BR102019027238A2 - COMPOSITION OF ORGANOGELS/OILS BASED ON COMBINATIONS OF WAXES AND VEGETABLE OILS - Google Patents

Abstract

composition of organogels/oilgels based on combinations of waxes and vegetable oils. The present invention relates to a composition of waxes with high, medium or low melting point and structuring agents in vegetable oils for the synthesis of oleogels/organogels. the present invention is inserted in the food sector, more specifically, with application as a raw material in food products (bakery products; shortenings; fillings; meat products, among others) resulting in a product with improved nutritional quality. moreover, oilgel can be a framework for the design of derived structures such as gelled emulsions, hybrid gels (mixture of oilgel with hydrogel) among others.

Description

COMPOSITION OF ORGANOGELS/OILS BASED ON COMBINATIONS OF WAXES AND VEGETABLE OILS field of invention

[1] The present invention relates to a composition of waxes combined with a structuring agent in vegetable oils for the synthesis of oleogels/organogels.

[2] The present invention is inserted in the food sector, more specifically, with application as a raw material in food products (bakery products; shortenings; fillings; meat products, among others) resulting in a product with improved nutritional quality. Furthermore, oilgel can be a framework for the design of derived structures such as gelled emulsions, hybrid gels (mixture of oilgel with hydrogel) among others.

Fundamentals of Invention

[3] Oleogels or organogels are promising systems in the food field and have been investigated in recent years. However, most systems have their composition defined in a random and empirical way. The merit of this proposal is the composition/formulation responsible for the unexpected effect, for example, in the case of positive interaction between structuring agents derived from fatty acids and waxes (mainly with high melting point) which in this case provide a system with interesting rheological and structural characteristics and better than using these components separately. The identification of this combination capable of promoting an improvement in the mechanical characteristics of the gel may be interesting from the point of view of using smaller amounts of oleogelator and reducing the waxy mouthfeel in the system.

[4] The present patent arises in response to the demand for products with new formats, with reduced or free trans fat content, with low levels of saturated lipids and greater amounts of mono and/or polyunsaturated fatty acids, capable of providing functionalities structural aspects of food products still giving nutritional appeal to them.

[5] Most of the formulations capable of forming oilgel are still defined empirically. After a process of inventive activity that began a few years ago, seeking to understand the science behind the gelation mechanisms in oil, it is understood that it is possible to rationalize the formation of oleogels by balancing mixtures of structuring agents by manipulating the type and proportion of wax in the composition. To this end, it is proposed mixtures between i) oleogelator "a" (for example those derived from fatty acids) and ii) waxes with high, medium or low melting points depending on the nature of the oleogelator "a" in order to provide positive interactions between these components eventually reducing the proportion of waxes resulting in the reduction of waxy mouthfeel.

[6] The use of ingredients with partial solubility in oil (oleogelators or structuring agents), which precipitate leading to the formation of a three-dimensional network capable of trapping the liquid phase and producing systems known as organogels or oleogels. The competence of oleogels to mimic the mechanical properties of solid fat opens up opportunities to develop new systems with nutritional and technological functionality appeal. These systems appear as an alternative to the conventional structuring of oils, commonly represented by systems with a high content of trans or saturated fat. Given the promising character of oleogels, studies have been carried out in the food grade scope, however, the identification of efficient structuring agents is still a challenge, since the structuring mechanisms and the combination of compatible ingredients (oil type and type structuring agent) are sciences not fully elucidated. In this proposal a multicomponent approach is presented.

[7] The advantage obtained is the elaboration of a composition responsible for an unexpected synergistic effect, in this case, a positive interaction between structuring agents such as those derived from fatty acids and waxes that provide a system with interesting rheological and structural characteristics and better than the separate use of these components. The identification of this combination capable of promoting an improvement in the mechanical characteristics of the gel may be interesting from the point of view of using smaller amounts of oleogelator.

[8] WO2018011226 refers to a composition in the form of an organogel containing an organic liquid and a structuring agent. The organic liquid is described as belonging to the group of vegetable oils. The structuring agent is disclosed as belonging to the group of vegetable, animal or fatty acid derivatives. Vegetable waxes, as claimed, also include a wide range of possibilities, such as sunflower wax, carnauba, among others. The percentage of structuring agent in the organogel, by mass, is 30%. It also refers to the gelling of a volatile organic liquid and at least one acidic resin in order to control and reduce the evaporation of the volatile organic liquid. In this way, the invention of the document makes use of materials that are not necessarily food-grade, since the use in cosmetics, perfumery or agricultural products is foreseen in the application part, in addition to the high amount of gelators that is not desirable in foods and increase the cost of formulation. Differently, the present invention is based on the structuring of long-chain liquid vegetable oils aimed at modulating texture in food systems. The inventors further demonstrate that the addition of resins in small portions to gel volatile organic solvents reduces their evaporation at room temperature. Therefore, it is understood that its use is associated with the gelation of volatile oils to reduce their volatility, which is different from the present invention.

[9] Patent application US20170319698 provides a gastric retentive gel composition comprising: (a) a hydrophobic or amphiphilic liquid gelled with an organogelator; (b) an active agent; and (c) a hard wax or wax-like additive, for controlled administration of the active agent to or through the upper gastrointestinal tract, in particular into or through the stomach. The gel composition forms a stable, floating and coherent material in the gastric environment and is not directly expelled from the stomach as a result of gastric emptying. The active agent is released from the composition in a controlled manner for absorption or local action. The document discloses a gastric retentive gel composition comprising a hydrophobic or amphiphilic liquid with an organogelator, an active agent and a wax or waxy additive. Glycerol monostearate is mentioned in the claims among the possibilities of wax additive and wax, as well as the group of synthetic or natural waxes. The inventors reveal that the addition of wax or wax additive, selected among triacylglycerides, mono and diglycerides, natural or synthetic waxes, fatty alcohols, fatty acids, alcohol esters and fatty acids, in the gel composition maintains the composition's integrity and allows greater homogeneity. That is, the action of these components was described as beneficial to the stability of the oil gel and plays a fundamental role in maintaining the integrity of the composition in the aqueous environment, being a barrier resistant to fluid.

[10] In contrast, the present invention outlines in a more systematic way the type of combination of structuring agents, in the case of vegetable and animal waxes (grouped according to the melting point) and a second component, to achieve desirable rheological properties. In the related document, the ingredients are defined by the issue of protection of the digestive environment, and not by the structural issue that can be built, as is the focus of the proposed invention.

[11] Patent document KR20190011351 refers to the process of formation of an oleogel, which consists of adding natural wax to vegetable oil, followed by heating and stirring until dissolution and cooling at room temperature. The solid oleogel obtained is further heated to a liquid state and used as a frying oil for food products. However, the oleogel would be composed only of an oleogelator, in this case waxes. Furthermore, this system is not mainly exploited as a texture agent but for other uses (frying oil) aiming at lower lipid rancidity. In addition, the document does not mention the multicomponent composition of the structuring agents for the formation of oil gels.

[12] In contrast, the present invention is characterized by a combination of oleogelators to improve the performance of oleogels as agents capable of promoting texture in order to replace semi-solid fats.

[13] The scientific article by Hwang et al (2013) entitled "Margarine from Organogels of Plant Wax and Soybean Oil" reveals the obtainment of organogels from vegetable wax (sunflower, rice and candelilla) and soybean oil, which were tested for suitability for incorporation into margarine. Sunflower wax, rice bran wax and candelilla wax were evaluated. The results demonstrate that the oilgel formed from soybean oil and sunflower wax obtained the best firmness, similar to that of a margarine containing 18 to 30% hydrogenated soybean oil. That is, the organogel formed would have the potential to replace hydrogenated oils, meeting the demand for products free of trans fats and greater nutritional value. In contrast, the present invention envisages the use of blends to achieve specific properties desired for oil gels in a multi-component approach, which differs these two documents. It also foresees the application of a strategy based on the mixture of structuring agents (ingredient engineering) to mimic the complex structure of solid fats. In this low, medium and high melting point waxes are combined with a second component to set desirable characteristics for the purpose of producing texture modifying agents. Therefore, the proposed invention would open up the opportunity of designing several structured systems for different applications.

Brief description of the invention

[14] The present invention relates to a composition of waxes combined with a structuring agent in vegetable oils for the synthesis of oleogels/organogels.

• - agente estruturante que pode ser ceras de alto (cera de girassol e carnaúba), médio (cera de abelha e candelila) e baixo ponto de fusão (cera de berry e fruta) com um segundo agente estruturante (derivados de ácidos graxos ou fosfolipídeos), onde a concentração total da mistura é de 0,1-15% (base mássica) sendo que a mistura pode conter de 0,199,9% de cera (base mássica) e 0,1-99,9% segundo agente estruturante (base mássica) cuja soma destes não ultrapasse os 15% na mistura total do sistema; e
• - óleos vegetais compostos por ácidos graxos mono e/ou poliinsaturados (óleo de girassol, óleo de girassol alto oleico, óleo de linhaça, óleo de milho, óleo de soja, óleo de canola, azeite de oliva) que devem apresentar-se em no mínimo 85% (base mássica) da composição do sistema gel.

[15] The composition is of high, medium or low melting point waxes and a second structuring agent in vegetable oils for the synthesis of oleogels/organogels and comprises the following components:

• - structuring agent which can be high (sunflower and carnauba wax), medium (beeswax and candelila) and low melting waxes (berry and fruit wax) with a second structuring agent (derived from fatty acids or phospholipids) , where the total concentration of the mixture is 0.1-15% (mass basis) and the mixture may contain 0.199.9% wax (mass basis) and 0.1-99.9% according to the structuring agent (base mass) whose sum does not exceed 15% of the total mixture of the system; and
• - vegetable oils composed of mono and/or polyunsaturated fatty acids (sunflower oil, high oleic sunflower oil, linseed oil, corn oil, soybean oil, canola oil, olive oil) which must be presented in the no. minimum 85% (mass basis) of the composition of the gel system.

Brief description of the figures

[16] Figure 1 shows the Deformation Scan (items a and c) and Frequency Scan (items b and d) for GMS and SHW-based oils at 5 °C (images a and b) or 25 °C (images c and d). Filled symbols refer to the elastic modulus (G') and empty symbols indicate the viscous modulus (G"). GMS0:100SHW (♦); GMS25:75SHW (▲);GMS50:50SHW (●); and GMS50:50SHW (); and GMS50:50SHW (); ■).

[17] Figure 2 shows the polarized light microscopy of multicomponent oil gels with a total concentration of 6% oleogelator (mass basis). Images referring to samples GMS25:75SHW at 5 °C (a); GMS25:75SHW at 25°C (b); GMS50:50SHW at 5 °C (c); GMS50:50SHW at 25°C (d); GMS75:25SHW at 5°C (e) and GMS75:25SHW at 25°C (f).

Detailed description of the invention

[18] The present invention relates to a composition of waxes combined with structuring agents in vegetable oils for the synthesis of oleogels/organogels.

• - agente estruturante que pode ser ceras de alto, médio e baixo ponto de fusão com um segundo agente estruturante (como por exemplo derivados de ácidos graxos ou fosfolipídeos) onde a concentração total da mistura pode abranger de 0-15% (base mássica), sendo que a mistura pode conter diferentes razão de ceras (0,1-99,9% base mássica) e do segundo agente estruturante (0,1-99,9% base mássica) cuja soma destes não ultrapasse os 15% na mistura total do sistema; e
• - óleos vegetais compostos por ácidos graxos mono e/ou poliinsaturados (óleo de girassol, óleo de girassol alto oleico, óleo de linhaça, óleo de milho, óleo de soja, óleo de canola, azeite de oliva) que devem apresentar-se em no mínimo 85% (base mássica) da composição do sistema gel.

[19] The composition of high, medium or low melting point waxes and structuring agents in vegetable oils for oleogel/organogel synthesis comprises the following components:

• - structuring agent which can be high, medium and low melting point waxes with a second structuring agent (such as fatty acid derivatives or phospholipids) where the total concentration of the mixture can range from 0-15% (mass basis), the mixture may contain different ratios of waxes (0.1-99.9% by weight) and the second structuring agent (0.1-99.9% by weight) whose sum does not exceed 15% in the total mixture of the system; and
• - vegetable oils composed of mono and/or polyunsaturated fatty acids (sunflower oil, high oleic sunflower oil, linseed oil, corn oil, soybean oil, canola oil, olive oil) which must be presented in the no. minimum 85% (mass basis) of the composition of the gel system.

• i) pesar o(s) agente(s)estruturante(s) de acordo com as devidas proporções nas respectivas combinações;
• ii) adicionar o óleo vegetal cuja proporção é de no mínimo 85 % (base mássica);
• iii) aquecer a mistura (oleogelators e o óleo), sob agitação, acima do ponto de fusão dos agentes estruturantes até completa homogeneização do sistema; e
• iv) resfriar a mistura a pelo menos a temperatura ambiente, para posterior armazenamento da amostra. Desta maneira, uma rede cristalina é estabelecida formando-se um sistema semi-sólido que apresenta textura dependente da composição. O armazenamento em condições controladas de temperatura (refrigeração ou ambiente) leva à formação de géis com propriedades mecânicas específicas. Logo, a estruturação ocorre pelo estabelecimento de redes cristalinas fortalecidas por eventuais interações positivas decorrentes de diferentes combinações de oleogelators.

[20] The process for obtaining the composition comprises the following steps:

• i) weigh the structuring agent(s) according to the appropriate proportions in the respective combinations;
• ii) add vegetable oil whose proportion is at least 85% (mass basis);
• iii) heat the mixture (oleogelators and the oil), under stirring, above the melting point of the structuring agents until complete homogenization of the system; and
• iv) cool the mixture to at least room temperature for later sample storage. In this way, a crystal lattice is established, forming a semi-solid system that presents a composition-dependent texture. Storage under controlled temperature conditions (refrigeration or ambient) leads to the formation of gels with specific mechanical properties. Therefore, structuring occurs through the establishment of crystalline networks strengthened by possible positive interactions arising from different combinations of oleogelators.

Letras minúsculas diferentes significam diferença estatística entre as diferentes formulações de cera e do segundo agente estruturante a 5 ou 25 ° C. Letras maiúsculas diferentes significam diferença estatística para cada formulação em diferentes temperaturas.
Tabela 2. Exemplos de combinações positivas para desenvolvimento de oleogel multicomponente

* Concentração total de ol _eogelator variando de 1-15% (massa)[21] The formation of mixed oil gels (understood more than one structuring component) with optimized technological function will occur through the appropriate combination of high, medium and low melting point waxes with a second structuring agent (such as for example , glycerol monostearate or phospholipids) for structuring vegetable oils composed of mono and/or polyunsaturated fatty acids. For example, hydrolyzed sunflower wax (SHW) when combined with glycerol monostearate (GMS) in linseed oil (FXO) results in a positive interaction, since both structuring agents by themselves are not able to provide structure in FXO at 25°C. Interestingly, gel formation was promoted even with a small addition of GMS, although the most suitable ingredient ratio varies from 0.1 to 99.9% on a mass basis, with a more elastic and dense network, as well as cohesion of the crystal with high liquid oil holding capacity. As shown in Figure 1, the rheological properties of mixed oils were superior in terms of elastic property (higher elastic modulus values) compared to single-component gels at either 5 or 25 °C. The high oil holding capacity of gels is shown in Table 1.
Table 1. Oil holding capacity (%) for mixed oils of hydrolyzed sunflower wax (SHW) combined with glycerol monostearate (GMS)

Different lowercase letters mean statistical difference between different wax formulations and the second structuring agent at 5 or 25°C. Different uppercase letters mean statistical difference for each formulation at different temperatures.
Table 2. Examples of positive combinations for multicomponent oilgel development

* Total concentration of ol _eogelator ranging from 1-15% (mass)

[22] For example, positive interactions between glycerol monostearate and a high melting point wax (Sunflower Hidrowax: 65-71 °C) have been observed. For sample preparation, the mixture was heated to 80 ± 2 °C (under constant magnetic stirring at 300 rpm) and kept isothermal for another 3 minutes. After heating, all samples were immediately placed in an ice bath for 30 min, with an estimated cooling rate of approximately 5 °C.min-1. The samples were stored for 48h at controlled temperature (5 ± 1 °C or 25 ± 1 °C). The 50:50 ratio in the mixture promotes the formation of gels with improved mechanical characteristics.

[23] These systems are stored under controlled temperature conditions (refrigeration or ambient) leading to the formation of gels with specific mechanical properties. Soon the structuring will take place by the establishment of crystalline networks strengthened by possible positive interactions established between different combinations of oleogelator (i.e. wax and monostearate).

[24] The microstructure of the system with the highest concentration of high melting point wax (GMS25:75SHW) was very similar at the two temperatures studied and presented small spherulites crystals (Figure 2 a and b). In the mixture of oleogelators containing the same proportion of wax and fatty acid derivative, at 5 °C, the crystals appear as tightly packed spherulites with some larger crystals (Figure 2 c and d). At room temperature (Figure 2-d) larger crystals of different shapes (branched crystals) were incorporated into small crystal species (zoom area). GMS-related crystals, which are the larger birefringent structures, coexist with the smaller crystals. Despite differences in microstructure and stronger rheological properties at refrigeration temperature, in the different formulations mentioned, gels were formed. With the predominance of the fatty acid derivative, there is still gel formation, although less rigid than the previous ones. The crystals can be seen radiating and branching outwards into an array of small needle-shaped crystals (Figure 2 e), while Figure 2 (f) reveals larger branched rosette-like crystals, which resemble the behavior. of pure GMS crystal.

Tabela 4. Média e desvio padrão dos módulos dinâmicos (reologia oscilatória) na frequência de 1 Hz para interação negativa de monoestearato de glicerol e cera de berry

[25] The inclusion of GMS showed a positive effect on the oilgel structure when mixed with SHW (GMS25: 75SHW, GMS50: 50SHW and GMS75: 25SHW), considering that neither SHW nor GMS formed gels when in single-component systems at 25 °C (Table 3). The highest elastic modulus (G') of the mixtures indicates that the combination of GMS and SHW positively influenced the gelation, resulting in a strengthened crystal lattice. On the other hand, negative interactions can occur as in the case of mixtures of glycerol monostearate and berry wax. As shown in Table 4, the addition of the fatty acid derivative in the mixture with berry wax led to a reduction in mechanical properties, compromising the formation of stronger gels.
Table 3. Mean and standard deviation of dynamic modules (oscillatory rheology) at the frequency of 1 Hz for positive interaction of glycerol monostearate and sunflower wax

Table 4. Mean and standard deviation of dynamic modules (oscillatory rheology) at the frequency of 1 Hz for negative interaction of glycerol monostearate and berry wax

Claims (1)

Composition characterized by being of high, medium or low melting point waxes and a second structuring agent in vegetable oils for the synthesis of oleogels/organogels and comprising the following components:

• - structuring agent which can be high (sunflower and carnauba wax), medium (beeswax and candelila) and low melting waxes (berry and fruit wax) with a second structuring agent (derived from fatty acids or phospholipids) , where the total concentration of the mixture is 0.1-15% (mass basis) and the mixture may contain 0.199.9% wax (mass basis) and 0.1-99.9% according to the structuring agent (base mass) whose sum does not exceed 15% of the total mixture of the system; and
• - vegetable oils composed of mono and/or polyunsaturated fatty acids (sunflower oil, high oleic sunflower oil, linseed oil, corn oil, soybean oil, canola oil, olive oil) which must be presented in the no. minimum 85% (mass basis) of the composition of the gel system.

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