JPS6192582A - Production of isovaleric acid and/or 2-methylbutyric acid - Google Patents
Production of isovaleric acid and/or 2-methylbutyric acidInfo
- Publication number
- JPS6192582A JPS6192582A JP21424684A JP21424684A JPS6192582A JP S6192582 A JPS6192582 A JP S6192582A JP 21424684 A JP21424684 A JP 21424684A JP 21424684 A JP21424684 A JP 21424684A JP S6192582 A JPS6192582 A JP S6192582A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- methylbutyric
- methylbutyric acid
- isovaleric acid
- isovaleric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 title claims abstract description 14
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 title claims abstract description 14
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 title claims abstract description 10
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims abstract description 7
- 244000005700 microbiome Species 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 241000222124 [Candida] boidinii Species 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 abstract description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- 241000233866 Fungi Species 0.000 abstract 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 230000000284 resting effect Effects 0.000 abstract 1
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229960002685 biotin Drugs 0.000 description 2
- 235000020958 biotin Nutrition 0.000 description 2
- 239000011616 biotin Substances 0.000 description 2
- 230000034303 cell budding Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229960000304 folic acid Drugs 0.000 description 1
- 235000019152 folic acid Nutrition 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002062 proliferating effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229960004172 pyridoxine hydrochloride Drugs 0.000 description 1
- 235000019171 pyridoxine hydrochloride Nutrition 0.000 description 1
- 239000011764 pyridoxine hydrochloride Substances 0.000 description 1
- ZUFQODAHGAHPFQ-UHFFFAOYSA-N pyridoxine hydrochloride Chemical compound Cl.CC1=NC=C(CO)C(CO)=C1O ZUFQODAHGAHPFQ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 235000019192 riboflavin Nutrition 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 229940068459 sodium pantothenate Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229960000344 thiamine hydrochloride Drugs 0.000 description 1
- 235000019190 thiamine hydrochloride Nutrition 0.000 description 1
- 239000011747 thiamine hydrochloride Substances 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
【発明の詳細な説明】 (産業上の利用分野)。[Detailed description of the invention] (Industrial application field).
本発明はイソ吉草酸及び/又は2−メチル酪酸の製造方
法に関する。The present invention relates to a method for producing isovaleric acid and/or 2-methylbutyric acid.
(発明の目的)
本発明者らは、メタノールを炭素源とするイソ吉草酸及
び/又はコーメチル酪酸の製造方法について種々検討し
た結果、カンデイダ属に属する微生物がメタノールをイ
ソ吉草酸及び/又はコーメチル酪酸に変換する能力を有
することを見出し、本発明に到遅した。(Purpose of the Invention) As a result of various studies on the production method of isovaleric acid and/or co-methylbutyric acid using methanol as a carbon source, the present inventors found that microorganisms belonging to the genus Candida convert methanol into isovaleric acid and/or co-methylbutyric acid. It was discovered that the present invention has the ability to convert into
すなわち5本発明の要旨は、カンデイダ属に属し、イソ
吉草酸及び/又はコーメチル酪酸を生産す゛る能力を有
する微生物を、炭素源としてメタノールを使用して培饗
し、培警物からイソ吉草酸及び/又は2−メチル酪酸を
得ることを特徴とするイソ吉草酸及び/又はコーメチル
酪酸の製造方法にある。In other words, the gist of the present invention is to cultivate a microorganism belonging to the genus Candida and having the ability to produce isovaleric acid and/or co-methylbutyric acid using methanol as a carbon source, and to extract isovaleric acid and co-methylbutyric acid from the cultured material. A method for producing isovaleric acid and/or co-methylbutyric acid, characterized by obtaining/or 2-methylbutyric acid.
(発明の構成) 以下、本発明の詳細な説明する。(Structure of the invention) The present invention will be explained in detail below.
本発明において使用される微生物はカンデイダ(Can
dida )属に属し、イン吉草酸及び/又はコーメチ
ル酪酸を生産する能力を有するものでアシ、たとえば、
カンデイダ ボイデイニイ(Candida boid
inii ) A−/ワ/7−3(微工研菌寄第 り!
ξ3号)が挙げられる。The microorganism used in the present invention is Candida (Candida).
dida) and has the ability to produce invaleric acid and/or co-methylbutyric acid.
Candida boid
inii) A-/Wa/7-3 (Feikoken Bacteriori!
ξ3).
この菌株は、土壌より分離されたものであり、その菌学
的性質は次のとおりである。This strain was isolated from soil, and its mycological properties are as follows.
■ 各培地における生育状態 /)YM液体培地、30″G13日間の生育状態。■ Growth status in each medium /) Growth status of YM liquid medium, 30″G, 13 days.
生育は良好で、培養液面に環状の皮膜が形成される。培
養液底部に沈澱を生ずる。Growth is good, and a ring-shaped film is formed on the surface of the culture solution. A precipitate forms at the bottom of the culture solution.
コ)YM平板寒天上の性質 30℃、3日間の培養で、生育は良好。h) Properties on YM flat plate agar Growth was good after culturing at 30°C for 3 days.
コロニーは、バター質、白色を呈する◎コロニー表面は
平滑;周縁は金縁〜やや波状、隆起状態は台状;輝光状
の光沢を呈する。細胞形態は、卵形〜楕円形、大きさ一
一/ 0.J X /、、?−,)、、l (平均J、
4 XコJ ) am h増殖様式は多極出芽、偽菌糸
を形成する。子のり胞子は形成されない。The colony is buttery and white in color. ◎ The colony surface is smooth; the periphery is gold-rimmed to slightly wavy, and the ridges are table-like; it has a luminous luster. Cell morphology is oval to oval, size 11/0. JX/,,? −, ),,l (average J,
4 X CoJ) am h Growth mode is multipolar budding, forming pseudohyphae. Ascospores are not formed.
、3)/、!r%メタノール含有液体培地、JO℃3日
間の生育状態。,3)/,! Growth state in liquid medium containing r% methanol, JO°C for 3 days.
生育は良好で培養液面に皮膜は殆ど形成されない。培養
液底部に少量の沈澱が形成される。Growth is good and almost no film is formed on the surface of the culture solution. A small amount of precipitate will form at the bottom of the culture solution.
■ 生理的性質 ■生育の範囲 pHλ〜デ 温度 io〜JO0C 37℃で生#せ ず。■ Physiological properties ■Growth range pHλ~de Temperature io~JO0C Raw at 37℃ figure.
■ 硝酸塩の同化 :あ リ
■ ゼラチン液化能:な し
■ Nap/ 耐性 :t−?チ
■ メタノール資化性:あ υ
■ ペクチン資化性:あ シ
■ ビタミン要求性:ビオチン
バントテン酸−〇a
■ 見解試験 (発酵性あシ:+9発酵性なl、:一ン
■ 炭素源の利用性(あシ:+、なしニー)l 属レベ
ルの同定
本菌株(A−/?/クー3)は、カロチノイド色素を生
産しない、偽菌糸を常に形成する、多極出芽によって増
殖する、子のり胞子を形成しないことからログ−の1ザ
・イーストl(−版・/970)に記載されているカン
デイダ(Candida )属に帰属することが判明し
た。■ Nitrate assimilation: Yes ■ Gelatin liquefaction ability: None ■ Nap/resistance: t-? ■ Methanol assimilation ability: A υ ■ Pectin assimilation ability: A ■ Vitamin requirement: Biotin bantothenic acid -〇a ■ Opinion test (Fermentability: +9 Fermentability: 1) ■ Carbon source Usability (reeds: +, none) Identification at the genus level This strain (A-/?/Ku3) does not produce carotenoid pigments, always forms pseudohyphae, grows by multipolar budding, Since it does not form ascospores, it was found that it belongs to the genus Candida, which is described in Log's 1 The Yeast I (-edition/970).
1v 種の同定
リー及び駒形(Lee & Komagata ) (
/?JrO)のメタノール資化菌の分類学的研究
’ Taxonomical 5tudy of me
thanolagsimilatingyedsts
’によればカンデイダ属の中にメタノール資化菌種とし
て3種を認めている。1v Species Identification Lee & Komagata (Lee & Komagata) (
/? Taxonomical study of methanol-assimilating bacteria by JrO)
thanolagsimilatinggyedsts
According to ', three species of methanol-assimilating bacteria are recognized within the genus Candeida.
(0,boidinii 、 O,cariosi’1
1gn1cola 。(0,boidinii, O,cariosi'1
1gn1cola.
0.1ipolytica 、 O,5uaciphi
la 、 O,utilis)。0.1ipolytica, O,5uaciphi
la, O. utilis).
これらの3種は、糖類の発酵能パターン及び糖類の資化
性パターンによって主に識別されている。These three types are mainly distinguished by their saccharide fermentability patterns and saccharide assimilation patterns.
本菌株(A−/9/7−.7)の糖類の発酵性試験及び
上記の炭素源の資化性パターンは、ロダー(lデフ0)
のザ・イースト及びリーと駒形(1910)Kよって記
載されているカンデイダ・ボイディニイ(Candid
a boidinii)の諸性質とよく合致する。The saccharide fermentability test and the above carbon source assimilation pattern of this strain (A-/9/7-.7)
Candida boidini as described by The East and Lee and Komagata (1910) K.
a boidinii).
よって本菌株(A−/9/7−j )はカンデイダ・ポ
イデイニイ(Candida boidinii )
と同定された。また本菌株(A−/ ? / 7−、
? )とカンデイダ・ボイデイニイ(0andla b
oidi−n11〕のAuthentio 5trai
n (工AM/ココ6り株)の形態上の特徴、糖類の発
酵能、炭素源の資化性、及び他の生理的性質について比
較検討したところ、本菌株(A−/ ? / ?−3)
の諸性質はカンデイダ・ポイディニイ(工AM/ココ6
デ)のそれらともよく一致した。Therefore, this strain (A-/9/7-j) is Candida boidinii.
was identified. In addition, this strain (A-/?/7-,
? ) and Candeida Voideinii (0andla b
oidi-n11]'s Authentio 5trai
A comparative study of the morphological characteristics, sugar fermentation ability, carbon source assimilation ability, and other physiological properties of this strain (A-/?/?-) was conducted. 3)
The properties of Candeida Poidini (Eng. AM/Coco6)
It was also in good agreement with those of D).
本発明において使用される培地としては、主炭素源とし
てメタノールを含むものであれば、特に制限されない。The medium used in the present invention is not particularly limited as long as it contains methanol as a main carbon source.
炭素源としては、メタノール以外に、種々の炭水化物、
有機酸等をさらに添加してもよく、窒素源としては、有
機アンモニウム塩、無機アンモニウム塩、尿素等を用い
ることができる。In addition to methanol, various carbohydrates,
An organic acid or the like may be further added, and organic ammonium salts, inorganic ammonium salts, urea, etc. can be used as the nitrogen source.
また、必要に応じ、無機物として各種リン酸塩、硫酸塩
等を使用することができ、必要に応じ各種有機栄養物を
添加することもできる。Furthermore, various phosphates, sulfates, etc. can be used as inorganic substances, and various organic nutrients can also be added as necessary.
イソ吉草酸及び/又は2−メチル酪酸の生産に際しては
、増殖菌体、休止菌体のいずれをも用いることができる
。In the production of isovaleric acid and/or 2-methylbutyric acid, both proliferating bacterial cells and dormant bacterial cells can be used.
培養物から目的物の採取、精製に際しては、一般に有機
化合物の採取、精製に用いられている方法を採用するこ
とができる。When collecting and purifying the target product from the culture, methods generally used for collecting and purifying organic compounds can be employed.
(実施例) 以下、実施例によシ、本発明をさらに説明する。(Example) The present invention will be further explained below with reference to Examples.
なお、実施例における物質の同定はガスクロマトグラフ
−質量分析等によシ標品と比較して行なった。The substances in the Examples were identified by comparison with standard samples by gas chromatography-mass spectrometry, etc.
(実施例1)
メタノ−” ” i71 b NHa01! ’I J
’ −K*HPOa / /i 。(Example 1) Methano-” ” i71 b NHa01! 'I J
' −K*HPOa / /i.
HeLtHPOi / I b MgSO4@?HtO
Oa!r & *塩酸ピリドキシンl■、ビオチンo、
oi〜、塩酸チアミン11n9、リボフラビン/ m9
%D−パントテン酸ナトリウム1In9、葉酸0.0
/ my 、 11FeSO4−7H!O/ my、Z
n80m−7H,O1mt;)、 0uBO*”jH*
OO,/ m9□、 Mn(4,・イニイA−/9/7
−J菌の斜面培養cJo0c、、y〜6日間)菌の一白
金耳を上記コルベンに接種し、/lコ往復/分の往復振
と9機で30℃IO日間培養を行ない、この培養物50
dよジイソ吉草酸J、0〜.コーメチル酪酸八k my
を得た(同時にプロピオン酸、イソ面酸を生成物として
得た)。HeLtHPOi / I b MgSO4@? HtO
Oa! r & *Pyridoxine hydrochloride l■, biotin o,
oi~, thiamine hydrochloride 11n9, riboflavin/m9
%D-sodium pantothenate 1In9, folic acid 0.0
/my, 11FeSO4-7H! O/ my, Z
n80m-7H, O1mt;), 0uBO*”jH*
OO,/m9□, Mn(4,・iniiA-/9/7
- Slant culture of J bacteriacJo0c,,y~6 days) A loopful of the bacteria was inoculated into the above Colben, and cultured at 30°C for IO days with 9 machines with reciprocating shaking of /l back and forth/min, and this culture 50
d diisovaleric acid J, 0~. Co-methylbutyric acid 8k my
(At the same time, propionic acid and isofaceic acid were obtained as products).
Claims (1)
草酸及び/又は2−メチル酪酸を生産する能力を有する
微生物を、炭素源としてメタノールを使用して培養し、
培養物からイソ吉草酸及び/又は2−メチル酪酸を得る
ことを 特徴とするイソ吉草酸及び/又は2−メチル酪酸の製造
方法。(1) Cultivating a microorganism belonging to the genus Candida and having the ability to produce isovaleric acid and/or 2-methylbutyric acid using methanol as a carbon source,
A method for producing isovaleric acid and/or 2-methylbutyric acid, which comprises obtaining isovaleric acid and/or 2-methylbutyric acid from a culture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21424684A JPS6192582A (en) | 1984-10-15 | 1984-10-15 | Production of isovaleric acid and/or 2-methylbutyric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21424684A JPS6192582A (en) | 1984-10-15 | 1984-10-15 | Production of isovaleric acid and/or 2-methylbutyric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6192582A true JPS6192582A (en) | 1986-05-10 |
| JPH0424986B2 JPH0424986B2 (en) | 1992-04-28 |
Family
ID=16652592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21424684A Granted JPS6192582A (en) | 1984-10-15 | 1984-10-15 | Production of isovaleric acid and/or 2-methylbutyric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6192582A (en) |
-
1984
- 1984-10-15 JP JP21424684A patent/JPS6192582A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0424986B2 (en) | 1992-04-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |