KR20160134144A - Method for Removing Urushiol of Lacquer - Google Patents

Abstract

The present invention relates to a lacquer composition and a method of manufacturing the same, and more particularly, to a lacquer composition which an urushiol monomer, which is an allergen present in an aqueous solution, an organic solvent, or a mixture thereof, is removed therefrom by reacting the urushiol monomer and inducing into a polymer; and to a method of manufacturing the same. According to the present invention, urushiol included in a solution containing the urushiol, such as a lacquer tree extract, is polymerized with other urushiol or other reactants so as to remove an urushiol monomer which is an allergen. The present invention allows an urushiol allergen present in a solution composition to be effectively removed at room temperature and room pressure without affecting other materials by using the characteristics of an enzyme merely targeting to a specific material. According to the present invention, the method comprises the following steps: preparing a lacquer solution containing urushiol; extracting and removing the urushiol by adding an organic solvent; and polymerizing the urushiol or making the urushiol react with a nitrogen containing material.

Description

Method for Removing Urushiol from Lacquer Solution "

The present invention relates to a method for removing uriciol from a solution phase through an enzyme reaction. In particular, the present invention relates to a composition for inducing an allergen urushiol remaining in a juice extract of a plant containing Rhus verniciflua or Uruciol to a polymer under normal temperature and normal pressure conditions using an enzyme polymerization reaction to remove toxicity and a method for producing the same.

Uruciol is a catechol-derived fatty acid contained mainly in deciduous trees belonging to the genus Anacardiaceae (Rhus vernicifera). When the bark of Rhus verniciflua is damaged, there is more than 70% of urushiol present in the grayish white emulsion which flows out. URUSHIOL is a monomer which is the main monomer for coating film formation of lacquer which has been used for thousands of years in East Asia including Korea, and is polymerized and dried by the enzyme lacase. The lacquer sap which has been used as a paint is detoxified after drying and curing and is no longer causing allergies, but it is known to be toxic when it is in monomer form.

The technique of removing urushiol from lacquer is required because of the medicinal effect of plants that produce lacquer and urushiol. It has been known that lacquer has been effective in eliminating eosinophilia and promoting blood circulation and has been effective against insomnia, abdominal pain, gastric acid disease, diabetes, and schizophrenia. In this connection, food such as lacquer, Has been widely used. In recent years, the flavonoid component of lacquer exhibits anti-angiogenic activity, inhibiting the proliferation and metastasis of cancer cells and inducing the differentiation of cancer cells into normal cells, and also has antioxidant, hangover and gastritis inhibitory effects It turned out.

Although new medicinal ingredients of lacquer tree and lacquer sap are continuously being studied, urushiol, a strong allergen, is obstructing the industrialization and utilization of lacquer. Currently, only water-soluble extracts of lacquer and stems from which urushiol has been removed are allowed in accordance with KFDA regulations. However, consumers are exposed to lacquer due to insecure removal of urushiol. According to the majority of studies, the major medicinal components of lacquer are mainly contained in the lacquer, but they are difficult to use due to the above-mentioned problems. In the case of the above-mentioned excellent medicinal flavonoids, only two kinds of picetin and foston exist in the lacquer wood and the outer cover, but in the case of the lacquer, there are 29 main flavonoids and 40 additional flavonoids. However, its effective extraction and detoxification is difficult. In the case of the most commonly used hot water extraction method, the lacquer is thinly sliced into primary drying. In this case, most of the lacquer sap is completely dried, making it impossible to extract the medicinal ingredient. Thus, in order to utilize various pharmacological effect substances contained in lacquer and lacquer sap, there is a desperate need for a method of completely detoxifying urushiol without destroying or losing these substances.

Ursiol, a fatty acid, is a transparent brown liquid with a basic color and viscosity similar to sesame oil. It is rapidly transformed into a polymer by inducing radical formation by an enzyme, lacase. Uruciol is a highly reactive substance, as it shows the formation of a film due to an enzyme reaction, not a strong chemical desiccant. Various remedies have been developed at present using this reactivity. Conventional techniques for the extract of Rhus verniciflua are as follows: a method for removing ricotta poison from rush extracts (Application No. KR 10-1999-0056704), a process for producing lacquer drinks (Application No. KR 10-2000-0033271) (Japanese Patent Application No. 10-2010-0113820), a method of extracting toxic russus extract (Application No. KR 10-2000-0055559), a method of extracting ruminal lacquer using herb extract and herbal medicine A functional beverage and its manufacturing method (Application No. KR 10-2001-0029280), a method for producing detoxified raspberry extract and use of the extract (Application No. KR 10-2008-0071302), a method for detoxifying russus extract (Patent Application No. KR 10-2009-0133912), a method for producing a rush extract (Application No.: KR 10-2004-0053411), a method for producing a rush extract (Application No.: KR 10-2004-0071944), detoxification method of poisoned lacquer and detoxified poison The use of blood extract (Application No. KR 10-2005-0049105), the effect of irradiation and peroxyacetic acid treatment on the reduction of urushiol of Rhus verniciflua Stokes and the physiological activities. MS thesis, Chonbuk National University, Gwangju, Korea (2010). These various methods for treating urushiol are roughly divided into heat treatment method, microbial fermentation method, and methods of applying energy such as electron beam or radiation.

Most of the urushiol removal techniques employ a method in which urushiol is introduced into a high polymer or a low polymer which does not cause the 'lacquer' by reacting with urushiol itself or with additive substances by high temperature or high temperature / high pressure treatment. Such a hydrothermal treatment and the like have been reported to be low in treatment efficiency and difficult to completely remove, and it is inevitable to destroy or deform the active ingredients present in the lacquer. In addition, the additives used in the heat treatment can not provide quantitative reaction induction and clear treatment standards as complex aggregates of organic materials such as herbal medicines. There is also a problem that it is difficult to confirm the efficacy of lacquer or lacquer itself in addition to these ingredients.

Another urushiol removal technique is a fermentation technique utilizing various fermenting microorganisms and mushroom strains. These techniques are based on the phenomenon that microorganisms absorb and decompose residual urushiol through metabolism. The blind spot for these techniques is that not only urushiol but also all the substances contained in the lacquer are subject to absorption degradation in microorganisms. Existing studies on active ingredients of lacquer have shown great potentials such as anticancer, stomach protection, and increased liver activity, all of which are related to components present in lacquer or lacquer itself. However, when the fermentation technique is used, the residual of the active ingredient may be difficult due to the metabolism of the microorganism, and the result may be different depending on the microorganisms used for fermentation and fermentation conditions.

Techniques for removing urushiol by exposing to energy such as electron beam or radiation have also been developed. These techniques are not only difficult to react with trace amounts of urushiol present in opaque solutions, but also have a number of problems, such as low industrial efficiency and consumer dissatisfaction. In addition to this, there are attempts to use organic solvents or other dangerous chemicals that can not be used for food production, but their practical value is very low.

Application Number: KR 10-1999-0056704 Application Number: KR 10-2000-0033271 Application Number: KR 10-2010-0113820 Application No.: KR 10-2000-0055559 Application number: KR 10-2001-0029280 Application Number: KR 10-2008-0071302 Application number: KR 10-2009-0133912 Application number: KR 10-2004-0053411 Application number: KR 10-2004-0071944 Application Number: KR 10-2005-0049105

 The effect of irradiation and peroxyacetic acid treatment on the reduction of urushiol of Rhus verniciflua Stokes and the physiological activities. MS thesis, Chonbuk National University, Gwangju, Korea (2010).

In order to solve the problems of the prior art as described above, the present invention relates to a method for producing urushiol, which comprises extracting urushiol or urushiol remaining in a solution by using a lacquer or a seaweed to polymerize with phenol oxidizing enzyme while minimizing deformation or destruction of other substances, And a method for introducing the intermediate into an easily separable intermediate.

In order to accomplish the above object, the present invention provides a method for removing uriciol,

(A) preparing an lacquer solution containing urushiol,

(B) adding an organic solvent to the lacquer solution to extract and remove urushiol, and

(C) supplying oxygen to the remaining liquid after the extraction to polymerize urushiol in the lacquer solution, or reacting the urushiol and the nitrogen containing material in the lacquer solution.

On the other hand, the method of removing uriciol from the lacquer of the present invention

(A) preparing an extract of Rhus verniciflua obtained by hot-extraction of Rhus verniciflua,

(B) adding an organic solvent to the lacquer solution containing urushiol to extract urushiol, and then preparing the remaining liquid, and

(C) adding the remaining liquid to the extract of Rhus verniciflua and supplying oxygen to cause polymerization of urushiol in the extract of Rhus verniciflua, or reacting the urushiol with the residue and the nitrogenous substance in the extract of Rhus verniciflua .

On the other hand, the method of removing uriciol from the lacquer of the present invention

(A) preparing a liquid to be treated containing urushiol,

(B) adding an organic solvent to the lacquer solution containing urushiol to extract urushiol, and then preparing the remaining liquid, and

(C) adding the residual liquid and a nitrogen-containing substance to the liquid to be treated and supplying oxygen to polymerize urushiol in the liquid to be treated, or reacting the urushiol with the nitrogen-containing substance .

Further, in the method for removing urushiol of the present invention, part of the extracted urushiol may be added to the liquid to be treated in the step (C).

Further, in the method for removing urushiol of the present invention, an enzyme selected from the group consisting of a lacase, a peroxidase, a catalase and a mixture thereof may be added to the target liquid in the step (C).

Further, in the method of removing urushiol of the lacquer of the present invention, in the step (C), a surfactant may be added to the liquid to be treated.

The urushiol removal method of the present invention may be based on the nitrogen-containing substance, enzyme, surfactant, lacquer or Rhus verniciflua extract.

In addition, the nitrogen-containing substance may be selected from the group consisting of glycoproteins, polysaccharides, proteins, amino acids, and mixtures thereof.

In addition, the method of removing urushiol from the lacquer of the present invention provides a method of depolymerizing and reacting urushiol if less than 15% of urushiol remains in an aqueous solution or a polar / nonpolar organic solvent or mixture according to conditions

In addition, the method for removing urushiol of the present invention provides a method for detoxifying a target mixture or an extract by adding a phenol oxidizing enzyme such as lacase, peroxidase, or catalase, and a mixture thereof, and performing a polymerization reaction.

In addition, the method of removing urushiol of the present invention is characterized in that the enzymatic reaction is carried out by adding reactants including radicals, uriciol and rapidly neutralized nitrogen groups such as gums, polysaccharides, glycoproteins, amino acids and proteins, A natural mixture is added to promote the polymerization reaction, thereby improving the efficiency of removal and decontamination.

Urushiol-containing lacquer, lacquer extract or Rhus verniciflua extract is polymerized with a phenol oxidizing enzyme such as lacase or reacted with protein having high reactivity with urushiol, and urushiol is removed from the lacquer or the like. Since the urushiol-free lacquer is detoxified only by enzymatic reaction at room temperature and pressure, it can be widely used for the separation of oriental medicine, health food or pharmacological substance.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description, numerous specific details, such as specific elements, are set forth in order to provide a thorough understanding of the present invention, and it is to be understood that the present invention may be practiced without these specific details, It will be obvious to those who have knowledge of. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

The urushiol removal method of the present invention,

(A) preparing an lacquer solution containing urushiol,

(B) adding an organic solvent to the lacquer solution to extract and remove urushiol, and

(C) supplying oxygen to the remaining liquid after the extraction to polymerize urushiol in the lacquer solution, or reacting the urushiol and the nitrogen containing material in the lacquer solution.

On the other hand, the method of removing uriciol from the lacquer of the present invention

(A) preparing an extract of Rhus verniciflua obtained by hot-extraction of Rhus verniciflua,

(B) adding an organic solvent to the lacquer solution containing urushiol to extract urushiol, and then preparing the remaining liquid, and

(C) adding the remaining liquid to the extract of Rhus verniciflua and supplying oxygen to cause polymerization of urushiol in the extract of Rhus verniciflua, or reacting the urushiol with the residue and the nitrogenous substance in the extract of Rhus verniciflua .

On the other hand, the method of removing uriciol from the lacquer of the present invention

(A) preparing a liquid to be treated containing urushiol,

(B) adding an organic solvent to the lacquer solution containing urushiol to extract urushiol, and then preparing the remaining liquid, and

(C) adding the residual liquid and a nitrogen-containing substance to the liquid to be treated and supplying oxygen to polymerize urushiol in the liquid to be treated, or reacting the urushiol with the nitrogen-containing substance .

Further, in the method for removing urushiol of the present invention, part of the extracted urushiol may be added to the liquid to be treated in the step (C).

Further, in the method for removing urushiol of the present invention, an enzyme selected from the group consisting of a lacase, a peroxidase, a catalase and a mixture thereof may be added to the target liquid in the step (C).

Further, in the method of removing urushiol of the lacquer of the present invention, in the step (C), a surfactant may be added to the liquid to be treated.

The urushiol removal method of the present invention may be based on the nitrogen-containing substance, enzyme, surfactant, lacquer or Rhus verniciflua extract.

In addition, the nitrogen-containing substance may be selected from the group consisting of glycoproteins, polysaccharides, proteins, amino acids, and mixtures thereof.

In addition, the method of removing urushiol from the lacquer of the present invention provides a method of depolymerizing and reacting urushiol if less than 15% of urushiol remains in an aqueous solution or a polar / nonpolar organic solvent or mixture according to conditions

In addition, the method for removing urushiol of the present invention provides a method for detoxifying a target mixture or an extract by adding a phenol oxidizing enzyme such as lacase, peroxidase, or catalase, and a mixture thereof, and performing a polymerization reaction.

In addition, the method of removing urushiol of the present invention is characterized in that the enzymatic reaction is carried out by adding reactants including radicals, uriciol and rapidly neutralized nitrogen groups such as gums, polysaccharides, glycoproteins, amino acids and proteins, A natural mixture is added to promote the polymerization reaction, thereby improving the efficiency of removal and decontamination.

Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to these embodiments.

Example

Example 1: Ursiol detoxification using lacquer extract

Two liters of natural lacquer from China and 2 ℓ of ethanol were mixed well and centrifuged at 1,500 rpm to carefully remove the supernatant. Two liters of water were added to the residue, which was taken up with the supernatant containing urushiol. Since the surface active material is contained in the lacquer, a considerable amount of urushiol is not removed by the solvent separation, so the toxicity is maintained. The lacquer extract contains an excess amount of lacquer which is necessary for drying and hardening of lacquer (about 10 times more than necessary for drying), and a nitrogenous substance and protein which react with urushiol. Therefore, the lacquer extract does not contain any additional phenol oxidizing enzyme or nitrogen- The reaction was carried out using a turret reactor. The result of 24-hour reaction at 25 ° C with air injection of 2 L per minute was examined by GC-MS, and urushiol was not detected.

The GC-MS detection method was as follows according to the recommendations of the Food and Drug Administration.

Column: 5% Diphenyl-95% Dimethylpolysiloxane (30 m ¡0.25 mm, 0.25 μm) or equivalent

Injection section: split mode (20: 1), 225 ° C

Column temperature: 90 占 폚 to 250 占 폚 (sample was injected at 90 占 폚, the temperature was raised to 250 占 폚 at 10 占 폚 / min, and maintained for 15 minutes)

Ionization mode: EI (Electron impact)

Ionization energy: 70 eV

Carrier gas and flow rate: helium, 1.0 mL / min

Selected ion masses (m / z): 73, 179, 207, 267, M + (462, 460, 464, 458)

Example 2: Detoxification of luculose extract added with urushiol

2 liters of natural lacquer from China and 2 liters of ethanol were mixed well and centrifuged at 1,500 rpm to cauterize the supernatant. The same volume of ethanol was added again to the supernatant, and the above procedure was repeated 3 times. To purify urushiol. 100 g of the separated urushiol was added to the water-containing residue used in Example 1, mixed well, and reacted for 48 hours using a bubble column reactor under the same conditions. As a result of the GC-MS analysis, urushiol was not detected.

Example 3: Detoxification of Rhus verniciflua extract with lacquer extract

About 2 kg of 10-year old lacquer tree was sampled and 2 mm sections were prepared. Since the lacquer sap present in the lacquer tree is dried when exposed to air at room temperature, the sample is immediately added to 4 L of water and heated for 1 hour to obtain an extract. To the extract was added 100 ml of the residue obtained by adding the water of Example 1, and the mixture was reacted for 24 hours using a bubble column reactor under the same conditions. No urushiol was detected by the GC-MS method.

Example 4: Uruciol removal using lacase and water-soluble albumin

30 ml of natural lacquer and 30 ml of acetonitrile were mixed and stirred for 1 hour at 1: 1, followed by centrifugation at 4,000 rpm for 10 minutes using a centrifuge. After separating the blue receptive layer formed in the lowest layer, 60 ml of water was added to 6 ml of the separated solution and diluted, and this was used as the lacase enzyme solution of the present invention. 50 ml of urushiol was dissolved in 0.5 l of isopropanol, and the solution was diluted with 3.5 l of water, and 30 g of water-soluble albumin and 5 g of PEG (Sigma) were added. Finally, 5 ml of lactase solution was added, and the resultant mixture was mixed well and reacted in a bubble column reactor for 24 hours under the same conditions. No urushiol was detected by the GC-MS method.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Of course it is possible. Accordingly, the scope of the present invention should not be construed as being limited to the above-described embodiments, but should be determined by equivalents to the appended claims, as well as the following claims.

Claims (13)

(A) preparing an lacquer solution containing urushiol,
(B) adding an organic solvent to the lacquer solution to extract and remove urushiol, and
(C) supplying oxygen to the remaining liquid after the extraction to polymerize urushiol in the lacquer solution, or reacting the urushiol with a nitrogen containing material in the lacquer solution. The method according to claim 1,
Wherein the extracted urushiol part of the step (B) is added to the remaining liquid after the extraction in step (C). The method according to claim 1,
Wherein the enzyme is selected from the group consisting of lacase, peroxidase, catalase and a mixture thereof in the remaining liquid after the extraction in step (C). The method according to claim 1,
Wherein the surfactant is added to the remnant remaining after the extraction in the step (C). (A) preparing an extract of Rhus verniciflua obtained by hot-extraction of Rhus verniciflua,
(B) adding an organic solvent to the lacquer solution containing urushiol to extract urushiol, and then preparing the remaining liquid, and
(C) adding the residual liquid to the Rhus verniciflua extract and adding oxygen to cause polymerization of urushiol in the Rhus verniciflua extract, or reacting the urushiol with the residue and the nitrogenous substance in the extract of Rhus verniciflua Of urushiol. The method of claim 5,
The method of removing urushiol of an oak lacquer according to claim 1, wherein in step (C), the extracted urushiol part of the step (B) is added to the rush extract. The method of claim 5,
A method for removing urushiol in an oak lacquer, comprising adding an enzyme selected from the group consisting of lacase, peroxidase, catalase, and a mixture thereof to the extract of Rhus verniciflua in step (C). The method of claim 5,
A method for removing urushiol in an oak lacquer, wherein in step (C), a surfactant is added to the lacquer extract. (A) preparing a liquid to be treated containing urushiol,
(B) adding an organic solvent to the lacquer solution containing urushiol to extract urushiol, and then preparing the remaining liquid, and
(C) adding the residual liquid and a nitrogen-containing substance to the liquid to be treated, and supplying oxygen to polymerize urushiol in the liquid to be treated, or reacting the urushiol and the nitrogen- Of urushiol. The method of claim 9,
The method of removing urushiol of an oak lacquer according to claim 1, wherein in step (C), the part of urushiol extracted in step (B) is added to the liquid to be treated. The method of claim 9,
A method for removing urushiol in an oak lacquer, wherein in step (C), an enzyme selected from the group consisting of a lacase, a peroxidase, a catalase and a mixture thereof is added to the liquid to be treated. The method of claim 9,
A method for removing urushiol in an oak lacquer, which comprises adding a surfactant to the liquid to be treated in the step (C). The method according to any one of claims 1 to 12,
Wherein the nitrogen-containing substance, the enzyme, and the surfactant are derived from lacquer or Rhus verniciflua extract.