US20030089472A1 - Laccase activity enhancers for pulp bleaching - Google Patents
Laccase activity enhancers for pulp bleaching Download PDFInfo
- Publication number
- US20030089472A1 US20030089472A1 US10/027,164 US2716401A US2003089472A1 US 20030089472 A1 US20030089472 A1 US 20030089472A1 US 2716401 A US2716401 A US 2716401A US 2003089472 A1 US2003089472 A1 US 2003089472A1
- Authority
- US
- United States
- Prior art keywords
- enzyme
- acid
- classification
- benzylidene
- black liquor
- 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.)
- Abandoned
Links
- 108010029541 Laccase Proteins 0.000 title claims abstract description 50
- 230000000694 effects Effects 0.000 title claims abstract description 38
- 238000004076 pulp bleaching Methods 0.000 title description 5
- 239000003623 enhancer Substances 0.000 title 1
- 102000004190 Enzymes Human genes 0.000 claims abstract description 78
- 108090000790 Enzymes Proteins 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 31
- 230000002708 enhancing effect Effects 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 20
- 229920005610 lignin Polymers 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 17
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 16
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 16
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 16
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 16
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 16
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011122 softwood Substances 0.000 claims description 11
- -1 potassium ferricyanide Chemical compound 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 238000004061 bleaching Methods 0.000 claims description 9
- OWQUYBAASOSGNO-CDNKMLFNSA-N 2-[[(Z)-N-(2-hydroxy-5-sulfoanilino)-C-phenylcarbonimidoyl]diazenyl]benzoic acid Chemical compound C1=CC=C(C=C1)/C(=N/NC2=C(C=CC(=C2)S(=O)(=O)O)O)/N=NC3=CC=CC=C3C(=O)O OWQUYBAASOSGNO-CDNKMLFNSA-N 0.000 claims description 8
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 claims description 8
- OKEAMBAZBICIFP-UHFFFAOYSA-N 3-oxido-2,1,3-benzoxadiazol-3-ium Chemical compound C1=CC=CC2=[N+]([O-])ON=C21 OKEAMBAZBICIFP-UHFFFAOYSA-N 0.000 claims description 8
- 108010015428 Bilirubin oxidase Proteins 0.000 claims description 8
- 108010031396 Catechol oxidase Proteins 0.000 claims description 8
- 102000030523 Catechol oxidase Human genes 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- IJCKBIINTQEGLY-UHFFFAOYSA-N N(4)-acetylcytosine Chemical compound CC(=O)NC1=CC=NC(=O)N1 IJCKBIINTQEGLY-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 8
- 229940043276 diisopropanolamine Drugs 0.000 claims description 8
- 239000011121 hardwood Substances 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 8
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims description 8
- 229940051142 metanil yellow Drugs 0.000 claims description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- 229960003512 nicotinic acid Drugs 0.000 claims description 8
- 235000001968 nicotinic acid Nutrition 0.000 claims description 8
- 239000011664 nicotinic acid Substances 0.000 claims description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- 229940107700 pyruvic acid Drugs 0.000 claims description 8
- 229960004889 salicylic acid Drugs 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims description 8
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 8
- 229950000244 sulfanilic acid Drugs 0.000 claims description 8
- 229940124530 sulfonamide Drugs 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 claims description 8
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 claims description 8
- 229940043798 zincon Drugs 0.000 claims description 8
- ZKHQWZAMYRWXGA-KQYNXXCUSA-J ATP(4-) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-J 0.000 claims description 7
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 7
- 229920001131 Pulp (paper) Polymers 0.000 claims description 7
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical group CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- MIYKHJXFICMPOJ-UHFFFAOYSA-N n-benzyl-1-phenylmethanimine Chemical compound C=1C=CC=CC=1CN=CC1=CC=CC=C1 MIYKHJXFICMPOJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- DVECLMOWYVDJRM-UHFFFAOYSA-N pyridine-3-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CN=C1 DVECLMOWYVDJRM-UHFFFAOYSA-N 0.000 claims description 7
- VSSGEDASAZNGHS-UHFFFAOYSA-N OC(=O)C1=CC=CC=C1NN=C(C=1C=CC=CC=1)N=NC1=CC(S(O)(=O)=O)=CC=C1O Chemical compound OC(=O)C1=CC=CC=C1NN=C(C=1C=CC=CC=1)N=NC1=CC(S(O)(=O)=O)=CC=C1O VSSGEDASAZNGHS-UHFFFAOYSA-N 0.000 claims description 6
- 229940045136 urea Drugs 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 108010024957 Ascorbate Oxidase Proteins 0.000 claims description 4
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 claims description 4
- 102000004005 Prostaglandin-endoperoxide synthases Human genes 0.000 claims description 4
- 108090000459 Prostaglandin-endoperoxide synthases Proteins 0.000 claims description 4
- 102000003425 Tyrosinase Human genes 0.000 claims description 4
- 108060008724 Tyrosinase Proteins 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 4
- 229920002678 cellulose Chemical class 0.000 claims description 2
- 239000001913 cellulose Chemical class 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 6
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 108091028043 Nucleic acid sequence Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- YARKTHNUMGKMGS-LQGKIZFRSA-N chembl3193980 Chemical compound COC1=C(O)C(OC)=CC(\C=N\N=C\C=2C=C(OC)C(O)=C(OC)C=2)=C1 YARKTHNUMGKMGS-LQGKIZFRSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- QGXCOCVWIKYPKW-UHFFFAOYSA-N 3-ethyl-2h-1,3-benzothiazole-6-sulfinic acid Chemical compound OS(=O)C1=CC=C2N(CC)CSC2=C1 QGXCOCVWIKYPKW-UHFFFAOYSA-N 0.000 description 1
- HJBLUNHMOKFZQX-UHFFFAOYSA-N 3-hydroxy-1,2,3-benzotriazin-4-one Chemical compound C1=CC=C2C(=O)N(O)N=NC2=C1 HJBLUNHMOKFZQX-UHFFFAOYSA-N 0.000 description 1
- HRRVLSKRYVIEPR-UHFFFAOYSA-N 6-hydroxy-5-nitroso-1H-pyrimidine-2,4-dione Chemical compound OC1=NC(O)=C(N=O)C(O)=N1 HRRVLSKRYVIEPR-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000002126 C01EB10 - Adenosine Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 108020004511 Recombinant DNA Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229960005305 adenosine Drugs 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- UMCBIDVJVPVDLH-UHFFFAOYSA-N diphosphono hydrogen phosphate;guanidine Chemical compound NC(N)=N.OP(O)(=O)OP(O)(=O)OP(O)(O)=O UMCBIDVJVPVDLH-UHFFFAOYSA-N 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GMJUGPZVHVVVCG-UHFFFAOYSA-N n-hydroxy-n-phenylacetamide Chemical compound CC(=O)N(O)C1=CC=CC=C1 GMJUGPZVHVVVCG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000008057 potassium phosphate buffer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010188 recombinant method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching processes
- D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/96—Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates
Definitions
- the present invention relates to the enhancement of enzyme activity and the activation of enzymes. More specifically, the present invention relates to mediators, enhancing agents, or activating agents that are useful in enhancing the activity of enzymes having laccase activity, especially in the field of pulp bleaching.
- Paper pulp is typically processed from wood through the Kraft (and other) processes.
- the process produces a pulp with a dark brown color, mostly due to the presence of lignin and lignin derivatives.
- the lignin has to be removed by a process known in the art as “delignification” or “bleaching.” This is typically done commercially in several stages in pulp mills, wherein lignin is first oxidized and then removed from the pulp.
- bleaching of Kraft pulp uses a large amount of chlorine or chlorine-containing compounds.
- the byproducts of such processes may include chlorinated compounds that are undesirable.
- bio-bleaching enzymes to biologically bleach pulp
- laccase family of enzymes which are copper-containing enzymes that are known to be good oxidizing agents in the presence of oxygen. Laccases are found in microbes, fungi, and higher organisms.
- Laccase enzymes are used for many other applications, including treatment of pulp waste water, de-inking, industrial color removal, bleach for laundry detergents, oral care teeth whiteners, and as catalysts or facilitators for polymerization and oxidation reactions.
- the oxidizing efficiency of a laccase can be improved or activated through the use of a mediator, also known as an enhancing agent or activator.
- Systems that include a laccase and a mediator are known in the art as laccase-mediator systems (LMS).
- mediators for use in a laccase-mediator system include HBT (1-hydroxybenzotriazole), ABTS [2,2′-azinobis(3-ethylbenzothiazoline-6-sulfinic acid)], NHA (N-hydroxyacetinilide), NHAA (N-acetyl-N-phenylhydroxylamine), HBTO (3-hydroxy-1,2,3-benzotriazin-4(3H)-one), and VIO (violuric acid).
- HBT 1-hydroxybenzotriazole
- ABTS 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfinic acid)
- NHA N-hydroxyacetinilide
- NHAA N-acetyl-N-phenylhydroxylamine
- HBTO 3-hydroxy-1,2,3-benzotriazin-4(3H)-one
- VIO violuric acid
- the invention provides a composition comprising an enzyme exhibiting laccase activity and an enzyme enhancing agent (also referred to as a mediator).
- the enzyme enhancing agent is selected from 2-thiouracil, sodium dimethyldithio carbonate hydrate, N-benzylidene-benzylamine, melamine, anthracene, dicyandiamide, sulfanilic acid, sulfanilamide,urea, salicylic acid, 3,4,5-trihydroxy-benzoic acid, ferric chloride, potassium ferricyanide, ascorbic acid, Zincon (o-[2-[alpha(2-hydroxy-5-sulfophenylazo)benzylidene]hydrazino]benzoic acid), diisopropanolamine, adenosine triphosphate, guanidine, cyanuric acid, Thiazol Yellow G, nicotinic acid, Metanil Yellow, hardwood black liquor, softwood black liquor, methanesulfonic acid, metanilic acid, s
- the invention also provides a process for oxidizing a substrate that comprises treating the substrate with a composition comprising an enzyme exhibiting laccase activity and an enzyme enhancing agent.
- the invention further provides a process for bleaching a lignin-containing material that comprises treating the material with an enzyme exhibiting laccase activity and an enzyme enhancing agent.
- the material is a wood pulp.
- the material is a wood pulp that is a raw material used to form a polysaccharide or a cellulose derivative.
- the invention provides a process for enhancing the activity of an enzyme exhibiting laccase activity that comprises adding an enzyme enhancing agent to the enzyme.
- the invention provides newly identified enzyme enhancing agents (also referred to as mediators) that enhance the activity of enzymes exhibiting laccase activity.
- the mediators of this invention are capable of enhancing the activities of laccase and laccase-related enzymes, i.e., enzymes exhibiting laccase activity.
- the enzymes exhibiting laccase enzyme activity include the laccase enzymes of enzyme classification EC 1.10.3.2, the catechol oxidase enzymes of enzyme classification EC 1.10.3.1, the monophenol monooxygenase enzymes of enzyme classification EC 1.14.99.1, the bilirubin oxidase enzymes of enzyme classification EC 1.3.3.5, and the ascorbate oxidase enzymes of enzyme classification EC 1.10.3.3.
- the EC (Enzyme Commission) number is based upon the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (IUBMB).
- the enzymes exhibiting laccase enzyme activity may be derived from microbial, fungal, or other sources. These enzymes can also be produced by recombinant methods that are well known to those skilled in the art, such as cultivating a host cell transformed with a recombinant DNA vector that includes a DNA sequence encoding a laccase (and, optionally, DNA sequences that permit the expression of the laccase DNA sequence) in a culture medium under conditions that permit the expression of the laccase, and recovering the enzyme from the culture.
- the composition of the invention can further include a hydrolase, such as xylanase.
- the enzyme enhancing agents of the invention are selected from 2-thiouracil, sodium dimethyldithio carbonate hydrate, N-benzylidene-benzylamine, melamine, anthracene, dicyandiamide, sulfanilic acid, sulfanilamide,urea, salicylic acid, 3,4,5-trihydroxy-benzoic acid, ferric chloride, potassium ferricyanide, ascorbic acid, Zincon (o-[2-[alpha(2-hydroxy-5-sulfophenylazo)benzylidene]hydrazino]benzoic acid), diisopropanolamine, adenosine triphosphate, guanidine, cyanuric acid, Thiazol Yellow G, nicotinic acid, Metanil Yellow, hardwood black liquor, softwood black liquor, methanesulfonic acid, metanilic acid, sulfamide, 3-pyridine sulfonic acid, benzofuroxan, t-butyl hydro
- Another aspect of the invention provides a process for oxidizing a substrate that comprises treating the substrate with a composition comprising an enzyme exhibiting laccase activity and an enzyme enhancing agent.
- the enzyme enhancing agent can be selected from one or the above described enzyme enhancing agents.
- the enhancing agent may be present in concentrations of from about 0.01 micromolar to about 1000 micromolar, more preferably from about 0.1 micromolar to about 250 micromolar and most preferably from about 0.5 to about 100 micromolar.
- the enzyme is used in amounts of from about 0.1 to 400 units (defined in Examples using ABTS as substrate) for 1 g dry pulp, more preferably from 1 to 200 units and even more preferably from about 10 to 100 units and most preferably from 20 to 50 units.
- the process of the invention can further include the step of adding an oxidizing agent, such as at least one of air, oxygen, and hydrogen peroxide.
- an oxidizing agent such as at least one of air, oxygen, and hydrogen peroxide.
- One embodiment of the invention provides a process for bleaching a lignin-containing material that comprises treating the material with an enzyme exhibiting laccase activity and an enzyme enhancing agent.
- the enhancing agent may be present in an amount of from about 0.1% to about 15% based on the weight of the dry lignin containing material, more preferably from about 0.1% to about 10% and even more preferably from about 0.5% to about 5% and most preferably from about 1% to about 4%.
- a lignin containing material is wood pulp.
- the process for bleaching a lignin-containing material can further include the step of adding an oxidizing agent, such as at least one of air, oxygen, and hydrogen peroxide.
- the mediators of the invention can be used, for example, for pulp bleaching. Laccase itself can bleach pulp only to a limited extent.
- the use of the mediators as disclosed herein enhances the activity of laccase in pulp bleaching. In this context, delignification and bleaching efficiency is defined by the “Kappa Number.”
- the specific activity was determined using ABTS (0.5 mM) as substrate.
- One unit of activity is equal to the umol of the oxidized product from ABTS per min per mg protein at pH 6.0 at 23° C.
- the activity of laccase was determined using syringaldazine as substrate.
- one unit of activity is equal to the change of 0.001 UV absorbance at A530nm per minute per ug protein in 2 ml of 100 mM, pH 5.5 potassium phosphate buffer, and 0.5 ml of 0.25 mM syringaldazine in methanol at 23° C.
- a softwood Kraft pulp was delignified using a laccase-mediator system.
- the Kraft process is well known to those skilled in the art and is described, for example, by Swen A. Rydholm in “Pulping Process”, Interscience Publishers, New York, N.Y. (1965), p. 576.
- the dried pulp was added to 80 ml of 50 mM phosphate, pH 5.5, and disintegrated in a blender. The pulp was then transferred to a 500 ml conical flask, and the blender was washed with 20 ml of the same buffer. The washed buffer and the pulp were combined. The mediator was added at 1-4% (w/w, based on the dry pulp) (Dosage) followed by the addition of the laccase. The pH of the pulp mixture was adjusted to 5.5 if needed. The flask was covered with an aluminum foil with holes punched through and incubated at 50° C. for 16 hrs on a rotary shaker at 200 rpm.
- the filtered pulp was repulped in the alkaline solution and incubated at 70° C. for 3 hrs.
- the pH of the pulp mixture should be between 11.7-12.00 during the entire treatment. After the treatment, the pulp mixture was filtered through a Buchner funnel, and the pulp was washed with water extensively, and then dried in a hood overnight.
- the delignification of the pulp was measured as the change in Kappa number according to TAPPI method T236 cm ⁇ 85. Briefly, a known mass of paper pulp (containing lignin) was reacted with an excess of potassium permanganate in acid solution for a specified period of time to oxidize the lignin. After the reaction, the residual permanganate was determined by titration.
- the Kappa number was defined as the volume (ml) of 0.1N potassium permanganate consumed by 1 g of moisture-free pulp in 0.5N sulfuric acid after a ten minute reaction time at 25° C. under conditions such that one-half of the permanganate remained unreacted.
- mediators of the invention also include mediators which are functionally equivalent to the mediators specifically recited herein, such equivalents having minor structural variations such as the addition of a methyl or ethyl substituent or the formation of a methyl ester from a carboxylic acid. Accordingly, this invention is not to be regarded as limited to the embodiments disclosed herein.
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Abstract
Description
- This application claims the benefit of U.S. Provisional Application No. 60/318,290, filed on Sep. 10, 2001.
- The present invention relates to the enhancement of enzyme activity and the activation of enzymes. More specifically, the present invention relates to mediators, enhancing agents, or activating agents that are useful in enhancing the activity of enzymes having laccase activity, especially in the field of pulp bleaching.
- Paper pulp is typically processed from wood through the Kraft (and other) processes. The process produces a pulp with a dark brown color, mostly due to the presence of lignin and lignin derivatives. For many applications, the lignin has to be removed by a process known in the art as “delignification” or “bleaching.” This is typically done commercially in several stages in pulp mills, wherein lignin is first oxidized and then removed from the pulp. Currently, bleaching of Kraft pulp uses a large amount of chlorine or chlorine-containing compounds. The byproducts of such processes may include chlorinated compounds that are undesirable.
- Recently, several research groups have been working with enzymes to biologically bleach pulp, referred to as “bio-bleaching”. An enzyme group that has received particular attention is the laccase family of enzymes, which are copper-containing enzymes that are known to be good oxidizing agents in the presence of oxygen. Laccases are found in microbes, fungi, and higher organisms.
- Laccase enzymes are used for many other applications, including treatment of pulp waste water, de-inking, industrial color removal, bleach for laundry detergents, oral care teeth whiteners, and as catalysts or facilitators for polymerization and oxidation reactions. For many applications, the oxidizing efficiency of a laccase can be improved or activated through the use of a mediator, also known as an enhancing agent or activator. Systems that include a laccase and a mediator are known in the art as laccase-mediator systems (LMS).
- There are several known mediators for use in a laccase-mediator system. These include HBT (1-hydroxybenzotriazole), ABTS [2,2′-azinobis(3-ethylbenzothiazoline-6-sulfinic acid)], NHA (N-hydroxyacetinilide), NHAA (N-acetyl-N-phenylhydroxylamine), HBTO (3-hydroxy-1,2,3-benzotriazin-4(3H)-one), and VIO (violuric acid). In addition, there are several compounds containing NH—OH or N—O that have been found to be useful as mediators.
- Functional groups and substituents of the above mediators have large effects on the LMS efficiency. Even within the same class of compounds, a substituent of a mediator can change the specificity of a laccase towards a specific substrate, such as pulp lignin, lignin derivatives or other fine chemicals, thereby increasing or decreasing mediator efficiency greatly. In addition, a mediator may be effective for one particular application but unsuitable for another application. Thus, there is a need to discover efficient mediators for specific applications. One such application is the bleaching of pulp, wherein it is also important that the mediators are not unduly expensive or hazardous. Thus, there is a need to identify additional mediators that activate laccase and/or enhance the activity of enzymes that exhibit laccase activity, particularly for pulp bleaching.
- The invention provides a composition comprising an enzyme exhibiting laccase activity and an enzyme enhancing agent (also referred to as a mediator). The enzyme enhancing agent is selected from 2-thiouracil, sodium dimethyldithio carbonate hydrate, N-benzylidene-benzylamine, melamine, anthracene, dicyandiamide, sulfanilic acid, sulfanilamide,urea, salicylic acid, 3,4,5-trihydroxy-benzoic acid, ferric chloride, potassium ferricyanide, ascorbic acid, Zincon (o-[2-[alpha(2-hydroxy-5-sulfophenylazo)benzylidene]hydrazino]benzoic acid), diisopropanolamine, adenosine triphosphate, guanidine, cyanuric acid, Thiazol Yellow G, nicotinic acid, Metanil Yellow, hardwood black liquor, softwood black liquor, methanesulfonic acid, metanilic acid, sulfamide, 3-pyridine sulfonic acid, benzofuroxan, t-butyl hydroperoxide, pyruvic acid, imidazole, N-acetylcytosine, and phenol.
- The invention also provides a process for oxidizing a substrate that comprises treating the substrate with a composition comprising an enzyme exhibiting laccase activity and an enzyme enhancing agent.
- The invention further provides a process for bleaching a lignin-containing material that comprises treating the material with an enzyme exhibiting laccase activity and an enzyme enhancing agent. In one embodiment of the invention, the material is a wood pulp. In another embodiment of the invention, the material is a wood pulp that is a raw material used to form a polysaccharide or a cellulose derivative.
- In addition, the invention provides a process for enhancing the activity of an enzyme exhibiting laccase activity that comprises adding an enzyme enhancing agent to the enzyme.
- The invention provides newly identified enzyme enhancing agents (also referred to as mediators) that enhance the activity of enzymes exhibiting laccase activity.
- The mediators of this invention are capable of enhancing the activities of laccase and laccase-related enzymes, i.e., enzymes exhibiting laccase activity. The enzymes exhibiting laccase enzyme activity include the laccase enzymes of enzyme classification EC 1.10.3.2, the catechol oxidase enzymes of enzyme classification EC 1.10.3.1, the monophenol monooxygenase enzymes of enzyme classification EC 1.14.99.1, the bilirubin oxidase enzymes of enzyme classification EC 1.3.3.5, and the ascorbate oxidase enzymes of enzyme classification EC 1.10.3.3. The EC (Enzyme Commission) number is based upon the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (IUBMB).
- The enzymes exhibiting laccase enzyme activity may be derived from microbial, fungal, or other sources. These enzymes can also be produced by recombinant methods that are well known to those skilled in the art, such as cultivating a host cell transformed with a recombinant DNA vector that includes a DNA sequence encoding a laccase (and, optionally, DNA sequences that permit the expression of the laccase DNA sequence) in a culture medium under conditions that permit the expression of the laccase, and recovering the enzyme from the culture. The composition of the invention can further include a hydrolase, such as xylanase.
- The enzyme enhancing agents of the invention are selected from 2-thiouracil, sodium dimethyldithio carbonate hydrate, N-benzylidene-benzylamine, melamine, anthracene, dicyandiamide, sulfanilic acid, sulfanilamide,urea, salicylic acid, 3,4,5-trihydroxy-benzoic acid, ferric chloride, potassium ferricyanide, ascorbic acid, Zincon (o-[2-[alpha(2-hydroxy-5-sulfophenylazo)benzylidene]hydrazino]benzoic acid), diisopropanolamine, adenosine triphosphate, guanidine, cyanuric acid, Thiazol Yellow G, nicotinic acid, Metanil Yellow, hardwood black liquor, softwood black liquor, methanesulfonic acid, metanilic acid, sulfamide, 3-pyridine sulfonic acid, benzofuroxan, t-butyl hydroperoxide, pyruvic acid, imidazole, N-acetylcytosine, and phenol.
- These enzyme enhancing agents of the invention can be classified into seven categories:
- Group 1
- Specific Compounds Containing Nitrogen
- a. guanidine
- b. cyanuric acid
- c. melamine
- d. dicyandiamide
- e. urea
- f. nicotinic acid
- g. N-benzylidene-benzylamine
- h. Metanil Yellow
- i. Zincon
- j. benzofuroxan
- k. imidazole
- l. N-acetyl cytosine
- m. Thiazol Yellow G
- Group 2
- Ascorbic Acid and Substituted Ascorbic Acid
- Group 3
- Salicylic Acid and 3,4,5-Trihydroxybenzoic Acid
- Group 4
- Materials From Pulp Processing
- a. hardwood black liquor
- b. softwood black liquor
- Group 5
- Specific Compounds Containing Sulfur
- a. sulfanilamide
- b. methanesulfonic acid
- c. sulfanilic acid
- d. 2-thiouracil
- e. metanilic acid
- f. sulfamide
- g. 3-pyridine sulfonic acid
- h. sodium dimethyldithio carbonate hydrate
- Group 6
- Specific Organic Compounds
- a. anthracene
- b. t-butyl hydroperoxide
- c. pyruvic acid
- d. diisopropanolamine
- e. adenosine triphosphate
- f. phenol (conditional)
- Group 7
- Specific Inorganic Compounds
- a. ferric chloride
- b. potassium ferricyanide
- The compounds listed in the above seven groups, their related structures, and structural analogs are all potential mediators for enzyme(s) that exhibit laccase activity.
- Another aspect of the invention provides a process for oxidizing a substrate that comprises treating the substrate with a composition comprising an enzyme exhibiting laccase activity and an enzyme enhancing agent. The enzyme enhancing agent can be selected from one or the above described enzyme enhancing agents.
- The enhancing agent may be present in concentrations of from about 0.01 micromolar to about 1000 micromolar, more preferably from about 0.1 micromolar to about 250 micromolar and most preferably from about 0.5 to about 100 micromolar.
- The enzyme is used in amounts of from about 0.1 to 400 units (defined in Examples using ABTS as substrate) for 1 g dry pulp, more preferably from 1 to 200 units and even more preferably from about 10 to 100 units and most preferably from 20 to 50 units.
- The process of the invention can further include the step of adding an oxidizing agent, such as at least one of air, oxygen, and hydrogen peroxide.
- One embodiment of the invention provides a process for bleaching a lignin-containing material that comprises treating the material with an enzyme exhibiting laccase activity and an enzyme enhancing agent. In this embodiment of the invention, the enhancing agent may be present in an amount of from about 0.1% to about 15% based on the weight of the dry lignin containing material, more preferably from about 0.1% to about 10% and even more preferably from about 0.5% to about 5% and most preferably from about 1% to about 4%. One example of a lignin containing material is wood pulp. The process for bleaching a lignin-containing material can further include the step of adding an oxidizing agent, such as at least one of air, oxygen, and hydrogen peroxide.
- The mediators of the invention can be used, for example, for pulp bleaching. Laccase itself can bleach pulp only to a limited extent. The use of the mediators as disclosed herein enhances the activity of laccase in pulp bleaching. In this context, delignification and bleaching efficiency is defined by the “Kappa Number.”
- Delignification of a Softwood Kraft Pulp Using a Laccase-Mediator System in the Presence of a Mediator
- The specific activity was determined using ABTS (0.5 mM) as substrate. One unit of activity is equal to the umol of the oxidized product from ABTS per min per mg protein at pH 6.0 at 23° C. The extinction coefficient of the oxidized ABTS is: ε(max) at 420 nm=36,000M−1 cm−1.)
- Alternatively, the activity of laccase (NS51003) was determined using syringaldazine as substrate. In this case, one unit of activity is equal to the change of 0.001 UV absorbance at A530nm per minute per ug protein in 2 ml of 100 mM, pH 5.5 potassium phosphate buffer, and 0.5 ml of 0.25 mM syringaldazine in methanol at 23° C.
- In the following example, a softwood Kraft pulp was delignified using a laccase-mediator system. The Kraft process is well known to those skilled in the art and is described, for example, by Swen A. Rydholm in “Pulping Process”, Interscience Publishers, New York, N.Y. (1965), p. 576.
- A softwood Kraft pulp, Kappa number 31.0, was treated with a laccase (NS51003, Novozymes A/S, Denmark) under the following conditions:
Enzyme dosage 45 units/g pulp pH 5.5 Temperature 50° C. Reaction time 16 hours Pulp consistency 2% - The dried pulp was added to 80 ml of 50 mM phosphate, pH 5.5, and disintegrated in a blender. The pulp was then transferred to a 500 ml conical flask, and the blender was washed with 20 ml of the same buffer. The washed buffer and the pulp were combined. The mediator was added at 1-4% (w/w, based on the dry pulp) (Dosage) followed by the addition of the laccase. The pH of the pulp mixture was adjusted to 5.5 if needed. The flask was covered with an aluminum foil with holes punched through and incubated at 50° C. for 16 hrs on a rotary shaker at 200 rpm.
- After the enzymatic treatment, the pulp mixture was filtered through a Buchner funnel and the pulp was washed with water. The pulp from the control experiment was treated at the same pH and temperature as described above in the absence of mediators.
- The washed pulp was then treated with an alkaline solution under the following conditions:
Pulp 2 g Water 200 ml NaOH 240 mg H2O2 (30%) 400 ul Temperature 70° C. Reaction time 3 hours - The filtered pulp was repulped in the alkaline solution and incubated at 70° C. for 3 hrs. The pH of the pulp mixture should be between 11.7-12.00 during the entire treatment. After the treatment, the pulp mixture was filtered through a Buchner funnel, and the pulp was washed with water extensively, and then dried in a hood overnight.
- The delignification of the pulp was measured as the change in Kappa number according to TAPPI method T236 cm−85. Briefly, a known mass of paper pulp (containing lignin) was reacted with an excess of potassium permanganate in acid solution for a specified period of time to oxidize the lignin. After the reaction, the residual permanganate was determined by titration. The Kappa number was defined as the volume (ml) of 0.1N potassium permanganate consumed by 1 g of moisture-free pulp in 0.5N sulfuric acid after a ten minute reaction time at 25° C. under conditions such that one-half of the permanganate remained unreacted. A linear relationship with the lignin content of the pulp and the measurement of the Kappa number had already been done on samples as low as 300 mg of pulp. The results are shown below.
Dosage Laccase Kappa # Kappa # Δ Mediator(s) (%) (%) (No Mediator) (Mediator) Kappa # 2-Thiouracil 4 0.2 29.3 27.7 −1.6 Sodium dimethyldithio 4 0.2 29.3 28.6 −0.7 carbonate hydrate N-Benzylidene- 4 0.1 28.6 28.3 −0.3 benzylamine Melamine 4 0.2 27.7 25.9 −1.8 Anthracene 0.5 0.1 28.7 26.6 −2.1 Dicyandiamide 4 0.2 27.1 25.8 −1.3 Sulfanilic acid 4 0.2 26.2 24.1 −2.1 Sulfanilamide 4 0.2 26.2 23.8 −2.4 Urea 4 0.2 26.1 25.1 −1 Salicylic acid 3.5 0.1 27.0 24.3 −2.7 3,4,5-Trihydroxy- 3.5 0.1 27.0 24.2 −2.8 benzoic acid Ferric chloride 8 0.2 26.2 25.3 −0.9 Potassium ferricyanide 1 0.2 26.2 25.0 −1.2 Ascorbic acid 1 0.2 26.1 24.7 −1.4 Zincon 4 0.2 24.2 19.4 −4.8 Diisopropanolamine 4 0.2 24.2 19.5 −4.7 Adenosine 4 0.2 24.2 23.1 −1.1 triphosphate Guanidine 1 0.1 27.6 27.2 −0.4 Cyanuric acid 4 0.2 24.9 24.2 −0.7 Thiazol Yellow G 3 0.2 24.9 21.9 −3.0 Nicotinic acid 3 0.2 24.9 24.0 −0.9 Metanil Yellow 4 0.2 31.0 29.4 −1.6 Hardwood black liquor 1 0.1 31.0 30.9 −0.1 Softwood black liquor 2.5 0.2 28.5 26.5 −2.0 Methanesulfonic acid 4 0.2 25.2 24.9 −0.3 Metanilic acid 4 0.1 31.0 30.1 −0.9 Sulfamide 4 0.2 26.2 26.0 −0.2 3-Pyridine sulfonic 3 0.2 24.5 22.9 −1.6 acid Benzofuroxan 4 0.1 31.0 29.9 −1.1 t-Butyl hydroperoxide 5 0.1 24.2 23.1 −1.1 Pyruvic acid 4 0.2 24.7 24.3 −0.4 Imidazole 4 0.2 24.7 22.0 −2.7 N-Acetylcytosine 4 0.2 28.6 28.3 −0.3 Phenol 1 0.2 26.1 25.0 −1.1 - It is to be understood that the above described embodiments are illustrative only and that modification throughout may occur to one skilled in the art. For example, a person of skill in the art will recognize that the mediators of the invention also include mediators which are functionally equivalent to the mediators specifically recited herein, such equivalents having minor structural variations such as the addition of a methyl or ethyl substituent or the formation of a methyl ester from a carboxylic acid. Accordingly, this invention is not to be regarded as limited to the embodiments disclosed herein.
Claims (19)
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US10/027,164 US20030089472A1 (en) | 2001-09-10 | 2001-12-20 | Laccase activity enhancers for pulp bleaching |
PCT/US2002/013050 WO2003023134A1 (en) | 2001-09-10 | 2002-04-24 | Laccase activity enhancers for pulp bleaching |
AU2002307553A AU2002307553A1 (en) | 2001-09-10 | 2002-04-24 | Laccase activity enhancers for pulp bleaching |
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US10/027,164 US20030089472A1 (en) | 2001-09-10 | 2001-12-20 | Laccase activity enhancers for pulp bleaching |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040112555A1 (en) * | 2002-12-03 | 2004-06-17 | Jeffrey Tolan | Bleaching stage using xylanase with hydrogen peroxide, peracids, or a combination thereof |
US9663899B2 (en) * | 2015-08-26 | 2017-05-30 | Solenis Technologies, L.P. | Method for making lignocellulosic paper and paper product |
US11384381B2 (en) * | 2016-07-13 | 2022-07-12 | Kikkoman Corporation | Reaction accelerating agent |
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Publication number | Priority date | Publication date | Assignee | Title |
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EP2588665B1 (en) * | 2010-07-01 | 2019-05-08 | Novozymes A/S | Bleaching of pulp |
CN109457526B (en) * | 2018-11-12 | 2021-07-23 | 复旦大学 | Nondestructive bleaching method for wikstroelia bark pulp |
CN114058026B (en) * | 2021-10-19 | 2023-02-17 | 江苏大学 | Thermoplastic filament containing enzyme modified lignin and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5885304A (en) * | 1993-06-29 | 1999-03-23 | Novo Nordisk A/S | Enhancement of laccase reactions |
US6087135A (en) * | 1997-12-19 | 2000-07-11 | Novo Nordisk A/S | Modification of polysaccharides by means of a phenol oxidizing enzyme |
US6103059A (en) * | 1993-06-16 | 2000-08-15 | Lignozym Gmbh | Process for delignification of a lignin containing pulp |
US6242245B1 (en) * | 1997-09-26 | 2001-06-05 | Consortium für elektrochemische Industrie GmbH | Multicomponent system for modifying, degrading or bleaching lignin or lignin-containing materials, and processes for its use |
-
2001
- 2001-12-20 US US10/027,164 patent/US20030089472A1/en not_active Abandoned
-
2002
- 2002-04-24 WO PCT/US2002/013050 patent/WO2003023134A1/en not_active Application Discontinuation
- 2002-04-24 AU AU2002307553A patent/AU2002307553A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6103059A (en) * | 1993-06-16 | 2000-08-15 | Lignozym Gmbh | Process for delignification of a lignin containing pulp |
US6358904B1 (en) * | 1993-06-16 | 2002-03-19 | Hans-Peter Call | Multicomponent bleaching system |
US5885304A (en) * | 1993-06-29 | 1999-03-23 | Novo Nordisk A/S | Enhancement of laccase reactions |
US6242245B1 (en) * | 1997-09-26 | 2001-06-05 | Consortium für elektrochemische Industrie GmbH | Multicomponent system for modifying, degrading or bleaching lignin or lignin-containing materials, and processes for its use |
US6087135A (en) * | 1997-12-19 | 2000-07-11 | Novo Nordisk A/S | Modification of polysaccharides by means of a phenol oxidizing enzyme |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040112555A1 (en) * | 2002-12-03 | 2004-06-17 | Jeffrey Tolan | Bleaching stage using xylanase with hydrogen peroxide, peracids, or a combination thereof |
US9663899B2 (en) * | 2015-08-26 | 2017-05-30 | Solenis Technologies, L.P. | Method for making lignocellulosic paper and paper product |
US11384381B2 (en) * | 2016-07-13 | 2022-07-12 | Kikkoman Corporation | Reaction accelerating agent |
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