DE19708670A1 - Use of peroxidase and manganese ions to decompose aromatic substances - Google Patents
Use of peroxidase and manganese ions to decompose aromatic substancesInfo
- Publication number
- DE19708670A1 DE19708670A1 DE1997108670 DE19708670A DE19708670A1 DE 19708670 A1 DE19708670 A1 DE 19708670A1 DE 1997108670 DE1997108670 DE 1997108670 DE 19708670 A DE19708670 A DE 19708670A DE 19708670 A1 DE19708670 A1 DE 19708670A1
- Authority
- DE
- Germany
- Prior art keywords
- substances
- aromatic
- peroxidase
- reaction
- added
- 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.)
- Withdrawn
Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 title claims abstract description 19
- 102000003992 Peroxidases Human genes 0.000 title claims abstract description 8
- 108040007629 peroxidase activity proteins Proteins 0.000 title claims abstract description 7
- 229910001437 manganese ion Inorganic materials 0.000 title 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 108010059896 Manganese peroxidase Proteins 0.000 claims description 17
- 230000033558 biomineral tissue development Effects 0.000 claims description 17
- 108010024636 Glutathione Proteins 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 102000004190 Enzymes Human genes 0.000 claims description 7
- 108090000790 Enzymes Proteins 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 7
- 229940088598 enzyme Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- 108010029541 Laccase Proteins 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 102000004316 Oxidoreductases Human genes 0.000 claims description 3
- 108090000854 Oxidoreductases Proteins 0.000 claims description 3
- 102000003425 Tyrosinase Human genes 0.000 claims description 3
- 108060008724 Tyrosinase Proteins 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 230000004992 fission Effects 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- 108010015776 Glucose oxidase Proteins 0.000 claims description 2
- 239000004366 Glucose oxidase Substances 0.000 claims description 2
- 241001360262 Hypholoma frowardii Species 0.000 claims description 2
- 229940116332 glucose oxidase Drugs 0.000 claims description 2
- 235000019420 glucose oxidase Nutrition 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims 1
- 241000221198 Basidiomycota Species 0.000 claims 1
- 241000355649 Clitocybula dusenii Species 0.000 claims 1
- 241000958510 Stropharia rugosoannulata Species 0.000 claims 1
- 230000001133 acceleration Effects 0.000 claims 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims 1
- 239000002738 chelating agent Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 239000001630 malic acid Substances 0.000 claims 1
- 235000011090 malic acid Nutrition 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 1
- -1 manganese (II) ions Chemical class 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract 2
- 229960003180 glutathione Drugs 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- IEEJAAUSLQCGJH-UHFFFAOYSA-N 2-amino-4,6-dinitrotoluene Chemical compound CC1=C(N)C=C([N+]([O-])=O)C=C1[N+]([O-])=O IEEJAAUSLQCGJH-UHFFFAOYSA-N 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000004021 humic acid Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 4
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 3
- 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OEGPRYNGFWGMMV-UHFFFAOYSA-N (3,4-dimethoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC OEGPRYNGFWGMMV-UHFFFAOYSA-N 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 2
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 2
- WJXSWCUQABXPFS-UHFFFAOYSA-N 3-hydroxyanthranilic acid Chemical compound NC1=C(O)C=CC=C1C(O)=O WJXSWCUQABXPFS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000007938 chlorocyclic compounds Chemical class 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001533 ligninolytic effect Effects 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- WRSMJZYBNIAAEE-UHFFFAOYSA-N 1-chlorodibenzofuran Chemical class O1C2=CC=CC=C2C2=C1C=CC=C2Cl WRSMJZYBNIAAEE-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 1
- 102000016680 Dioxygenases Human genes 0.000 description 1
- 108010028143 Dioxygenases Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 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
- 108010001336 Horseradish Peroxidase Proteins 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 102000008109 Mixed Function Oxygenases Human genes 0.000 description 1
- 108010074633 Mixed Function Oxygenases Proteins 0.000 description 1
- 241000198632 Nematoloma Species 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZTOJFFHGPLIVKC-CLFAGFIQSA-N abts Chemical compound S/1C2=CC(S(O)(=O)=O)=CC=C2N(CC)C\1=N\N=C1/SC2=CC(S(O)(=O)=O)=CC=C2N1CC ZTOJFFHGPLIVKC-CLFAGFIQSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- DXBHBZVCASKNBY-HVRMQOCCSA-N benzo[a]anthracene Chemical compound C1=CC=CC=2C1=C1[14CH]=C3C=CC=CC3=CC1=CC=2 DXBHBZVCASKNBY-HVRMQOCCSA-N 0.000 description 1
- FMMWHPNWAFZXNH-DOMIDYPGSA-N benzo[a]pyrene-7-14c Chemical compound C1=C2C3=CC=C[14CH]=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-DOMIDYPGSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000003938 benzyl alcohols Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 230000007515 enzymatic degradation Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 150000005573 methoxybenzenes Chemical class 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009979 protective mechanism Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- BBEAQIROQSPTKN-GLYGZDRESA-N pyrene Chemical compound C1=CC=C2[14CH]=[14CH]C3=CC=CC4=[14CH][14CH]=C1C2=C34 BBEAQIROQSPTKN-GLYGZDRESA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000004102 tricarboxylic acid cycle Effects 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002676 xenobiotic agent Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/02—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by biological methods, i.e. processes using enzymes or microorganisms
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biomedical Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Mineralisierung (Abbau zu CO2) und zum Abbau von nieder- und hochmolekularen aromatischen Substanzen und Substanzgemischen, wie Nitroaromaten, polycyclischen aromatischen Kohlenwasserstoffen (PAK), Chloraromaten, Azofarbstoffen, Huminstoffen und Ligninen, zur Eliminierung dieser Verbindungen aus der Umwelt sowie zur Gewinnung von niedermolekularen, nichtaromatischen Spaltprodukten.The invention relates to a process for mineralization (degradation to CO 2 ) and for the degradation of low and high molecular weight aromatic substances and substance mixtures, such as nitroaromatics, polycyclic aromatic hydrocarbons (PAHs), chloroaromatics, azo dyes, humic substances and lignins, for eliminating these compounds from the Environment and for the extraction of low-molecular, non-aromatic fission products.
Das Verfahren kann vielseitig in (umwelt-)technischen und industriellen Anwendungen, so in der Boden- und Wasserreinigung zur Eliminierung unerwünschter, insbesondere toxischer und/oder mutagener, aromatischer Verbindungen, aus Wässern und Böden (z. B. Nitroaromaten, Aniline, Phenole, PAKs, Chloraromaten, Heterocyclen, Humin- und Fulvinsäuren) sowie in der holz- und zelluloseverarbeitenden Industrie angewendet werden. Damit wird eine Testung der biologischen Abbaubarkeit von neuen Produkten, Stoffen z. B. der chemischen und pharmazeutischen Industrie oder die biologische Charakterisierung umweltschützender Verfahren möglich. Darüber hinaus kann das Verfahren zur Detoxifikation von Xenobiotika und anderen umweltrelevanten Stoffen eingesetzt werden. Ebenso ist auch eine Intergration in die Stoff- und Verfahrensentwicklung denkbar.The process can be versatile in (environmental) technical and industrial Applications, such as in soil and water purification for elimination undesirable, especially toxic and / or mutagenic, aromatic Compounds from water and soil (e.g. nitro aromatics, anilines, Phenols, PAHs, chloroaromatics, heterocycles, humic and fulvic acids) as well as in the wood and cellulose processing industry. This will test the biodegradability of new ones Products, fabrics e.g. B. the chemical and pharmaceutical industry or the biological characterization of environmentally protective processes is possible. In addition, the method for detoxification of xenobiotics and other environmentally relevant substances are used. There is also one Integration into the material and process development possible.
Es ist allgemein bekannt [z. B. Alloway, B.J. und D.C. Ayres, 1996: Schadstoffe in der Umwelt, S. 339, Spektrum Akademischer Verlag Heidelberg, Berlin, Oxford; Melzer, R. und J. Stadtmüller, 1993: Thermische Behandlung organisch- und schwermetallverunreinigter Böden. In: Abbau industrieller Schadstoffe. B. Wuster (Hrsg.), S. 1-30, Verl. TÜV Rheinland], aromatische Verbindungen physikochemisch durch thermische Behandlung (Verbrennung) oder mittels starker Oxidationsmittel (Ozon, Peroxide, Fenton-Reagenz) in Verbindung mit Photonen zu mineralisieren.It is well known [e.g. B. Alloway, B.J. and D.C. Ayres, 1996: Pollutants in the environment, p. 339, Spektrum Akademischer Verlag Heidelberg, Berlin, Oxford; Melzer, R. and J. Stadtmüller, 1993: Thermal Treatment of soil contaminated with organic and heavy metals. In: dismantling industrial pollutants. B. Wuster (ed.), Pp. 1-30, publ. TÜV Rheinland], aromatic compounds physicochemically by thermal treatment (Combustion) or using strong oxidizing agents (ozone, peroxides, Mineralize Fenton reagent) in conjunction with photons.
Eine Verbrennung ist allerdings mit einem erheblichen apparativen Aufwand (Spezialöfen) und einem hohen Energieverbrauch (Strom, Kohle, Öl bzw. Gas) verbunden. Ein weiterer Nachteil ist die Bildung hochtoxischer Sekundärverbindungen, die insbesondere während der Abkühlphase der Öfen entstehen (z. B. chlorierte Dibenzodioxine und Dibenzofurane) und die Umwelt belasten [z. B. Koch, R. 1989: Chlordibenzofurane und -dioxine. In: Umweltchemikalien, S. 145, VCH Verlag, Weinheim]. Eine Oxidation aromatischer Verbindungen mit Ozon oder Peroxiden (einschließlich Fenton- Reagenz) sind problematisch, da die verwendeten Chemikalien in hohen Konzentrationen eingesetzt werden müssen, äußerst aggressiv und umweltgefährdend sind (bzw. es entstehen in Nebenreaktionen umweltgefährdende Stoffe). Außerdem werden nur bestimmte Aromaten umgesetzt.Incineration, however, requires considerable equipment (Special ovens) and high energy consumption (electricity, coal, oil or Gas) connected. Another disadvantage is the formation of highly toxic Secondary connections, especially during the cooling phase of the ovens arise (e.g. chlorinated dibenzodioxins and dibenzofurans) and the Pollute the environment [e.g. B. Koch, R. 1989: Chlorodibenzofurans and dioxins. In: Environmental chemicals, p. 145, VCH Verlag, Weinheim]. An oxidation aromatic compounds with ozone or peroxides (including fenton Reagent) are problematic because the chemicals used are high Concentrations must be used, extremely aggressive and are environmentally hazardous (or arise in side reactions environmentally hazardous substances). In addition, only certain aromatics implemented.
Es ist außerdem möglich [z. B. Gleim, D., 1994: Abbauverhalten altlastenrelevanter Schadstoffe, Abschlußbericht zum Forschungsprojekt 14807430 des BMFT, DECHEMA e.V., Frankfurt a.M.] aromatische Verbindungen biologisch mit Hilfe spezieller Organismen (Bakterien, Pilze, Pflanzen) zu Kohlendioxid zu mineralisieren. Diese Mineralisierungs verfahren erfordern jedoch immer den gesamten Organismus (Bakterien, Pilze, Pflanzen). Damit verbunden sind erhebliche Aufwendungen zur Aufrechterhaltung der Lebensfunktionen der Organismen (Kohlenstoff- und Stickstoffquellen, z. B. Zucker, Aminosäuren, Vitamine). Es muß unter sterilen/semisterilen Bedingungen sowie in teuren Apparaturen (Fermentoren) gearbeitet werden. Die Verweilzeiten der aromatischen Substanzen sind relativ hoch, da die Abbauprozesse nur sehr langsam vonstatten gehen. Hochspezifische Enzyme (u. a. Monooxygenasen, Dioxygenasen) greifen die aromatischen Substrate meist intrazellulär an; die eigentliche Mineralisierung des aromatisch gebundenen Kohlenstoffs erfolgt immer intrazellulär (Zitronensäurezyklus) und benötigt eine große Zahl von Cofaktoren und Enzymen (mindestens 10 verschiedene Enzyme). Letztgenannte sind teilweise mit Membranen assoziiert und instabil.It is also possible [e.g. B. Gleim, D., 1994: Degradation Behavior Contaminated pollutants, final report on the research project 14807430 of the BMFT, DECHEMA e.V., Frankfurt a.M.] aromatic Connections biologically with the help of special organisms (bacteria, fungi, Plants) to mineralize to carbon dioxide. This mineralization However, procedures always require the entire organism (bacteria, Mushrooms, plants). This entails considerable expenses for Maintaining the vital functions of organisms (carbon and Nitrogen sources, e.g. As sugar, amino acids, vitamins). It must be under sterile / semisterile conditions as well as in expensive equipment (Fermenters) can be worked. The residence times of the aromatic Substances are relatively high because the breakdown processes are very slow take place. Highly specific enzymes (including monooxygenases, Dioxygenases) usually attack the aromatic substrates intracellularly; the actual mineralization of the aromatically bound carbon takes place always intracellular (citric acid cycle) and requires a large number of Cofactors and enzymes (at least 10 different enzymes). The latter are partially associated with membranes and are unstable.
Darüber hinaus ist prinzipiell bekannt [z. B. Hatakka, A., 1994: FEMS Microbiol. Rev. 13, 125-135; Barr, D.P. and S.D. Aust, 1994, Environ. Sci. Technol. 28, 78A-87A], daß ligninolytische und nichtligninolytische Oxidasen (Laccasen) und Peroxidasen (Lignin-, Mangan-, Meerrettichperoxidasen) in der Lage sind, aromatische Strukturen in makromolekularen Substanzen (Lignine, Huminstoffe, Melanine) sowie niedermolekularen Aromaten (u. a. Phenole, Benzylalkohole, Methoxybenzene, Benzoesäuren) unspezifisch anzugreifen, was zur Bildung hydroxylierter oder chinoider Derivate sowie zu Ringspaltungsprodukten führt. Letztere cyclisieren spontan zu nichtaromatischen Ringsystemen (Lactone); niedermolekulare Spaltprodukte (C1-C4) aus dem aromatischen Ring entstehen allerdings nicht. Die Oxydationsreaktionen können durch bestimmte Mediatoren [z. B. 2,2'-Azinobis-(3-ethylbenzothiazolin-6- sulfonsäure), Veratrylalkohol, 3-Hydroxyanthranilsäure] verstärkt und das angreifbare Substratspektrum damit erweitert werden. Die Mineralisierung des aromatischen Kohlenstoffes selbst erfordert jedoch die eingangs beschriebenen Verfahrensanwendungen mit den besagten Nachteilen.In addition, it is known in principle [e.g. B. Hatakka, A., 1994: FEMS Microbiol. Rev. 13, 125-135; Barr, DP and SD Aust, 1994, Environ. Sci. Technol. 28, 78A-87A] that ligninolytic and non-ligninolytic oxidases (laccases) and peroxidases (lignin, manganese, horseradish peroxidases) are capable of aromatic structures in macromolecular substances (lignins, humic substances, melanins) and low-molecular aromatics (including phenols, To attack benzyl alcohols, methoxybenzenes, benzoic acids) unspecifically, which leads to the formation of hydroxylated or quinoid derivatives and to ring cleavage products. The latter spontaneously cyclize to non-aromatic ring systems (lactones); however, low-molecular cleavage products (C 1 -C 4 ) from the aromatic ring do not arise. The oxidation reactions can be controlled by certain mediators [e.g. B. 2,2'-Azinobis (3-ethylbenzothiazoline-6-sulfonic acid), veratryl alcohol, 3-hydroxyanthranilic acid] and the vulnerable substrate range can be expanded. However, mineralization of the aromatic carbon itself requires the process applications described at the outset with the disadvantages mentioned.
Aufgabe der vorliegenden Erfindung ist es, nieder- und makromolekulare, aromatische Natur- und Fremdstoffe aufwandgering, insbesondere mit gerin gem Energie- und Chemikalieneinsatz, umweltfreundlich, ohne erhöhte An forderungen an sterile bzw. semisterile Reaktionsführung und mit möglichst kurzen Inkubationszeiten zu mineralisieren und niedermolekulare, nichtaro matische Spaltprodukte zu erzeugen.The object of the present invention is to convert low and macromolecular aromatic natural and foreign substances require little effort, especially with little according to energy and chemical use, environmentally friendly, without increased requirements for sterile or semi-sterile reaction control and with if possible Mineralize short incubation times and low molecular weight, non-Aaro to produce matical fission products.
Die Aufgabe wird erfindungsgemäß durch ein zellfreies, enzymatisches Verfahren zur Mineralisierung von Aromaten basierend auf einem Katalyse system aus Peroxidase, Mangan(II)ionen und Thiolen gelöst.The object is achieved by a cell-free, enzymatic Process for mineralization of aromatics based on catalysis System composed of peroxidase, manganese (II) ions and thiols.
Es werden Peroxidase, vorzugsweise Mangan-Peroxidase aus Basidiomyce ten, unter gleichzeitiger Zugabe und/oder Nachdosierung von Man gan(II)ionen und Thiolen, vorzugsweise reduziertes Glutathion, eingesetzt, die unter Bildung hochreaktiver Komplexe, welche als starke Oxidationsmit tel wirken, den Kohlenstoff in der aromatischen Substanz zu Kohlendioxid und niedermolekularen, nichtaromatischen Verbindungen (aliphatische Carbonsäuren) oxidieren. Die Peroxidase fungiert dabei als "Motor" des Oxi dationsprozesses, der ständig reaktive Mangan(III)ionen aus Man gan(II)ionen regeneriert, die ihrerseits mit den Glutathionmolekülen in Wechselwirkung treten und das eigentlich wirksame Oxidans bilden. Dieses Oxidans kann in dem erfindungsgemäßen Verfahren den Ringkohlenstoff aromatischer Verbindungen bis zum Kohlendioxid bzw. zu niedermolekula ren, aliphatischen Verbindungen oxidieren und damit quasi eine "kalte Verbrennung" bewirken. Durch zusätzliche Zugabe von Phenoloxidasen läßt sich der Mineralisierungsprozeß weiter beschleunigen und die Kohlen stoffumsetzung erhöhen.There are peroxidase, preferably manganese peroxidase from Basidiomyce ten, with the simultaneous addition and / or replenishment of Man gan (II) ions and thiols, preferably reduced glutathione, are used, which with the formation of highly reactive complexes, which act as strong oxidation act, the carbon in the aromatic substance to carbon dioxide and low molecular weight, non-aromatic compounds (aliphatic Oxidize carboxylic acids). The peroxidase acts as the "engine" of the Oxi dation process, the constantly reactive manganese (III) ions from Man gan (II) ions regenerated, which in turn with the glutathione molecules in Interact and form the actually effective oxidant. This Oxidant can the ring carbon in the inventive method aromatic compounds down to carbon dioxide or low molecular weight oxidize aliphatic compounds and thus quasi a "cold Combustion ". By adding phenol oxidases the mineralization process accelerate further and the coals increase material conversion.
Die Erfindung soll nachstehend anhand von Ausführungsbeispielen näher erläutert werden. Zum besseren Verständnis der erfinderischen Verfahrens wirkung ist den Ausführungsbeispielen eine Zeichnung beigefügt.The invention is intended to be explained in more detail below on the basis of exemplary embodiments are explained. For a better understanding of the inventive method Effect is a drawing attached to the embodiments.
In dieser zeigen: In this show:
Fig. 1 Mineralisierung von [14C]-ringmarkiertem 2-Amino-4,6-dinitro toluol (0.09 µCi/ml 7.7 pm) durch ein Mangan-Peroxidase- Präparat des Weißfäulepilzes Nematoloma frowardi in Gegenwart von Glutathione im Vergleich zum Kontrollansatz ohne Enzym . Fig. 1 Mineralization of [ 14 C] ring-labeled 2-amino-4,6-dinitro toluene (0.09 µCi / ml 7.7 pm) by a manganese peroxidase preparation of the white rot fungus Nematoloma frowardi in the presence of glutathione compared to the control approach without enzyme .
Fig. 2a Chromatographische Auftrennung (HPLC) und Bilanzierung des radioaktiven Rückstandes im Reaktionsansatz einer Kontrolle, die 14C-AmDNT, aber keine Mangan-Peroxidase enthielt. (Diagramm A). Fig. 2a Chromatographic separation (HPLC) and accounting for the radioactive residue in the reaction mixture of a control which contained 14 C-AmDNT but no manganese peroxidase. (Diagram A).
Fig. 2b Chromatographische Auftrennung und Bilanzierung des radio aktiven Rückstandes im Reaktionsansatz einer partiell durch das Katalysesystem Mangan-Peroxidase/Mangan(II)ionen/Glutathion mineralisierten 14C-AmDNT-Probe. (Diagramm B). Fig. 2b Chromatographic Separation and accounting for the radioactive residue in the reaction mixture of a partially ions by the catalysis system manganese peroxidase / manganese (II) / glutathione mineralized 14 C-AmDNT sample. (Diagram B).
Fig. 3 Mineralisierung verschiedener uniform 14C-markierter Phenole durch die Mangan-Peroxidase des Weißfäulepilzes Nematoloma frowardii in Gegenwart von Glutathione: Fig. 3 mineralization of different uniform 14 C-labeled phenols by manganese peroxidase of Weißfäulepilzes Nematoloma frowardii in the presence of Glutathione:
im Vergleich zum Kontrollansatz ohne Enzym compared to Control approach without enzyme
nach drei Tagen. after three days.
Bis auf Beispiel E beziehen sich die Ausführungsbeispiele auf radioaktiv markierte 14C-Verbindungen, da nur über eine Freisetzung von radioaktiven Kohlendioxid (14CO2) aus 14C-ringmarkierten, aromatischen Substraten eine echte Mineralisierung nachgewiesen werden kann.Except for Example E, the exemplary embodiments relate to radioactively labeled 14 C compounds, since true mineralization can only be detected by releasing radioactive carbon dioxide ( 14 CO 2 ) from 14 C-ring-labeled, aromatic substrates.
0,1 µCi ringmarkiertes 2-Amino-4,6-dinitrotoluol (2-AmDNT) werden in einem gasdichtverschließbaren Gefäß zusammen mit Natriummalonat-Puffer (50 mM, pH 4,5), Manganchlorid (MnCl2; 1 mM), Glutathion (10 mM), Glukose (15 mM), Glukose-Oxidase (0,04 Units) und Mangan-Peroxidase (2 Units) in einem Gesamtvolumen von 1 ml bei 24°C geschüttelt (150 upm). Alle 24 Stunden wird der Gasraum über der Reaktionslösung mit steriler, CO2-freier, angefeuchteter Luft gespült und der Luftstrom durch zwei Scintillationsgefäße geleitet die flüchtige organische Verbindungen bzw. CO2 auffangen. Anschließend wird die Radioaktivität mittels "Liquid-Scintilation- Counting" (LSC) bestimmt. Fig. 1 demonstriert die Freisetzung von 14CO2 aus 14C-2-AmDNT über einen Zeitraum von 5 Tagen. Es wird deutlich, daß bereits nach 48 Stunden bei der oberen Kurve 0.1 µCi ring-labeled 2-amino-4,6-dinitrotoluene (2-AmDNT) are sealed in a gas-tight container together with sodium malonate buffer (50 mM, pH 4.5), manganese chloride (MnCl 2 ; 1 mM), glutathione ( 10 mM), glucose (15 mM), glucose oxidase (0.04 units) and manganese peroxidase (2 units) in a total volume of 1 ml at 24 ° C. shaken (150 rpm). Every 24 hours, the gas space above the reaction solution is flushed with sterile, CO 2 -free, humidified air and the air flow is passed through two scintillation vessels to collect the volatile organic compounds or CO 2 . The radioactivity is then determined by means of "liquid scintilation counting" (LSC). Figure 1 demonstrates the release of 14 CO 2 from 14 C-2 AmDNT over a 5 day period. It becomes clear that after 48 hours at the top curve
im Vergleich zur unteren Kurve compared to the lower curve
mehr als 30% des Ringkohlenstoffs mineralisiert sind, nach 5 Tagen über 50%. Kontrollen, die keine Mangan-Peroxidase enthielten, wiesen keine Freisetzung von 14CO2 auf (siehe untere Kurve in Fig. 1). Eine Untersuchung der im Reaktionsansatz verbleibenden Restradioaktivitäten mittels "High-Performance-Liquid-Chromatography" (HPLC) und LSC ergibt, daß die Ausgangsverbindung (14C-2-AmDNT) in den Proben mit Mangan-Peroxidase nicht mehr nachweisbar ist und sich nur noch 14C-markierte, hochpolare, niedermolekulare, nichtaromatische Produkte nachweisen lassen, die mit reinem Wasser als Laufmittel zusammen mit diesem von der Säule eluiert werden (Fig. 2b).more than 30% of the ring carbon is mineralized, after 5 days over 50%. Controls that did not contain manganese peroxidase showed no release of 14 CO 2 (see lower curve in FIG. 1). An examination of the residual radio activities remaining in the reaction mixture by means of "high-performance liquid chromatography" (HPLC) and LSC shows that the starting compound ( 14 C-2-AmDNT) is no longer detectable in the samples with manganese peroxidase and is only Have 14 C-labeled, highly polar, low molecular weight, non-aromatic products detected, which are eluted from the column together with pure water as the solvent ( Fig. 2b).
In den Mangan-Peroxidase-freien Proben erfolgt kein Abbau des 14C-AmDNT, und die Radioaktivität ist ausschließlich für den Peak des 2-AmDNT nachweisbar (Fig. 2a). [Trennbedingungen: 5 µm RP-18 Säule, 125 mm, 4,6 mm (Firma Merck, Darmstadt), Methanol/Wasser-Gradient 0%-50%, vol/vol, 45 min, Flußrate 1 ml/min; Proben über jeweils 2 min in Scintillationsgefäßen sammeln (Scintilationscocktail: Opti fluor, Packard Instrument B.V., Groningen, Niederlande) Bestimmung der Radioaktivität mittels LSC].No degradation of the 14 C-AmDNT takes place in the samples free of manganese peroxidase, and the radioactivity can only be detected for the peak of the 2-AmDNT ( FIG. 2a). [Separation conditions: 5 μm RP-18 column, 125 mm, 4.6 mm (Merck, Darmstadt), methanol / water gradient 0% -50%, vol / vol, 45 min, flow rate 1 ml / min; Collect samples for 2 min each in scintillation vials (scintillation cocktail: Opti fluor, Packard Instrument BV, Groningen, The Netherlands) determination of radioactivity using LSC].
Durch eine Immobilisierung der Mangan-Peroxidase läßt sich die Stabilität des Enzyms erhöhen und der Prozeß ohne weitere Zugabe von neuer Manganperoxidase mehrere Male wiederholen.Immobilizing the manganese peroxidase allows the stability of the Enzyme increase and the process without the addition of new ones Repeat manganese peroxidase several times.
0,1 µCi 14C-2-Amino-4,6-dinitrotoluol werden wie unter Beispiel A1 inkubiert. Zusätzlich enthält der Ansatz 1 Unit einer Laccase und 1 mM 2-Methylphenol. Auf diese Weise wird eine Beschleunigung des Mineralsierungsprozesses erreicht, der bereits nach 48 Stunden zu einer 40%igen Umsetzung der Ausgangsverbindung zu 14CO2 führt.0.1 µCi 14 C-2-amino-4,6-dinitrotoluene are incubated as in Example A1. In addition, the batch contains 1 unit of a laccase and 1 mM 2-methylphenol. In this way, the mineralization process is accelerated, which leads to a 40% conversion of the starting compound to 14 CO 2 after only 48 hours.
0,1 µCi eines Gemisches, bestehend aus uniform ringmarkierten 14C-Hydroxylamino-nitrotoluolen (OHAmDNTs; 23%), 14C-4-Amino-2,6- nitrotoluol (4-AmDNT; 32%), 14C-2-Amino-4,6-dinitrotoluol (2-AmDNT; 31%) sowie unbekannten 14C-Metaboliten des 14C-2,4,6-Trinitrotoluols (14%), werden wie unter Beispiel A beschrieben inkubiert. In 5 Tagen werden ca. 20% des aromatischen Ringkohlenstoffs dieses komplexen Gemisches zu 14CO2 umgesetzt. 0.1 µCi of a mixture consisting of uniformly ring-labeled 14 C-hydroxylamino-nitrotoluenes (OHAmDNTs; 23%), 14 C-4-amino-2,6-nitrotoluene (4-AmDNT; 32%), 14 C-2- Amino-4,6-dinitrotoluene (2-AmDNT; 31%) and unknown 14 C metabolites of 14 C-2,4,6-trinitrotoluene (14%) are incubated as described in Example A. In 5 days, about 20% of the aromatic ring carbon of this complex mixture is converted to 14 CO 2 .
0,1 µCi verschiedener, radioaktiv markierter PAKs werden, wie unter Beispiel A beschrieben, inkubiert (uniform ringmarkiertes 14C-Phenanthren, [4,5,9,10- 14C]-Pyren, [1,2,3,4,4a,10a-14C]-Anthracen, [7-14C]-Benzo(a)pyren und [12- 14C]-Benz(a)anthracen). Im Ergebnis werden innerhalb von 96 Stunden 3% des Phenanthrens, 7% des Pyrens, 5% des Anthracens, 4% des Benzo(a)pyrens und 3% des Benzo(a)anthracens zu 14CO2 mineralisiert., 0.1 uCi of different radiolabeled PAHs are as described in Example A, incubated (uniform ring labeled 14 C-phenanthrene, [4,5,9,10- 14 C] pyrene, [1,2,3,4, 4a, 10a-14 C] anthracene, [7- 14 C] -benzo (a) pyrene and [12- 14 C] benz (a) anthracene). As a result, within 96 hours 3% of the phenanthrene, 7% of the pyrene, 5% of the anthracene, 4% of the benzo (a) pyrene and 3% of the benzo (a) anthracene are mineralized to 14 CO 2 .
0,1 µCi von jeweils Brenzkatechin (= Catechol; Cat, 2 mCi/mmol), Tyrosin (Tyr, 457 mCi/mmol), Pentachlorphenol (PCP, 10,4 mCi/mmol), Phenol (Phl, 8,7 mCi/mmol), 2,4-Dichlorphenol (2,4-DCP, 9,3 mCi/mmol) wurden eingesetzt. Die Verbindungen wurden wie unter Beispiel A1 inkubiert. Bereits nach 3 Tagen waren die Ausgangsstoffe zu 9-48% zu Kohlendioxid abgebaut (Fig. 3). Die Restradioaktivität bestand aus hochpolaren, nichtaromatischen Abbauprodukten. Nicht dargestellt ist die Mineralisierung der phenolischen Verbindungen ohne Glutathion, welche ebenfalls zwischen zwischen 8 und 42% lag.0.1 µCi of pyrocatechol (= catechol; Cat, 2 mCi / mmol), tyrosine (Tyr, 457 mCi / mmol), pentachlorophenol (PCP, 10.4 mCi / mmol), phenol (Phl, 8.7 mCi / mmol) mmol), 2,4-dichlorophenol (2,4-DCP, 9.3 mCi / mmol) were used. The compounds were incubated as in Example A1. Already after 3 days, the raw materials were 9-48% degraded to carbon dioxide ( Fig. 3). The residual radioactivity consisted of highly polar, non-aromatic degradation products. The mineralization of the phenolic compounds without glutathione, which was also between 8 and 42%, is not shown.
25 mg Braunkohle-Huminsäuren werden in 100 ml Natriummalonat-Puffer (50 mM, pH 4.5) gelöst. Der Reaktionsansatz enthält weiterhin: Manganchlorid (2 mM), Glutathione (0,5 mM), Dimethylformamid (0.1%), 50 Units Mangan-Peroxidase und 5 Units Laccase. Der Ansatz wird bei 37°C 24 bis 72 Stunden geschüttelt (180 upm); anschließend werden durch Zugabe von Salzsäure die Huminsäuren ausgefällt und gewaschen. Nach Trocknung wird der Gewichtsverlust bestimmt. Er liegt nach 24 Stunden bei 40% und nach 72 Stunden bei 60%.25 mg of lignite-humic acids are in 100 ml of sodium malonate buffer (50 mM, pH 4.5) dissolved. The reaction approach also contains: Manganese chloride (2 mM), glutathione (0.5 mM), dimethylformamide (0.1%), 50 units of manganese peroxidase and 5 units of laccase. The approach is at 37 ° C Shaken for 24 to 72 hours (180 rpm); then by adding the humic acids precipitated from hydrochloric acid and washed. After drying weight loss is determined. It is 40% and after 24 hours after 72 hours at 60%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19928052A1 (en) * | 1998-06-16 | 2000-01-27 | Rainer Haas | Decomposition of organoarsenic compounds, especially chemical warfare agents, by exposure to aqueous medium containing trivalent manganese ions |
| DE19909546C1 (en) * | 1999-03-04 | 2000-06-29 | Consortium Elektrochem Ind | Enzymatic oxidation system, e.g. for lignin oxidation, bleaching, chemical synthesis or waste water treatment, comprises a manganese oxidase, an oxidizing agent and manganese ions |
-
1997
- 1997-03-04 DE DE1997108670 patent/DE19708670A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19928052A1 (en) * | 1998-06-16 | 2000-01-27 | Rainer Haas | Decomposition of organoarsenic compounds, especially chemical warfare agents, by exposure to aqueous medium containing trivalent manganese ions |
| DE19928052C2 (en) * | 1998-06-16 | 2003-01-30 | Rainer Haas | Process for the decomposition of arsenic organic compounds |
| DE19909546C1 (en) * | 1999-03-04 | 2000-06-29 | Consortium Elektrochem Ind | Enzymatic oxidation system, e.g. for lignin oxidation, bleaching, chemical synthesis or waste water treatment, comprises a manganese oxidase, an oxidizing agent and manganese ions |
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