Preparation method and application of nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex

Abstract

The invention discloses a preparation method and application of a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, and relates to the technical field of starch-protein-lipid complexes, including the following steps: extracting endogenous lipids from fully mature tropical fruit pulp by supercritical carbon dioxide extraction, and extracting endogenous proteins from immature tropical fruit pulp powder by isoelectric deposition; after high-temperature ultrasonic gelation of tropical fruit starch, mixing with endogenous proteins and endogenous lipids, and obtaining a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex after ultrasonic complexation; drying, ball milling, and sieving the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex. The particle size of the ternary complex reaches the nanometer level, and the resistance to thermal decomposition, enzymolysis, and freeze-thaw stability are significantly improved, the particle stability is good, and the probiotics can be coordinated to proliferate and prevent or alleviate type II diabetes and hyperlipidemia.

Description

Technical Field

[0001] The invention belongs to the technical field of starch-protein-lipid complexes, and particularly relates to a preparation method and application of a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex. Background Art

[0002] Common fruits in tropical areas include breadfruit (Artocarpus artilis (Parkinson) Fosberg), avocado (Persea americana Mill.), Artocarpus integer, lucuma nervosa A. DC, sugar apple (Annona squamosa), jackfruit (Artocarpus heterophyllus Lam), and banana (Musabasjoo Siebold). Guangxi and Hainan are the main production areas of scarce tropical fruits. The fresh fruit yield is generally high (≥1.5 tons / mu), the cost is low (≤6 yuan / kg), the flavor and texture are good, and the color is good. Therefore, it has been widely loved by consumers as a high-quality scarce resource. The fat, protein, and crude starch contents of immature tropical fruits are greater than 0.31%, 6.30%, and 80.00%, respectively, while the fat content of fully mature fruits is usually greater than 6.90%. However, due to its high mineral content, it leads to a high cracking rate and a short shelf life (<5 days). A large number of cracked and unsalable fruits are discarded, resulting in a waste of starch, protein, and lipid resources. At present, methods for extracting starch from breadfruit, avocado, sweet potato, custard apple, jackfruit, and banana have been reported. The preparation method is simple and the purity is high (>99%), but there are few reports on the extraction of endogenous proteins and lipids from tropical fruits.

[0003] Starch, fat and protein are the three main macronutrients in the human diet. Starch is a semi-crystalline superpolymer composed of straight-chain starch and branched starch connected by α-1, 4 and α-1, 6 glycosidic bonds. Different encapsulation polymerization of straight and branched chains will form A-type, B-type or C-type crystal structures. Studies have found that compared with conventional starch (such as rice, corn and wheat starch), the content and characteristics of starch granule synthases are different (including BEIIb, SSIIa, GBSSI) due to differences in growth environment and climate.

[0004] At present, the commonly used methods for preparing starch ternary complexes include high-pressure microfluidization, twin-screw extrusion or rapid viscosity analyzer. However, the ternary complex prepared by the above method has a low composite index, takes a long time, generates more unstable type I complexes, and usually has high requirements for mechanical equipment, and the process is complicated and the steps are cumbersome, and sometimes even requires chemical means to assist in preparation. For example, Chinese patent CN201711343345.7 discloses a starch complex and a method for preparation, which is green and environmentally friendly but takes too long; Chinese invention patent CN201110284838 discloses a method for preparing starch-oil complexes using a high-pressure homogenizer. Although this method has a good treatment effect, it is difficult to experiment under industrial conditions and is not suitable for large-scale preparation of starch complexes; Chinese invention patent CN201710347007 discloses a method for preparing lotus seed starch complexes using microwave-ultrasound, but chemical washing is required and ultra-high pressure pretreatment must be performed first, and the steps are cumbersome. Summary of the invention

[0005] The purpose of the present invention is to provide a preparation method and application of a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex. The particle size of the ternary complex reaches the nano-scale, the composite rate is significantly improved, and the particle stability is good.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] The present invention provides a method for preparing a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, comprising the following steps:

[0008] A) extracting endogenous lipids from fully ripe tropical fruit pulp by supercritical carbon dioxide extraction, and extracting endogenous proteins from immature tropical fruit pulp powder by isoelectric precipitation;

[0009] B) gelling tropical fruit starch by high temperature ultrasound, mixing it with endogenous protein and endogenous lipid, and obtaining a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex by ultrasound complexation;

[0010] C) Drying, ball-milling and sieving the nano-sized tropical fruit starch-endogenous protein-endogenous lipid ternary complex.

[0011] Preferably, the method for extracting endogenous lipids from ripe tropical fruit pulp is: injecting fully ripe tropical fruit pulp powder into a carbon dioxide supercritical extraction device (preferably a carbon dioxide supercritical extraction instrument), extracting crude oil using extraction and separation methods, and then purifying and collecting endogenous lipids.

[0012] Preferably, in the method for preparing the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, the tropical fruit is breadfruit, avocado, sweet potato, custard apple, jackfruit or banana.

[0013] Preferably, in the preparation method of the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, the pressure during extraction is 20-35Mpa and the temperature is 40-60°C, preferably in an extraction tank; the pressure during separation is 4-10Mpa and the temperature is 40-60°C, preferably in a separation kettle; the rotary evaporation method is used for purification, the temperature is 50-70°C, preferably in a rotary evaporator.

[0014] Preferably, the ultrasonication is performed in an ultrasonic cell disruptor, and the ball milling is performed in a light ball mill.

[0015] Preferably, the method for extracting endogenous protein from unripe tropical fruit pulp powder is as follows: mixing the unripe tropical fruit pulp powder with distilled water, centrifuging, taking the supernatant, adjusting the pH of the supernatant to 3.6-5.0 with hydrochloric acid (HCl) for isoelectric precipitation, centrifuging, re-dissolving the obtained precipitate and dialyzing to extract the endogenous protein.

[0016] Preferably, in the method for extracting endogenous protein from unripe tropical fruit pulp powder, the unripe tropical fruit pulp powder is mixed with distilled water at a ratio of 1:10 (w / w), centrifuged at 5000×g for 15 min, the hydrochloric acid concentration is 1 M, the temperature is 4°C during isoelectric precipitation, and after the isoelectric precipitation is completed, centrifuged at 6000×g for 20 min; the obtained precipitate is redissolved in distilled water, and endogenous globulin and albumin are dialyzed using a 6-10 kDa dialysis membrane.

[0017] Preferably, the method for gelling tropical fruit starch by high temperature ultrasound is: mixing tropical fruit starch with distilled water and ultrasonically treating; the power of ultrasonic treatment is 400-600W, the treatment time is 10-30min, and the treatment temperature is 80-100°C; more preferably, the power of ultrasonic treatment is 400-580W, the treatment time is 15-30min, and the treatment temperature is 85-100°C; most preferably, the power of ultrasonic treatment is 470-550W, the treatment time is 15-25min, and the treatment temperature is 90-95°C.

[0018] Preferably, in the method of high-temperature ultrasonic gelation of tropical fruit starch, tropical fruit starch and distilled water are mixed at a ratio of 1:20 to 30 (w / w); more preferably, tropical fruit starch and distilled water are mixed at a ratio of 1:22 to 28 (w / w); most preferably, tropical fruit starch and distilled water are mixed at a ratio of 1:22 to 26 (w / w).

[0019] Preferably, in the preparation method of the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, after the tropical fruit starch is mixed with the endogenous protein and the endogenous lipid, the ultrasonic power is 500-600 W, the treatment temperature is 90-100° C., and the treatment time is 10-30 min; more preferably, the ultrasonic power is 500-570 W, the treatment temperature is 90-97° C., and the treatment time is 15-30 min; most preferably, the ultrasonic power is 530-570 W, the treatment temperature is 93-97° C., and the treatment time is 15-25 min.

[0020] Preferably, in the method for preparing the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, the mass ratio of tropical fruit starch, endogenous lipid and endogenous protein is 1:0.1-0.4:0.2-0.6; more preferably, the mass ratio is 1:0.2-0.4:0.3-0.6; and most preferably, the mass ratio is 1:0.2-0.3:0.3-0.5.

[0021] Preferably, in the preparation method of the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, the rotation speed during ball milling is 120-400 r / min, the processing time is 100-200 h, and the sieving is performed using a 400-800 mesh sieve; more preferably, the rotation speed during ball milling is 200-400 r / min, and the processing time is 130-200 h; most preferably, the rotation speed during ball milling is 250-300 r / min, and the processing time is 130-170 h.

[0022] Preferably, in the preparation method of the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, the drying is vacuum freeze drying; the specific parameters of the vacuum freeze drying are freeze drying to a moisture mass percentage of ≤10% under the condition that the temperature of the upper material layer is 50-80°C, the vacuum degree is 30-60Pa, the temperature of the cold trap in the machine is -80--40°C, the temperature of the heating plate is 50-80°C, the temperature is raised to 50-80°C within 10-90min, and freeze drying is performed for 24h; more preferably, freeze drying to a moisture mass percentage of ≤10% under the condition that the temperature of the upper material layer is 60°C-70°C.

[0023] In the process of extracting endogenous protein and endogenous lipid of the present invention, the power, processing time, temperature, rotation speed and the like of the ultrasonic cell disruptor and the light ball mill belong to the overall technical solution, and they support each other in function and have an interactive relationship. Only by the above-mentioned coordinated cooperation can the technical problem of the present invention be solved and the technical effect of the present invention be achieved, which is the key to significantly reducing the particle size of the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, significantly improving the composite index, resistance to thermal decomposition, resistance to enzymolysis, and freeze-thaw stability, alleviating the blood sugar response in the body, increasing the acid production of probiotic fermentation, and having good particle stability.

[0024] The invention prepares a tropical fruit starch-endogenous protein-endogenous lipid ternary complex based on ultrasound and ball milling technology. No toxic or harmful reagents are used in the process method, and the preparation process is greatly optimized. Compared with other methods, the invention saves process costs, increases complexation speed, and improves particle stability, greatly increases the composite index, does not pollute the environment, is simpler to operate, has low cost, and is suitable for large-scale industrial automation production.

[0025] A nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex is prepared according to the preparation method, wherein: the purity of endogenous lipid is 76.35% to 90.64%, the purity of endogenous protein is 70.02% to 91.88%, the particle morphology of the endogenous ternary complex of tropical starch sample presents irregular polygons, but the microstructure is compact, with fewer holes, the average particle size is 71.24 to 142.80 nm, the composite index is 71.13 to 88.79%, and the molecular weight is 5.25 to 9.95×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystal structure, a crystallinity of 19.89-37.76%, a mean square nanometer surface roughness of 6.21-16.45 nm, a gelation temperature of 90.79-110.71 °C, a glycemic index of 55.99-80.48, and a first-order digestion kinetic rate constant of 2.79-9.88×10 -2 min ～1 The real-time release rate of blood glucose in the body is 2.133~10.275mmol / L, the amount of short-chain fatty acids produced by probiotic fermentation in the intestinal wall is 2.76~5.77ug / mg.FW of n-propyl acetate; 1.92~3.10ug / mg.FW of propyl propionate; 0.33~1.90ug / mg.FW of propyl butyrate; 0.00~0.08ug / mg.FW of propyl valerate; 0.00~0.26ug / mg.FW of propyl caproate. The blood lipid smear showed that the body fat was low, the oil solubility was 110.45~277.69%, the water solubility was 83.67~185.72%, and the water separation rate after three freeze-thaw cycles was in the range of 11.72~66.89%.

[0026] The nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex is used in preparing drugs for preventing or treating type II diabetes, hyperlipidemia, hypertension and obesity.

[0027] At present, tropical fruit starch usually shows low semi-crystalline lamella thickness, high molecular typing index, gelatinization temperature and gel hardness, resulting in low digestibility. Endogenous fats usually show superior emulsification and preservative properties. Endogenous proteins, mainly globulins and albumins, are widely present in tropical unripe fruits and usually have good antioxidant and other biological activities. However, due to the high cohesion of the molecular cross-linking network of tropical fruit starch, the endogenous proteins and fats attached to the surface of starch granules are difficult to remove during mass production of starch. Therefore, a large amount of starch-lipid-protein complexes are formed during industrial heating, which may affect the flavor, texture, taste, sensory properties and digestibility of the finished food. In addition, the starch in the current starch ternary complex is a modified starch. Since the ternary complex particles are composed of type I complexes with poor stability and type IIb complexes with good stability, they have a "multi-system supramolecular structure". The above characteristics make the particle size of the ternary complex usually large, about 10-200 μm, and the particle morphology is sponge-like. In order to solve this problem, the present invention provides a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, the emulsifying activity of endogenous globulin and albumin can increase the composite index of starch-lipid-protein, and at the same time, after nano-processing, such as ball milling, the particle size can be reduced to below 1000nm. At the same time, compared with natural starch, the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex of the present invention has a higher content of resistant starch and fast-digestible starch, indicating that it can reduce basic dietary diseases (such as type II diabetes, hyperlipidemia, colon cancer) while also providing essential nutrition for the human body and increasing human immunity.

[0028] The existing steps for preparing ternary complex particles are extremely complicated. Most of them require physical and chemical means to pre-treat completely gelatinized starch, and then high-pressure homogenization and other methods to assist the ternary complex. The fine structure of the modified starch is usually severely damaged. For example, the long side chains of amylopectin are sheared, which has certain defects of excessive fine structure damage. The present invention greatly reduces the modification steps, only selects low-temperature and high-temperature ultrasound for complexation, and uses distilled water as the medium to perform hyperconjugated complexation of starch with a high degree of complexation. The particle stability is further improved by ball milling. While consuming less raw materials, it ensures that the prepared finished product reaches the quality that can be used in batches, and in some aspects it is even better than the existing level.

[0029] The present invention discloses the following technical effects:

[0030] The invention provides a method for preparing a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex. The method belongs to a physical heat treatment process, and the preparation method is simple, suitable for mass production, and the method is green and environmentally friendly. The prepared complex particles have the advantages of high composite index, significantly reduced particle size, significantly improved resistance to enzymolysis and pyrolysis, and good stability during refrigeration. In addition, in vivo experiments after rats were gavaged found that after eating the endogenous ternary complex, the rate of increase of blood sugar index in the body can be alleviated, the efficiency of probiotic fermentation and acid production can be increased, thereby improving the intestinal pH environment and coordinating the proliferation of probiotics, and blood lipids are reduced so as to reduce body fat rate. Therefore, in summary, the method can prevent or alleviate type II diabetes, hyperlipidemia, hypertension, and obesity. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0032] Figure 1 It is a schematic diagram of the particle size comparison between the jackfruit starch ternary composite (nano ternary composite) and the jackfruit gelatinized starch (native starch paste) of Example 1;

[0033] Figure 2 Schematic diagram of the microscopic morphology comparison between the ternary complex of egg yolk fruit starch (ternary complex, left) and the gelatinized egg yolk fruit starch (native starch paste, right) of Example 2;

[0034] Figure 3 This is a schematic diagram of the comparison of blood lipid smears of the sugar apple starch ternary complex and the sugar apple gelatinized starch (native starch paste) in Example 6;

[0035] Figure 4 It is a schematic diagram comparing the digestion kinetics of the breadfruit starch ternary complex of Example 3 and the jackfruit starch ternary complex of Example 1;

[0036] Figure 5 It is a schematic diagram of monitoring blood glucose response in vivo of the endogenous ternary complex of egg yolk fruit starch in Example 2 and the endogenous ternary complex of annona starch in Example 6;

[0037] Figure 6 It is a schematic diagram of a differential calorimetric scanner comparison of the ternary composite of the jianmi la starch of Example 4 and the ternary composite of the banana starch of Example 5;

[0038] Figure 7It is a schematic diagram comparing the in vivo probiotic fermentation acid production characteristics of the endogenous ternary complex of jackfruit starch in Example 1 and the endogenous ternary complex of corn starch in Comparative Example 1;

[0039] Figure 8 This is a schematic diagram comparing the freeze-thaw stability of the banana starch ternary complex of Example 5 and the rice starch ternary complex of Comparative Example 2;

[0040] Fig. 9 Schematic diagram of the oil absorption ratio of the egg yolk fruit starch ternary complex of Example 2 and the wheat starch ternary complex of Comparative Example 3. DETAILED DESCRIPTION

[0041] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0042] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0043] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0044] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0045] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0046] The tropical fruit starches in the embodiments of the present invention were all purchased.

[0047] Unless otherwise specified, the "%" in the ethanol concentration in the embodiments of the present invention refers to the mass fraction.

[0048] The preparation method of jackfruit gelatinized starch (native starch paste) in the embodiment of the present invention is: jackfruit starch and distilled water are mixed in a ratio of 1:20 (w / w), and jackfruit starch paste is prepared by magnetic stirring at 95° C. and 200 rpm for 30 min, and the starch paste is vacuum dried at 60° C. for 24 h to prepare jackfruit native starch gelatinized starch.

[0049] The preparation method of the egg yolk fruit gelatinized starch (native starch paste) in the embodiment of the present invention is: egg yolk fruit starch and distilled water are mixed in a ratio of 1:20 (w / w), and the egg yolk fruit starch paste is prepared by magnetic stirring at 95° C. and 200 rpm for 30 minutes, and the starch paste is vacuum dried at 60° C. for 24 hours to prepare the egg yolk fruit native starch gelatinized starch.

[0050] The embodiment of the present invention provides a method for preparing a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex, comprising the following steps:

[0051] A) extracting endogenous lipids from fully ripe tropical fruit pulp by supercritical carbon dioxide extraction, and extracting endogenous proteins from immature tropical fruit pulp powder by isoelectric precipitation;

[0052] B) gelling tropical fruit starch by high temperature ultrasound, mixing it with endogenous protein and endogenous lipid, and obtaining a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex by ultrasound complexation;

[0053] C) drying, ball-milling and sieving the nano-sized tropical fruit starch-endogenous protein-endogenous lipid ternary complex to obtain the nano-sized tropical fruit starch-endogenous protein-endogenous lipid ternary complex.

[0054] The present invention is mainly based on the fact that when ultrasonic waves are excited in distilled water, cavitation bubbles can be formed, and then high fluidity is generated during the bubble bursting process. The mass transfer and heat exchange of ligands (endogenous proteins and endogenous lipids) and receptors (tropical fruit starch) in the reaction medium are strengthened in combination with high temperature, thereby improving the gelatinization degree and the composite rate in a relatively short time. First, starch is a superpolymer, and it is necessary to complex with the ligand residues after the amylose is completely precipitated. Therefore, high-temperature ultrasound causes the semi-crystalline structure of starch to swell rapidly, and it is convenient to make the contents in the crystal cell precipitate rapidly without destroying the amylose chain and shearing the branched starch. Second, starch has a hydrogen-oxygen polar molecular structure, and it is easy to cause molecular polarization under the action of the lipid-charged electrode head and the protein-charged amide second zone. Moreover, the spiral cavity depth of tropical fruit starch is generally more than twice the length of the hydrocarbon chain of fatty acids, so fatty acids can better form spiral complexes with starch molecules, and its negatively charged carboxyl group as a bridging medium can be more stably self-assembled with proteins to form a ternary complex. Third, since the particle size of the initially formed ternary complex particles is generally large, the rough starch surface is full of channels linking the amorphous regions inside the particles, and the nano surface also presents a high fractal dimension. The ball milling technology can reduce the characteristic distance between each half-crystal layer of the particles, making the amorphous region more compact, thereby reducing the particle size, reducing the roughness, reducing the fractal dimension, and reducing the number of surface enzymatic hydrolysis channels. Therefore, the ternary prepared by ultrasound and ball milling technology has stronger resistance to thermal decomposition, enzymatic hydrolysis and freeze-thaw stability. The existing physical auxiliary modification technology (hydrothermal treatment, microwave, high-pressure homogenization, etc.) mainly focuses on the preparation method of the ternary complex and the improvement of its main performance (digestibility), and needs to be pre-treated with high temperature and high pressure or assisted by chemical means. On this basis, the present invention not only saves the step of chemical enzyme means, but also horizontally expands the influence of the composite index and particle size of the ternary complex on thermal decomposition, freeze-thaw stability, in vitro and in vivo blood sugar response, and intestinal probiotic fermentation characteristics. Research, and has many advantages such as low energy consumption, less heat production, and short time consumption.

[0055] Example 1 Preparation of endogenous ternary complex of nano-jackfruit starch by ultrasonic-ball milling technology

[0056] Extraction of endogenous lipids from mature jackfruit: Peel 11kg of fully mature jackfruit fruit, dry it at 60℃ for 24h, grind 5kg of dried pulp to prepare pulp powder, pass through a 50-mesh sieve, take 3kg of pulp powder and place it in a large extraction tank in a carbon dioxide supercritical extractor, start the instrument and set the pressure parameters of the extraction tank and separation kettle to 27Mpa and 7Mpa respectively, and the temperature of the extraction tank and separation kettle is 45℃. The collected crude oil is then purified by a rotary evaporator (60℃) to obtain 130.60g of endogenous lipids without co-soluble impurities.

[0057] Extraction of endogenous protein from immature jackfruit: 11 kg of immature jackfruit fruit was peeled, dried at 60°C for 24 h, 5.5 kg of dried pulp was ground to prepare pulp powder, sieved through a 50-mesh sieve, 3 kg of immature fruit powder was mixed with 30 kg of distilled water in a blender (500 rpm, 30 min), the mixed suspension was centrifuged at 5000 × g for 15 min, and the supernatant after centrifugation was taken. The supernatant was adjusted to pH 4.4 with 1 M HCl at 4°C for isoelectric precipitation. After complete precipitation, the sediment sample was centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with 8 kDa dialysis membrane for 200.11 g of endogenous globulin and albumin.

[0058] Preparation of jackfruit starch-endogenous protein-endogenous lipid complex: Place 300 g of jackfruit starch in the sample pool of an ultrasonic cell disruptor, add 8.4 kg of distilled water to the pool, and gelatinize at a power of 470 W and a temperature of 90° C. for 25 min; continue to add 90 g of endogenous lipids and 150 g of endogenous protein to the pool, maintain the power at 530 W; the temperature is 93° C. for 25 min, dehydrate using a vacuum filter, and collect the wet sample.

[0059] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. The flocculent precipitate is dried and dehydrated in a freeze vacuum dryer (70°C, cold trap -70°C, vacuum degree 33Pa, 24h) to a water content of 6%. The freeze-dried sample is placed in a light ball mill and milled at a speed of 250r / min for 170h. The obtained complex is passed through a 700-mesh sieve and packaged to obtain a ternary complex. After packaging, 410.5g of the ternary complex is obtained.

[0060] The ternary complex extracted by the present invention was tested for physical and chemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The purity of endogenous lipids was 90.64%, the purity of endogenous proteins was 91.88%, the irregular polygonal morphology of the particles of the ternary complex was reduced, the sponge structure disappeared, the particle surface was relatively smooth, the average particle size was 71.24 nm, the composite index was 88.79%, and the molecular weight was 9.95×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 37.76%, a mean square nano-surface roughness of 7.12 nm, a gelation temperature of 110.71 °C, an in vitro glycemic index of 55.99, and a first-order digestion kinetic rate constant of 2.78 × 10 -2 min -1The real-time release rate of blood glucose in the body is 2.890~5.177mmol / L. The amount of short-chain fatty acids produced by probiotic fermentation in the intestinal wall is 5.77ug / mg.FW of n-propyl acetate; 3.10ug / mg.FW of propyl propionate; 0.74ug / mg.FW of propyl butyrate; 0.01ug / mg.FW of propyl valerate; 0.01ug / mg.FW of propyl caproate. The blood lipid smear shows that the blood lipid density is low, the oil solubility is 110.45%, the water solubility is 83.67%, and the freeze-thaw water separation rate is in the range of 11.72~30.99%.

[0061] Example 2 Preparation of endogenous ternary complex of nano-egg yolk fruit starch by ultrasonic-ball milling technology

[0062] Extraction of endogenous lipids from egg yolk fruit: 15 kg of mature egg yolk fruit was peeled, dried at 60 ° C for 24 hours, and 7 kg of dried pulp was ground to prepare pulp powder, which was passed through a 50-mesh sieve. 4 kg of egg yolk fruit powder was placed in a large extraction tank in a carbon dioxide supercritical extractor. The instrument was started and the pressure parameters of the extraction tank and separation kettle were set to 25 MPa and 6 MPa respectively, and the temperature of the extraction tank and separation kettle was 55 ° C. The collected crude oil was then purified by a rotary evaporator (60 ° C) to remove co-soluble impurities and obtain 122.8 g of endogenous lipids.

[0063] Extraction of endogenous protein from egg yolk fruit: 13 kg of immature egg yolk fruit was peeled, dried at 60°C for 24 h, 7 kg of dried pulp was ground to prepare pulp powder, sieved through a 50-mesh sieve, 4 kg of egg yolk fruit powder was mixed with 40 kg of distilled water in a blender (500 rpm, 30 min), the mixed suspension was centrifuged at 5000 × g for 15 min, and the supernatant after centrifugation was taken. The supernatant was adjusted to pH 4.0 with 1 M HCl at 4°C for isoelectric precipitation. After complete precipitation, the sediment sample was centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with a 7 kDa dialysis membrane to remove 122.6 g of endogenous globulin and albumin.

[0064] Preparation of custard starch-endogenous protein-endogenous lipid complex: Place 200 g of custard starch in the sample pool of an ultrasonic cell disruptor, add 4.4 kg of distilled water to the pool, and gelatinize at a power of 580 W and a temperature of 85° C. for 15 min; continue to add 40 g of endogenous lipids and 60 g of endogenous protein to the pool, adjust the power to 570 W, set the temperature to 97° C. for 15 min, dehydrate using a vacuum filter, and collect the wet sample.

[0065] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. Dry and dehydrate the flocculent precipitate in a freeze vacuum dryer (60°C, cold trap -70°C, vacuum degree 40Pa, 24h) to a water content of 7%. Place the freeze-dried sample in a light ball mill and mill at a speed of 200r / min for 130h. After ball milling, the obtained complex is sieved through a 600-mesh sieve and packaged to obtain 208.7g of ternary complex.

[0066] The ternary complex of egg yolk fruit starch extracted by the present invention is tested for physical and chemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The purity of endogenous lipids is 79.95%, the purity of endogenous proteins is 82.31%, and the particle morphology of the ternary complex is a sponge-like multi-fractal dimension microstructure, but the particles are compact, the number of channels inside the particles is small, the average particle size is 88.45nm, the composite index is 79.96%, and the molecular weight is 7.88×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 30.65%, a mean square nano-surface roughness of 9.46 nm, a gelation temperature of 96.31 °C, a glycemic index of 70.25, and a first-order digestion kinetic rate constant of 6.63 × 10 -2 min -1 The real-time release rate of blood glucose in the body is 2.997~6.918mmol / L. The amount of short-chain fatty acids produced by probiotic fermentation in the intestinal lining are 4.69ug / mg.FW of n-propyl acetate; 2.55ug / mg.FW of propyl propionate; 0.81ug / mg.FW of propyl butyrate; 0.03ug / mg.FW of propyl valerate; 0.00ug / mg.FW of propyl caproate. The blood lipid smear shows that the unit blood lipid amount is small, with oil solubility of 160.55%, water solubility of 140.27%, and the water separation rate of three freeze-thaw cycles is in the range of 22.60~41.99%.

[0067] Example 3 Preparation of endogenous ternary complex of nano breadfruit starch by ultrasonic-ball milling technology

[0068] Extraction of endogenous lipids from mature breadfruit: 18 kg of fully mature breadfruit was peeled, dried at 60°C for 24 hours, 10 kg of dried pulp was ground to prepare pulp powder, sieved through a 50-mesh sieve, 5 kg of pulp powder was placed in a large extraction tank in a carbon dioxide supercritical extractor, the instrument was started and the pressure parameters of the extraction tank and separation kettle were set to 20 MPa and 40 MPa respectively, and the temperature of the extraction tank and separation kettle was 40°C. The collected crude oil was then purified by a rotary evaporator (50°C) to remove co-soluble impurities and obtain 179.8 g of endogenous lipids.

[0069] Extraction of endogenous protein from immature breadfruit: 16 kg of immature breadfruit was peeled, dried at 60°C for 24 h, 10 kg of dried pulp was ground to prepare pulp powder, sieved through a 50-mesh sieve, 5 kg of immature fruit powder was mixed with 50 kg of distilled water in a blender (500 rpm, 30 min), the mixed suspension was centrifuged at 5000 × g for 15 min, and the supernatant was taken after centrifugation. The supernatant was adjusted to pH 3.6 with 1 M HCl at 4°C for isoelectric precipitation. After complete precipitation, the sediment sample was centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with a 6 kDa dialysis membrane to remove 164.5 g of endogenous globulin and albumin.

[0070] Preparation of breadfruit starch-endogenous protein-endogenous lipid complex: Place 100 g of seedless breadfruit starch provided by the Spice and Beverage Research Institute of the Chinese Academy of Tropical Agricultural Sciences in the sample cell of an ultrasonic cell disruptor, add 2 kg of distilled water to the cell, and gelatinize at a power of 400 W and a temperature of 80°C for 10 min; continue to add 10 g of endogenous lipids and 20 g of endogenous protein to the cell, adjust the power to 500 W, set the temperature to 90°C for 10 min, dehydrate with a vacuum filter, and collect the wet sample.

[0071] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. Dry and dehydrate the flocculent precipitate in a freeze vacuum dryer (50°C, cold trap -40°C, vacuum degree 30Pa, 24h) until the water content is 10%. Place the freeze-dried sample in a light ball mill and mill at a speed of 120r / min for 100h. After ball milling, the complex is passed through a 400 mesh

[0072] After sieving and packaging, 90.7 g of the ternary complex was obtained.

[0073] The ternary complex extracted by the present invention was tested for physical and chemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The purity of endogenous lipids was 79.25%, the purity of endogenous proteins was 78.44%, the particle morphology of the ternary complex was irregular polygonal, the surface showed a small amount of sponge-like structure, the surface was relatively rough, but there were fewer holes, the structure was compact, the average particle size was 92.15nm, the composite index was 81.62%, and the molecular weight was 7.71×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 25.07%, a mean square nano-surface roughness of 12.49 nm, a gelation temperature of 93.87 °C, a glycemic index of 71.65, and a first-order digestion kinetic rate constant of 9.71×10 -2 min -1The real-time release rate of blood glucose in the body is 3.221~9.600mmol / L. The amount of short-chain fatty acids produced by probiotic fermentation in the intestinal wall are 4.28ug / mg.FW of n-propyl acetate; 2.32ug / mg.FW of propyl propionate; 1.88ug / mg.FW of propyl butyrate; 0.04ug / mg.FW of propyl valerate; 0.00ug / mg.FW of propyl caproate. The blood lipid smear shows that the unit blood lipid amount is relatively small, with oil solubility of 166.5% and water solubility of 157.9%. The water separation rate of three freeze-thaw cycles is in the range of 21.35~46.13%.

[0074] Example 4 Preparation of endogenous ternary complex of nano-tipped honey starch by ultrasonic-ball milling technology

[0075] Extraction of endogenous lipids from Sharp Honeydew: 20 kg of mature Sharp Honeydew was peeled, dried at 60°C for 24 hours, 14 kg of dried pulp was ground to prepare pulp powder, passed through a 50-mesh sieve, 7 kg of fruit powder was placed in a large extraction tank in a carbon dioxide supercritical extractor, the instrument was started and the pressure parameters of the extraction tank and separation kettle were set to 35 MPa and 10 MPa respectively, and the temperature of the extraction tank and separation kettle were both 60°C. The collected crude oil was then purified by a rotary evaporator (70°C) to remove co-soluble impurities and obtain 233.18 g of endogenous lipids.

[0076] Extraction of endogenous protein from Sharp Honeydew: 19 kg of immature Sharp Honeydew peeled, dried at 60°C for 24 h, 14 kg of dried pulp ground to prepare pulp powder, sieved through a 50-mesh sieve, 7 kg of Sharp Honeydew powder mixed with 70 kg of distilled water in a blender (500 rpm, 30 min), centrifuged the mixed suspension at 5000 × g for 15 min, and took the supernatant after centrifugation. The supernatant was adjusted to pH 5.0 with 1 M HCl at 4°C for isoelectric precipitation. After complete precipitation, the sediment sample was centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with a 10 kDa dialysis membrane to remove 369.19 g of endogenous globulin and albumin.

[0077] Preparation of Amla starch-endogenous protein-endogenous lipid complex: Place 500 g of Amla starch in the sample pool of an ultrasonic cell disruptor, add 15 kg of distilled water to the pool, and gelatinize at a power of 600 W and a temperature of 100°C for 30 min; continue to add 200 g of endogenous lipids and 300 g of endogenous protein to the pool, maintain the power at 600 W; the temperature is 100°C for 30 min, dehydrate with a vacuum filter, and collect the wet sample.

[0078] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. The flocculent precipitate is dried and dehydrated in a freeze vacuum dryer (80°C, cold trap -80°C, vacuum degree 60Pa, 24h) to a water content of 5%. The freeze-dried sample is placed in a light ball mill and milled at a speed of 400r / min for 200h. The obtained complex is passed through an 800-mesh sieve and packaged to obtain 731.5g of the ternary complex.

[0079] The starch extracted by the present invention was tested for physical and chemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The endogenous lipid purity was 76.35%, the endogenous protein purity was 70.02%, and the particle morphology of the ternary complex showed irregular polygons, but the microstructure was loose, with more holes and larger pores, the average particle size was 100.66nm, the composite index was 81.35%, and the molecular weight was 5.51×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 24.59%, a mean square nano-surface roughness of 12.69 nm, a gelation temperature of 92.79 °C, a glycemic index of 77.89, and a first-order digestion kinetic rate constant of 9.83 × 10 -2 min -1 The real-time release rate of blood glucose in the body is 3.410~9.995mmol / L. The amount of short-chain fatty acids produced by probiotic fermentation in the intestinal wall is 3.43ug / mg.FW of n-propyl acetate; 2.05ug / mg.FW of propyl propionate; 0.82ug / mg.FW of propyl butyrate; 0.04ug / mg.FW of propyl valerate; 0.12ug / mg.FW of propyl caproate. The blood lipid smear shows that the unit blood lipid amount is relatively large, with oil solubility of 200.90% and water solubility of 188.46%. The water separation rate of three freeze-thaw cycles is in the range of 30.05~50.07%.

[0080] Example 5 Preparation of endogenous ternary complex of nano banana starch by ultrasonic-ball milling technology

[0081] Extraction of endogenous lipids from banana: 40 kg of immature bananas were peeled, dried at 60°C for 24 hours, 20 kg of dried pulp was ground to prepare pulp powder, sieved through a 50-mesh sieve, 10 kg of banana powder was placed in a large extraction tank in a carbon dioxide supercritical extractor, the instrument was started and the pressure parameters of the extraction tank and separation kettle were set to 30 MPa and 8 MPa respectively, and the temperatures of the extraction tank and separation kettle were both 45°C. The collected crude oil was then purified by a rotary evaporator (55°C) to remove co-soluble impurities and obtain 1.95 kg of endogenous lipids.

[0082] Extraction of endogenous protein from banana: 38 kg of mature banana was peeled, dried at 60°C for 24 h, 20 kg of dried pulp was ground to prepare pulp powder, 10 kg of banana powder was taken through a 50-mesh sieve and mixed with 100 kg of distilled water in a blender (500 rpm, 30 min), the mixed suspension was centrifuged at 5000 × g for 15 min, and the supernatant was taken after centrifugation. The supernatant was adjusted to pH 4.7 with 1M HCl at 4°C for isoelectric precipitation. After complete precipitation, the sediment sample was centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with 9 kDa dialysis membrane to remove 2.97 kg of endogenous globulin and albumin.

[0083] Preparation of banana starch-endogenous protein-endogenous lipid complex: Place 700 g of banana starch in the sample pool of an ultrasonic cell disruptor, add 1.82 kg of distilled water to the pool, and gelatinize at a power of 470 W and a temperature of 95°C for 23 min; continue to add 175 g of endogenous lipids and 245 g of endogenous protein to the pool, adjust the power to 550 W, set the temperature to 95°C for 20 min, dehydrate using a vacuum filter, and collect the wet sample.

[0084] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. Dry and dehydrate the flocculent precipitate in a freeze vacuum dryer (68°C, cold trap -60°C, vacuum degree 45Pa, 24h) to a water content of 6%. Place the freeze-dried sample in a light ball mill and mill at a speed of 300r / min for 150h. After ball milling, the obtained complex is sieved through a 500-mesh sieve and packaged to obtain 813.6g of ternary complex.

[0085] The starch extracted by the present invention was tested for physicochemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The endogenous lipid purity was 81.35%, the endogenous protein purity was 75.02%, and the particle morphology of the ternary complex showed irregular polygons, but the microstructure was compact, with fewer holes and smaller pores. The average particle size was 71.31 nm, the composite index was 81.13%, and the molecular weight was 8.21×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 30.97%, a mean square nano-surface roughness of 6.21 nm, a gelation temperature of 99.24 °C, a glycemic index of 67.89, and a first-order digestion kinetic rate constant of 3.83 × 10 -2 min -1The real-time release rate of blood glucose in the body is 2.133~5.992mmol / L, the amount of short-chain fatty acids produced by probiotic fermentation in the intestinal lining is 4.91ug / mg.FW of n-propyl acetate; 2.26ug / mg.FW of propyl propionate; 1.90ug / mg.FW of propyl butyrate; 0.08ug / mg.FW of propyl valerate; 0.26ug / mg.FW of propyl caproate, the blood lipid smear shows that the blood lipid density is low, the blood lipid smear shows that the body fat rate is low, the oil solubility is 145.67%, the water solubility is 90.27%, and the freeze-thaw water separation rate is in the range of 20.05~40.07%.

[0086] Example 6 Preparation of endogenous ternary complex of nano-sugar apple starch by ultrasonic-ball milling technology

[0087] Extraction of endogenous lipids from sugar apple: 30 kg of immature sugar apples were peeled, dried at 60°C for 24 hours, 17 kg of dried pulp was ground to prepare pulp powder, sieved through a 50-mesh sieve, 9 kg of fruit powder was placed in a large extraction tank in a carbon dioxide supercritical extractor, the instrument was started and the pressure parameters of the extraction tank and separation kettle were set to 23 MPa and 5 MPa respectively, and the temperature of the extraction tank and separation kettle was 48°C. The collected crude oil was then purified by a rotary evaporator (52°C) to remove co-soluble impurities and obtain 421.9 g of endogenous lipids.

[0088] Extraction of endogenous protein from sugar apple: 28 kg of mature sugar apples were peeled, dried at 60°C for 24 h, and 17 kg of dried pulp was ground to prepare pulp powder, which was passed through a 50-mesh sieve. 9 kg of sugar apple powder was mixed with 90 kg of distilled water in a blender (500 rpm, 30 min), and the mixed suspension was centrifuged at 5000 × g for 15 min, and the supernatant was taken after centrifugation. The supernatant was adjusted to pH 4.1 with 1 M HCl at 4°C for isoelectric precipitation. After complete precipitation, the sediment sample was centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with a 7 kDa dialysis membrane to remove 395.20 g of endogenous globulin and albumin.

[0089] Preparation of custard apple starch-endogenous protein-endogenous lipid complex: Place 400 g of custard apple starch in the sample pool of an ultrasonic cell disruptor, add 10 kg of distilled water to the pool, and gelatinize at a power of 520 W and a temperature of 92° C. for 20 min; continue to add 110 g of endogenous lipids and 150 g of endogenous protein to the pool, adjust the power to 540 W, set the temperature to 94° C. for 18 min, dehydrate with a vacuum filter, and collect the wet sample.

[0090] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. Dry and dehydrate the flocculent precipitate in a freeze vacuum dryer (65°C, cold trap -65°C, vacuum degree 40Pa, 24h) until the water content is 9%. Place the freeze-dried sample in a light ball mill and mill at a speed of 270r / min for 140h. After ball milling, the obtained complex is sieved through a 700-mesh sieve and packaged to obtain 437.9g ​​of the ternary complex.

[0091] The ternary complex of sugar apple starch extracted by the present invention was tested for physical and chemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The purity of endogenous lipids was 80.41%, the purity of endogenous proteins was 82.67%, the particle morphology of the complex was irregular polygonal, the surface was relatively rough, and it showed a sponge-like fractal morphology with only a small number of surface pores. The average particle size was 142.80 nm, the composite index was 71.13%, and the molecular weight was 5.25×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 19.89%, a mean square nano-surface roughness of 16.45 nm, a gelation temperature of 90.79 °C, a glycemic index of 80.48, and a first-order digestion kinetic rate constant of 9.88 × 10 -2 min -1 The real-time release rate of blood glucose in the body is 3.407~10.275mmol / L. The amount of short-chain fatty acids produced by probiotic fermentation in the intestinal wall are 2.76ug / mg.FW of n-propyl acetate; 1.92ug / mg.FW of propyl propionate; 0.33ug / mg.FW of propyl butyrate; 0.00ug / mg.FW of propyl valerate; 0.04ug / mg.FW of propyl caproate. The blood lipid smear shows that the body fat is relatively normal, with oil solubility of 277.69% and water solubility of 185.72%. The water precipitation rate after three freeze-thaw cycles is in the range of 40.15~66.89%.

[0092] Comparative Example 1 Preparation of endogenous ternary complex of nano corn starch by ultrasonic-ball milling technology

[0093] Extraction of corn endogenous lipids: 10 kg of corn was peeled, ground with a pulverizer to prepare seed powder, passed through a 50-mesh sieve, 3 kg of corn powder was placed in a large extraction tank in a carbon dioxide supercritical extractor, and the instrument was started to set the pressure parameters of the extraction tank and separation kettle to 27 MPa and 7 MPa respectively, and the temperature of the extraction tank and separation kettle was 45 ° C. The collected crude oil was then purified by a rotary evaporator (60 ° C) to obtain 140.31 g of endogenous lipids without co-soluble impurities.

[0094] Extraction of endogenous protein from immature corn: 11 kg of immature corn was peeled, dried at 60°C for 24 hours, 6 kg of dried pulp was ground to prepare corn flour, passed through a 50-mesh sieve, 3 kg of immature corn flour was mixed with 30 kg of distilled water in a blender (500 rpm, 30 min), the mixed suspension was centrifuged at 5000 × g for 15 min, and the supernatant after centrifugation was taken. The supernatant was adjusted to pH 4.4 with 1M HCl at 4°C for isoelectric precipitation. After complete precipitation, the sediment sample was centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with an 8 kDa dialysis membrane to remove 241.65 g of endogenous globulin and albumin.

[0095] Preparation of corn starch-endogenous protein-endogenous lipid complex: Place 300 g of corn starch in the sample pool of an ultrasonic cell disruptor, add 8.4 kg of distilled water to the pool, and gelatinize at a power of 470 W and a temperature of 90°C for 25 min; continue to add 90 g of endogenous lipids and 150 g of endogenous protein to the pool, maintain the power at 530 W; the temperature is 93°C for 25 min, dehydrate using a vacuum filter, and collect the wet sample.

[0096] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. The flocculent precipitate is dried and dehydrated in a freeze vacuum dryer (70°C, cold trap -70°C, vacuum degree 33Pa, 24h) to a water content of 6%. The freeze-dried sample is placed in a light ball mill and milled at a speed of 250r / min for 170h. The obtained complex is passed through a 700-mesh sieve and packaged to obtain a ternary complex. After packaging, 377.29g of the ternary complex is obtained.

[0097] The corn starch ternary complex extracted by the present invention was tested for physicochemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The endogenous lipid purity was 69.74%, the endogenous protein purity was 71.35%, and the particle morphology of the ternary complex showed an obvious fractal structure, the particles were loose, and the particles had more holes. The average particle size was 155.25nm, the composite index was 72.14%, and the molecular weight was 4.39×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 18.71%, a mean square nano-surface roughness of 14.02 nm, a gelation temperature of 89.03 °C, a glycemic index of 87.72, and a first-order digestion kinetic rate constant of 10.27 × 10 -2 min -1The real-time release rate of blood glucose in the body is: 4.556~12.595mmol / L. The amount of short-chain fatty acids produced by probiotic fermentation in the intestinal wall are 1.71ug / mg.FW of n-propyl acetate; 1.38ug / mg.FW of propyl propionate; 0.24ug / mg.FW of propyl butyrate; 0.01ug / mg.FW of propyl valerate; 0.01ug / mg.FW of propyl caproate. The blood lipid smear shows that the body fat density is relatively high, with an oil solubility of 330.34% and a water solubility of 244.61%. The water separation rate after three freeze-thaw cycles is in the range of 50.82-73.79%. Compared with the jackfruit starch ternary complex of Example 1, the corn starch nano endogenous ternary complex particles have larger pore size and more pores, and the composite index, molecular weight, crystallinity, mean square nano surface roughness, and gelation temperature are significantly reduced. The characteristic distance between lamellae, particle size, oil solubility, water solubility, and three freeze-thaw water separation rate increase, resulting in a significant increase in digestion rate, glycemic index, and blood glucose response in the body. The fermentation and acid production performance of probiotics on the intestinal wall is significantly reduced, which makes the proliferative environment of probiotics in the intestine worse.

[0098] Comparative Example 2 Preparation of endogenous ternary complex of nano rice starch by ultrasonic-ball milling technology

[0099] Extraction of endogenous lipids from rice: 20 kg of rice was peeled, ground with a grinder to prepare rice flour, passed through a 50-mesh sieve, 10 kg of rice flour was placed in a large extraction tank in a carbon dioxide supercritical extractor, and the instrument was started to set the pressure parameters of the extraction tank and the separation kettle to 30 MPa and 8 MPa respectively, and the temperatures of the extraction tank and the separation kettle were both 45 ° C. The collected crude oil was then purified by a rotary evaporator (55 ° C) to remove the co-soluble impurities and obtain 1.66 kg of endogenous lipids.

[0100] Extraction of endogenous protein from rice: 20 kg of rice was peeled, ground with a grinder to prepare seed powder, passed through a 50-mesh sieve, 10 kg of rice powder was mixed with 100 kg of distilled water in a blender (500 rpm, 30 min), the mixed suspension was centrifuged at 5000 × g for 15 min, and the supernatant after centrifugation was taken. The supernatant was adjusted to pH 4.7 with 1 M HCl at 4 ° C for isoelectric precipitation. After complete precipitation, the sediment sample was then centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with a 9 kDa dialysis membrane to remove 2.45 kg of endogenous globulin and albumin.

[0101] Preparation of rice starch-endogenous protein-endogenous lipid complex: 700 g of rice starch is placed in the sample pool of an ultrasonic cell disruptor, 1.82 kg of distilled water is added to the pool, and gelatinization is performed at a power of 470 W and a temperature of 95° C. for 23 min; 175 g of endogenous lipid and 245 g of endogenous protein are continuously added to the pool, and the power is adjusted to 550 W; the temperature is 95° C. for 20 min, and the sample is dehydrated using a vacuum filter to collect the wet sample.

[0102] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. Dry and dehydrate the flocculent precipitate in a freeze vacuum dryer (68°C, cold trap -60°C, vacuum degree 45Pa, 24h) to a water content of 6%. Place the freeze-dried sample in a light ball mill and mill at a speed of 300r / min for 150h. After ball milling, the obtained complex is sieved through a 500-mesh sieve and packaged to obtain 588.7g of ternary complex.

[0103] The endogenous ternary complex of rice starch extracted by the present invention is tested for physicochemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The endogenous lipid purity is 66.71%, the endogenous protein purity is 69.95%, and the particle morphology of the ternary complex shows irregular polygons, but the microstructure is loose, with more holes and larger pores, the average particle size is 149.21nm, the composite index is 70.88%, and the molecular weight is 3.96×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 18.78%, a mean square nano-surface roughness of 27.87 nm, a gelation temperature of 89.99 °C, a glycemic index of 90.32, and a first-order digestion kinetic rate constant of 12.98 × 10 -2 min -1The real-time release rate of blood glucose in the body is: 4.215~14.668mmol / L, the amount of short-chain fatty acids produced by probiotic fermentation in the intestinal lining is 1.46ug / mg.FW of n-propyl acetate; 0.37ug / mg.FW of propyl propionate; 0.00ug / mg.FW of propyl butyrate; 0.00ug / mg.FW of propyl valerate; 0.00ug / mg.FW of propyl caproate, the blood lipid smear shows that the body fat density is relatively high, the oil solubility is 322.61%, the water solubility is 240.20%, and the water separation rate after three freeze-thaw cycles is in the range of 45.77~70.08%. The corn starch nano endogenous ternary complex particles are compared with the banana starch ternary complex in Example 5. The particles have larger pore size and more pores. The composite index, molecular weight, crystallinity, mean square nano surface roughness, and gelation temperature are significantly reduced. The characteristic distance between the lamellae and the digestion rate are significantly increased, resulting in a higher particle size, glycemic index, higher oil solubility, water solubility, and three freeze-thaw water separation rate. In summary, it leads to a significant increase in blood sugar response in the body, a significant increase in body fat density, a significant reduction in the fermentation and acid production performance of the probiotics in the intestinal wall, and a worse proliferative environment for probiotics in the intestine.

[0104] Comparative Example 3 Preparation of endogenous ternary complex of nano wheat starch by ultrasonic-ball milling technology

[0105] Extraction of endogenous lipids from wheat: 9 kg of wheat was peeled, ground with a pulverizer to prepare seed powder, passed through a 50-mesh sieve, 4 kg of wheat flour was placed in a large extraction tank in a carbon dioxide supercritical extractor, and the instrument was started to set the pressure parameters of the extraction tank and separation kettle to 25 MPa and 6 MPa respectively, and the temperature of the extraction tank and separation kettle was 55 ° C. The collected crude oil was then purified by a rotary evaporator (60 ° C), and 141.4 g of endogenous lipids were obtained by removing co-soluble impurities.

[0106] Extraction of endogenous protein from wheat: 9 kg of wheat was dehulled, ground with a grinder to prepare seed powder, passed through a 50-mesh sieve, 4 kg of wheat flour was mixed with 40 kg of distilled water in a blender (500 rpm, 30 min), the mixed suspension was centrifuged at 5000 × g for 15 min, and the supernatant after centrifugation was taken. The supernatant was adjusted to pH 4.0 with 1 M HCl at 4 ° C for isoelectric precipitation. After complete precipitation, the sediment sample was then centrifuged (6000 × g, 20 min), the supernatant was poured out, and the precipitate was re-dissolved with distilled water. This solution was dialyzed with a 7 kDa dialysis membrane to remove 119.28 g of endogenous globulin and albumin.

[0107] Preparation of wheat starch-endogenous protein-endogenous lipid complex: Place 200 g of wheat starch in the sample pool of an ultrasonic cell disruptor, add 4.4 kg of distilled water to the pool, and gelatinize at a power of 580 W and a temperature of 85°C for 15 min; continue to add 40 g of endogenous lipids and 60 g of endogenous protein to the pool, adjust the power to 570 W, set the temperature to 97°C for 15 min, dehydrate using a vacuum filter, and collect the wet sample.

[0108] Preparation of ternary complex: Wash with 30% ethanol three times to remove free lipids and proteins, centrifuge at 5000×g for 15 min. Dry and dehydrate the flocculent precipitate in a freeze vacuum dryer (60°C, cold trap -70°C, vacuum degree 40Pa, 24h) to a water content of 7%. Place the freeze-dried sample in a light ball mill and mill at a speed of 200r / min for 130h. After ball milling, the obtained complex is sieved through a 600-mesh sieve and packaged to obtain 190.40g of the ternary complex.

[0109] The wheat starch ternary complex extracted by the present invention was tested for physicochemical properties, microscopic characteristics, in vivo and in vitro digestion properties, and probiotic fermentation acid production properties. The endogenous lipid purity was 72.36%, the endogenous protein purity was 73.66%, the particle morphology of the ternary complex was sponge-like multi-fractal dimension microstructure, the particles were loose, and there were many channels inside the particles. The average particle size was 167.78nm, the composite index was 72.14%, and the molecular weight was 4.11×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystalline structure, a crystallinity of 26.66%, a mean square nano-surface roughness of 23.67 nm, a gelation temperature of 90.01 °C, a glycemic index of 82.10, and a first-order digestion kinetic rate constant of 11.48 × 10 -2 min -1The real-time release rate of blood glucose in the body is: 3.990~13.276mmol / L. The amount of short-chain fatty acids produced by probiotic fermentation in the intestinal lining are 1.68ug / mg.FW of n-propyl acetate; 0.58ug / mg.FW of propyl propionate; 0.07ug / mg.FW of propyl butyrate; 0.00ug / mg.FW of propyl valerate; 0.00ug / mg.FW of propyl caproate. The blood lipid smear shows that the body fat rate is relatively high, with an oil solubility of 270.34% and a water solubility of 220.55%. The water separation rate after three freeze-thaw cycles is in the range of 35.21-66.87%. Compared with the egg yolk fruit starch ternary complex of Example 2, the wheat starch nano endogenous ternary complex particles have more pores and larger pore size, and the composite index, molecular weight, crystallinity, mean square nano surface roughness, and gelation temperature are significantly reduced. The characteristic distance between lamellae, particle size, oil solubility, water solubility, and three freeze-thaw water separation rates are increased, resulting in a significant increase in the digestion kinetic constant and in vitro and in vivo blood glucose response, and a significant decrease in the acid production of intestinal probiotic fermentation.

[0110] Figure 1 Schematic diagram of the particle size comparison between the endogenous ternary complex of jackfruit starch (nano ternary complex) and the gelatinized jackfruit starch (native starch paste) in Example 1. Figure 1 It can be seen that the jackfruit starch ternary complex has smaller particle pore size and greater volume density than jackfruit gelatinized starch.

[0111] Figure 2 Schematic diagram of the microscopic morphology comparison of the ternary complex of egg yolk fruit starch (ternary complex, left) and the gelatinized egg yolk fruit starch (native starch paste, right) in Example 2. Figure 2 It can be seen that compared with the original starch paste, the egg yolk fruit starch ternary complex has smaller particles, fewer pores, more uniform morphology, and more compact and smooth particles.

[0112] Figure 3 Schematic diagram of blood lipid smear comparison of the ternary complex of sugar apple starch and sugar apple gelatinized starch (native starch paste) in Example 6, Figure 3 It can be seen that the body fat rate of the ternary complex of sugar apple starch is lower than that of sugar apple gelatinized starch after digestion in the body.

[0113] Figure 4 Schematic diagram of the digestion kinetics comparison of the breadfruit starch ternary complex of Example 3 and the jackfruit starch ternary complex of Example 1. Figure 4 It can be seen that the breadfruit starch ternary complex has a faster enzymatic hydrolysis rate than the jackfruit starch ternary complex, and the real-time digestive enzyme hydrolysis rate is higher.

[0114] Figure 5 Schematic diagram of monitoring blood glucose response in vivo of the endogenous ternary complex of egg yolk fruit starch in Example 2 and the endogenous ternary complex of annona starch in Example 6. Figure 5It can be seen that the blood sugar response rate produced by metabolism in the body after consumption of the egg yolk fruit starch ternary complex is lower than that of the sugar apple starch ternary complex.

[0115] Figure 6 Schematic diagram of differential calorimetry comparison of the ternary composite of the ternary composite of the smilax starch in Example 4 and the ternary composite of the banana starch in Example 5. Figure 6 It can be seen that the banana starch ternary complex has stronger thermal resistance and heat stability than the pointed melaleuca starch ternary complex.

[0116] Figure 7 Schematic diagram of the comparison of the in vivo probiotic fermentation acid production characteristics of the endogenous ternary complex of jackfruit starch in Example 1 and the endogenous ternary complex of corn starch in Comparative Example 1. Figure 7 It can be seen that the probiotic fermentation metabolism of jackfruit starch is greater than that of corn starch, and it can synergize the proliferation of other probiotics after improving the intestinal environment.

[0117] Figure 8 Schematic diagram showing the freeze-thaw stability comparison between the banana starch ternary complex of Example 5 and the rice starch ternary complex of Comparative Example 2. Figure 8 It can be seen that the freeze-thaw water separation of banana starch ternary composite is weaker than that of rice starch ternary composite, which indicates that it has a longer shelf life and less texture change during storage.

[0118] Fig. 9 Schematic diagram of the oil absorption ratio of the egg yolk fruit starch ternary complex of Example 2 and the wheat starch ternary complex of Comparative Example 3, Fig. 9 It can be seen that the oil-insolubleness of the egg yolk fruit starch ternary complex is stronger than that of the wheat starch ternary complex, indicating that its structure is more compact.

[0119] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. Use of a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex in the preparation of a drug for preventing or alleviating type II diabetes, hyperlipidemia, hypertension, and obesity, characterized in that: The method for preparing the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex comprises the following steps: A) extracting endogenous lipids from fully ripe tropical fruit pulp by supercritical carbon dioxide extraction, and extracting endogenous proteins from immature tropical fruit pulp powder by isoelectric precipitation; B) gelling tropical fruit starch by high temperature ultrasound, mixing it with endogenous protein and endogenous lipid, and obtaining a nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex by ultrasound complexation; C) drying, ball milling and sieving the nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex; The method for gelling tropical fruit starch by high temperature ultrasound is as follows: mixing tropical fruit starch with distilled water and subjecting to ultrasound treatment; the power of ultrasound treatment is 400-600W, the treatment time is 10-30min, and the treatment temperature is 80-100℃; After the tropical fruit starch is mixed with endogenous protein and endogenous lipid, the ultrasonic power is 500-600W, the treatment temperature is 90-100℃, and the treatment time is 10-30min; The mass ratio of tropical fruit starch, endogenous lipids and endogenous proteins is 1:0.1-0.4:0.2-0.6; The speed of ball milling is 120-400 r / min, and the processing time is 100-200 h; The nano-scale tropical fruit starch-endogenous protein-endogenous lipid ternary complex has an endogenous lipid purity of 76.35% to 90.64%, an endogenous protein purity of 70.02% to 91.88%, and an endogenous ternary complex of tropical starch samples. The particle morphology is irregular polygonal, but the microstructure is compact and has fewer holes. The average particle size is 71.24 to 142.80 nm, the composite index is 71.13 to 88.79%, and the molecular weight is 5.25 to 9.95×10 6 g / mol, characteristic distance between crystalline lamellae and amorphous regions It has a V-type crystal structure, a crystallinity of 19.89-37.76%, a mean square nanometer surface roughness of 6.21-16.45 nm, a gelation temperature of 90.79-110.71 °C, a glycemic index of 55.99-80.48, and a first-order digestion kinetic rate constant of 2.79-9.88×10 -2 min -1 The real-time release rate of blood glucose in the body was 2.133~10.275mmol / L, and the amount of short-chain fatty acids produced by probiotic fermentation in the intestinal wall was 2.76~5.77μg / mg.FW of n-propyl acetate; 1.92~3.10μg / mg.FW of propyl propionate; 0.33~1.90μg / mg.FW of propyl butyrate; 0.00~0.08μg / mg.FW of propyl valerate; 0.00~0.26μg / mg.FW of propyl caproate. The blood lipid smear showed that the body fat was low, with oil solubility of 110.45~277.69%, water solubility of 83.67~185.72%, and the water separation rate of three freeze-thaw cycles was in the range of 11.72~66.89%.

2. The use according to claim 1, characterized in that: The method for extracting endogenous lipids from ripe tropical fruit pulp is as follows: fully ripe tropical fruit pulp powder is sampled into a carbon dioxide supercritical extraction device, crude oil is extracted by extraction and separation methods, and then endogenous lipids are purified and collected.

3. The use according to claim 2, characterized in that: The pressure during extraction is 20-35Mpa; the pressure during separation is 4-10Mpa; the purification is carried out by rotary evaporation at a temperature of 50-70°C.

4. The use according to claim 1, characterized in that: The method for extracting endogenous protein from unripe tropical fruit pulp powder is as follows: the unripe tropical fruit pulp powder is mixed with distilled water, centrifuged, the supernatant is taken, the pH of the supernatant is adjusted to 3.6-5.0 with hydrochloric acid for isoelectric precipitation, centrifuged, the obtained precipitate is redissolved and then dialyzed to extract the endogenous protein.

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