JPS62296877A - Immobilization carrier for cell or microorganism composed of carbon or graphite having modified surface - Google Patents
Immobilization carrier for cell or microorganism composed of carbon or graphite having modified surfaceInfo
- Publication number
- JPS62296877A JPS62296877A JP61140960A JP14096086A JPS62296877A JP S62296877 A JPS62296877 A JP S62296877A JP 61140960 A JP61140960 A JP 61140960A JP 14096086 A JP14096086 A JP 14096086A JP S62296877 A JPS62296877 A JP S62296877A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- graphite
- group
- microorganisms
- cells
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 244000005700 microbiome Species 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 27
- 239000010439 graphite Substances 0.000 title claims abstract description 27
- 125000000524 functional group Chemical group 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 239000000571 coke Substances 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 5
- 239000006229 carbon black Substances 0.000 claims abstract description 5
- 239000004917 carbon fiber Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000001963 growth medium Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 230000003100 immobilizing effect Effects 0.000 description 12
- 238000007493 shaping process Methods 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002294 plasma sputter deposition Methods 0.000 description 5
- 238000005842 biochemical reaction Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 239000005373 porous glass Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000002785 anti-thrombosis Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 241000220010 Rhode Species 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
（産業上の利用分野）
本発明は、微生物の固定化に適した無機担体に関し、特
に、その表面に酸素、硫黄、ハロゲン、水素、窒素の中
から選ばれる少なくとも一種の元素を含む官能基が導入
され、表面の化学的性質が改質されたことにより、細胞
又は微生物との親和性が向上した、バイオリアクター、
培養地に適した改質された表面を有する炭素若しくは黒
鉛質から成る担体に関する。Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an inorganic carrier suitable for immobilizing microorganisms, and in particular contains oxygen, sulfur, halogen, hydrogen, and nitrogen on its surface. A bioreactor that has improved compatibility with cells or microorganisms by introducing a functional group containing at least one element selected from among the above and modifying the chemical properties of the surface.
The present invention relates to a carrier made of carbon or graphite and having a modified surface suitable for culture media.
従来、細胞又は微生物を固定化する無機担体としては多
孔質のガラス、セラミックス、金属、活性炭等が知られ
ている。Conventionally, porous glass, ceramics, metals, activated carbon, etc. are known as inorganic carriers for immobilizing cells or microorganisms.
（発明が解決しようとする問題点）
従来の細胞又は微生物の固定化方法の多くは、細胞や微
生物を高分子膜で覆ったり（包括法）架橋剤で化学的に
結合させる化学結合法という、細胞や微生物の本来の生
態系から大きく掛は離れた方法であり、同定化状態での
増殖が制限されたり、高分子膜が生化学反応の基質や生
成物の移動を妨げるなど、リアクターとしての問題を有
していた。これに対し、物理吸着或いは親和力による固
定化では、細胞や微生物の本来の生態系に最も近い状態
が実現できる。(Problems to be Solved by the Invention) Many of the conventional methods for immobilizing cells or microorganisms involve chemical bonding, in which cells or microorganisms are covered with a polymer membrane (inclusion method) or chemically bonded with a crosslinking agent. This method is far removed from the original ecosystem of cells and microorganisms, and it is difficult to use as a reactor, as growth in the identified state is restricted and the polymer membrane impedes the movement of substrates and products of biochemical reactions. I had a problem. On the other hand, immobilization by physical adsorption or affinity can achieve a state closest to the original ecosystem of cells and microorganisms.
また、担体は有ａＪＢ体と無機担体に大別され、無機担
体においては、有機担体と比較して強度、耐熱性に優れ
、再生利用が可能であり、殺菌しやすいという利点を有
している。しかし、物理吸着或いは親和力による固定化
に用いられる多孔質のガラス、セラミックス、金属、活
性炭等の無機担体においては、表面の特性、例えば、親
水性、親油性等を自由に制御しえない欠点、換言すれば
種々の細胞や微生物に対する親和性を制御しえない欠点
を有していた。また、多くの担体は高価であり、賦形の
自由度も小さいものであった。In addition, carriers are broadly classified into organic carriers and inorganic carriers, and inorganic carriers have the advantages of superior strength and heat resistance, recyclability, and ease of sterilization compared to organic carriers. . However, inorganic supports such as porous glass, ceramics, metals, and activated carbon used for immobilization by physical adsorption or affinity have the disadvantage that surface properties such as hydrophilicity and lipophilicity cannot be freely controlled; In other words, it has the disadvantage that it is not possible to control the affinity for various cells and microorganisms. Furthermore, many carriers are expensive and have limited flexibility in shaping.
従来の無［７８体の内、活性炭を除いては、これらの担
体が生化学反応生成物に混入した場合、特にその生成物
が食品、医薬品である場合には、その有害性が問題であ
った。一方、活性炭については、人体に対する安全性は
、炭素質であるがゆえに著しく高いが、本来、気体や化
学種の吸着用として作られているため、超微細な細孔を
多数有し、そのため強度が著しく低いという欠点を有し
ていた。Of the 78 conventional carriers, with the exception of activated carbon, there is a problem of toxicity when these carriers are mixed into biochemical reaction products, especially when the products are foods or medicines. Ta. On the other hand, activated carbon is extremely safe for the human body because it is carbonaceous, but since it was originally made to adsorb gases and chemical species, it has many ultra-fine pores, which makes it very strong. It had the disadvantage of being extremely low.
（問題点を解決するための手段及び作用）本来、炭素若
しくは黒鉛質は人体に対する安全性が高いばかりでなく
、生体親和性に伊れ、抗血栓性を有することが知られて
いる。(Means and effects for solving the problem) It is known that carbon or graphite is not only highly safe for the human body, but also biocompatible and has antithrombotic properties.
本発明は、表面に導入された官能基によって、表面の化
学的性質を変化させ、各種の細胞又は微生物の固定化に
適するように表面が改質された、炭素若しくは黒鉛質か
ら成る担体の提供を目的としている。The present invention provides a carrier made of carbon or graphite whose surface has been modified to be suitable for immobilizing various cells or microorganisms by changing the chemical properties of the surface by a functional group introduced onto the surface. It is an object.
即ち、細胞や微生物はその種類により生態系が異なり、
異なったｐＨを好み、異なった化学的性質を示す表面に
対して親和性を示す。そこで本発明においては、物理的
強度が高く、安価であり、賦形性に優れ、且つ無機担体
の利点を兼ね備えている炭素若しくは黒鉛材料の表面に
、各々の細胞や微生物に適した官能基が導入された担体
を提供することにより、より高い反応効率を有するリア
クターや、より高い培養効率を有する培養地の実現を目
的としている。In other words, cells and microorganisms have different ecosystems depending on their type.
They prefer different pHs and exhibit affinities for surfaces exhibiting different chemical properties. Therefore, in the present invention, a functional group suitable for each cell or microorganism is added to the surface of carbon or graphite material, which has high physical strength, is inexpensive, has excellent shapeability, and has the advantages of an inorganic carrier. By providing the introduced carrier, the aim is to realize a reactor with higher reaction efficiency and a culture medium with higher culture efficiency.
以下、本発明を構成する官能基、炭素若しくは黒鉛質に
ついて説明する。The functional group, carbon, or graphite constituting the present invention will be explained below.
本発明の官能基は酸素、硫黄、ハロゲン、水素、窒素の
中から選ばれるいずれか少なくとも一種の元素を含むヒ
ドロキシル基、カルボニル基、アルデヒド基、カルボキ
シル基、アミン基の中から選ばれる一種若しくは二種以
上であり、その導入により界面のｐＨを変化させたり、
細胞や微生物と水素結合や化学結合を形成させたり、カ
ルシウムイオン等の金属イオンを介して静電的に固定化
することもできる。The functional group of the present invention is one or two selected from hydroxyl group, carbonyl group, aldehyde group, carboxyl group, and amine group containing at least one element selected from oxygen, sulfur, halogen, hydrogen, and nitrogen. It is more than a species, and its introduction changes the pH of the interface,
It is also possible to form hydrogen bonds or chemical bonds with cells or microorganisms, or to electrostatically immobilize them via metal ions such as calcium ions.
本発明の官能基の炭素若しくは黒鉛質への導入について
は、プラズマスパッタリング、乾式酸化、湿式酸化、還
元などが利用できるが、一度導入した官能基を他の官能
基に置換する場合には、通常の有機化学的手法が使用で
き、特にヒドロキシル基、カルボニル基、アルデヒド基
、カルボキシル基のような含酸素官能基の導入は容易で
ある。Plasma sputtering, dry oxidation, wet oxidation, reduction, etc. can be used to introduce the functional group of the present invention into carbon or graphite. However, when replacing a functional group once introduced with another functional group, Organic chemical methods can be used, and it is particularly easy to introduce oxygen-containing functional groups such as hydroxyl groups, carbonyl groups, aldehyde groups, and carboxyl groups.
また、アミノ基の導入の場合にはアンモニアガスによる
プラズマスパッタリング及び含酸素官能基の有機化学的
置換が利用できるが、前者を用いることが好適である。Furthermore, in the case of introducing an amino group, plasma sputtering using ammonia gas and organic chemical substitution of oxygen-containing functional groups can be used, but it is preferable to use the former.
次に本発明の炭素若しくは黒鉛質についてはカーボンフ
ァイバー、コークス、カーボンブラックの中から選ばれ
る一種若しくは二種以上の組み合わせ、あるいは、これ
らを骨材とした成形体であり、用途に応じた賦形がなさ
れ、且つ多孔質体であることが好ましい。また、これら
については炭素質であっても黒鉛質であっても木質的に
差はないが、賦形に機械加工を要する場合には黒鉛質が
有利である。また、成形時に賦形がなされる場合或いは
特に賦形を必要としない場合には炭素質が好適であり、
一般的に炭素質の方が固く、高い強度を有する。例えば
高炉用コークスなどは、強度に優れ、安価であり、充分
な多孔性を備えており、流動床で用いる担体として好ま
しく、カーボンファイバーのマントやクロス、或いはこ
れらを熱硬化性樹脂等を用いて賦形した後、炭素化した
ものは固定床や培養地に適している。Next, the carbon or graphite of the present invention is one or a combination of two or more selected from carbon fiber, coke, and carbon black, or a molded product using these as an aggregate, and shaped according to the purpose. The material is preferably porous. Furthermore, although there is no difference in wood quality between carbonaceous and graphite materials, graphite materials are advantageous when machining is required for shaping. In addition, carbonaceous material is suitable when shaping is done during molding or when shaping is not particularly required.
Carbonaceous materials are generally harder and have higher strength. For example, coke for blast furnaces has excellent strength, is inexpensive, and has sufficient porosity, making it suitable as a carrier for use in fluidized beds. After shaping and carbonizing, it is suitable for fixed beds and culture media.
（発明の効果）
以上説明した如く、本発明の固定化担体は本来人体に対
し高い安全性を有する炭素若しくは黒鉛質の表面に導入
された官能基によって、表面の化学的性質を変化させ、
各種の細胞又は微性物の固定化に適するように表面が改
質された担体である。そして、種類により生態系が異な
り、異なったｐＨを好み、異なった化学的性質を示す表
面に対して親和性を示す細胞や微生物に適した官能基が
導入された担体を提供することができる。このためより
高い反応効率を有するリアクターや、より高い培養効率
を有する培養地を提供しうる。また、本発明の担体は物
理的強度が高く、安価であり、賦形性に優れ、且つ無機
担体の利点を兼ね備えている。これらの作用により産業
」二に大きく寄与する効果が期待できる。(Effects of the Invention) As explained above, the immobilization carrier of the present invention changes the chemical properties of the surface by the functional group introduced into the surface of carbon or graphite, which originally has high safety for the human body.
A carrier whose surface has been modified to be suitable for immobilizing various cells or microorganisms. In addition, it is possible to provide a carrier into which functional groups suitable for cells and microorganisms that have different ecosystems depending on the type, prefer different pH values, and exhibit affinities for surfaces that exhibit different chemical properties. Therefore, a reactor with higher reaction efficiency and a culture medium with higher culture efficiency can be provided. Further, the carrier of the present invention has high physical strength, is inexpensive, has excellent shapeability, and has the advantages of an inorganic carrier. These effects can be expected to greatly contribute to industry.
手続ネ市正書 （自発）
昭和６２年０２月３日
昭和６１年特許願第１４０９６０号
２、発明の名称
改質された表面を有する炭素若しくは黒鉛質から成る細
胞又は微生物の固定化担体
３、補正をする者
事件との関係 特許出願人
住 所 岐阜県大垣市神田町二丁目１番地５、補正の
内容
別紙のとおり（補正の対象に記載した事項以外は内容に
変更なし）。Procedural City Authorization (Spontaneous) February 3, 1985 Patent Application No. 140960 of 1988 2, Title of Invention Immobilization carrier for cells or microorganisms made of carbon or graphite having a modified surface 3, Relationship with the case of the person making the amendment Patent applicant address: 2-1-5, Kanda-cho, Ogaki City, Gifu Prefecture, contents of the amendment as shown in the attached sheet (no changes to the contents other than those stated in the subject of amendment).
６、添付書類の目録
ｌ）全文訂正明細書 １通
２）図面 １通
明 却１ 書
１．９！、明の名称
改質された表面を有する炭素若しくは黒鉛質から成る細
胞又は微生物の固定化担体
２、特許請求の範囲
ｌ）少なくとも表面に、酸素、硫黄、ハロゲン。6. List of attached documents l) Full text correction statement 1 copy 2) Drawings 1 copy Clearance 1 copy 1.9! , Ming Name Immobilization carrier for cells or microorganisms made of carbon or graphite having a modified surface 2, Claims 1) At least on the surface, oxygen, sulfur, halogen.
水素、窒素の中から選ばれるいずれか少なくとも一種の
元素を含む官能基が、導入されて存在することを特徴と
する改質された表面を有する炭素若しくは黒鉛質から成
る細胞又は微生物の固定化相体。An immobilized phase of cells or microorganisms made of carbon or graphite and having a modified surface characterized by the presence of introduced functional groups containing at least one element selected from hydrogen and nitrogen. body.
２）前記官能基は、ヒドロキシル基、カルボニル基、ア
ルデヒド基、カルボキシル基、アミノ基の中から選ばれ
る一種若しくは二種以上であることを特徴とする特許請
求の範囲第１項記載の固定化担体。2) The immobilization carrier according to claim 1, wherein the functional group is one or more selected from hydroxyl group, carbonyl group, aldehyde group, carboxyl group, and amino group. .
３ ） １ｉ７ｉ記炭素若しくは黒鉛質は、カーボンフ
ァイバー、コークス、カーボンブラックの中から選ばれ
る一種若しくは二種以上の組み合わせ、あるいは、これ
らを骨材とした成形体であることを特徴とする特許請求
の範囲第１項記載の固定化担体。3) A patent claim characterized in that the carbon or graphite described in 1i7i is one or a combination of two or more selected from carbon fiber, coke, and carbon black, or a molded article using these as aggregates. The immobilization carrier according to scope 1.
４）前記炭素若しくは黒鉛質は、多孔質体であることを
特徴とする特許請求の範囲第１項記載の固定化担体。4) The immobilization carrier according to claim 1, wherein the carbon or graphite is a porous material.
３、発明の詳細な説明
（産業上の利用分野）
本発明は、微生物の固定化に適した無機担体に関し、特
に、その表面に酸素、硫黄、ハロゲン、水素、窒素の中
から選ばれる少なくとも一種の元素を含む官能基が導入
され、表面の化学的性質が改質されたことにより、細胞
又は微生物との親和性が向上した、バイオリアクター、
培養地に適した改質された表面を有する炭素若しくは黒
鉛質から成る担体に関する。3. Detailed description of the invention (industrial application field) The present invention relates to an inorganic carrier suitable for immobilizing microorganisms, and in particular, the present invention relates to an inorganic carrier suitable for immobilizing microorganisms, and in particular, at least one type selected from oxygen, sulfur, halogen, hydrogen, and nitrogen is added to the surface of the inorganic carrier. A bioreactor that has improved affinity with cells or microorganisms due to the introduction of functional groups containing elements and modification of the surface chemical properties.
The present invention relates to a carrier made of carbon or graphite and having a modified surface suitable for culture media.
（従来の技術）
従来、細胞又は微生物を固定化する無機担体としては多
孔質のガラス、セラミックス、金属、活性炭等が知られ
ている。(Prior Art) Porous glass, ceramics, metals, activated carbon, and the like have been known as inorganic carriers for immobilizing cells or microorganisms.
（９，明か解決しようとする問題点）
従来の細胞又は微生物の固定化方法の多くは、細胞や微
生物を高分子膜で茨ったり（包括法）架橋剤で化学的に
結合させる化学結合法という、細胞や微生物の本来を生
態系から大きく掛は離れた方法であり、固？化状態での
増殖が制限されたり、高分子膜が生化学反応のノ＾賀や
生成物の移動を妨げるなど、リアクターとしての問題を
有していた。(9. Problems clearly sought to be solved) Many of the conventional methods of immobilizing cells or microorganisms involve chemical bonding, in which cells or microorganisms are spread over a polymer membrane (inclusion method) or chemically bonded using a crosslinking agent. This is a method that greatly separates the nature of cells and microorganisms from the ecosystem, and it is a method that is completely different from the nature of cells and microorganisms. However, it has problems as a reactor, such as growth being restricted under chemical conditions, and the polymer membrane interfering with the flow of biochemical reactions and the movement of products.
これに対し、物理吸着或いは親和力による固定化ては、
細胞や微生物の本来の生１ム系に最も近い状態か実現て
きる。In contrast, immobilization by physical adsorption or affinity
The state closest to the original biological system of cells and microorganisms can be achieved.
また、担体は右機旧体と無機担体に大別され、無機担体
においては、有ａ担体と比較して強度、耐熱性に優れ、
再生利用が可能であり、殺菌しやすいという利点を有し
ている。In addition, carriers are broadly classified into dexterous carriers and inorganic carriers, and inorganic carriers have superior strength and heat resistance compared to aluminum carriers.
It has the advantage of being recyclable and easy to sterilize.
しかし、物理吸着或いは親和力により固定化に用いられ
る多孔質のガラス、セラミックス、金属、活性炭等の無
機担体においては、表面の特性、例えば、親木性、親油
性等を自由に制御しえない欠点、換言すれば種々の細胞
や微生物に対する親和性を制御しえない欠点を有してい
た。However, inorganic supports such as porous glass, ceramics, metals, and activated carbon used for immobilization by physical adsorption or affinity have the disadvantage that surface properties such as wood-philicity and lipophilicity cannot be freely controlled. In other words, it had the disadvantage that it was not possible to control the affinity for various cells and microorganisms.
また、多くの担体は高価であり、賦形の自由度も小さい
ものであった。Furthermore, many carriers are expensive and have limited flexibility in shaping.
従来の無機担体の内、活性炭を除いては、これらの担体
か生化学反応生成物に混入した場合、特にその生成物が
食品、医薬品である場合には、その有害性か問題てあっ
た。Among conventional inorganic carriers, with the exception of activated carbon, there have been concerns about the harmfulness of these carriers when they are mixed into biochemical reaction products, especially when the products are foods or medicines.
一方、活性炭については、人体に対する安全性は、炭素
質であるがゆえに著しく高いか、本来、気体や化学種の
吸着用として作られているため、超微細な細孔を多数有
し、そのため強度か著しく低いという欠点を有していた
。On the other hand, activated carbon is either extremely safe for the human body because it is carbonaceous, or because it is originally made to adsorb gases and chemical species, it has many ultra-fine pores, which makes it very strong. It had the disadvantage of being extremely low.
（問題点を解決するための手段及び作用）本来、炭素若
しくは黒鉛質は人体に対する安全性か高いばかりでなく
、生体親和性に優れ、抗血栓性を有することか知られて
いる。(Means and effects for solving the problem) It is known that carbon or graphite is not only highly safe for the human body, but also has excellent biocompatibility and antithrombotic properties.
本発明は、表面に導入された官能基によって、表面の化
学的性質を変化させ、各種の細胞又は微生物の固定化に
適するように表面が改質された、炭素若しくは黒鉛質か
ら成る担体の提供を目的としている。The present invention provides a carrier made of carbon or graphite whose surface has been modified to be suitable for immobilizing various cells or microorganisms by changing the chemical properties of the surface by a functional group introduced onto the surface. It is an object.
即ち、細胞や微生物はその種類により生態系か異なり、
異なったＰＨを好み、異なった化学的性質を示す表面に
対して親和性を示す。In other words, cells and microorganisms have different ecosystems depending on their type.
They prefer different PHs and exhibit affinities for surfaces exhibiting different chemical properties.
そこで本発明においては、物理的強度が高く、安価であ
り、賦形性に優れ、且つ無機担体の利点を兼ね罰えてい
る炭素若しくは黒鉛材料の表面に、各々の細胞や微生物
に適した官能基が導入された担体を提供することにより
、より高い反応効率を有するリアクターや、より高い培
養効率を有する培養地の実現を目的としている。Therefore, in the present invention, a functional group suitable for each cell or microorganism is added to the surface of a carbon or graphite material that has high physical strength, is inexpensive, has excellent formability, and has the advantages of an inorganic carrier. By providing a carrier into which is introduced, the aim is to realize a reactor with higher reaction efficiency and a culture medium with higher culture efficiency.
以下、本発明なａ成する官能基、炭素若しくは黒鉛質に
ついて説明する。The functional group, carbon or graphite that constitutes the present invention will be explained below.
本発明の官能基は酸素、硫＜４、ハロゲン、水素、窒素
の中から選ばれるいずれか少なくとも一種の元素を含む
ヒドロキシル基、カルボニル基、アルデヒド基、カルボ
キシル基、アミノ基の中から選ばれる一種若しくは二種
以上であり、その導入により界面のｐＨを変化させたり
、細胞や微生物と水素結合や化学結合を形成させたり、
カルシウムイオン等の金属イオンを介して静電的に固定
化することもできる。The functional group of the present invention is one selected from a hydroxyl group, a carbonyl group, an aldehyde group, a carboxyl group, and an amino group containing at least one element selected from oxygen, sulfur <4, halogen, hydrogen, and nitrogen. or two or more types, and their introduction changes the pH of the interface, forms hydrogen bonds and chemical bonds with cells and microorganisms,
Immobilization can also be done electrostatically via metal ions such as calcium ions.
本発明の官能基の炭素若しくは黒鉛質への導入について
は、プラズマスパッタリング、乾式酸化、５ｉＩ式酸化
、還元などが利用てきるか、一度導入した官能基を他の
官能基に′ｊ！Ｉ検する場合には、通常の＃機化学的手
法か使用てき、特にヒドロキシル基、カルボニル基、ア
ルデヒド基、カルボキシル基のような含酸素官能基の導
入は容易である。In order to introduce the functional group of the present invention into carbon or graphite, plasma sputtering, dry oxidation, 5iI oxidation, reduction, etc. can be used, or the functional group once introduced can be transformed into another functional group. In the case of I-detection, conventional mechanochemical techniques can be used, and it is particularly easy to introduce oxygen-containing functional groups such as hydroxyl groups, carbonyl groups, aldehyde groups, and carboxyl groups.
また、アミノ基の導入の場合にはアンモニアガスによる
プラズマスパッタリング及び含酸素官能ノルの有機化学
的置換が利用できるか、前者を用いることかなｆ過であ
る。In addition, in the case of introducing an amino group, plasma sputtering using ammonia gas and organic chemical substitution of oxygen-containing functional groups can be used, or it is better to use the former.
次に本発明の炭素若しくは黒鉛質についてはカーボンフ
ァイバー、コークス、カーボンブラックの中から選ばれ
る〜・種若しくは二種以上の組み合わせ、あるいは、こ
れらを骨材とした成形体であり、Ｊ１１途に応した賦形
かなされ、且つ多孔質体であることか好ましい。Next, the carbon or graphite of the present invention is a species selected from carbon fiber, coke, carbon black, or a combination of two or more species, or a molded product using these as an aggregate, and is suitable for J11 applications. It is preferable that the material be shaped into a porous material.
また、これらについては炭素質であっても黒鉛質てあっ
ても本質的に差はないが、賦形に機械加工を要する場合
には黒鉛質か有利である。Although there is essentially no difference whether the material is carbonaceous or graphite, graphite is advantageous if machining is required for shaping.
また、成形時に賦形かなされる場合或いは特に賦形を必
要としない場合には炭素質か好適であり、一般的に炭素
質の方が固く、高い強１■を有する。In addition, carbonaceous materials are suitable when shaping is performed during molding or when shaping is not particularly required, and carbonaceous materials are generally harder and have higher strength 1.
例えば高炉用コークスなどは、強度に優れ、安価てあり
、充分な多孔性を備えており、流動床で用いる担体とし
て好ましく、カーボンファイバーのマットやクロス、或
いはこれらを８硬化性樹脂等を用いて賦形した後、炭素
化したものは固定度や培養地に適している。For example, coke for blast furnaces has excellent strength, is inexpensive, and has sufficient porosity, making it suitable as a carrier for use in fluidized beds. After shaping, carbonization is suitable for fixation and culture.
（実施例）
次いで１本発１」の実施例に付き説明するつ実施例１゜
まず、微生物を固定するための固定化担体として、スム
ーズサーフ −ｙ−スカーボン（５Ｍ０ＯＴＩＩ ５Ｕ
ＩＩＦＡＣＥ ＣＡＲＢＯＮ ： ｆ＆多気孔径の範囲
孔無し）、デンスサーフェスカーボン（ＤＥＮＣＥ
５ＵＲＦＡＣＥ ＧＡＩＩＢＯＮ：最多気孔径の範囲
１０〜コＯｐｓ ）、ラフサーフェスカーボン（ＲＯＵ
ＧＩＩ ５ＵＲＦＡＣＩＥ （：Ａ１１ＢＯＮ ：最多
気孔径の範囲１５０〜３００ ｇｍ ）の３種に付き、
酸素ガスプラズマ処理を施して酸素、硫黄、ハロゲン、
水素、窒素の中から選ばれるいずれか少なくとも一種の
元素を含むヒトロギシル基、カルボニル基、アルデヒド
基、カルボキシル基の中から選ばれる一種若しくは：、
種以上の官飽基を導入したものと、未処理のもの、合計
６種を用いて、培地にグルコース・ペプトン培地を用い
、試験槽内で前記固定化担体を、嫌気性メタン発酵菌と
ともに共存させ、前記固定化担体への付若量の経時変化
を測定した。(Example) Next, we will explain about the example of ``1 bottle 1.'' Example 1 First, as an immobilization carrier for immobilizing microorganisms, Smooth Surf-y-Scarbon (5M0OTII 5U
IIFACE CARBON: f & multi-pore diameter range (no pores), dense surface carbon (DENCE
5URFACE GAIIBON: Maximum pore diameter range
10～CoOps), rough surface carbon (ROU
For the three types of GII 5URFACIE (:A11BON: maximum pore diameter range 150-300 gm),
Oxygen gas plasma treatment removes oxygen, sulfur, halogen,
One or more selected from hytrogycyl, carbonyl, aldehyde, and carboxyl groups containing at least one element selected from hydrogen and nitrogen;
A total of 6 types were used, including those with more than one type of functional group introduced and those that were untreated, and a glucose/peptone medium was used as the culture medium, and the immobilized carrier coexisted with anaerobic methane fermenting bacteria in a test tank. The changes over time in the amount of adhesion to the immobilization carrier were measured.
尚、酸素ガスプラズマ処理を施した前記３！！の固定化
担体を用いた実験では１ＭＬＳＳ濃度を。In addition, the above-mentioned 3! which was subjected to oxygen gas plasma treatment! ! In experiments using immobilized carriers, the concentration was 1 MLSS.
１５００璽ｇ／Ｉ、ｐＨを７，７に設定して行った。The test was carried out at a temperature of 1500 g/I and a pH of 7.7.
また、未処理の前記３種の固定化押体を用いた実験テハ
、ＭＬＳＳａｌｆを、１０００ｍｇ／ｌ、 ｐ Ｈを７
，９に設定して行った。結果を第１図に示す。In addition, in an experiment using the three types of untreated immobilized bodies, MLSSalf was used at 1000 mg/l and pH was 7.
, 9. The results are shown in Figure 1.
（発明の効果）
以り説明した如く、本発明の固定化担体は１本来人体に
対し高い安全性を有する炭素若しくは黒鉛質の表面に導
入された官能基によって、表面の化学的性質を変化させ
、各種の細胞又は微生物の固定化に適するように表面が
改質された押体である。(Effects of the Invention) As explained above, the immobilization carrier of the present invention changes the chemical properties of the surface by introducing a functional group into the surface of carbon or graphite, which is inherently highly safe for the human body. , a pressed body whose surface has been modified to be suitable for immobilizing various cells or microorganisms.
そして、種類により生態系か異なり、異なったｐＨを好
み、異なった化学的性質を示す表面に対して親和性を示
す細胞や微生物に適した官衡基が導入された担体を提供
することができる。In addition, it is possible to provide a carrier into which a functional group suitable for cells and microorganisms that have different ecosystems depending on the type, prefer different pH values, and exhibit affinities for surfaces with different chemical properties.
このためより高い反応効率を有するリアクターや、より
高い培五効率を有する培養地を提供しつる。Therefore, a reactor with higher reaction efficiency and a culture medium with higher culture efficiency can be provided.
また、＊、発明の担体は物理的強度が高く、安価であり
、賦形性に優れ、且つ無機担体の利点を兼ね備えている
。*The carrier of the invention has high physical strength, is inexpensive, has excellent shapeability, and has the advantages of an inorganic carrier.
これらの作用により産業トに大きく寄与する効果が期待
できる。These effects can be expected to greatly contribute to industrial development.
第１ＩΔは実施例１についての固定化相体への微生物（
嫌気性メタン発酵菌）の付着有機炭素計の経時変化を示
すグラフである。
第１
ζ−
Δ−−−スムーズ サーフェス カーボンｌ−−デンス
サーフェス カーボン
０−−ラフ サーフェス カーボン
へ一一一スムーズ サーフェス カーボンローデンス
サーフェス カーボン
ローデンス サーフェス カーボン
Δ、口、Ｏ印は、酸素ガスプラズマスパッタリングを施
し、表面に官能基を導入した固定イー巨体を、Δ、ＣＩ
、０印は、未処理の固定化担体を示す。The first IΔ is the microorganism (
It is a graph showing changes over time in the attached organic carbon meter of anaerobic methane fermentation bacteria. 1st ζ− Δ−−−Smooth surface Carbon l−−Dens surface Carbon 0−−Rough surface One to one smooth surface to carbon Carbon loadance
Surface Carbon Rhodes Surface Carbon Δ, mouth, and O mark are fixed E giant bodies that have been subjected to oxygen gas plasma sputtering and functional groups have been introduced to the surface. Δ, CI
, 0 mark indicates untreated immobilization carrier.
Claims (1)
窒素の中から選ばれるいずれか少なくとも一種の元素を
含む官能基が、導入されて存在することを特徴とする改
質された表面を有する炭素若しくは黒鉛質から成る細胞
又は微生物の固定化担体。 ２）前記官能基は、ヒドロキシル基、カルボニル基、ア
ルデヒド基、カルボキシル基、アミノ基の中から選ばれ
る一種若しくは二種以上であることを特徴とする特許請
求の範囲第１項記載の固定化担体。 ３）前記炭素若しくは黒鉛質は、カーボンファイバー、
コークス、カーボンブラックの中から選ばれる一種若し
くは二種以上の組み合わせ、あるいは、これらを骨材と
した成形体であることを特徴とする特許請求の範囲第１
項記載の固定化担体。 ４）前記炭素若しくは黒鉛質は、多孔質体であることを
特徴とする特許請求の範囲第１項記載の固定化担体。[Claims] 1) Oxygen, sulfur, halogen, hydrogen,
An immobilization carrier for cells or microorganisms made of carbon or graphite and having a modified surface characterized by the presence of introduced functional groups containing at least one element selected from nitrogen. 2) The immobilization carrier according to claim 1, wherein the functional group is one or more selected from hydroxyl group, carbonyl group, aldehyde group, carboxyl group, and amino group. . 3) The carbon or graphite is carbon fiber,
Claim 1, characterized in that it is one or a combination of two or more selected from coke and carbon black, or a molded article using these as aggregates.
Immobilization carrier as described in section. 4) The immobilization carrier according to claim 1, wherein the carbon or graphite is a porous material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61140960A JPS62296877A (en) | 1986-06-16 | 1986-06-16 | Immobilization carrier for cell or microorganism composed of carbon or graphite having modified surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61140960A JPS62296877A (en) | 1986-06-16 | 1986-06-16 | Immobilization carrier for cell or microorganism composed of carbon or graphite having modified surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62296877A true JPS62296877A (en) | 1987-12-24 |
Family
ID=15280817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61140960A Pending JPS62296877A (en) | 1986-06-16 | 1986-06-16 | Immobilization carrier for cell or microorganism composed of carbon or graphite having modified surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62296877A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01171643A (en) * | 1987-12-28 | 1989-07-06 | Kohjin Co Ltd | Carrier for immobilizing microorganism |
| JP2012527242A (en) * | 2009-05-20 | 2012-11-08 | キシレコ インコーポレイテッド | Bioprocess method |
| JP2014505650A (en) * | 2010-12-30 | 2014-03-06 | オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー | Graphene derivative-carbon nanotube composite material and manufacturing method thereof |
-
1986
- 1986-06-16 JP JP61140960A patent/JPS62296877A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01171643A (en) * | 1987-12-28 | 1989-07-06 | Kohjin Co Ltd | Carrier for immobilizing microorganism |
| JP2012527242A (en) * | 2009-05-20 | 2012-11-08 | キシレコ インコーポレイテッド | Bioprocess method |
| JP2016105715A (en) * | 2009-05-20 | 2016-06-16 | キシレコ インコーポレイテッド | Bioprocessing method |
| JP2017221228A (en) * | 2009-05-20 | 2017-12-21 | キシレコ インコーポレイテッド | Bioprocessing method |
| KR20180008938A (en) * | 2009-05-20 | 2018-01-24 | 질레코 인코포레이티드 | Bioprocessing |
| JP2014505650A (en) * | 2010-12-30 | 2014-03-06 | オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー | Graphene derivative-carbon nanotube composite material and manufacturing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2126722C (en) | Functional ceramics | |
| US6107067A (en) | Porous, non-macroporous, inorganic oxide carrier body for immobilizing microorganisms for bioremediation | |
| Kowalska et al. | Biodegradation of phenols and cyanides using membranes with immobilized microorganisms | |
| JPS6029474B2 (en) | Fixed protein and its production method | |
| Niu et al. | Nitric oxide removal by wastewater bacteria in a biotrickling filter | |
| Bolton et al. | Procedure to quantify biofilm activity on carriers used in wastewater treatment systems | |
| Zhao et al. | Facile fabrication of flexible ceramic nanofibrous membranes for enzyme immobilization and transformation of emerging pollutants | |
| JPS62296877A (en) | Immobilization carrier for cell or microorganism composed of carbon or graphite having modified surface | |
| CN113307359B (en) | Composite carrier material for biological fluidized bed and preparation method thereof | |
| US6159370A (en) | Solvent and acid resistant membrane on the basis of polyacrylnitrile (PAN) and a comonomer copolymerized therewith and a method of manufacturing such a membrane | |
| US20040188351A1 (en) | Method for reducing an adsorption tendency of molecules or biological cells on a material surface | |
| WO2021146212A1 (en) | Microbe-based systems, compositions, and methods thereof | |
| JPS60501739A (en) | Immobilized enzyme composition and its manufacturing method | |
| Vasileva et al. | Study on the behaviour of glucose oxidase immobilized on microfiltration polyamide membrane | |
| WO1999006425A1 (en) | Oxidized styrenic polymers for dna binding | |
| KR102432539B1 (en) | Media for Water Treatment Using Zeolite and Preparation Method thereof | |
| JPS63202382A (en) | Immobilized microorganism group | |
| JPH0193444A (en) | Bacteria-controlling glass microbead and manufacture | |
| Chester et al. | Advancements in biofilm carriers and gas-permeable membranes: assessment of zeolite technologies for shortcut nitrogen removal applications in wastewater | |
| Wingard Jr et al. | Epoxidation of propylene utilizing Nocardia corallina immobilized by gel entrapment or adsorption | |
| Vacková et al. | The possibility of using encapsulated nitrifiers for treatment of reject water coming from anaerobic digestion | |
| CN110452901A (en) | A kind of immobilization biological reaction filter plate and its preparation method and application | |
| JPH0191783A (en) | Inorganic carrier with surface layer containing amine for fixing microbe or cell, their manufacture and use | |
| JPS6279784A (en) | Carrier for immobilizing enzyme or such and made of carbon material | |
| Ogunbadejo et al. | Immobilization of Cyclodextrin glycosyltransferase onto three dimensional‐hydrophobic and two dimensional‐hydrophilic supports: A comparative study |