JP4182193B2 - Selective extraction and separation of xylidyne dyes - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for selectively extracting and separating a xylidyne pigment produced in a woody part by L. japonica which is a kind of wood-rotting fungi.
[0002]
[Prior art]
As a method for extracting and separating organic substances produced so far by wood-rotting fungi , (1) a method of extracting cells with an organic solvent, then separating the extract by liquid chromatography or column chromatography, and concentrating to dryness and, (2) of the fungus powder, with water 50-135 ° C. for 15 minutes to about 3 hours, or under a pressure of 0.1 to 0.2 MPa, extracted with hot water for 1 hour before and after minutes 30 at about 120 ° C. Then, only a method (Japanese Patent Laid-Open No. 9-238697) for extracting a sugar-protein complex from the extracted aqueous solution fraction using alcohol is known.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for efficiently and selectively extracting and separating a xylidyne pigment produced in a wood part by Rhododendron salekin belonging to a wood-rotting fungus.
[0004]
[Means for Solving the Problems]
The present inventors have conducted various studies on a method for selectively separating xylidyne pigments in the product of Rhododendron salkin , a kind of wood-rotting fungi , and as a result, water in different states was used as an extraction solvent. By extracting woody flour or bacteria containing the product in two stages, it was found that the easily soluble component and the hardly soluble component in the product can be extracted and separated separately, and the present invention was completed based on this finding It came to do.
[0005]
That is, in the present invention, the fungus powder of Rhododendron salekin or the wood powder containing the same is first treated with steam or hot water at 100 to 140 ° C. under an open pressure until the color of the extract becomes almost transparent. Te After extracting separated easily soluble components, more selective the residue Kishiridain based pigment, which comprises processing to extract and separate the flame soluble component of the blue dye at a high temperature of the pressurized hot water than 100 ° C. An extraction separation method is provided.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The Rhododendron fungus used in the present invention belongs to the Aspergillus fungus (Amycota subfamily), and the mushroom (fruit body) is formed in the wood decay part.
[0007]
[0008]
In the method of the present invention, the woody material containing the organic substance produced by Rokushogusarekin or the powder of the fungus body itself is used as a raw material, and the product is extracted and separated in two steps. That is, in the first stage, first, the above wood powder or fungus powder is treated with water vapor or hot water at a temperature of 100 to 140 ° C., preferably 120 to 135 ° C. under an open pressure, Extract and separate readily soluble components. If the temperature at this time is less than 100 ° C., the extraction is not performed efficiently, and if it exceeds 140 ° C., active ingredients such as pigments and physiologically active substances in the product are decomposed and cannot be recovered.
[0009]
Although this extraction process is performed under an open pressure, the pressure in the system may rise to about 0.2 to 0.3 MPa due to pressure loss due to sample filling. By this first stage treatment, readily soluble components in the product, such as low molecular weight phenol derivatives, are extracted and separated. This first stage of extraction is performed until the color of the extract becomes transparent.
[0010]
Next, in the second stage of the method of the present invention, the residue of the first stage is further treated with pressurized hot water at a temperature higher than 100 ° C., and relatively hardly soluble components in the product are extracted and separated. To do. At this stage, it is necessary to pressurize the water at a temperature higher than the vapor pressure so that hot water having a temperature higher than 100 ° C. maintains a complete liquid state. The pressure applied at this time is about 0.5 to 2 MPa.
[0011]
By this extraction with pressurized hot water, a hardly soluble pigment in the product, that is, a xylidyne pigment is extracted and separated. At this time, if a small amount of alkali, for example, alkali hydroxide such as sodium hydroxide or potassium hydroxide is added to the pressurized hot water, the extraction rate of the hardly soluble component can be remarkably improved. The amount of alkali added is preferably in the range of 0.001 to 0.1 mol / liter. When the amount added exceeds 0.1 mol / liter, components such as hemicellulose that are to be removed as a residual component are extracted, and the purity of useful pigments decreases, and when it is less than 0.001 mol / liter, The effect of improving the extraction speed becomes insufficient.
[0012]
By this second stage treatment, an aqueous solution containing a xylidyne dye , which is a relatively hardly soluble component in the product, is obtained. An acid is added to the aqueous solution, by adjusting the pH to 3 or less, Kishiridain based dye having a phenolic hydroxyl group to come deposited as a precipitate. When this is recovered by a normal filtration method or a centrifugal separation method, a solid pigment powder is obtained .
[0013]
Next, the method of the present invention will be specifically described with reference to the accompanying drawings. FIG. 1 is an explanatory view showing an example of an apparatus suitable for carrying out the method of the present invention. This device includes a high-pressure pump 1 for supplying water, a hot water preparation unit 2 for converting the water into hot water, an extraction unit 3 filled with raw material powder and capped at both ends with a sintered filter so as not to flow out, It comprises a cooling unit 4 for cooling the extract flowing out together with hot water from the extraction unit, and a pressure-holding valve 5 for maintaining the inside of the system at a constant pressure.
[0014]
In order to carry out the method of the present invention with such an apparatus, the extractor 3 is filled with a cell powder or woody powder containing the raw product of Rokushosarekin , which is first prepared in the hot water preparation unit 2 100. Water vapor or hot water at ˜140 ° C. is supplied under open pressure and extraction is continued until the colored extract is clear. This extract is cooled by the cooling unit 4 and is collected as an aqueous solution containing a readily soluble component in the receiver through the pressure holding valve 5.
[0015]
Next, the pressure in the system is increased to 0.5 to 2 MPa by the pressure holding valve 5, and hot water adjusted to a temperature higher than 100 ° C. in the hot water preparation unit 2 is supplied to the extraction unit 3, and the product Process until the useful components in it are completely extracted. The extract is cooled by the cooling unit 4 and is collected as an aqueous solution containing a hardly soluble component in the receiver through the pressure holding valve 5. Thus, as useful ingredients in products of good show Gusa les Kin, can be recovered Kishiridain based dyes.
[0016]
【The invention's effect】
According to the method of the present invention, it can be efficiently selectively extract separated Kishiridain based dye contained in Kishiridai emissions based color containing bacteria which had been produced in wood by six Sho Gusa les Kin.
[0017]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[0018]
Example 1
Is Rokushougusare Kin using the apparatus of the structure of FIG. 1 by pulverizing wood materials containing blue pigment produced was extracted useful components from the raw material adjusted to the following particle size 1 mm. That is, 0.7 g of the sample was charged into the extraction unit 3, and distilled water was supplied to the extraction unit 3 at a flow rate of 10 ml / min with the high-pressure pump 1. The water becomes steam or hot water at a predetermined temperature while passing through the hot water preparation unit 2 constituted by a coil installed in a heated salt bath, and flows into the extraction unit 3 from the lower part of the extraction unit to extract the sample. did. The extract flowed out of the extraction unit 3 together with hot water, cooled, and then led to a receiver under atmospheric pressure through the pressure holding valve 5. When the holding valve 5 was opened to atmospheric pressure and the hot water temperature was 130 ° C., a brown aqueous solution was obtained, and the color of the extract obtained in an extraction time of about 40 minutes became almost transparent. Thereafter, the pressure in the system was raised to 2 MPa by the pressure-holding valve 5, and pressurized hot water at the same temperature was circulated. As a result, the extract began to have a bluish color and extraction of the blue pigment was started. The extraction of the dye continued for 5 hours or more, and during this time, it was confirmed that the color of the aqueous solution became darker when the pressurized hot water temperature was increased, but the brown component flowed out again at 140 ° C or higher. It was able to extract and separate the Kishiridain based dye in this manner.
[0019]
Example 2
To the same sample as in Example 1, hot water at 130 ° C. was allowed to flow at 10 ml / min for 40 minutes under pressure release, and then a 0.01 mol / liter sodium hydroxide aqueous solution was added at 2 MPa at 10 ml / min. The dye was extracted by flowing at a flow rate. As a result, a dark blue-green dye aqueous solution was obtained, and the extraction continued for about 2 hours, but after that, contamination of the brown component was observed. When a small amount of 3.5% by mass hydrochloric acid was added to the aqueous dye solution thus obtained to adjust the pH to 3 or less, the dye component was precipitated. When this was separated by filter paper, a solid blue dye and a transparent filtrate were obtained. Obtained. It was able to extract and separate the Kishiridain based dye in this manner.
[0020]
The same procedure as in Reference Example Example 2, with respect to the mass of Hiirotake samples instead of Rokushougusare Kin, after a 130 ° C. hot water, under pressure relief, was flowed for 40 minutes at 10 ml / min, 0.01 mol / A liter-concentrated sodium hydroxide aqueous solution was flowed at a flow rate of 10 ml / min at 2 MPa to extract the dye. As a result, a dark red dye aqueous solution was obtained, and the extraction continued for about 3 hours. In this way, the phenoxazine type pigment could be extracted and separated.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of an example of an apparatus suitable for use in the method of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 High pressure pump 2 Hot water preparation part 3 Extraction part 4 Cooling part 5 Holding pressure valve

Claims (2)

First, extract the soluble powder component by treating the fungus powder of Roshshogusarekin or the woody powder containing it with steam or hot water at 100-140 ° C under open pressure until the color of the extract becomes almost transparent. After separation, further residue selective extraction separation method Kishiridain based coloring and extracting separating a high temperature of the pressurized hot water is treated with flame-soluble component of the blue dye than 100 ° C..   The selective extraction / separation method according to claim 1, wherein pressurized hot water containing an alkali is used.

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