 105 (maximum bulk density 0.26) were kindly provided by JRS Pharma Oy (Nastola, Finland). The desulfonated cellulose nanocrystal (DS-CNC) slurry was purchased from Cellulose Lab (Fredericton, Canada). The slurry was freeze-dried and then ground for 1 minute using a Siebtechnik Tema vibratory mill (Rijswijk, the Netherlands) equipped with concentric stainless steel disks. The average particle size of the crystalline cellulose decreased in the following order (data provided by the manufacturer): Arbocel (55 μm), Vivapur (15 μm), and DS-CNC (width 10 - 20 nm, length 50 - 400 nm). All celluloses were dried in a vacuum oven at 30 - 40 °C for 5 days before use. Myverol 18-04K saturated monoglyceride (fatty acid composition: 42 - 48%, C16:0, 50 - 60% C18:0; melting point 68.05 ± 0.5 °C) was donated by Kerry Ingredients and Flavours (Bristol, UK). Rapeseed oil from Raisio was purchased from a local supermarket. Isobutanol was purchased from Merck KGaA (Darmstadt, Germany).

[0071] Oil gel preparation

[0072] First, an oil gel containing monoglyceride was prepared by mixing 5% monoglyceride with rapeseed oil at 80 °C for at least 10 minutes. Then the molten mixture was blended with increasing weight fractions (0, 2.5, 5, 10, 20, 30, 40, and 50%) of crystalline cellulose (Arbocel, Vivapur, or DS-CNC). The blends were mixed at 80 °C for at least 10 minutes using a magnetic stirrer (or a spatula for samples containing 40% and 50% crystalline cellulose). Then the samples were poured into containers for further analysis and crystallized by immersing the containers in a 20 °C water bath (10 - 20 minutes). The samples were stored overnight at room temperature before analysis. A dispersion of cellulose was prepared by mixing 40% cellulose in rapeseed oil at room temperature. All concentrations are expressed as mass percentages (% w / w).

[0073] Macroscopic photographs

[0074] Aliquots of the oil gels were placed on a black cardboard base and imaged using a 12 MP camera with an f / 2.2 aperture. The photographs were taken in a photographic cabinet under a D65 light source.

[0075] Rheology

[0076] Large amplitude oscillatory shear (LAOS) and small amplitude oscillatory shear (SAOS) measurements were carried out on a Discovery HR-2 hybrid rheometer (TA Instruments, Delaware, USA) with a 20 mm parallel plate geometry. Sandpaper with an average particle size of 600 was adhered to both plates to prevent the sample from sliding during the measurement. The sample was carefully placed between the plates with a gap of 3 - 3.5 mm. Before the measurement, the axial force was stabilized for 2 - 3 minutes. For LAOS and SAOS measurements, oscillatory strains of 0.001 - 1000% and 0.001 - 100% were applied respectively, with an angular frequency of 2 rad / s. To study the recovery of the organogel, two amplitude sweeps were recorded during the SAOS measurement. First, an oscillatory strain of 0.001 - 100% was applied, then left to stand for 5 minutes, and a second sweep was performed on the same sample with an oscillatory strain of 0.001 - 100%. All measurements were carried out at 22 °C. The measurement data were collected in transient mode through Trios software 5.1 (TA Instruments). The sampling time was 8 cycles of a sine wave, with 191.75 points per cycle. The yield stress and critical strain % were calculated as the intersection of two straight lines in the stress - strain curve (Dinkgreve et al., 2016, Journal of Non - Newtonian Fluid Mechanics, 238, 233 - 241, https: / / doi.org / 10.1016 / j.jnnfm.2016.11.001). The analysis of the LAOS response was carried out according to Macias - Rodriguez et al., 2018, Rheologica Acta, https: / / doi.org / 10.1007 / s00397 - 018 - 1072 - 1.

[0077] The recovery ratio (R r ) of the organogel sample was calculated using the following equation:

[0078]

[0079] where G * 1 and G * 2 are the average complex moduli of the first and second amplitude sweeps in the viscoelastic region respectively.

[0080] The relationship between the recovery ratio and the cellulose concentration was fitted using a single correlation model:

[0081] R r = R r0 +(P - R r0 )·(1 - e -k·C ) (Equation 2)

[0082] where R r0 is the theoretical recovery ratio of the neat oil gel (set to 0.6339), P is the plateau value, i.e., the maximum theoretical recovery ratio (equal to 1 in this case), k is the rate constant, and C is the cellulose concentration, expressed as a weight percentage relative to the total weight of the composite oil gel.

[0083] The complex modulus G is fitted as a function of cellulose concentration using the Krieger-Dougherty type equation (Krieger and Dougherty, 1959, Transactions of the Society of Rheology, 3, 137 - 152, https: / / doi.org / 10.1122 / 1.548848): * as a function of cellulose concentration:

[0084]

[0085] where G * 0 is the complex modulus at 0% cellulose concentration, C max is the maximum mass cellulose concentration (the vertical asymptote of the hyperbolic function), and n is the fitting constant. For further data analysis, the cellulose concentration is divided by a scaling factor that is arbitrarily chosen to be positively correlated with the cellulose particle size and is set to Arbocel = 1; Vivapur = 1.08; DS-CNC = 2.7.

[0086] The recovery ratio and G (both as functions of cellulose concentration) are fitted using TableCurve 2D version 5.01 (Jandel Scientific Software, San Rafael, CA, USA). A non-linear regression analysis is performed. The least-squares function minimization is carried out using the Levenberg-Marquardt algorithm. The goodness of fit is evaluated based on the fitting statistical parameters (R * , p, standard error) and residual analysis. 2

[0087] Polarizing microscopy

[0088] The microstructure of the oil gels is analyzed using an Axio Lab A1 polarizing microscope (Zeiss, Oberkochen, Germany) connected to an Axiocam 305 color microscope (Zeiss). An aliquot of the sample is placed in the middle of a glass slide, and a glass coverslip is placed over the sample in the center and gently pressed. The sample is analyzed using a 20x objective lens at room temperature. Images are acquired and processed using the application software ZEN 2.6 (Zeiss). The images are saved in tiff format, 2464 × 2056 pixels.

[0089] Accelerated oil release test

[0090] Pour approximately 1.2 - 1.3 mL of the molten sample into a 1.5 - mL microtube (Eppendorf, Hamburg, Germany) and cool it in a water bath at 20 °C for 10 minutes. After leaving it overnight at room temperature, centrifuge the sample at 17000 rpm (27464×g) for 30 minutes using a temperature - controlled SL 8R centrifuge (Thermo Scientific, Osterode am Harz, Germany) set at 20 °C. Preliminary tests confirmed that multiple centrifugations do not raise the temperature of the sample, which remains at 21 ± 1 °C. Immediately invert the Eppendorf tube after centrifugation and drain the oil for 5 minutes. Then remove the residual oil with absorbent paper. Calculate the released oil as the percentage of the mass of the expressed oil relative to the total mass of the sample or the total mass of the oil contained in the oleogel.

[0091] Data analysis

[0092] Unless otherwise specified, all determination results are expressed as the mean ± standard deviation of at least two measurements (n ≥ 2×2) from two experimental replicates. Statistical analysis was performed using R software version 3.5.1. The Bartlett's test was used to evaluate the homogeneity of variances. One - way ANOVA was performed and the Tukey's test was used as a post - hoc test to determine significant differences between the means (p < 0.05).

[0093] Macroscopic, microscopic, and nanostructures of oleogels

[0094] The monoglyceride - based oleogels presented as soft, semi - solid, spreadable lipid materials ( Figure 1 , pure oleogels). After adding cellulose particles, composite oleogels with seemingly higher opacity were obtained. Gradual addition of cellulose turned the oleogel into a moldable material (20% to 40% Arbocel or Vivapur, or 30% to 50% DS - CNC), and finally into a brittle material (50% Arbocel or Vivapur)( Figure 1) This indicates that the size and concentration of the filler affect the overall structure of the oleogel. As a result, microcrystalline cellulose Arbocel and Vivapur exhibit better structuring ability at lower concentrations than DS-CNC. Composite oleogels obtained with the largest and smallest sized celluloses (Arbocel at 40% concentration and DS-CNC at above 10% concentration) were granular, while the composite oleogels containing Vivapur appeared smooth at all concentrations studied. Without monoglyceride, even 40% cellulose could not produce a stable gel. The dispersion of cellulose and oil separated over time (data not shown), indicating the synergistic effect of monoglyceride and cellulose in oil structuring.

[0095] Microscopic analysis was carried out to understand the effect of cellulose particles on the microstructure of the oleogel. Figure 2 Polarized light micrographs of pure oleogel, microcrystalline and nanocrystalline cellulose dispersed in oil, and composite oleogels with increasing weight fractions of Arbocel, Vivapur, and DS-CNC are shown. Arbocel and Vivapur in oil appear as elongated fibers, with the first being longer than the second. On the other hand, DS-CNC in oil appears as spherical aggregates; most of them are smaller compared to Arbocel and Vivapur. Thus, the total interfacial area increases relatively in the order of Arbocel, Vivapur, and DS-CNC. The pure oleogel consists of monoglyceride microcrystals in the form of platelet-like interconnected sizes between 10 and 50 μm. When cellulose is added to the oleogel at any concentration, the morphology of the monoglyceride crystals changes from a platelet-like structure to a spherulitic structure, with sizes of 100 - 200 μm at lower cellulose weight fractions ( Figure 2 white arrows in). As the amount of cellulose increases, a gradually blocked microstructure of cellulose and monoglyceride crystals is observed. At the same cellulose weight fraction, the blocking phenomenon in the oleogel with nanocrystalline cellulose (DS-CNC) is less obvious. Increasing the cellulose concentration to 40% and 50% results in a very dense microstructure (data not shown).

[0096] The change in the microstructure of monoglyceride crystals observed after adding cellulose can be attributed to its role as a nucleation site during monoglyceride crystallization. The presence of particles or foreign substances is known to change the morphology of lipid crystals. If the foreign substance can be wetted by the crystallizing molecules, heterogeneous nucleation occurs as the energy barrier for forming stable nuclei decreases. Due to the affinity between cellulose and monoglyceride, crystallization can start from the surface of cellulose microcrystals and nanocrystals.

[0097] Rheological properties and oil holding capacity

[0098] The rheological properties of neat oil gels and composite oil gels formed from all three celluloses at different concentrations were evaluated. The oil gels exhibited gel-like behavior, i.e., G′>G″ for all systems studied (data not shown), and a yield stress σ y , which was regarded as the maximum "peak stress" beyond which flow was induced. The addition of all cellulose fillers increased the stiffness of the composite oil gels, which was manifested as an increase in modulus and yield stress from approximately 10 2 to 10 4 Pa, depending on their weight fractions ( Figure 3 A to 3D). The order of reinforcement was Arbocel>Vivapur>DS-CNC, which was inversely proportional to their relative interfacial areas. As the filler concentration increased, the composite oil gels became more brittle because G * = σ / γ. In most cases, stable flow was not obtained when the strain value > 100%. To further explore these effects, oscillatory tests were conducted to measure the residual elasticity after induced flow, which was simplified to the relative "recovery" ratio (Equations 1 and 2)( Figure 4 A), and the complex modulus G * was scaled as a function of the weight fraction (Equation 3)( Figure 4 B). It was observed that cellulose retained the elasticity of the oil gels, and microcrystalline celluloses Arbocel and Vivapur were superior to nanocrystalline cellulose (DS-CNC) at higher weight fractions. This was also observable in the higher rate constant (k) values obtained from fitting the recovery ratio using a single correlation model ( Figure 5 A, inset). A possible explanation is that larger particles occupy a greater volume and protect the neat oil gel network from damage compared to smaller particles of the same weight fraction. Scaling the modulus revealed that, based on weight fraction, microcrystalline cellulose was a more effective structuring agent than nanocrystalline cellulose ( Figure 4 B). This could be seen from the strong "jump" in the complex modulus and yield stress of the microcrystalline-based composites at 40% concentration when the filler approached the maximum packing fraction of the solid. Nonlinear local measurements of elasticity and viscosity elucidated by Lissajous curves (data not shown) did not show differences between the fillers, providing conclusive evidence that cellulose-based fillers act as particulate rigid fillers.

[0099] The oil gel network had poor resistance to retaining a large amount of incorporated oil under high shear conditions, which greatly limited the application of oil gels. Therefore, the oil retention capacity measured in an accelerated oil release test by centrifuging the samples showed a dependence on the concentration and size of the cellulose particles. The neat oil gel with a monoglyceride crystal network released approximately 25% of the oil(Figure 5 )。When the cellulose weight fraction is below 30%, regardless of the cellulose size, the amount of oil released by the composite organogel is higher than that of the pure organogel. When the concentration exceeds 30%, the effect of microcrystalline cellulose (Arbocel and Vivapur) depends on the cellulose size, and less oil is released compared to DS-CNC and the pure organogel.

[0100] The addition of filler particles may increase defects or change the tortuous path in the gel-particle medium, thus facilitating the escape of oil from the matrix at low concentrations. As the cellulose concentration increases to the maximum packing fraction in the composite system, the escape of oil decreases due to the increase in tortuosity. The decrease in oil release is also attributed to the increase in surface tension above the clogging points, which is caused by geometric constraints and reduces the fluidity of the system, changing from an "over-wet" to a "dry-like" appearance. Compared to the platelet-like crystals observed in the pure organogel, the spherulites observed in the composite organogel have a lower structuring ability. The lower oil retention capacity of the composite organogel contradicts the strong mechanical properties observed in the previous section. It should be noted that for the oil release test, an aliquot of the molten organogel was directly cooled in an Eppendorf tube and centrifuged to observe the oil release, avoiding sample transfer as in the rheological measurement process. Therefore, the observed oil release data may be overestimated and most favorable for the pure organogel.

[0101] The above results demonstrate the size-dependent role of crystalline cellulose in the structural enhancement of monoglyceride-based organogels. Cellulose particles are inactive fillers in the composite organogel, provide a solid matrix for the growth of monoglyceride crystals, and enable better assembly of monoglyceride molecules. This effect is obvious in organogels containing microcrystalline cellulose particles. At the microstructural level, the crystal morphology of monoglyceride changes from a platelet-like structure to spherulites. There is no obvious change in the thermal properties of the organogel. Crystalline cellulose improves the mechanical properties and elastic recovery of the organogel, and this effect depends on size and concentration. At a given weight fraction in the composite system, microcrystalline cellulose Arbocel and Vivapur exhibit better structuring ability than nanocrystalline cellulose DS-CNC. The observed effect can be interpreted as due to the clogged microstructure of cellulose particles and monoglyceride crystals, and for microcrystalline cellulose, this clogged microstructure is obvious when it exceeds 30%. The observed effect also applies to the oil retention capacity of the composite organogel during the accelerated oil release test. Less oil is released from the clogged structure of microcrystalline cellulose above 30%.

[0102] Example 2

[0103] Croissant preparation

[0104] The composite oil gel containing 30% Vivapur was tested as a laminating agent in croissants. Three types of croissants were prepared using butter, the oil gel, and a 1:3 ratio of butter and the oil gel as the laminating agent. First, the croissant dough was prepared by placing 500 g of special wheat flour ( Myllyn Paras, Finland), 55 g of edible sugar, 40 g of unsalted butter, and 12 g of salt in a kneading bowl at low speed. 11 g of dry instant yeast was mixed with 140 g of tap water and 140 g of refrigerated whole milk with 3% fat and added to the mixture. The ingredients were mixed at low speed for 4 minutes. The dough was divided into three equal parts, spread on a floured parchment paper, and placed in the freezer for 30 minutes. 93.3 g of the shortening (butter, the oil gel, or a mixture of butter and the oil gel) was rolled into the dough, and the dough was given three single folds with a 30-minute interval between each fold. The dough was rolled into a thin sheet and given one three-layer fold. The dough was placed in a 4-degree refrigerator and chilled for 15 minutes. This step was repeated twice. The dough was rolled into a 60 * 100 cm rectangle with a thickness of approximately 3 mm. The dough was cut into 20-cm-long strips along the length direction, and then the strips were divided into triangles. A 2-cm small incision was made in the center of the top of the triangle, and then it was rolled into a tight roll while stretching the dough. The croissants were placed on parchment paper, brushed with egg wash twice, proofed, and baked at 220 degrees Celsius for 20 - 30 minutes.

[0105] Croissant

[0106] The composite oil gel (30% Vivapur) gives the croissant a more uniform and better-leavened structure, and it has a lower greasiness than the croissant using only butter as the shortening ( Figure 6 ).

[0107] It is obvious to those skilled in the art that with the progress of technology, this basic idea can be implemented in various ways. Therefore, the embodiments are not limited to the above examples; on the contrary, they can vary within the scope of the claims.

[0108] The foregoing embodiments may be used in any combination with each other. A number of embodiments may be combined together to form further embodiments. The methods, products or uses disclosed herein may include at least one of the foregoing embodiments. It should be understood that the above benefits and advantages may relate to one embodiment or may relate to a number of embodiments. Embodiments are not limited to those that solve any or all of the stated problems or have any or all of the stated benefits and advantages. It should also be understood that a reference to "one" item means one or more of these items. The term "comprising" as used in this specification means including the features or acts that follow, but does not exclude the presence of one or more additional features or acts.

Claims

1. A composition comprising a mixture, said mixture comprising an oleogel and a filler, wherein said oleogel comprises a liquid or semi-solid fat composition and an optional gelling agent, and wherein said filler is in the form of solid particles.

2. The composition according to claim 1, wherein said filler comprises or is: cellulose, such as crystalline cellulose; resistant modified starch; xylan nanocrystals; chitin nanocrystals; starch, such as resistant starch; β-glucan; or any mixture or combination thereof.

3. The composition according to claim 1 or 2, wherein the composition comprises from about 10 to about 50% (w / w), or 20% to 45% (w / w), or 30% to 40% (w / w) of the filler.

4. The composition according to any one of claims 1-3, wherein said filler is blended with said oleogel.

5. The composition according to any one of claims 1-4, wherein the average particle size of said solid particles is in the range of 100 nm to 150 μm, or in the range of 10 to 100 μm.

6. The composition according to any one of claims 1-5, wherein the aspect ratio of said solid particles is in the range of 1:1000000 to 1:

1.

7. The composition according to any one of claims 1-6, wherein said liquid or semi-solid fat composition comprises or is: vegetable oil, such as rapeseed oil, canola oil and / or palm oil; long-chain triacylglycerols; medium-chain triacylglycerols; short-chain triacylglycerols; or any combination or mixture thereof.

8. The composition according to any one of claims 1-7, wherein said gelling agent comprises or is: monoglycerides, waxes, fatty acids, fatty alcohols, ethyl cellulose, or any mixture or combination thereof.

9. The composition according to any one of claims 1-8, wherein the composition is a semi-solid or solid composition.

10. The composition according to any one of claims 1-9, wherein the composition is a composite oleogel.

11. The composition according to any one of claims 1-10, wherein the composition has a complex modulus in the range of 0.1–1.1 MPa and / or a yield stress in the range of 0.07-6 kPa.

12. A food product comprising the composition according to any one of claims 1-11, or prepared using the composition according to any one of claims 1-11.

13. The food product according to claim 12, wherein the food product is a baked product, such as a croissant, puff pastry or Danish pastry; dough, such as laminated dough; spread; ice cream; chocolate; or a meat or dairy analogue, such as a cheese imitation.

14. A method of producing the composition according to any one of claims 1-11, wherein the method comprises mixing a liquid or semi-solid fat composition, a gelling agent and a filler at a temperature above the melting point of the gelling agent; and cooling the mixture to obtain the composition.

15. Use of the composition according to any one of claims 1-11 in dough lamination.

16. A method of preparing a laminated dough, the method comprising providing a dough and a composition according to any one of claims 1-11; disposing the composition on the dough so as to form a layered composition, the layered composition comprising a composition layer located on a dough layer; and folding the layered composition once or more than once on itself to form a laminated dough.

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