DE1492703A1 - Process for the production of candied fruits - Google Patents

Description

DR.-ING. BY KREISLER DR.-ING. SCHÖNWALD DR.-ING. TH. MEYER DR. FUES

COLOGNE 1, DEICHMANNHAUS

Cologne, the jJO. August I965 Fu / Ax / Pa .

Dr. Expl.

Takeda Chemical Industries, Ltd.

27, Doshomachi 2-chome, Higashi-ku, Osaka, Japan.

Process for the production of candied fruits

The invention is based on the finding that the enzyme mixture produced by microorganisms of the genus Trametes is formed to facilitate the candying of fruit can if the fruits are treated with this enzyme mixture during their processing into candied fruits will. This treatment will significantly reduce the time it takes to candy fruit.

By the known methods candied fruits are prepared as follows: The fruits are harvested before they are ripe full ä constantly. Fresh fruits are stored in a dilute solution of sulphurous acid or sulfur dioxide and a lime solution to bleach the color, harden the tissues and preserve the fruits until they are used. Reveals that have been kept in this lye are thoroughly leached several times in hot water before the beginning of the candying process in order to completely remove the taste of the sulfur dioxide. Before leaching, cherries are removed from the gelatinous gels and carefully pitted. Apricots are pitted without cutting the fruit in half. Plums, plums and other whole fruits are often pierced with copper wire. In the manufacture of candied peaches, fresh fruits and preserved fruits are used without

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the intermediate stage of storage in sulphurous acid is used. After the fruits have been pretreated in sulphurous acid in the manner described and made tender by boiling or after the fresh fruits have been cooked, they are placed in a syrup which contains sucrose and / or glucose in a relatively low concentration. Canned fruits are placed in this syrup straight from the can. The dipping in the syrup is carried out with a gradual increase in the sugar concentration of the syrup. For example, the fruits are placed in a syrup containing about 30 wt -.% Containing sucrose and / or glucose. The mixture is left to stand at room temperature. After an immersion time of 24 hours or more, the syrup is drained from the fruit and brought to a concentration of about 35% by weight by adding sucrose and / or glucose. The mixture is again left to stand for 24 to 48 hours. The concentration of the syrup is then in the manner described at 40 percent - increased%, to which is allowed to stand, the fruit more hours.. The process is repeated on the following days, increasing the sugar concentration by 5% by weight / day, until the syrup has reached a concentration of about $ 80. This concentration is maintained until the sugar concentration between the fruit and the syrup has equalized. The fruits are kept in this heavy syrup for at least 3 weeks until they have become plump and impregnated with the syrup. With this candying process, the sugar concentration of the syrup must be increased slowly, as the fruits shrink if the increase is rapid.

As already mentioned, the known candying processes require a long time. To shorten the candying time, a method has been proposed, for example, in which the fruits are boiled in the syrup during candying. According to another proposal, the fruit is frozen abruptly and candied while 'they are heated to about 66 ⁰ C. The so

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however, the proposed methods are considered technically useless viewed, as they have the disadvantage, among other things, that very extensive systems are required and the quality of the after this process candied fruit is bad.

According to the invention, the time required for candying is considerably shortened. The invention relates to a process for candying fruits, which is characterized in that the juicy fruits used as starting material are treated with the enzyme mixture formed by microorganisms of the Trametes genus at the latest at the start of the candying process. M.

The enzyme mixture used according to the invention to shorten the time required for candying the fruit is made by incubating microorganisms of the genus Trametes. Examples of microorganisms that can be used according to the invention are mentioned below:

Trametes purpurea Cooke

Trametes Kusanoana Imaz.

Tramfeetes malicola Berk, et Curt.

Trametes cinnabarina (Jacq.) Fr.

Trametes sanguinea (L. ex Fr.) Lloyd I

Trametes suaveolens (L.) Fr.

Trametes albida (Fr.) Bourd. et GaIz.

Trametes heteromorpha (Fr.) Lloyd

Trametes dickinsii Berk.

Trametes trogii Berk.

Trametes palisoti (Fr.) Imaz.

Trametes acuta (Bark.) Imaz.

Trametes serpens Fr.

Trametes sendaiensis Yas.

Trametes muellerl Berk.

Trametes hispida Bagl.

Trametes ljubarskyi Pilat

Trametes aneba (Berk.) Imaz. 909808/09 '! ?

Microorganisms are sometimes known by two or more different names, but the names mentioned here are based the microorganisms on the system described in "Mycological Flora of Japan" by Seiya Ito, edited by Yokendo, Tokyo, 1959 ».

The microorganisms can be incubated in a liquid or solid medium. In general, the usage is a liquid medium for the production of the enzyme mixture on an industrial scale. In most cases it is advisable to cultivate the microorganisms of the genus ™ Trametes in submerged culture. Generally done the cultivation stationary or with shaking or with ventilation.

The culture media used must be carbon and nitrogen sources which can be assimilated by the microorganisms of the genus Trametes. Examples of assimilable carbon sources are starch, dextrin, sucrose, lactose, maltose, glucose, molasses and glycerine. Examples of assimilable Sources of nitrogen are inorganic or organic compounds, such as ammonium salts, various types of Nitrates, corn steep liquor, peptone, polypeptone, meat extract, fc soybean cake, soybean flour, wheat flour, hess extract, Urea or various amino acids. Mineral salts such as calcium, magnesium, potassium, sodium, zinc, Copper or iron salts, vitamins or growth factors are added to the culture medium as auxiliary nutrients.

The incubation conditions must be set so that * · The amount of the enzyme mixture formed is maximum. These co conditions, e.g. the pH value of the medium, the incubation

_o ; temperature and duration vary depending on the type of microorganisms, • the components of the medium, etc. The BebrUtung is common in allo conveniently carried out at a temperature _ * from 25 to 32 ⁰ C. The enzyme mixture accumulated in the culture liquid usually reaches * ° after several

ten hours to several hundred hours a maximum. Of the

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The pH of the medium is generally preferably maintained at 3.0 to 6.0. The enzyme mixture can be separated from the culture liquid by the methods generally known for this purpose. It can be adsorbed on various adsorbents or precipitated by some precipitants. In addition, general methods of separation can be used, for example precipitation near the isoelectric point, salting out or dialysis or a combination of these measures for recovery and purification. The enzyme mixture is usually contained in the culture filtrate. Accordingly, it may be advantageous to separate the enzyme from the culture mixture or from the culture liquid by filtration or centrifugation% tion. For example, a culture filtrate containing the enzyme mixture can be salted out by adding an inorganic salt, such as sodium sulfate or ammonium sulfate, or separated out by adding a hydrophilic organic solvent, such as methanol, ethanol, n-propanol or acetone. The amount of these salts or hydrophilic organic solvents to be added differs depending on the nature of the salts or the hydrophilic organic solvents. For example, ammonium sulfate is preferably added to the culture filtrate up to 70% saturation. When using a hydrophilic organic solvent, 70 # saturation may be preferable. Gege- λ appropriate, the crude enzyme mixture obtained can be purified, for example by repeated salting out with ammonium sulfate. When using ammonium sulfate, the fraction of the enzyme mixture can generally be obtained at 10 to 50 # saturation.

The enzyme mixture consists of many types of enzymes, e.g. cellulase, CMC-ase, hemicellulase, protease, peptidase, Glur; anase, RNA-de polymer a se, saccharase, maltese, lactase, Xylanase, inulase, dextranase, mannase, α-amylase, ß-amylase, Lipase, pectinase and cellobiase.

The enzyme mixture is preferably used after one

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Purification has been subjected to its protease activity has been increased to greater than 100,000 units / g as determined by the method described in the Journal of General Physiology ", 22, page 79 (1938) is described with the exception that the reaction temperature 45 ° C and the pH 2.5- is. It is noteworthy that the effect of shortening the candying time does not occur at all when pure protease is used, and that the effect only when used of the mixture of the aforementioned enzymes occurs.

W For the purposes of the invention, materials containing the enzyme mixture, for example, the culture fluids, the culture, the cell bodies or the mycelium, can be used as such of the material without any further treatment when the protease activity is sufficiently high.

In the method according to the invention, the time for candying is shortened by the fact that the speed of the impregnation the fruit is increased with sugar without the fruit shrinking. This is achieved by being juicy Fruits as the starting material are treated with the enzyme mixture by the beginning of candying at the latest. The effect The shortening of the candying time according to the invention is found in all cases in which juicy fruits are used as the starting material can be used for the production of candied fruits. The effect, however, is particularly emphasized at Use of stone fruits such as cherries, apricots, plums, Plums, breastberries (jujube) and peaches. Among the stone fruits are relatively small fruits, such as cherries, Plums and apricots, more suitable as starting material for the process according to the invention. When using cherries the time required to bring the sugar concentration of the cherries to about 72 wt .- ^, to about 4 to 5 Days are shortened without the cherries shrinking (see Example 1), while with the usual procedure, in which no treatment is made with the enzyme mixture, at least 3 weeks are required for the same purpose.

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In the method according to the invention, the treatment of the fruits used with the enzyme mixture should not be made later than at the beginning of the candying process. The enzyme treatment can be done at an appropriate time in the preparation of the fruit before candying or in the initial stages of candying. The enzyme mixture causes not only a shortening of the candying time, but also in the case of the production of candied fruits, such as Maraschino cherries that need to be bleached before candying, a bleaching of the fruit. The enzyme treatment can can be made by dipping the fruit in an aqueous solution containing the enzyme mixture. The aqueous ™

Solution that is used for treatment preferably contains about 0.01 to 1.00 wt. # of the enzyme mixture, if the protease activity of the enzyme mixture is more than 100,000 units / g amounts to. The enzyme treatment is preferably carried out at a temperature between 20 and 45 ° C and at a pH value between 2.0 and 6.0 performed under stationary conditions. The duration of the enzyme treatment is different depending on the The type of fruit used, the amount of fruit, the concentration of the enzyme mixture, etc. Generally sufficient 1 to 2 days to completely soak the fruit with the enzyme mixture.

If the enzyme treatment is done at the same time as candying In the initial phase of candying, the fruits are dipped into the sugar syrup to which the enzyme mixture is added been 1st.

The fruits soaked with the enzyme mixture can be used in a shorter time Time to be soaked with the sugar. The sugar concentration in the syrup can be increased so quickly that it is possible to shorten the duration of the candling to about a third to a sixth of the usual time for the known methods, without the juicy fruits shrinking.

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In the following examples, the quantities given are based on weight, unless otherwise stated. The two The strains of Trametes sanguinea (L.ex Pr.) Lloyd used in the experiments described are of the American type Culture Collection (ATCC), Washington, D.C, U.S.A. and accession number ATCC-I4622.

example 1

10 kg of cherries are preserved in 10 liters of a lye which contains >% sodium hydrogen sulfite and 0.1% calcium chloride. The concentration of sulfur dioxide in the lye is kept above 0.7 # by adding sodium hydrogen sulfite. After a storage period of about 3 months, the cherries are pitted and the stems removed and then immersed in about 10 liters of an oily calcium chloride solution to harden the tissue. The cherries are heated to boiling with constant changes of the water in order to reduce the sulfur dioxide content below 500 ppm.

Trametes sanguinea (L.ex Fr.) Lbyd (ATCC-14622) is inoculated on a sterilized aqueous medium which has a pH of 6.0 and contains 4 % sucrose, 2% glucose, 3 % soybean cake, 1% corn steep liquor, Contains 0.2 $ ammonium sulfate, 0.2 # potassium dihydrogen phosphate, 0.1 $ magnesium sulfate (as heptahydrate) and 0.05 # copper sulfate. The medium is stirred at 160 rpm while 500 liters of air / minute are introduced. Incubation is carried out at 28 ° C. for 140 hours. After adjusting the pH to 4.0 with ammonium sulfate, the culture liquid is filtered. Then 200 kg of aramonium sulfate are added to the 400 liters of platinum obtained, a precipitate being formed. The precipitate is separated by centrifugation and dried at 35 ⁰ C, using 4 kg of the crude enzyme powder. In 15OO ml distilled water ', 150 g of the crude enzyme powder dissolved and dlalysiert 1 day at 4 ⁰ C. The dialyzed solution is concentrated to 220 ml and salted out with ammonium sulfate at 10 to 50% saturation. This gives an enzyme mixture which has a protease activity of 187,700 units / g, determined according to

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the method described in "Journal of General Physiology", 22, Page 79 (1938) is described, but with a reaction temperature of 45 ° C and a pH of 2.5 were used. 10 g of the enzyme mixture thus obtained are dissolved in 10 liters of water solved. The solution is adjusted to pH 3.0 by adding citric acid.

The cherries are placed in the enzyme solution prepared in this way at 45 ° C. for 24 hours. After the enzyme treatment, the cherries are placed in 10 liters of water. 250 ml of a dye solution containing 3 * 5 g of erytfrosine and 1.5 g of Ponceau R (both commercially available red dyes from Hodogaya Kagaku Kabushiki Kaisha, Japan) are added to the vegetable, while the temperature is kept at 80 ° C. The mixture is left to stand for 15 minutes, after which 100 ml of an aqueous tartaric acid solution is added. The mixture is held at 80 ° C. for an additional 40 minutes. This will color the cherries and deactivate the enzymes in the cherries. The cherries are dipped in 10 liters of a syrup containing 40 # sucrose. The mixture is left to stand for 24 hours at room temperature, whereupon all of the syrup is drained from the dip tank and brought to a concentration of 60% by adding sucrose. The cherries are placed in the 60 # sucrose syrup, whereupon the mixture is left to stand at room temperature. After 24 hours, the syrup is drained from the dip tank and brought to a concentration of 70 $ by adding sucrose. After staying in 70 # syrup for 24 hours, its concentration on the catfish described is brought to 80 #. After 24 hours of immersion, the syrup is brought back to $ 80 by adding sucrose, after which the cherries are left in the syrup for an additional 24 hours.

~, Achieved at the above-mentioned candying time of 5 days

^ T the concentration of sucrose in the cherries about 72Ji,

<£> without the cherries shrinking. The cherries will turn out

taken to the syrup and dried in the usual way.

In comparison tests carried out without enzyme treatment

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It took 21 days to treat the cherries with sucrose to a concentration of about 72 # soak without the cherries shrinking.

Example 2

10 kg of fresh cherries are bleached for 2 days in 10 liters kept an aqueous solution having a pH of 4.0, 0.2 $ of the enzyme mixture used in Example 1 contains

ο
and held at 25 C. The cherries are pitted and the stems removed and then placed in 10 liters of an aqueous calcium chloride solution in order to harden the tissue of the cherries. After coloring in the manner described in Example 1, the cherries are candied for 5 days in the manner described in Example 1, the sugar concentration in the cherries reaching about $ 70 without the cherries shrinking. The cherries are removed from the syrup and dried in the usual way.

example J>

10 kg plums are held Jt months in 10 liters of the liquor described in Example. 1 After removing from the liquor, the plums are pierced with copper wires and then kept for 2 days in 10 liters of an aqueous solution which has a pH of 4.5, 0.1 $ of the enzyme mixture mentioned in Example 1 and at 45 ° C is held. The plums are placed in 10 liters of water and then kept at 80 ° C for 2 hours, which deactivates the enzymes remaining in the fruit. The plums are candied for 5 days in the manner described in Example 1, the sugar concentration in the fruits reaching about 70% without the fruits shrinking. The plums are removed from the syrup and dried in the usual way.

In comparative tests carried out without prior enzyme treatment, it took 22 days for the sugar concentration in the plums to reach 70% without any

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the fruits shredded.

example

10 kg of apricots are kept in 10 liters of the liquor described in Example 1 for 3 months. After removal from the liquor, the. Pitted apricots. They are then kept for 2 days in 10 liters of an aqueous solution having a pH of 3 * 0, 0,2Ji of the enzyme mixture described in Example 1 contains and maintained at 40 ⁰ C. The apricots are then placed in 10 liters of water and kept at 80 ° C for 2 hours, which deactivates the enzymes remaining in the fruit. The apricots are candied for 6 days in the manner described in Example 1, the sugar concentration in the apricots reaching about 70 ° without the apricots shrinking. The treated apricots are removed from the syrup and dried in the usual way.

In comparative tests that were carried out without prior enzyme treatment, 23 days were required to achieve the Apricots to a sugar concentration of about 70 # too soak without the apricots shrinking.

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Claims (4)

H92703 - 12 claims 1. Process for the production of candied fruits using juicy fruits as starting material, thereby characterized in that the juicy fruit starting material with one formed by microorganisms of the genus Trametes Treated enzyme mixture and this treatment does not later than at the beginning of candying. 2. The method according to claim 1, characterized in that the 'fruit raw material in an aqueous phase and about 0.01 to 1 wt -.% Of said enzyme mixture containing solution at a pH V / ert of about 2.0 to 6.0, and is immersed at a temperature of about 15 to 50 ° C. 3. The method according to claim 1 and 2, characterized in that one works with an enzyme mixture formed by the microorganism Trametis Sanguinea (L.ex Fr.) Lloyd. 4. The method according to claim 1 to J5, characterized in that stone fruits, in particular cherries, apricots, plums, plums and / or breastberries (jujube) are subjected to the treatment. 909808/091?