JPH04253744A - Conductive polymeric material and its production - Google Patents
Conductive polymeric material and its productionInfo
- Publication number
- JPH04253744A JPH04253744A JP3562091A JP3562091A JPH04253744A JP H04253744 A JPH04253744 A JP H04253744A JP 3562091 A JP3562091 A JP 3562091A JP 3562091 A JP3562091 A JP 3562091A JP H04253744 A JPH04253744 A JP H04253744A
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- pyrrole
- polymer material
- chitosan
- organic acid
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000463 material Substances 0.000 title abstract 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920001661 Chitosan Polymers 0.000 claims abstract description 26
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- 239000012985 polymerization agent Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 229920001940 conductive polymer Polymers 0.000 claims description 42
- 239000002861 polymer material Substances 0.000 claims description 37
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 229920000128 polypyrrole Polymers 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 11
- 125000000524 functional group Chemical group 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 2
- 230000003647 oxidation Effects 0.000 abstract 2
- 239000001301 oxygen Substances 0.000 abstract 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 abstract 1
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 108090000790 Enzymes Proteins 0.000 description 22
- 102000004190 Enzymes Human genes 0.000 description 22
- 229940088598 enzyme Drugs 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000003100 immobilizing effect Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 108010015776 Glucose oxidase Proteins 0.000 description 5
- 239000004366 Glucose oxidase Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 229940116332 glucose oxidase Drugs 0.000 description 5
- 235000019420 glucose oxidase Nutrition 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic carboxylic acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007974 sodium acetate buffer Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 244000126010 Pithecellobium dulce Species 0.000 description 1
- 235000002194 Pithecellobium dulce Nutrition 0.000 description 1
- 235000007891 Pithecellobium lobatum Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical class OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は水に溶解可能であり、か
つ、酵素の固定化に有用な官能基を有する、新規な導電
性高分子材料およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel conductive polymer material which is soluble in water and has a functional group useful for immobilizing enzymes, and a method for producing the same.
【０００２】0002
【従来の技術】導電性高分子材料は、電気、電子分野の
みならず、多くの産業分野から注目されている。2. Description of the Related Art Conductive polymer materials are attracting attention not only in the electrical and electronic fields but also in many industrial fields.
【０００３】従来から知られているポリアセチレン、ポ
リピロール、ポリチオフェン、ポリアニリン等の導電性
高分子は機械的強度が小さく、またいかなる溶媒にも不
溶であるため、その加工が容易でないという問題があっ
た。そのため最近ではピロールなどの複素５員環の３位
を直鎖アルキル基やカルボキシル基などで置換した単量
体を用い、これを電気化学的あるいは化学的に酸化重合
する方法や、ポリ塩化ビニルやポリスチレン等を、クロ
ロホルムやジメチルホルムアミド等の極性を有する非水
溶液中でピロールを酸化重合させる方法（特開平２−２
９４３２４号公報）により、有機溶媒に溶解可能な導電
性高分子材料を得られることが知られている。Conventionally known conductive polymers such as polyacetylene, polypyrrole, polythiophene, and polyaniline have low mechanical strength and are insoluble in any solvent, so they have the problem of not being easy to process. Therefore, recently, methods have been developed to use monomers in which the 3-position of a five-membered heterocyclic ring such as pyrrole is substituted with a straight-chain alkyl group or carboxyl group, and electrochemically or chemically oxidatively polymerize this, A method of oxidatively polymerizing polystyrene, etc. to pyrrole in a polar non-aqueous solution such as chloroform or dimethylformamide (Japanese Unexamined Patent Publication No. 2-2-2)
94324), it is known that a conductive polymer material soluble in an organic solvent can be obtained.
【０００４】ところで、酵素の固定化が可能な導電性高
分子材料は、酵素電極やバイオセンサー等としての利用
が可能である。従来の酵素電極は酵素の固定化部分と電
極部分が完全に分離しており、これを一体化した酵素の
固定化が可能な導電性高分子材料の開発が期待されてい
る。By the way, conductive polymer materials capable of immobilizing enzymes can be used as enzyme electrodes, biosensors, and the like. In conventional enzyme electrodes, the enzyme immobilization part and the electrode part are completely separated, and there are expectations for the development of conductive polymer materials that can integrate enzyme immobilization.
【０００５】また、酵素は生体由来であるので水系での
み活性を示すため、酵素活性を維持し、なおかつ加工成
形が可能な導電性高分子を得るためには水溶性の性質を
有し、かつ、酵素の固定化が可能な導電性高分子材料を
得ることが必要である。従来から知られている酵素の固
定化が可能な導電性高分子を得る方法としては、ポリピ
ロールを電解重合させると同時に酵素を吸着させて、ポ
リピロールのマトリックス中に包括的に酵素を固定化す
る方法が知られている（アナリテイカルケミストリー（
Ａｎａｌｉｔｉｃａｌ Ｃｈｅｍｉｓｔｒｙ）、５８巻
、１４号、２９７９頁、１９８６年、特開昭６２−１１
５２８５号公報）。[0005] Furthermore, since enzymes are derived from living organisms, they show activity only in aqueous systems. Therefore, in order to maintain enzyme activity and to obtain conductive polymers that can be processed and molded, it is necessary to have water-soluble properties and Therefore, it is necessary to obtain a conductive polymer material capable of immobilizing enzymes. A conventionally known method for obtaining a conductive polymer capable of immobilizing an enzyme is to electropolymerize polypyrrole and simultaneously adsorb the enzyme to comprehensively immobilize the enzyme in the polypyrrole matrix. is known (Analytical Chemistry)
(Analytical Chemistry), Volume 58, No. 14, Page 2979, 1986, Japanese Patent Publication No. 1986-11
5285).
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
方法では導電性高分子の成形加工が困難であるばかりで
なく、酵素の活性は低下し、また包括法による酵素の固
定化の操作は非常に繁雑であるという問題点がある。本
発明の目的は上記の問題点を解決した、水溶性であるた
め容易に成形加工が可能であり、かつ酵素の固定化に有
用な官能基を有する導電性高分子材料およびその製造方
法にある。[Problems to be Solved by the Invention] However, in the above method, not only is it difficult to mold the conductive polymer, but also the activity of the enzyme is decreased, and the operation of immobilizing the enzyme by the entrapment method is extremely difficult. The problem is that it is complicated. The object of the present invention is to provide a conductive polymer material that solves the above problems, is water-soluble, can be easily molded, and has a functional group useful for immobilizing enzymes, and a method for producing the same. .
【０００７】[0007]
【課題を解決するための手段】本発明は上記の目的を達
成するためになされたものであって、その要旨はキトサ
ンとポリピロールとを主成分とする導電性高分子材料で
あり、またその製法である。[Means for Solving the Problems] The present invention has been made to achieve the above object, and its gist is a conductive polymer material whose main components are chitosan and polypyrrole, and a method for producing the same. It is.
【０００８】以下に、本発明を詳細に説明する。本発明
において用いられるキトサンは希有機酸水溶液に溶解で
きるものであれば特に限定されるものでなく、キトサン
あるいはキチンの脱Ｎ−アセチル化物の脱アセチル化度
が５０〜１００％のものを例示することができる。また
、上記キトサンを化学修飾して得られるキトサン誘導体
群も含まれる。The present invention will be explained in detail below. The chitosan used in the present invention is not particularly limited as long as it can be dissolved in a dilute organic acid aqueous solution, and chitosan or chitin de-N-acetylated products with a degree of deacetylation of 50 to 100% are exemplified. be able to. It also includes a group of chitosan derivatives obtained by chemically modifying the chitosan described above.
【０００９】そして、本発明においてピロールとは、ピ
ロールあるいはピロールの誘導体も含む。また、本発明
でポリピロールとは、ピロールが酸化反応により重合し
導電性を発現したものを示す。[0009] In the present invention, pyrrole also includes pyrrole or pyrrole derivatives. Furthermore, in the present invention, polypyrrole refers to pyrrole that is polymerized through an oxidation reaction and exhibits conductivity.
【００１０】本発明の導電性高分子材料はポリピロール
が全体の組成中２０〜７０重量％の範囲で存在すること
が好ましい。２０重量％未満の場合、導電性は著しく低
下する。また、本発明の製造方法ではポリピロールの割
合が７０重量％を越えるような本発明の導電性高分子材
料を得ることは困難である。[0010] In the conductive polymer material of the present invention, polypyrrole is preferably present in an amount of 20 to 70% by weight in the total composition. When the amount is less than 20% by weight, the conductivity is significantly reduced. Further, with the production method of the present invention, it is difficult to obtain the conductive polymer material of the present invention in which the proportion of polypyrrole exceeds 70% by weight.
【００１１】さらに、本発明の導電性高分子材料はピロ
ールをキトサンの希有機酸溶液中で攪拌しながら重合さ
せるため、キトサンとポリピロールとは均一に混合して
いる。均一でない場合は、得られた導電性高分子材料に
導電性が均一に付与されない。Furthermore, since the conductive polymer material of the present invention polymerizes pyrrole in a dilute organic acid solution of chitosan while stirring, chitosan and polypyrrole are uniformly mixed. If it is not uniform, conductivity will not be uniformly imparted to the obtained conductive polymer material.
【００１２】本発明の導電性高分子材料はキトサンおよ
び酸化重合剤を含む希有機酸中でピロールを酸化重合さ
せた後、有機溶媒中で析出させるという方法により製造
することができる。The conductive polymer material of the present invention can be produced by a method in which pyrrole is oxidatively polymerized in a dilute organic acid containing chitosan and an oxidative polymerization agent, and then precipitated in an organic solvent.
【００１３】ピロールの酸化重合は、例えばキトサンを
溶解した希有機酸中に、酸化重合剤およびピロールを攪
拌しながら加えるという方法により行われる。この時、
酸化重合剤あるいはピロールのどちらを先に希有機酸中
に加えてもよく、予め、両者を希有機酸中に溶解させた
状態で加えてもよい。また、この際の溶液の攪拌が十分
でないと、酸化反応が部分的に進行し、導電性が均一な
導電性高分子材料が得られない恐れがある。The oxidative polymerization of pyrrole is carried out, for example, by adding the oxidative polymerizing agent and pyrrole to a dilute organic acid in which chitosan is dissolved while stirring. At this time,
Either the oxidative polymerization agent or the pyrrole may be added to the dilute organic acid first, or both may be added in a state in which they are dissolved in the dilute organic acid in advance. Furthermore, if the solution is not sufficiently stirred at this time, the oxidation reaction may proceed partially, and there is a risk that a conductive polymer material with uniform conductivity may not be obtained.
【００１４】また、このときキトサンを溶解した希有機
酸溶液中に、得られる導電性高分子材料の加工性を向上
させるために可塑剤を添加しても差し支えないが、その
分量によっては導電性が著しく低下する恐れがある。At this time, a plasticizer may be added to the dilute organic acid solution in which chitosan is dissolved in order to improve the processability of the resulting conductive polymer material, but depending on the amount, the conductivity may decrease significantly.
【００１５】有機酸はキトサンを溶解できるものであれ
ば特に限定されず、たとえば蟻酸、酢酸などの脂肪族カ
ルボン酸、安息香酸、フェニル酢酸などの芳香族カルボ
ン酸をあげることができる。用いる希有機酸の濃度は１
〜５％程度が望ましい。１％未満の場合はキトサンが十
分に溶解しないことがある。The organic acid is not particularly limited as long as it can dissolve chitosan, and examples include aliphatic carboxylic acids such as formic acid and acetic acid, and aromatic carboxylic acids such as benzoic acid and phenylacetic acid. The concentration of the dilute organic acid used is 1
~5% is desirable. If it is less than 1%, chitosan may not be sufficiently dissolved.
【００１６】キトサンの希有機酸溶液中の濃度は２重量
％以下であることが望ましい。２％を越える場合、得ら
れる導電性材料の導電性が著しく低下する恐れがある。The concentration of chitosan in the dilute organic acid solution is preferably 2% by weight or less. If it exceeds 2%, the conductivity of the resulting conductive material may be significantly reduced.
【００１７】ピロールの酸化重合剤はキトサンの希有機
酸溶液に溶解できるものであれば特に限定されず、パラ
トルエンスルホン酸第二鉄塩、塩化第二鉄、過酸化水素
、過マンガン酸カリウム、重クロム酸カリウムなどを例
示することができる。その量は後に加えるピロールのモ
ル数の３倍程度がのぞましい。これ以下の量である場合
、ピロールの酸化重合が十分に進行せず、得られる導電
性材料の導電性が著しく低下することがある。The oxidative polymerization agent for pyrrole is not particularly limited as long as it can be dissolved in the dilute organic acid solution of chitosan, and examples include ferric paratoluenesulfonate, ferric chloride, hydrogen peroxide, potassium permanganate, Examples include potassium dichromate. The amount is preferably about three times the number of moles of pyrrole to be added later. If the amount is less than this, the oxidative polymerization of pyrrole may not proceed sufficiently, and the conductivity of the resulting conductive material may be significantly reduced.
【００１８】ピロールの酸化重合はキトサンおよび酸化
重合剤を含んだ希有機酸混合溶液中で行うが、用いるピ
ロールの量は混合溶液の重量％として１．５〜３％程度
が望ましい。１．５％以下の場合、得られる導電性材料
の導電性が著しく低下するばかりでなく導電性が得られ
ない場合がある。また、３％以上の場合ピロールのモル
数の３倍量程度に相当するピロールの酸化重合剤がキト
サンの希有機酸水溶液に溶解できない可能性がある。The oxidative polymerization of pyrrole is carried out in a dilute organic acid mixed solution containing chitosan and an oxidative polymerization agent, and the amount of pyrrole used is preferably about 1.5 to 3% by weight of the mixed solution. If it is less than 1.5%, not only the conductivity of the resulting conductive material is significantly reduced, but also conductivity may not be obtained. Further, if the amount is 3% or more, there is a possibility that the pyrrole oxidative polymerization agent, which is equivalent to about three times the number of moles of pyrrole, cannot be dissolved in the dilute organic acid aqueous solution of chitosan.
【００１９】重合の際の温度は１℃〜５℃程度が望まし
い。これ以上の温度であると、得られる導電性高分子材
料の導電性が低下する恐れがあり、またこれ以下の場合
は、重合系が凍結する恐れががある。重合時間は８時間
以上が望ましく、これより重合時間が短いと、ピロール
が完全に重合しないことがある。The temperature during polymerization is preferably about 1°C to 5°C. If the temperature is higher than this, there is a risk that the conductivity of the resulting conductive polymer material will decrease, and if the temperature is lower than this, there is a risk that the polymerization system will freeze. The polymerization time is preferably 8 hours or more; if the polymerization time is shorter than this, the pyrrole may not be completely polymerized.
【００２０】本発明の導電性高分子材料は重合終了後、
多量の有機溶媒中で脱溶媒し、分散させることにより得
ることができる。After the conductive polymer material of the present invention is polymerized,
It can be obtained by desolvation and dispersion in a large amount of organic solvent.
【００２１】本発明で用いる有機溶媒とは水と混和し、
前記の有機酸および酸化重合剤を溶解し、かつ、キトサ
ンおよびポリピロールを溶解させないものである。アセ
トン、エチルアルコール、メチルアルコ−ルなどを例示
できる。その量は重合終了後の反応溶液の体積の１０倍
以上が望ましい。それ以下であると、導電性高分子材料
が十分に析出しない場合がある。[0021] The organic solvent used in the present invention is one that is miscible with water;
It dissolves the above-mentioned organic acid and oxidative polymerization agent, but does not dissolve chitosan and polypyrrole. Examples include acetone, ethyl alcohol, and methyl alcohol. The amount is desirably 10 times or more the volume of the reaction solution after completion of polymerization. If it is less than that, the conductive polymer material may not be sufficiently deposited.
【００２２】析出後、上記の有機溶媒で十分に洗浄後、
乾燥することにより本発明の導電性高分子材料を得るこ
とができる。このようにして得られた本発明の導電性高
分子材料は、ｐＨが７以下の水に溶解が可能で、また、
酵素の固定化に有用な官能基を有している。After the precipitation, after washing thoroughly with the above organic solvent,
The conductive polymer material of the present invention can be obtained by drying. The conductive polymer material of the present invention thus obtained can be dissolved in water with a pH of 7 or less, and
Contains functional groups useful for immobilizing enzymes.
【００２３】このようにして得られた本発明の導電性高
分子材料に酵素を固定化することにより、酵素電極をは
じめ、広範囲の分野で応用が可能である。本発明の導電
性高分子材料を構成するキトサン分子に、酵素を共有結
合法またはイオン結合法により、化学的に結合すること
により酵素を固定化することができる。By immobilizing an enzyme on the conductive polymer material of the present invention thus obtained, it can be applied in a wide range of fields including enzyme electrodes. The enzyme can be immobilized by chemically bonding the enzyme to the chitosan molecules constituting the conductive polymer material of the present invention by a covalent bonding method or an ionic bonding method.
【００２４】また、この導電性高分子材料を希有機酸溶
液に溶解後、アルカリ・ホルマリン混合溶液からなる凝
固液中にノズルにより滴下し、さらに架橋処理を行うこ
とにより、化学的に安定でかつ、操作性の優れた真球状
のビーズに成形することが可能である。[0024] Furthermore, after dissolving this conductive polymer material in a dilute organic acid solution, it is dropped into a coagulating solution consisting of an alkali/formalin mixed solution through a nozzle, and further crosslinking treatment is performed to make it chemically stable and It is possible to form beads into perfectly spherical beads with excellent operability.
【００２５】[0025]
【実施例】本発明をさらに詳細に説明するために以下に
実施例を述べるが、本発明はこれらに限定されるもので
はない。EXAMPLES Examples will be described below to explain the present invention in more detail, but the present invention is not limited thereto.
【００２６】実施例１
０．７ｇのキトサン（脱Ｎ−アセチル化度約８０％、平
均分子量約１００万）を５０ｍｌの水に分散させた後、
０．５ｍｌの酢酸を加えて溶解させ、５℃まで冷却した
。別の容器中において、ピロールの酸化重合剤であるパ
ラトルエンスルホン酸第二鉄塩三水和物５．０ｇを水１
０ｍｌに溶解させ５℃まで冷却した後、キトサンの酢酸
溶液と混合した。激しく攪拌しながらピロール１．０ｍ
ｌを滴下し、滴下終了後、溶液が均一になった後に攪拌
を停止し、５℃で約８時間静置した。重合終了後、６０
０ｍｌのアセトン中に反応液を滴下すると、黒色フレー
ク状の導電性材料が得られた。これをろ過、分離しさら
にアセトンで洗浄後、乾燥させ、本発明の導電性高分子
材料が得られた。得られた本発明の導電性高分子材料１
．０ｇを１０ｍｌの水に溶解したところ、完全に溶解し
粘稠な溶液となった。これを３×３ｃｍ程度の広さの濾
紙に含浸させ乾燥させたところ導電性を有し、１×１０
−４Ｓ／ｃｍ−１程度の導電率を示した。表１に結果を
示す。Example 1 After dispersing 0.7 g of chitosan (degree of de-N-acetylation about 80%, average molecular weight about 1 million) in 50 ml of water,
0.5 ml of acetic acid was added to dissolve the mixture, and the mixture was cooled to 5°C. In another container, 5.0 g of paratoluenesulfonic acid ferric salt trihydrate, which is an oxidative polymerization agent for pyrrole, was added to 1 liter of water.
After dissolving in 0 ml and cooling to 5° C., the mixture was mixed with an acetic acid solution of chitosan. Add 1.0 m of pyrrole while stirring vigorously.
After the dropwise addition was completed and the solution became uniform, stirring was stopped and the mixture was allowed to stand at 5° C. for about 8 hours. After completion of polymerization, 60
When the reaction solution was dropped into 0 ml of acetone, a black flake-like conductive material was obtained. This was filtered, separated, washed with acetone, and dried to obtain the conductive polymer material of the present invention. Obtained conductive polymer material 1 of the present invention
．． When 0 g was dissolved in 10 ml of water, it completely dissolved and became a viscous solution. When this was impregnated into a filter paper with a size of about 3 x 3 cm and dried, it became conductive and 1 x 10
It exhibited a conductivity of about -4S/cm-1. Table 1 shows the results.
【００２７】実施例２〜６
実施例１と同様の方法でポリピロールとキトサンの混合
割合を変えて導電性高分子材料を得た。その１．０ｇを
１０ｍｌの水に溶解し、この溶液を３×３ｃｍ程度の広
さの濾紙に含浸させ乾燥させてその導電率を測定した。
表１に結果を示す。Examples 2 to 6 Conductive polymer materials were obtained in the same manner as in Example 1 by changing the mixing ratio of polypyrrole and chitosan. 1.0 g of the solution was dissolved in 10 ml of water, and a filter paper with a size of about 3 x 3 cm was impregnated with this solution, dried, and its electrical conductivity was measured. Table 1 shows the results.
【００２８】[0028]
【表１】[Table 1]
【００２９】実施例７
実施例１と同様の方法でポリピロールの割合を７５重量
％として導電性高分子材料の製造を試みたが、この割合
のポリピロールを得るためのピロールを酸化重合させる
ために十分な酸化重合剤をキトサンの希有機酸溶液中で
溶解させるのは不可能であった。Example 7 An attempt was made to produce a conductive polymer material using the same method as in Example 1 with a polypyrrole content of 75% by weight. It was not possible to dissolve the oxidative polymerization agent in a dilute organic acid solution of chitosan.
【００３１】実施例８
実施例１で得られた本発明の導電性高分子材料１．０ｇ
を７０ｍｌの水に分散溶解後、０．５ｍｌの酢酸を加え
て完全に溶解した。また、１０ｇの水酸化ナトリウムを
１５０ｍｌの水に溶解し、３５％のホルムアルデヒド水
溶液を加えて凝固液とした。前記の導電性高分子材料溶
液をノズル（直径１．５ｍｍ）を用いてこの凝固液に滴
下すると真球状単分散性の黒色ビーズが得られた。これ
らのビーズの平均粒径は約１．５ｍｍであった。さらに
エピクロロヒドリン１２ｍｌ、１Ｎ水酸化ナトリウム１
６ｍｌ、純水５２ｍｌの混合溶液中で５分間架橋処理を
施すと耐酸性のビ−ズとなった。得られたビーズ５ｇを
０．０１Ｍ酢酸ナトリウム緩衝溶液１０ｍｌに分散させ
、所定量のグルコースオキシターゼを加えた後、５℃で
４時間以上振とうしてグルコースオキシターゼをイオン
結合法により固定化した。０．０１Ｍ酢酸ナトリウム緩
衝溶液中でグルコースを基質として酵素活性を測定した
ところ、ｐＨおよび温度変化に対する安定性は、固定化
しないグルコースオキシターゼに比べて大幅に向上して
いた。Example 8 1.0 g of the conductive polymer material of the present invention obtained in Example 1
After dispersing and dissolving in 70 ml of water, 0.5 ml of acetic acid was added to completely dissolve. Further, 10 g of sodium hydroxide was dissolved in 150 ml of water, and a 35% formaldehyde aqueous solution was added to obtain a coagulating liquid. When the conductive polymer material solution was dropped into this coagulated liquid using a nozzle (diameter 1.5 mm), true spherical monodisperse black beads were obtained. The average particle size of these beads was approximately 1.5 mm. Additionally, 12 ml of epichlorohydrin, 1 N sodium hydroxide,
Acid-resistant beads were obtained by crosslinking for 5 minutes in a mixed solution of 6 ml and 52 ml of pure water. 5 g of the obtained beads were dispersed in 10 ml of 0.01 M sodium acetate buffer solution, a predetermined amount of glucose oxidase was added thereto, and the mixture was shaken at 5° C. for 4 hours or more to immobilize glucose oxidase by an ionic bonding method. When enzyme activity was measured using glucose as a substrate in a 0.01M sodium acetate buffer solution, the stability against pH and temperature changes was significantly improved compared to non-immobilized glucose oxidase.
【００３２】応用例１
実施例１で得られた導電性高分子材料０．５ｇを３ｍｌ
の水に溶解して粘稠溶液を調製し、この溶液を直径０．
５ｍｍ程度の白金線先端に直径１ｍｍ程度の球状に付着
させた。実施例８と同様の凝固液中で固化すると白金線
先端にＮ−メチレン化した本発明の導電性高分子が球状
に形成した。次いで実施例８と同様の方法でこれに架橋
を施した。この白金線を０．０１Ｍ酢酸ナトリウム緩衝
溶液１０ｍｌに分散させ、所定量のグルコースオキシタ
ーゼを加えた後、５℃で４時間以上振とうし、グルタル
アルデヒド２３％水溶液３ｍｌを加え、８分程度振とう
した。この操作により白金線先端に形成した本発明の導
電性高分子材料にグルコースオキシダーゼが固定化され
た。この白金線を用いて、参照電極を飽和カロメル電極
として一定量のヨウ化物イオン存在下において反応速度
検出法によりグルコースを定量したところ、グルコース
が０．０１〜０．１Ｍの濃度範囲で定量可能であった。Application Example 1 3 ml of 0.5 g of the conductive polymer material obtained in Example 1
A viscous solution is prepared by dissolving the solution in water with a diameter of 0.
A spherical shape with a diameter of about 1 mm was attached to the tip of a platinum wire of about 5 mm. When solidified in the same coagulation solution as in Example 8, the N-methylene conductive polymer of the present invention was formed in a spherical shape at the tip of the platinum wire. Next, this was crosslinked in the same manner as in Example 8. Disperse this platinum wire in 10ml of 0.01M sodium acetate buffer solution, add a predetermined amount of glucose oxidase, shake at 5°C for more than 4 hours, add 3ml of 23% glutaraldehyde aqueous solution, and shake for about 8 minutes. did. Through this operation, glucose oxidase was immobilized on the conductive polymer material of the present invention formed at the tip of the platinum wire. Using this platinum wire, glucose was quantified by a reaction rate detection method in the presence of a certain amount of iodide ions with a saturated calomel electrode as a reference electrode. there were.
【００３３】[0033]
【発明の効果】本発明の方法によれば、水に溶解可能で
あるため加工成形が容易で、かつ、酵素の固定化に有用
な官能基を有する導電性高分子材料が容易に得られる。
さらに、本発明の導電性高分子材料は任意の導電性を均
一に付与することができる。従って、本発明の導電性高
分子材料は導電性を有する酵素固定化担体としてバイオ
センサー等、広範囲な分野に応用が可能である。さらに
、得られた導電性高分子材料は操作性が容易でかつ、化
学的に安定な粒状に成形加工して長期間保存しておくこ
とができる。According to the method of the present invention, it is possible to easily obtain a conductive polymer material which is soluble in water and therefore easy to process and mold, and which has a functional group useful for immobilizing enzymes. Furthermore, the conductive polymer material of the present invention can uniformly impart any desired conductivity. Therefore, the conductive polymer material of the present invention can be applied as a conductive enzyme-immobilized carrier in a wide range of fields such as biosensors. Furthermore, the obtained conductive polymer material is easy to operate and can be molded into chemically stable granules and stored for a long period of time.
Claims (2)
することを特徴とする導電性高分子材料。1. A conductive polymer material comprising chitosan and polypyrrole as main components.
中でピロールを酸化重合させた後、有機溶媒中で析出さ
せることを特徴とする請求項１記載の導電性高分子材料
の製造方法。2. The method for producing a conductive polymer material according to claim 1, wherein the pyrrole is oxidatively polymerized in a dilute organic acid containing chitosan and an oxidative polymerization agent, and then precipitated in an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3562091A JPH04253744A (en) | 1991-02-04 | 1991-02-04 | Conductive polymeric material and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3562091A JPH04253744A (en) | 1991-02-04 | 1991-02-04 | Conductive polymeric material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04253744A true JPH04253744A (en) | 1992-09-09 |
Family
ID=12446904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3562091A Pending JPH04253744A (en) | 1991-02-04 | 1991-02-04 | Conductive polymeric material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04253744A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0773975A1 (en) * | 1994-08-04 | 1997-05-21 | WALLACE, Gordon George | Conducting electroactive biomaterials |
| CN102153671A (en) * | 2010-02-12 | 2011-08-17 | 财团法人工业技术研究院 | Chitosan-conducting polymer mixed polymer composition with oxidation resistance |
| CN102262114A (en) * | 2011-04-22 | 2011-11-30 | 武汉工程大学 | Electrochemical preparation method of electrode modified by polypyrrole-chitosan-enzyme composite film |
| TWI400276B (en) * | 2009-12-03 | 2013-07-01 | Ind Tech Res Inst | Chitosan-conductive polymer hybrid polymer composition with antioxidant properties |
| JP2015516172A (en) * | 2012-05-17 | 2015-06-11 | シージェイ チェイルジェダン コーポレイション | Enzyme-immobilized bead manufacturing apparatus and enzyme-immobilized bead manufacturing method using the same |
| CN106750579A (en) * | 2016-12-16 | 2017-05-31 | 重庆科技学院 | The preparation method of polypyrrole shitosan composite conductive thin film |
-
1991
- 1991-02-04 JP JP3562091A patent/JPH04253744A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0773975A1 (en) * | 1994-08-04 | 1997-05-21 | WALLACE, Gordon George | Conducting electroactive biomaterials |
| EP0773975A4 (en) * | 1994-08-04 | 1998-06-10 | Gordon George Wallace | Conducting electroactive biomaterials |
| TWI400276B (en) * | 2009-12-03 | 2013-07-01 | Ind Tech Res Inst | Chitosan-conductive polymer hybrid polymer composition with antioxidant properties |
| CN102153671A (en) * | 2010-02-12 | 2011-08-17 | 财团法人工业技术研究院 | Chitosan-conducting polymer mixed polymer composition with oxidation resistance |
| CN102262114A (en) * | 2011-04-22 | 2011-11-30 | 武汉工程大学 | Electrochemical preparation method of electrode modified by polypyrrole-chitosan-enzyme composite film |
| JP2015516172A (en) * | 2012-05-17 | 2015-06-11 | シージェイ チェイルジェダン コーポレイション | Enzyme-immobilized bead manufacturing apparatus and enzyme-immobilized bead manufacturing method using the same |
| JP2017029164A (en) * | 2012-05-17 | 2017-02-09 | シージェイ チェイルジェダン コーポレイション | Apparatus for producing enzyme-immobilized beads and method for producing enzyme-immobilized beads using the same |
| US9738886B2 (en) | 2012-05-17 | 2017-08-22 | Cj Cheiljedang Corporation | Apparatus for preparing immobilized-enzyme beads and method for preparing immobilized-enzyme beads using same |
| US9777263B2 (en) | 2012-05-17 | 2017-10-03 | Ch Cheiljedang Corporation | Apparatus for preparing immobilized-enzyme beads and method for preparing immobilized-enzyme beads using same |
| CN106750579A (en) * | 2016-12-16 | 2017-05-31 | 重庆科技学院 | The preparation method of polypyrrole shitosan composite conductive thin film |
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