KR20100119343A - Method for preparing deodored and decolored fucoidan - Google Patents

Abstract

PURPOSE: A method for preparing deodorized and decolored fucoidan is provided to effectively eliminate the strong odor and heavy color of seaweed while the phytonutrient component of the fucoidan is maintained. CONSTITUTION: Light is radiated to fucoidan solution at the temperature between 40 and 80 degrees Celsius for 3 to 4 hours in order to decolor the fucoidan solution. The light is selected from a group including solar light, ultraviolet ray, visible ray, and infrared ray. The decolored fucoidan solution is in contact with an adsorbing agent in order to deodorize the fucoidan solution. The absorbing agent is selected from a group including activated carbon, silica-gel, diatomite, zeolite, bentonite, alumina, charcoal, and the mixture of the same.

Description

Method for preparing deodorized and discolored fucoidan {Method for Preparing Deodored and Decolored Fucoidan}

The present invention relates to a method for producing decolorized and deodorized fucoidan and to deodorized and decolorized fucoidan prepared therefrom, and more particularly, to a method for preparing decolorized and deodorized fucoidan using light irradiation and an adsorbent simultaneously or using an ultrafiltration membrane. It is about.

Fucoidan is a major polysaccharide that forms brown algae together with laminaran and alginic acid, and contains 3 to 5% of kelp and seaweed. Fucoidan is a sulfated heteropolysaccharide, containing galactose, mannose, xylose, glucuronic acid, etc., mainly having L-fucose having a backbone composed of α-1,2 or α-1,3 bonds.

Fucoidan with various physiological activities is extracted and purified from algae and sold in various forms, but the extracted fucoidan remains strong flavor and dark color of the algae, which does not meet consumer preferences.

Therefore, when developing fucoidan extract as a main ingredient such as health supplements, moisturizers, cosmetics, fucoidan powder, etc., the strong flavor and dark color of algae need to be reduced or removed. Because it may be represented by a trace component, it is difficult to completely remove the flavor and color.

Conventional fragrance or color removal methods include the addition of other fragrance or color components and the removal of fragrance or color components from products. More specific methods include absorption, catalytic contacting, adsorption, oxidation and reduction, and condensation. , Biodegradation, ion exchange, filtration and the like.

Fucoidan-containing products are often targeted at people who are sensitive to the aroma and color of algae, such as patients and children. It is desirable to.

The flavor component of brown algae is known as the terpene system and the color components are known to be chlorophyll, carotenoids, xanthophyll and fucoxanthin. The components are those which do not affect the bioactive effect of fucoidan, so removing them is effective for deodorization or decolorization. However, research on the removal of these components from seaweed products has not been reported in Korea as well as abroad.

Accordingly, the present inventors have made efforts to solve the above problems, and as a result, the inventors have confirmed that the fragrance and color of fucoidan can be removed by simultaneously using light irradiation and an adsorbent, or by using ultrafiltration, thereby completing the present invention. .

It is an object of the present invention to provide a method for producing fucoidan decolorized and deodorized in order to improve the palatability of fucoidan.

In order to achieve the above object, the present invention (a) a step of decolorizing by irradiating light to the fucoidan solution at a temperature of 40 ~ 80 ℃; And (b) contacting the decolorized fucoidan solution with an adsorbent to deodorize the aroma of fucoidan.

The present invention also comprises the steps of (a) contacting the fucoidan solution with an adsorbent to deodorize the flavor of fucoidan; And (b) irradiating light to the deodorized fucoidan solution at a temperature of 40 ° C. to 80 ° C. to provide a method for producing decolorized and deodorized fucoidan.

The present invention also provides a method for producing decolorized and deodorized fucoidan, characterized in that the fucoidan solution is permeated through an ultrafiltration membrane having a cutoff of 100 kDa to 500 kDa.

When using the method of manufacturing the discolored and deodorized fucoidan according to the present invention, while maintaining the various physiologically active components of fucoidan, it is possible to simply and effectively remove only the strong aroma and dark color of seaweeds, fucoidan prepared therefrom May be useful for the production of fucoidan-containing products for people who are sensitive to the aroma and color of algae, such as patients and children.

Examples of color components of fucoidan include carotenoids, xanthophyll, fucoxanthin, and chlorophyll.

There are about 300 kinds of carotinoids in nature, and among them, a kind of hydrocarbon containing only carbon and hydrogen without oxygen in the molecule is classified as carotene and xanthophyll. do. Carotene is a red or reddish violet crystal having a β-ion ring or a group at both ends, and there are many isomers. The main ones are α-carotene, β-carotene, 膨 -carotene, lycopene and the like. Xanthophyll refers to pigments containing oxygen in the form of hydroxy group, carbonyl group or epoxide in carotenoids. Fucoxanthin is a carotenoid pigment that contains oxygen and can be called xanthophylls. Fucoxanthin is fat-soluble, has a large number of conjugated double bonds, yellow to red color, and high unsaturation, so it is easily oxidized and destroyed by heat, acid, light irradiation, metal ions, peroxides, peroxidase, etc., at a wavelength of 300 to 500 nm. There is a characteristic with a specific absorption band.

Chlorophyll is a derivative of forbin in which a cyclopentane ring is linked to a cyclic tetrapyrrole in which four pyrroles are bound by a methine group —CH═, with one Mg atom coordinated in the center of the tetrapyrrole ring and propionyl of pyrrole ring IV. Pyrrole or farnesol ester-bonded to the group. There are many chlorophylls in nature and brown algae contain chlorophyll C.

Terpene, a fragrance component of fucoidan, is a generic term for hydrocarbons and derivatives thereof composed of a polymer comprising isoprene as a structural unit, also called terpenoids and isoprenoids. Typical oils are essential oils, which are the fragrances of plants, and most of the pigments, resins, and rubbers are formally contained in terpenes. Terpenes in essential oils are produced in the early stages of biosynthesis, in which acetic acid passes through squalene to cholesterol through the action of enzymes in the body of a plant. Terpenes are classified as monoterpene, sesquiterpene, and triterpene hydrocarbons based on the number of side chain C units (hereinafter referred to as isoprene units). And alcohols, aldehydes, ketones, and carboxylic acids having a carbon skeleton such as these terpene hydrocarbons. Isoprene itself is a compound belonging to hemiterpene.

In the present invention, when using the light irradiation and the adsorbent at the same time, or using ultrafiltration while maintaining the various bioactive components of fucoidan, it was intended to confirm that only the strong aroma and dark color of seaweed can be removed.

In the present invention, when the fucoidan irradiated with light at a constant temperature, the dark green of the fucoidan is changed to yellowish brown or reddish brown, but it was confirmed that the fragrance component remains as it is.

In the present invention, it was also confirmed that when the adsorbent and fucoidan were contacted, the flavor component of fucoidan was removed, but no color change occurred.

In an embodiment of the present invention, it was confirmed that fucoidan decolorized and deodorized may be prepared by irradiating fucoidan solution at a temperature of 50 ° C. and contacting the irradiated fucoidan solution with activated carbon or silica gel.

Therefore, the present invention in one aspect, (a) irradiating the fucoidan solution at a temperature of 40 ~ 80 ℃ to decolorize; And (b) contacting the decolorized fucoidan solution with an adsorbent to deodorize the aroma of fucoidan.

In another aspect, the present invention comprises the steps of (a) contacting the fucoidan solution with an adsorbent to deodorize the flavor of fucoidan; And (b) irradiating the deodorized fucoidan solution at a temperature of 40 ° C. to 80 ° C. to decolorize the light.

In the present invention, the light may be characterized in that the sunlight, ultraviolet light, visible light, infrared light having a wavelength of 320 ~ 2500nm.

 The light is preferably irradiated for 3 to 4 hours. When the light irradiation time is less than 3 hours, the decolorization (decomposition) effect is weak, and when more than 4 hours, fucoidan is deteriorated.

In the present invention, decolorization means that dark green, which is an inherent color of fucoidan, is changed to pale yellowish brown, pale reddish brown, or transparent color.

The light irradiation is preferably carried out at a temperature of 40 ~ 80 ℃. If the temperature to perform the light irradiation is less than 40 ℃ fucoidan decolorizing effect is weak, if it exceeds 80 ℃ fucoidan is a problem that is deteriorated.

In the present invention, the adsorbent may be selected from the group consisting of activated carbon, silica gel, diatomaceous earth, zeolite, bentonite, alumina, charcoal and mixtures thereof.

The amount of the adsorbent may be 5 to 30 parts by weight based on 100 parts by weight of dried fucoidan. If the amount of the adsorbent is less than 5 parts by weight, the deodorizing effect is weak, and if it exceeds 30 parts by weight, the deodorizing effect does not increase any more, only the amount of use is increased and economically undesirable.

Although the concentration of the fucoidan solution used in the present invention is not particularly limited, it is preferable to use 5 wt% to 20 wt%.

In the method of manufacturing the decolorized and deodorized fucoidan according to the present invention, the decolorization step of fucoidan by the light irradiation and the deodorization step of fucoidan using an adsorbent may be performed by changing the order, or two steps may be simultaneously performed in a single process. have.

That is, the fucoidan solution may be decolorized by performing light irradiation while contacting with an adsorbent to deodorize it.

As the method of contacting the fucoidan solution with the adsorbent, a method in which the fucoidan solution passes through the column filled with the adsorbent, a method of mixing the adsorbent and the fucoidan solution, and stirring or shaking may be exemplified. In the light irradiation step, light must be transmitted, and thus, the reactor vessel material is preferably glass, acrylic, polycarbonate, or the like.

Fucoidan prepared by the above method has the characteristics that terpenes are removed by 50% or more, the L value (lightness) is 40 or more, the a value (redness) is -4.0 or more, and the b value (yellowness) is 8.0 or more when measuring a color difference meter. .

On the other hand, the present invention predicted that fucoidan decolorized and deodorized could be produced even when using an ultrafiltration membrane.

In another embodiment of the present invention, after passing the fucoidan solution to the ultrafiltration membrane having a cutoff of 100 kDa to 500 kDa, the deodorization and decolorization effects of the ultrafiltration membrane could be confirmed using gas chromatography and a color difference meter.

Therefore, in another aspect, the present invention relates to a method for producing decolorized and deodorized fucoidan, characterized in that the fucoidan solution is permeated through an ultrafiltration membrane having a cutoff of 100 kDa to 500 kDa.

The ultrafiltration membrane is a membrane capable of fractionating a substance dissolved or dispersed in a liquid by particle size or molecular weight size. In the present invention, the ultrafiltration membrane can be used without limitation, but it is preferable to use a cutoff range of the molecular weight that can be fractionated is 100 kDa to 500 kDa. When the cutoff of the ultrafiltration membrane is less than 100 kDa, fucoidan having excellent decolorizing and deodorizing effects can be obtained, but the yield is low, and there is a concern that the bioactive components of fucoidan are removed, and when it exceeds 500 kDa, decolorizing and deodorizing The effect may be weak.

When the fucoidan solution is permeated to the ultrafiltration membrane, the pressure is preferably 1 to 4 bar, more preferably at 2.4 to 2.6 bar. If the pressure is less than 1 bar, there is a problem of low production speed, if it exceeds 4 bar there is a high device cost problem.

Fucoidan prepared by the above method has the characteristics that terpenes are removed by 60% or more, the L value (lightness) is 80 or more, the a value (redness) is 2.0 or more, and the b value (yellowness) is 10.0 or more when the colorimeter is measured. Usually, when fucoidan with a molecular weight of 100 kDa or more is concentrated about 10% by weight, it is known to exhibit an opaque color.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples.

Example 1: Confirm the decolorization effect of fucoidan by light irradiation

In order to confirm the discoloration of fucoidan by light irradiation, a) air atmosphere + light blocking, b) nitrogen atmosphere + light c) air color + light decoloring experiments were performed.

After 200 ml of fucoidan solution containing 10% by weight of fucoidan (manufactured by Halim Fucoidan, weight average molecular weight 50,000 to 100,000) was added to an Erlenmeyer flask, the reaction was carried out at 50 ° C. for 4 hours and the reaction was carried out. The result was confirmed.

As shown in FIG. 1, the color change was minimal when the light was contacted with the air and the light was blocked. However, when the light was irradiated in a nitrogen atmosphere and the light was irradiated in an air atmosphere, the color of the fucoidan solution was dark green to yellowish brown. It was confirmed that the change. That is, it was confirmed that there is a color change by oxidation of oxygen in the air, but it is very weak and the color change by light is strong.

In order to confirm the appropriate light irradiation time, the color change of the changed fucoidan solution was measured using a color difference meter (COLORI-METER JC801S) for each time zone while irradiating light in an oxygen atmosphere, and the results are shown in Table 1 below.

TABLE 1

Sample L value (lightness)
0 to 100
black white a value (redness)
-80 to 100
green red b value (yellowness)
-80 to 80
blue yellow Standard (water) 91.7 0.28 2.69 Discoloration Fucoidan 36.94 -5.48 5.25 Discoloration 1h 38.94 -4.44 6.59 Discoloration 2h 41.54 -4.22 8.25 Discoloration 3h 43.07 -3.47 9.12 Discoloration 4h 44.03 -2.76 9.2 Discoloration 5h 45.62 -2.39 9.79 Discoloration 6h 45.83 -0.67 11.12 Discoloration 7h 45.82 -0.68 11.11 Discoloration 8h 45.83 -0.67 11.12

As shown in Table 1, the color change was insignificant enough to be detected by the naked eye until 2 hours, but it was confirmed that a certain color change occurred after about 3 hours, and after 6 hours, the color change was no longer changed. there was.

Example 2: Confirmation of deodorizing effect of fucoidan by adsorbent

In order to confirm the discoloration and deodorization of fucoidan by the adsorbent, activated carbon (900-1000 m ² / g) and silica gel (5-10 mesh, Daejeong Chemical) were used as the adsorbent.

1.0 g of adsorbent was added to 100 ml of fucoidan solution containing 10 wt% of fucoidan (manufactured by Halim Fucoidan, weight average molecular weight 50,000 to 100,000), followed by shaking at 150 rpm. At this time, the Erlenmeyer flask was in an air atmosphere at 50 ° C., and light was blocked. After 4 hours of adsorption, the color change was visually observed but there was no particular change.

On the other hand, in the fucoidan treated with the adsorbent, the sensory test by 10 sensory test personnel was confirmed by the grading method, and the algae odor was weakened.

Gas chromatograph (GC) was used to more quantitatively confirm the deodorizing effect of fucoidan. 10 ml of dichloromethan (CH ₂ Cl ₂ , 99.5%, Junsei) was mixed with 90 ml of the adsorbent before and after treatment for 10 minutes at room temperature and allowed to stand for phase separation. The supernatant was discarded and the lower layer of Dichloromethan in which the odor component was analyzed was transferred to a new vial and analyzed. Before the analysis, sodium sulfite (Na ₂ SO ₃ , 95%, Junsei) was added to completely remove traces of water present in the sample, and 1 μl of sample was injected into GC, and a split mode (20: 1) was used. . Gas chromatographic flame ionization detector (GC HP6890 / FID) was used under the analysis conditions of Table 2 below. Standard samples were α-pinene (C ₁₀ H ₁₆ , 98.5%, Fluka), menthol (C ₁₀ H ₂₀ O, 99.0%, Aldrich), geraniol (C ₁₀ H ₁₈ O, 99.0%, Fluka) and Ethanol (CH ₃ OH, 99.8%, Carlo Erba).

TABLE 2

Part Parameter Condition Column HP-1 methyl Siloxane 30 m (L) * 0.25 mm (ID) *
0.25㎛ (Film Thickness)
Oven Initial Temp 70 ℃ Rate 5 ℃ / min Carrier gas flow Column flow (N2) 1ml / min

 FIG. 2 is a graph showing gas chromatograph results of fucoidan solution before contact with an adsorbent. Terpenes, alphapinene and geraniol, were detected, and geraniol was smaller than alphapinene (geraniol: alpha). Pinene = 3.8: 14.2).

After analyzing the content of terpenes remaining in the fucoidan solution after contact with the adsorbent by GC, the fucoidan solution in contact with activated carbon contained 100% of alphapinene and geraniol in the fucoidan solution not in contact with the adsorbent. In this case, it was confirmed that alphapinene was reduced to 50.1% and geraniol to 49.80%.

In the case of fucoidan solution in contact with silica gel, alphapinene and geraniol were 63.2% and geraniol when the content of alphapinene and geraniol in the fucoidan solution which was not in contact with the adsorbent was 100%, respectively. It was confirmed that the reduction.

Example 3: Confirmation of decolorization and deodorizing effect of fucoidan by light irradiation and adsorbent

In order to confirm the discoloration and deodorization of fucoidan by light irradiation and adsorbent, the method described in Example 1 and Example 2 was performed simultaneously.

100 ml of fucoidan solution and 1.0 g of activated carbon (900-1000 m ² / g) containing 10% by weight of fucoidan (manufactured by Halim Fucoidan, weight average molecular weight 50,000-100,000) were put in a Erlenmeyer flask, and the temperature was 50 ° C. Was irradiated with sunlight and shaken at 150 rpm.

As a result, after about 4 hours, a clear color change of the fucoidan solution appeared, and it was confirmed through GC that the same amount of alphapinene and geraniol as in Example 2 were adsorbed.

As a result, it was confirmed that deodorization and decolorization of the fucoidan solution could proceed simultaneously by the light irradiation and the adsorbent, and it was confirmed that the decolorization rate by the light irradiation was slightly delayed because the light irradiation was disturbed by the activated carbon used as the adsorbent. .

Example 4: Deodorization and decolorization of fucoidan by ultrafiltration membrane

In order to confirm the deodorizing and decolorizing effects of fucoidan by ultrafiltration membranes, ultrafiltration membranes with cutoffs of 100 kDa and 500 kDa were used. A feed pressure of 2.5 bar was applied and 1 liter of the fucoidan solution (10 wt% concentration) was filtered for about 4 hours. GC was used to confirm the filtrate recovery, the filtrate weight average molecular weight, the amount of α-pinene and geraniol, and the results are shown in Table 3.

[Table 3]

Ultrafiltration membrane Filtrate recovery rate (%) Filtrate weight
Average molecular weight (Da) α-pinene ^a) geraniol ^b) 100kDa 25.5 38,048 4.8 1.7 500kDa 47.1 52,066 7.2 2.9

^{a) the} stock is 14.2, ^{b) the} stock is 3.8

From Table 3, when the ultrafiltration membrane having a cutoff of 100 kDa is used, the filtrate recovery rate is low, but the deodorizing effect is excellent. It was confirmed that the fall compared to the used.

In addition, the decolorization effect of the fucoidan solution filtered through the ultrafiltration membrane using a color difference meter was confirmed, and the results are shown in Table 4.

[Table 4]

Sample L value (lightness)
0 to 100
black white a value (redness)
-80 to 100
green red b value (yellowness)
-80 to 80
blue yellow Standard (water) 96.27 2.7 11.06 Fucoidan 36.94 -5.48 5.25 100 K 95.22 2.97 13.61 500 K 84.79 4.41 21.35

As shown in Table 4 and Figure 3, when using the cutoff (100kDa) ultrafiltration membrane, it was confirmed that the transparent fucoidan solution can be obtained more decolorized than the cutoff (500kDa) ultrafiltration membrane.

Therefore, by using the ultrafiltration membrane according to the cut-off in consideration of the yield, decolorization, deodorization degree can be prepared fucoidan solution decolored and deodorized.

As described above in detail the specific parts of the present invention, it is apparent to those skilled in the art that such specific description is merely a preferred embodiment, thereby not limiting the scope of the present invention. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

1 is a photograph of a fucoidan solution irradiated with light according to an embodiment of the present invention.

2 is a graph showing a gas chromatograph result of the fucoidan solution before contact with the adsorbent.

Figure 3 is a photograph of the fucoidan solution filtered by the ultrafiltration membrane in accordance with an embodiment of the present invention.

Claims (8)

Process for preparing decolorized and deodorized fucoidan comprising the following steps: (a) decolorizing the fucoidan solution by irradiating with light at a temperature of 40 ° C. to 80 ° C .; And (b) deodorizing the aroma of fucoidan by contacting the decolorized fucoidan solution with an adsorbent. Process for preparing decolorized and deodorized fucoidan comprising the following steps: (a) contacting the fucoidan solution with an adsorbent to deodorize the aroma of fucoidan; And (b) irradiating the deodorized fucoidan solution at a temperature of 40 ° C. to 80 ° C. to decolorize the light. The method of claim 1 or 2, wherein the light is selected from the group consisting of sunlight, ultraviolet light, visible light and infrared light. The method of claim 1 or 2, wherein the light is irradiated for 3 to 4 hours. The method of claim 1 or 2, wherein the adsorbent is selected from the group consisting of activated carbon, silica gel, diatomaceous earth, zeolite, bentonite, alumina, charcoal and mixtures thereof. The method of claim 1 or 2, wherein the amount of the adsorbent is 5 to 30 parts by weight based on 100 parts by weight of dried fucoidan. A method for producing decolorized and deodorized fucoidan, characterized in that the fucoidan solution is permeated through an ultrafiltration membrane having a cutoff of 100 kDa to 500 kDa. The method of claim 7, wherein the fucoidan solution is characterized in that permeate the ultrafiltration membrane at a pressure of 1 ~ 4 bar.

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