• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    in a process for hydrating a nitrile compound by the action of a micro-organism having nitrilase activity to convert the nitrile compound into the corresponding amide compound, the performances such as yield and reaction velocity are markedly enhanced by irradiation of the micro-organism with light. The process of the present invention is characterized in that (a) the micro-organism having nitrilase activity is a positive gram-staining micro-organism, (b) the microbial cells are allowed to accept light energy of at least about 1 x 10-2 pE/g microbial cells second before termination of the hydration reaction, and (c) the hydration reaction is carried out in a vessel composed at least partly of a non-light transmitting material.
    公开号:SU1530101A3
    申请号:SU843764662
    申请日:1984-07-11
    公开日:1989-12-15
    发明作者:Сатох Есиаки；Накасима Ясутака；Еномото Конехико；Фудзивара Ацуси；Дой Тосиаки
    申请人:Нитто Кагаку Когио Кабусики Кайся (Фирма)；Мицубиси Рэйон Ко, Лтд (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the field of biotechnology and. can be used in the production of amide microbiologically.
    The purpose of the invention is the acceleration of the method.
    Example 1. Washed bacterial cells of strain N-77 (Corynebacterium) are obtained by aerobic cultivation of the strain in a medium (pH) consisting of glucose 1, peptone 0.5 yeast extract 0.3, wort extract 0.3% and ferrous sulfate (ill) "7 0.05%, and washing the cells with phosphate buffer 0.05 M, the cells are dispersed in phosphate buffer, 05 M) pH 7.7 in a dark place to obtain a dispersion of cells having
    concentration of 3.5 g of dried cells / / l. The resulting cell suspension is divided into two parts. One of them is left under for an hour when irradiated with a light energy of 1.5 x 10 µU / g Cl. in c, using two sets of fluorescent fluorescent lamps with a wavelength of 400-800 nm with a power of W, and this sample is designated hereinafter as exposure to light. The other part was left at C ° C in a dark place for 4 hours, and this sample is hereinafter referred to as exposure to darkness.
    When using each of the cell suspensions, acrylamide is obtained from acrylonitrile and the rate of
    SL
    SA9

    cm
    reaction in terms of the amount of acrylamide obtained in this way.
    In the case of bacteria kept in the light, a mixture of 0.088 cells (here and below, the number is the mass of dry cells), 1 part of acrylonitrile and 98.912 parts of 0.05 M phosphate buffer (pH 7.7) are reacted 10 ° C in a 50 ml reactor for 20 minutes with stirring under the conditions described, hereinafter referred to as the reaction under irradiation conditions. In the case of bacteria maintained in the dark, this reaction is repeated, but does not provide illumination, and is referred to as the reaction in dark conditions. After completion of the reaction, the acrylamide contained in each reaction solution in which the reaction was stopped is subjected to a quantitative analysis using gas chromatography. As a result, the amount of acrylamyl (AA) per unit number of bacterial cells was 1.1 μmol AA / mg Cl. min in the reaction under irradiation and bacteria, exposed to light, and 0.3 µmol AA / mg Cl. min in the reaction in dark conditions and bacteria maintained in the dark. The relationship between these indicators (i.e., the reaction under irradiation and bacteria exposed to light / the reaction under conditions of darkness and bacteria maintained in the dark) 121.
    In the examples, the value of 41, And µmol / mg CL. the min obtained for the reaction under irradiation and bacteria exposed to light, according to example 1, is indicated by a relative indicator of 100 and. Thus, the value obtained in Example 1 for the reaction under conditions of darkness and bacteria maintained in the dark, O, 83 U.
    Examples 2-13. The reaction solution having the composition shown in Table 1 was prepared using bacterial cells kept in the light and separately kept in the dark obtained in Example 1 The reaction solution was reacted according to the procedure of Example 1. The corresponding amide compounds contained in the solution after completion reactions, subjected to quantitative analysis using gas chromatography to obtain the results shown in table 2.
    Q 0 5 „
    five
    0
    five
    0
    Examples H-18. Washed bacterial cells are obtained by preparing, according to the method of example 1, the strains of the following genus: Bacillus (CBS-9) in example 1, Bacteridium (CBS- (96) in example 15, Micrococcus (CBS-E7} in example 1b, Brevibact erium (CBS-717 ) in example 17 and Nocardla (N-775) in example l8. The washed cells are treated according to the procedure of example 1 to obtain cells that are exposed to light and darkness respectively. When cells are used in the following composition, acrylamide is obtained from acrylonitrile and the reaction rate is studied from 1PG a view of the amount of acrylamide obtained in this way.
    In the case of strains kept in the light, a mixture of 0.088 cells, 1 part acrylonitrile and 98.912 parts 0.05 M phosphate buffer (pH 7.7) is reacted for 20 minutes at 10 ° C under stirring conditions (reaction - qi under irradiation conditions). In the case of strains kept in the dark, the reaction is repeated with the difference that no illumination is produced (reaction in the dark). The acrylamide contained in each solution after the completion of the reaction is subjected to a quantitative analysis using gas throat diffraction to obtain the results shown in Table 3 (comparative data on the effect of light on amide production).
    Examples 19-21 and comparative examples 1 and 2. Washed bacterial cells of strain N-77 are obtained by aerobic cultivation of the strain in medium (pH 7.2) containing glucose 1/0, peptone 0.5, yeast extract 0.3, malt extract 0.3% and iron sulfate (W) 7 0.05%, and washing the obtained cells with 0.05 M phosphate buffer. The cells are dispersed in 0.05 M phosphate buffer (pH 7.7) in a dark place to obtain a bacterial solution with a concentration of 22.72 mg / ml.
    1 ml of each cell suspension was loaded into 50 ml steel reactors and 2 ml of 0.05 M phosphate buffer (pH 7.7) was added. The resulting cell suspension is irradiated with the light source used in Example 1 at 0 ° C for 1 or 20 hours, with the amount of incoming light energy being controlled as shown in
    tab. in a way with a slop (a filtrate having different optical sites and placed in the top part of a reactor.
    25 ml of a 5 acrylonitrile solution (in a 0.05 M phosphate buffer solution, pH 7.7) is added to each cell suspension that is irradiated with light. The mixture is reacted for 20 minutes under the same conditions of light irradiation. For comparison, the reactions are carried out in the same way, but using a cell suspension without light irradiation or when irradiated with light energy less than 1x10 2 µU / g Cg. with.
    The amount of acrylamide contained in these reaction solutions is quantitatively analyzed by gas chromatography to determine the reaction rate. The results are shown in table 4. (There is no irradiation on the rate of hydration reaction).
    PRI me R 22. Washed bacterial cells of strain N-77 are obtained by aerobic cultivation of the strain in medium (pH 7.2), containing glucose lij peptone 0.5%, yeast extract 0.3%, malt extract 0.3% and ferrous sulfate (w) 7 0.05%, and washing the obtained cells with 0.05 M phosphate buffer. Then, parts of the obtained cells (water content: 75%), .5 parts of acrylamide, 0.5 parts of K, K-methylene bisacrylamide, and 40 parts of 0.05 M phosphate buffer (pH 7.7) are mixed to form homogeneous suspension. To this was added 5 parts of a 5% aqueous solution of dimethylaminopropionitrile and 1C parts of a 2.5% aqueous solution of potassium persulfate. The mixture is polymerized at 1 ° C for 30 minutes. The resulting lumpy gel containing bacterial cells is crushed into fine particles and the particles are completely washed with 0.05 M phosphate buffer (pH 7.7) to obtain 100 hours of immobilized bacterial cells. The mobilized cells are treated with 0.05 M phosphate buffer (pH 7.7) to obtain a solution with a concentration of 3.5 g dry cells per liter. The solution of immobilized cells is divided into two portions. One was left at 0 ° C for 4 hours under the same conditions of light irradiation as in example 1, (exposure to light), and another portion


    016
    left at 0 ° C in a dark place for 4 hours (exposure in the dark).
    When using immobilized cells in the following formulations, acrylonitrile is obtained respectively in acrylamide. The reaction rate is studied from the point of view of the amount of acrylamide obtained in this way. In the case of bacteria, exposed to light, a mixture of 0.5 part gel of immobilized cells, 2.5 part acrylonitrile and 97 part 0.05 M phosphate buffer (pH 7.7) is irradiated with light in the indicated conditions and reacted with U ° C under stirring conditions for 20 minutes (reaction under light). In the case of bacteria exposure in the dark, this reaction is carried out with the exception that no light is irradiated (reaction in the dark).
    In each of the solutions after completion of the reaction, the acrylamide is subjected to quantitative analysis using gas chromatography. As a result, the reaction rate during illumination and exposure to light is 20.0 U, and in the case of reaction in the dark and exposure to darkness 0.4, and so the ratio of these indicators is 50.0.
    Examples 23 and Z. Immobilized cells of strain N-77 are exposed to light using the procedure of Example 22. k parts of the resulting immobilized cells, 2.5 parts of acrylonitrile and 9.5 parts of 0.05 M phosphate buffer (pH 7.7) are mixed and placed into a 2.5 L cubic vessel of stainless steel, the upper part of which is open. The mixture is irradiated in a vessel through an open upper surface (I cm2) using the same light source with a wavelength of 400-800 nm as in example 1, with light energy 2, i8x10 2 µU / g Cl. with or cold lamps with a power of 100 W with a light energy of 1.86 x 10 µU / g C. c and reacted. at 0 ° C. and stirring for 20 minutes, respectively. The acrylamide contained in each of the solutions upon completion of the reaction is subjected to a quantitative analysis by gas chromatography. The results are shown in Table 5. (the effect of the intensity of light irradiation on the rate of hydration reaction).
    Example 25 and comparative example 3. Immobilized cells
    the strain was prepared according to the method 22 Q, the parts of the obtained immobilized cells, .6 parts, 0.0025 M of an aqueous solution of sodium sulfate and 1.8 parts of acrylonitrile were mixed and placed in a 1 L separable glass flask, having a part made opaque The mixture in the flask is irradiated with a Cool ligbt-type lamp with a wavelength of 400-800 nm and a power of 150 W from a distance of 20 cm from the reaction solution (luminous energy of about 7x10 μE / / g c.) While simultaneously adjusting the pH to 8.5 by adding 0 , 05b sodium hydroxide solution and is reacted by adjusting the concentration of acrylonitrile in the reaction system at a level of 2% by gradually adding 17.2 parts of acrylonitrile. In this way, 10 parts of the solution are obtained upon completion of the reaction, which contains 20 acrylamides. The amount of unreacted acrylonitrile 100 million or less after 25 hours after the start of the reaction.
    In a comparative example, the reaction is repeated under the same conditions, but no light irradiation is used. The reaction solution contains not more than 1% acrylamide 25 hours after the start of the reaction.
    Reference Example 1. Strain N-77 is cultured according to the method of Example 1. The resulting N-77 β-cells are destroyed at a low temperature using a French press to obtain a cell suspension. The suspension is processed to remove amino acids and dialyzed to obtain a crude enzyme solution in the form of a fraction saturated with 50% ammonium sulfate, which contains protein at a concentration of 3.9 protein / ml. The solution is divided into 2 portions. One portion is maintained at 10 ° C for A h under the same conditions of irradiation with light as in Example 1 (exposure to light). The other portion is kept at 10 ° C for an hour in a dark place (exposure to darkness). When using a crude enzyme solution in the following formulations, acrylonitride is obtained from acrylonitrile, respectively. The rate of the reaction is studied in terms of the amount of acrylamide obtained in this way.
    In the case of bacteria, after exposure to light, a mixture of 2.5 parts of crude enzyme solution, 2.5 parts of acrylo
    five
    Q p 5
    0
    Q
    five
    five
    nitrile and V5.0 h. 0.05 M phosphate buffer is irradiated with light under the conditions described and reacted with and stirred for 20 minutes. In the case of bacteria exposure in the dark, the reaction is repeated under the same conditions, with the exception that lighting is not used. The acrylamide contained in each of the solutions after completion of the reaction is subjected to a quantitative analysis using gas chromatography. As a result, the amount of acrylamide (AA) obtained in this way amounts to US $ 3 µmol AA / mg protein min, in the case of exposure to light and reaction with irradiation, and 102 µmol AA / mg protein min in case of exposure to darkness and reaction without irradiation. The ratio of these indicators is 1.01. Thus, the effect of light irradiation is not observed.
    Reference Example 2. This experiment shows that bacteria that do not show nitrilase activity, but that have a different enzyme activity, do not experience a change in enzyme activity under the action of light irradiation.
    Washed Brevibacterium ammoniagenes (IMI) cells are obtained by aerobic cultivation of the strain in medium (pH 7.2) containing glucose, O, 5% sodium fumarate, 0.2 urea, 0.2% disubstituted potassium phosphate, 0.05% magnesium sulfate . and% solution after soaking the corn. The cells are dispersed in 0.05 M phosphate buffer (pH 7.7) in the dark to obtain a cell suspension having a concentration of 30.0 DBhzou. The bacterial solution is divided into two portions. One was left at 30 ° C for 1 hour at a distance of 20 cm from the Cool Beam lamp with a power of 150 W with a light energy of 7x102 µU / g Cl. with (exposure to light). Another portion was left at 30 ° C for 1 hour in the dark (exposure in the dark). When using these bacterial solutions in the following formulations, fumaric acid produces malic acid. The reaction rate is studied in comparison with the amount obtained in this way malic acid.
    In the case of a bacterial solution, after exposure to light, a mixture of 50 parts of the obtained bacterial solution,
    8 parts of sodium fumral and 42 m. 0.05% And phosphate buffer (pI 7.7) react at 30 ° C and stirring for 1 m under the irradiation conditions described. In the case of a bacterial solution, after aging in the dark, the reaction is carried out same conditions, but in the absence of light. Fumaric acid is precipitated by the addition of 2N HC1 and removed from the solution after the completion of the reaction, after which the malic acid content in each of the solutions after the completion of the reaction is determined by the color-measuring method using 2.7 naphthalene diol. As a result, the quantities of malic acid Bj iO μmol / OD h in the case of reaction and exposure to light, and 3.3b μmol / OD in the case of reaction and exposure to darkness. The ratio of indicators is 0.95. Thus, the effect of light irradiation is not observed.
    Examples 26-28. The method according to Examples 2-13 is carried out with the exception that a different type of nitriles is used and the amount of nitriles used is 2.5 meters.
    The results are shown in table 6 (obtaining amides from nitriles)
    The use of the method allows to intensify the hydration process when used on an industrial scale.
    five
    five
    consisting at least in part of material that is not skipped.
    2. The method according to claim 1, characterized in that the effect of light energy in an amount of at least µU / g CL. with.
    3. The method according to claim 1, characterized in that a suspension of the strain N-77 of the genus Corynehacteriiini is used. N-776 strain of the genus Nocardia, CBS- + g strain of the Bacillus genus, CBS-iSt strain of the Bacteridium genus, Micrococcus strain of the genus or CBS-717 strain of the Brevibacterium genus.
    4. The POP.1 method, characterized in that acetonitrile, propionitrile, n-butyronitrile, p-butyronitrile, n-valeronitrile, acrylonitrile, methacrylonitrile, benzonitrile, cyanopyridine, malononitrile, auctioniitrile, furanonitrile, chloroacetonitrile, PI-hydroxypropionitrile, amino-acetonitrile or B-aminopropylnitrile.
    Table 1
    Invention Formula
    1. A method of producing an amide by hydrating the starting nitrile compound with a suspension of gram-positive microorganisms with nitrilase activity at a temperature of 0-20 ° C and a pH of 6-9, followed by isolation of the target product, characterized in that to accelerate the process - The cells are exposed to light energy in an amount of not less than 1 x xy µu / g CL.s with a wavelength of 200-800 nm before and / or after contacting them with a nitrile compound, while the hydration reaction is carried out in a vessel,
    35
    IMECHANE
    The number of bacterial cells 0,088 wt.h. pH 7.7.
    2Acetonitrile
    3Metacrylonitrile Valeronitrile
    5 Cyanopyridine
    6Benzonitrile
    7 Propionitrile
    8n-Butyronitrile
    9Malononitrile
    10Succinonitrile
    11 Fumaronitrile
    12 (5-hydroxypropio
    Acetoamide 20,62,010,3
    Methacrylamide 82,21, 7
    ValeramidI, 20,720,2
    Nicotinamide 6,5,62,9
    Benzamid12,30,717,6
    Propioamide 102,03,529,
    n-Butylamide 220,05,738,9
    Malonamid119,0,29, O
    Succinamide 3 43,010,233.6
    Fumaramidb1,11,5 40,7 -Hydroxypro-Supplied light-speed energy, µU / g Cl. with the reaction
    (and)
    2, "8 X 10-2 6.7 1.86 X 10 31.9
    Ta6gitsa2
    Table3
    Table
    Table5
    Isobutyronitrile Isobutyramide
    Amino Acetonite - Amino Acetrylamide
    -Aminopropio-ui-aminopro-nitrile-piperidamide
    Table

    ABOUT
    7.2 12.0
    25.7 18.3
    权利要求:
    Claims (4)
    [1]
    1. The method of producing amide by hydration of the initial nitrile compound with a suspension of gram-positive microorganisms having nitrilase activity at a temperature of 020 ° C and pH 6-9, followed by isolation of the target product, characterized in that, in order to accelerate the method, the suspension of microorganisms mOV 45 is exposed to light energy in an amount not less than 1 x w * 2 MKE / g kl.s of wavelength 200 800 nm before and / or after contacting them with a nitrile compound with 50 hydration reaction was carried out in a vessel composed at m D partially of a material impervious reduced.
    [2]
    2. The method of pop. 1, characterized in that they are exposed to light energy in an amount of not less than 2x10 2 μE / g cells. from.
    [3]
    3. The method of pop. 1, characterized in that they use a suspension of strain N-774 of the genus Corynebacteriuni. strain N-776 of the genus Nocardia, strain CBS-494 of the genus Bacillus, strain CBS-496 of the genus Bacteridium, strain CBS-497 of the genus Micrococcus or strain CBS-717 of the genus Brevibacterium.
    [4]
    4. The method of Pop. 1, characterized in that acetonitrile, propionitrile, n-butyronitrile, p-butyronitrile, n-valeronitrile, acrylonitrile, methacrylonitrile, benzonitrile, cyanopyridine, malononitrile, succitrile, furanonitrile, chloroacetonitre are used as the nitrile compound β-hydroxypropionitrile, aminoacetonitrile or β-aminopropionitrile.
    Table 1
    Example h Starting nitrile, m.h. -0.05 M phosphate buffer, parts by weight 2 Acetonitrile 1 98,912 3 Methacrylonitrile 58,912 4. Valeronitrile 0.25 99,662 5 Cyanopyridine 1 98,912 6 Benzonitrile 0.125 99,787 7 Propionitrile 1 98,912 8 n-Butyronitrile 1 98,912 9 Malononitrile 1 98,912 10 Succinonitrile 1 98,912 eleven Fumaronitrile 1 98,912 12 Chloroacetonitrile 1 98,912 thirteen δ-Hydroxylpropionitrile 1 98,912
    Note. The number of bacterial cells, 088 wt.h. pH 7.7.
    I I
    Table 2
    Examples ------- t ----------- Starting nitrile compound The resulting amide compounds Exposure to light reaction during irradiation (s) Exposure Ratio in the dark - reaction in the dark(and) indicators for two modes 2 Acetonitrile Acetoamide 20.6 2.0 10.3 3 Methacrylonitrile Methacrylamide 82,2 1.8 45.7 4 Valeronitrile Valeramide 14.2 0.7 20,2 5 Cyanopyridine Nicotinamide 16,4 5,6 2.9 6 Benzonitrile Benzamide 12.3 0.7 17.6 7 Propionitrile Propioamide 102.0 3,5 29.4 8 n-butyronitrile n-butylamide 220.0 5.7 38.9 9 Malononitrile Malonamide 119.0 4.1 29.0 10 Succinonitrile Succinamide 343.0 10,2 33.6 eleven Fumaronitrile Fumaramide 61.1 1,5 40.7 12 β-hydroxypropio- Hydroxypro nitrile pioamide 56.4 9.0 6.3 thirteen Chloroacetonitrile Chloracetamide 289.0 6.5 44.5
    Table 3
    Examples Genus of bacteria used Strains Exposure to light - reaction upon exposure(and) Exposure in the dark is a reaction in the dark. (and) The ratio of indicators for two modes 14 Bacillus CBS-494 57.0 21.8 2.6 fifteen Bacteridium CBS-496 108,4 59.6 1.8 16 Micrococcus Cbs-497 61.8 27.5 2.2 17 Brevibacterium Cbs-717 106.8 - 1.7 62.8 18 Nocardia N-775 33.0 2.7 12.0
    Table ^
    Examples and body measures comparable The supplied light energy, μE / g CL from Reaction rate after Reaction rate after irradiation 20 h (U) exposure for 1(and) INh 191x10 ' 2 . 7.89.7 202x10-2 13,417.0 211x10 31.634.0 10 0.290.29 25x10 ' 32,43.6t a b l and c a
    At- Served light guide Speed measures energy, m kE / g cl from reactions(and) 23 2.48 X 10-2 6.7 24 1, 86 X 10 31.9
    Table 6
    Examples Starting nitrile compound The resulting amide compounds Reactions with light exposure Reactions Reaction with without light light exposure / reaction without light 26 Isobutyronitrile Isobutyramide 7.2 0 27 Aminoacetonitol Aminoacet 185 7.2 25.7 28 rile amide β-aminopropio- / 3-aminopro 220 12.0 18.3 nitrile pionamide
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB417863A|1932-04-12|1934-10-11|Paul Liebesny|A method of influencing technically useful micro-organisms, and ferments|
    US3880717A|1971-03-30|1975-04-29|Leonid Borisovich Rubin|Method of cultivating microorganisms|
    DE2215113C3|1971-03-30|1975-01-02|Univ Moskovsk|Method for cultivating microorganisms|
    IT1162484B|1978-03-29|1987-04-01|Nitto Chemical Industry Co Ltd|PE PROCEDURE TO PRODUCE ACRYLAMIDE OR METHACRYLAMIDE USING MICROORGANISMS|
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    GB8616160D0|1986-07-02|1986-08-06|Shell Int Research|Difluorobenzamide|
    US5206158A|1986-07-02|1993-04-27|Gist-Brocades N.V.|Process for the preparation of difluorobenzamide|
    SG48037A1|1990-11-14|1998-04-17|Nitto Chemical Industry Co Ltd|Biology process for production-alpha-hydroxyamide or alpha-hydroxy acid|
    TW422882B|1994-02-01|2001-02-21|Sumitomo Chemical Co|Process for production of amide compounds using microorganism|
    US5599698A|1994-12-27|1997-02-04|Montefibre S.P.A.|Modified materials based on polyacrylonitrile and process for their production|
    GB9525372D0|1995-12-12|1996-02-14|Allied Colloids Ltd|Enzymes, their preparation and their use in the production of ammonium acrylate|
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    US6060265A|1996-12-18|2000-05-09|Cytec Technology Corporation|Methods for the detoxification of nitrile and/or amide compounds|
    US5863750A|1996-12-18|1999-01-26|Cytec Tech Corp|Methods for the detoxification of nitrile and/or amide compounds|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP58125588A|JPH0235B2|1983-07-12|1983-07-12|
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