NZ615725B2 - Imprinted polymer that binds heterocyclic compounds and methods of use - Google Patents
Imprinted polymer that binds heterocyclic compounds and methods of use Download PDFInfo
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- NZ615725B2 NZ615725B2 NZ615725A NZ61572513A NZ615725B2 NZ 615725 B2 NZ615725 B2 NZ 615725B2 NZ 615725 A NZ615725 A NZ 615725A NZ 61572513 A NZ61572513 A NZ 61572513A NZ 615725 B2 NZ615725 B2 NZ 615725B2
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- Prior art keywords
- polymer
- agricultural chemical
- imprinted
- molecule
- aqueous liquid
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- 229920000642 polymer Polymers 0.000 title claims abstract description 173
- 150000002391 heterocyclic compounds Chemical class 0.000 title description 2
- 239000003905 agrochemical Substances 0.000 claims abstract description 95
- 239000005828 Pyrimethanil Substances 0.000 claims abstract description 34
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 30
- BPYKTIZUTYGOLE-IFADSCNNSA-N bilirubin Chemical compound N1C(=O)C(C)=C(C=C)\C1=C\C1=C(C)C(CCC(O)=O)=C(CC2=C(C(C)=C(\C=C/3C(=C(C=C)C(=O)N\3)C)N2)CCC(O)=O)N1 BPYKTIZUTYGOLE-IFADSCNNSA-N 0.000 claims abstract description 29
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 29
- 239000005783 Fluopyram Substances 0.000 claims abstract description 19
- KVDJTXBXMWJJEF-UHFFFAOYSA-N fluopyram Chemical compound ClC1=CC(C(F)(F)F)=CN=C1CCNC(=O)C1=CC=CC=C1C(F)(F)F KVDJTXBXMWJJEF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001408 amides Chemical class 0.000 claims abstract description 13
- 125000004433 nitrogen atoms Chemical group N* 0.000 claims abstract description 13
- 239000005788 Fluxapyroxad Substances 0.000 claims abstract description 11
- SXSGXWCSHSVPGB-UHFFFAOYSA-N Fluxapyroxad Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1C1=CC(F)=C(F)C(F)=C1 SXSGXWCSHSVPGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005924 Pirimiphos-methyl Substances 0.000 claims abstract description 10
- QHOQHJPRIBSPCY-UHFFFAOYSA-N Pirimiphos-methyl Chemical group CCN(CC)C1=NC(C)=CC(OP(=S)(OC)OC)=N1 QHOQHJPRIBSPCY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 230000003247 decreasing Effects 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 235000014101 wine Nutrition 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000005906 Imidacloprid Substances 0.000 claims description 4
- YWTYJOPNNQFBPC-UHFFFAOYSA-N Imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 claims description 4
- 229960004546 Thiabendazole Drugs 0.000 claims description 4
- WJCNZQLZVWNLKY-UHFFFAOYSA-N Tiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229940056881 imidacloprid Drugs 0.000 claims description 4
- 239000004308 thiabendazole Substances 0.000 claims description 4
- 235000010296 thiabendazole Nutrition 0.000 claims description 4
- 125000002009 alkene group Chemical group 0.000 claims description 3
- 235000012041 food component Nutrition 0.000 claims description 3
- 239000005417 food ingredient Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3aR,7aS)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical group C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-N 0.000 claims description 2
- 229950000294 Azaconazole Drugs 0.000 claims description 2
- CJJOSEISRRTUQB-UHFFFAOYSA-N Azinphos-methyl Chemical group C1=CC=C2C(=O)N(CSP(=S)(OC)OC)N=NC2=C1 CJJOSEISRRTUQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005730 Azoxystrobin Substances 0.000 claims description 2
- WFDXOXNFNRHQEC-GHRIWEEISA-N Azoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 claims description 2
- 239000005740 Boscalid Substances 0.000 claims description 2
- 239000005745 Captan Substances 0.000 claims description 2
- 229940117949 Captan Drugs 0.000 claims description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N Diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005630 Diquat Substances 0.000 claims description 2
- 229960002125 Enilconazole Drugs 0.000 claims description 2
- PZBPKYOVPCNPJY-UHFFFAOYSA-N Enilconazole Chemical compound ClC1=CC(Cl)=CC=C1C(OCC=C)CN1C=NC=C1 PZBPKYOVPCNPJY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005899 Fipronil Substances 0.000 claims description 2
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N Fipronil Chemical group NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 claims description 2
- FQKUGOMFVDPBIZ-UHFFFAOYSA-N Flusilazole Chemical compound C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 FQKUGOMFVDPBIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005795 Imazalil Substances 0.000 claims description 2
- 239000005867 Iprodione Substances 0.000 claims description 2
- ONUFESLQCSAYKA-UHFFFAOYSA-N Iprodione Chemical compound O=C1N(C(=O)NC(C)C)CC(=O)N1C1=CC(Cl)=CC(Cl)=C1 ONUFESLQCSAYKA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005811 Myclobutanil Substances 0.000 claims description 2
- HZJKXKUJVSEEFU-UHFFFAOYSA-N Myclobutanil Chemical compound C=1C=C(Cl)C=CC=1C(CCCC)(C#N)CN1C=NC=N1 HZJKXKUJVSEEFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005857 Trifloxystrobin Substances 0.000 claims description 2
- AKNQMEBLVAMSNZ-UHFFFAOYSA-N azaconazole Chemical group ClC1=CC(Cl)=CC=C1C1(CN2N=CN=C2)OCCO1 AKNQMEBLVAMSNZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940118790 boscalid Drugs 0.000 claims description 2
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 claims description 2
- SYJFEGQWDCRVNX-UHFFFAOYSA-N diquat Chemical compound C1=CC=[N+]2CC[N+]3=CC=CC=C3C2=C1 SYJFEGQWDCRVNX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229940013764 fipronil Drugs 0.000 claims description 2
- ONCZDRURRATYFI-QTCHDTBASA-N methyl (2Z)-2-methoxyimino-2-[2-[[(E)-1-[3-(trifluoromethyl)phenyl]ethylideneamino]oxymethyl]phenyl]acetate Chemical compound CO\N=C(/C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-QTCHDTBASA-N 0.000 claims description 2
- INFDPOAKFNIJBF-UHFFFAOYSA-N paraquat Chemical compound C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 INFDPOAKFNIJBF-UHFFFAOYSA-N 0.000 claims description 2
- QXJKBPAVAHBARF-BETUJISGSA-N procymidone Chemical compound O=C([C@]1(C)C[C@@]1(C1=O)C)N1C1=CC(Cl)=CC(Cl)=C1 QXJKBPAVAHBARF-BETUJISGSA-N 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 28
- 239000002245 particle Substances 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N ABCN Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004971 Cross linker Substances 0.000 abstract description 7
- 239000003999 initiator Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 229920000193 polymethacrylate Polymers 0.000 abstract description 4
- BHBPJIPGXGQMTE-UHFFFAOYSA-N ethane-1,2-diol;2-methylprop-2-enoic acid Chemical group OCCO.CC(=C)C(O)=O.CC(=C)C(O)=O BHBPJIPGXGQMTE-UHFFFAOYSA-N 0.000 abstract description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 229920000058 polyacrylate Polymers 0.000 abstract description 3
- 239000012085 test solution Substances 0.000 description 19
- 239000000725 suspension Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000944 Soxhlet extraction Methods 0.000 description 6
- 230000000875 corresponding Effects 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 210000004080 Milk Anatomy 0.000 description 3
- 239000012491 analyte Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000000855 fungicidal Effects 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 238000003306 harvesting Methods 0.000 description 3
- 230000000749 insecticidal Effects 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229940036592 ANTHELMINTICS Drugs 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229920000344 Molecularly imprinted polymer Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 235000013334 alcoholic beverage Nutrition 0.000 description 2
- 230000000507 anthelmentic Effects 0.000 description 2
- 239000000921 anthelmintic agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000002363 herbicidal Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 235000019520 non-alcoholic beverage Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-Vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- 229940013317 Fish Oils Drugs 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 235000019754 Grower Diet Nutrition 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000005923 Pirimicarb Substances 0.000 description 1
- YFGYUFNIOHWBOB-UHFFFAOYSA-N Pirimicarb Chemical compound CN(C)C(=O)OC1=NC(N(C)C)=NC(C)=C1C YFGYUFNIOHWBOB-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 230000036462 Unbound Effects 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 210000002268 Wool Anatomy 0.000 description 1
- 230000000895 acaricidal Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 230000003115 biocidal Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000002538 fungal Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000002285 radioactive Effects 0.000 description 1
- 235000019991 rice wine Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000020254 sheep milk Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
Abstract
The disclosure relates to a method for the removal of an agricultural chemical having a heterocyclic ring comprising 1-3 nitrogen atoms from an aqueous liquid, comprising: (a) contacting an imprinted polymer imprinted with the agricultural chemical molecule, wherein the matrix of the polymer has been prepared from one or more monomers including bilirubin or a mono-or di-ester or amide thereof, with an aqueous liquid to remove at least a portion of the agricultural chemical, and (b) separating the aqueous liquid with decreased agricultural chemical content from the polymer binding agricultural chemical, wherein the agricultural chemical having a heterocyclic ring comprising 1-3 nitrogen atoms is selected from pyrimethanil, fluopyram, pirimiphos-methyl and fluxapyroxad, and wherein the imprinted polymer is a noncovalently imprinted polymer that includes bilirubin-containing crosslinked polyacrylates and polymethacrylates, preferably the crosslinker is ethyleneglycoldimethacrylate, and wherein 1,1’-azobis (cyclohexanecarbonitrile) (ABCHC) may be used as a polymerisation initiator. For example the polymers are prepared by mixing the agricultural chemical molecule (pyrimethanil) with bilirubin; ethylenedimethylacrylic acid (EDMA) and methanol, then adding 1,1’-azobis (cyclohexanecarbonitrile) (ABCHC, initiator). The mixture is then polymerized in a water bath at 65 degrees Celsius for about 24 h. The resultant polymer is ground, sieved, and particle sorted to give 30-63 micrometer particles. The target molecule is then removed by extraction with methanol. een prepared from one or more monomers including bilirubin or a mono-or di-ester or amide thereof, with an aqueous liquid to remove at least a portion of the agricultural chemical, and (b) separating the aqueous liquid with decreased agricultural chemical content from the polymer binding agricultural chemical, wherein the agricultural chemical having a heterocyclic ring comprising 1-3 nitrogen atoms is selected from pyrimethanil, fluopyram, pirimiphos-methyl and fluxapyroxad, and wherein the imprinted polymer is a noncovalently imprinted polymer that includes bilirubin-containing crosslinked polyacrylates and polymethacrylates, preferably the crosslinker is ethyleneglycoldimethacrylate, and wherein 1,1’-azobis (cyclohexanecarbonitrile) (ABCHC) may be used as a polymerisation initiator. For example the polymers are prepared by mixing the agricultural chemical molecule (pyrimethanil) with bilirubin; ethylenedimethylacrylic acid (EDMA) and methanol, then adding 1,1’-azobis (cyclohexanecarbonitrile) (ABCHC, initiator). The mixture is then polymerized in a water bath at 65 degrees Celsius for about 24 h. The resultant polymer is ground, sieved, and particle sorted to give 30-63 micrometer particles. The target molecule is then removed by extraction with methanol.
Description
IMPRINTED POLYMER THAT BINDS HETEROCYCLIC COMPOUNDS AND
METHODS OF USE
TECHNICAL FIELD
This invention relates to a molecularly imprinted polymer capable of binding agricultural
chemicals having heterocyclic rings and to applications using the polymer.
BACKGROUND
Crops are vulnerable to fungal diseases, insect attack and competition from weeds in many of
the locations where they are grown. Consequently growers frequently treat their crops with
agricultural chemicals. When used, agricultural chemical residues are often present in low
amounts in crops that are harvested. Additionally, products resulting from the harvested crop
also contain low amounts of agricultural chemical residues, including juice and oils.
Avoiding or reducing agricultural chemical use near to harvest time results in a corresponding
decrease of the concentration levels of agricultural chemicals in harvested crops and the
resulting products, but can have a corresponding decrease in crop yield and quality if
agricultural chemicals are not used.
The presence of agricultural chemicals in wine for example is of concern for several reasons
including that retailers and consumers prefer wine to be free of agricultural chemicals.
Consequently certain agricultural chemicals which are highly effective and offer the advantage
of a later harvest of higher quality wine are not used as they consistently leave unacceptable
levels of agricultural chemical residue in wine.
Agricultural chemicals as insecticides, herbicides and other biocides applied to crops can also
end up in drinking water supplies, eventually being consumed by humans and animals.
Agricultural chemicals can also contaminate the environment, particularly where water runs
from the site of application of the chemical into nearby streams, rivers and lakes, or from
production processes discharging waste water into streams, rivers and lakes. One example of
such a process is carpet making using wool, where the waste water used in the production of
woollen carpet contains agricultural chemicals such as insecticides and anthelmintics.
Molecularly-imprinted polymers are polymers with an antibody-like ability to bind and
discriminate between molecules. These are formed by the synthesis of cross-linked polymers
in the presence of templates, which may be the small molecule of interest and removal of the
small molecule from the template to generate a structure complementary to the template
structure or to an analogous structure. The polymer before removal of a small molecule may
bind the small molecule covalently or it may be bound non-covalently.
To date the commercialisation of such polymers has generally not been successful. One
reason for this is that the existing polymers used do not bind the target molecules with
sufficient specificity in aqueous biological samples. Another reason for the lack of
commercialisation of polymers relates to the difficulties of scaling up the use of polymer
technologies, something which the current invention has overcome.
It is an object of this invention to provide a new binding material for use in binding agricultural
chemicals containing heterocyclic rings, that can be used with aqueous samples, and/or
methods using these binding materials, or at least to provide the public with a useful choice.
DISCLOSURE OF THE INVENTION
In one aspect, the invention provides an imprinted polymer imprinted with an agricultural
chemical molecule having a heterocyclic ring, wherein the matrix of said polymer has been
prepared from one or more monomers including bilirubin or a mono-or di-ester or amide
thereof, preferably bilirubin, and wherein the heterocyclic ring has 1-3 nitrogen atoms.
In a further aspect, the invention provides a method for preparing such an imprinted polymer
comprising polymerising one or more monomers including bilirubin mono- or di-ester or amide
thereof in the presence of an agricultural chemical molecule to be imprinted, and subsequently
at least partly removing the molecule to be imprinted, wherein the agricultural chemical has a
heterocyclic ring with 1-3 nitrogen atoms.
The imprinted polymers according to the invention can be prepared in a variety of ways. The
common feature is that the imprinting molecule is incorporated during the polymerisation or
crosslinking process and then later removed. In one alternative bilirubin-containing polymers
are crosslinked in the presence of the agricultural chemical.
Preferably the polymerisation is an alkene polymerisation. Preferably in addition to bilirubin
(or mono-or di-ester or amide thereof) the mixture contains one or more further alkenes
having more than one alkene group, for example monomers containing two acrylate or two
methacrylate groups or one of each type of group or three or more groups independently
selected from acrylate and methacrylate. These types of monomers serve as crosslinkers. The
polymerisation may also include monoalkenes e.g. methacrylic acid, vinylpyridines,
hydroxyethylmethacrylate, acrylamide. These serve as co-monomers.
Non-covalent interactions between the imprinting molecule and the polymer are generally
used. The polymer is formed by adding the imprinting molecule during formation or
crosslinking of the polymer. The polymer is selected so there will be electrostatic interaction,
hydrogen bond formation or hydrophobic interactions with the imprinting molecule creating
binding sites for the imprinting molecule.
Preferred noncovalently imprinted polymers include bilirubin-containing crosslinked
polyacrylates and polymethacrylates, preferably bilirubin-containing crosslinked
polymethacrylates. The preferred crosslinker is ethyleneglycoldimethacrylate. Preferably the
mole ratio of co-monomer to crosslinker is in the ratio 0:1 to 1:15 preferably 0:1 to 1:10. The
preferred mole ratio of bilirubin to the crosslinker is 1:20 to 1:1, preferably 1:20 to 1:4.
In preferred embodiments of the invention the polymer to be used in the assay is ground
repeatedly to reduce non-specific binding. Preferably the particle size of at least 50% by
weight of the polymer is in the range 38 to 150 microns. More preferably more than 80% of
the material consists of particles in that size range.
The imprinting molecule may be removed by extraction with a suitable solvent. Soxhlet
extraction using an appropriate solvent is preferred.
Binding of the imprinting molecule to the above described polymers may be detected in a
manner analogous to radioimmunoassays. For example radiolabelled imprinting molecule (for
14 3
example [C or H] imprinting molecule) may be incorporated into a sample. Binding of the
radioactive imprinting molecule to the polymer will be inversely related to the amount of
imprinting molecule present in the sample. The binding of the imprinting molecule may be
determined after separating the polymer from the liquid medium. This may conveniently be
achieved by centrifugation.
Alternatively imprinting molecule binding to bilirubin-containing polymers may be detected by
for example change in fluorescence of the polymer. Detection of the binding may also be by
detecting unbound imprinting molecule by the high-pressure liquid chromatography (HPLC)
method or a detection method appropriate for the target molecule.
In this specification an "agricultural chemical" means chemical products used in agriculture,
including insecticides, herbicides, acaricides, anthelmintics and fungicides. In certain preferred
embodiments the agricultural chemical is a fungicide. The term "agriculture" means the
cultivation of animals, plants, fungi, and other life forms for the purpose of providing food,
fibre, bio-fuel, drugs and other products used to sustain and enhance human life.
In this specification an “analogue or derivative” of a agricultural chemical molecule is a
molecule that has the same basic structure as the agricultural chemical to be imprinted, and
when used to imprint a polymer, produces a polymer that binds the agricultural chemical more
strongly than the corresponding non-imprinted polymer. The analogue or derivative will also
generally bind to a polymer imprinted with the agricultural chemical, more strongly than to a
non-imprinted polymer. The analogue or derivative generally has the same ring structure.
In another aspect, the invention provides a method for the removal of an agricultural chemical
having a heterocyclic ring from an aqueous liquid, preferably a drink or an ingredient of a drink
or food, comprising:
a) contacting an imprinted polymer imprinted with the agricultural chemical molecule, wherein
the matrix of the polymer has been prepared from one or more monomers including bilirubin
or a mono-or di-ester or amide thereof, with an aqueous liquid to remove at least a portion of
the agricultural chemical, and
b) separating the aqueous liquid with decreased agricultural chemical content from the
polymer binding agricultural chemical,
wherein the heterocyclic ring has 1-3 nitrogen atoms.
In a further aspect, the invention provides a method for removal of an agricultural chemical
having a heterocyclic ring from an aqueous liquid, preferably a drink or an ingredient of a drink
or food, comprising:
a) contacting an imprinted polymer prepared by polymerising one or more monomers including
bilirubin or a mono-or di-ester or amide thereof in the presence of the agricultural chemical
molecule, and subsequently at least partly removing the agricultural chemical molecule, and
b) separating the aqueous liquid with decreased agricultural chemical content from the
polymer binding agricultural chemical, wherein the heterocyclic ring has 1-3 nitrogen atoms.
The contacting may involve passage of the aqueous liquid through a filter formed from or
coated with the imprinted polymer. Such a filter may be formed from another polymer and
have the imprinted polymer coated on it. Alternatively the filter may be a bed of particles of
the imprinted polymer.
The contacting may alternatively be achieved by coating a paddle or stirrer with the imprinted
polymer. The polymer may for example be coated onto Teflon. Imprinted polymer coated
paddles and stirrers are advantageously used with an aqueous liquid that is difficult to filter.
The separating includes passage of the liquid so that it is no longer in contact with the
imprinted polymer. This includes movement to an area away from a filter formed from or
coated with the imprinted polymer. Separating also includes physical removal of a paddle or
stirrer coated with the imprinted polymer from aqueous liquid with decreased agricultural
chemical content.
The invention is useful for removing an agricultural chemical from aqueous liquids that have
contamination with an agricultural chemical having a heterocyclic ring with 1-3 nitrogen atoms,
including waste water, alcoholic beverages, non-alcoholic beverages and food ingredients. The
invention may also be used to remove such an agricultural chemical from aqueous plant-
derived fertiliser. Alcoholic beverages that may be treated using the method of the invention
typically comprise up to 20% (w/v) ethanol. For example, the method may be used with
beer, rice wine and wine. The method is particularly useful for wine. The method may also be
used at higher alcohol contents, for example with whiskeys. In particularly preferred methods,
the aqueous liquid is wine and the agricultural chemical is selected from pyrimethanil,
fluopyram and pirimiphos-methyl, especially pyrimethanil.
Non-alcoholic beverages usefully treated using the polymer included water, carbonated drinks
and fruit based drinks. Other food ingredients usefully treated include milk, including cows’
milk, goats’ milk and sheep’s milk, and oils, including fish oils.
Separation may be achieved by allowing the polymer to settle out of the liquid and decanting
the treated liquid. The separating may be achieved in a filtration process by allowing the liquid
to pass through the filter. A centrifugation step may also be used to separate the treated
liquid from the polymer.
The polymer may be reused. Bound agricultural chemicals may be released by, for example,
contacting the polymer with acid. Such a change may be achieved by washing the polymer
with an aqueous acid, for example aqueous HCl. A pH of 1-3 is preferred. Other methods of
releasing agricultural chemicals include washing with an organic solvent or a mixture of an
organic solvent and water. An increased temperature may also be used to remove bound
agricultural chemicals.
One advantage of the invention is that it allows the increased use of agricultural chemical
closer to the harvest date than previously. This can lead to reduced crop losses and higher
quality product once the agricultural chemical residue has been removed.
In preferred agricultural chemicals, the heterocyclic ring with 1-3 nitrogen atoms is 5- or 6-
membered.
In one embodiment, the agricultural chemical molecule used in forming the imprinted polymer
has a single nitrogen in a non-aromatic 5 or 6 membered heterocycle, preferably a 5
membered heterocycle, for example captan or procymidone.
In another embodiment, the agricultural chemical molecule used in forming the imprinted
polymer has a heterocyclic ring with two nitrogens, preferably a pyrazole ring, more preferably
selected from fipronil and fluxapyroxad.
In another embodiment, the agricultural chemical molecule used in forming the imprinted
polymer has three nitrogens in a heterocyclic ring, and is preferably selected from
azaconazole, azinphos-methyl, flusilazole, imidacloprid, myclobutanil and thiabendazole.
In another embodiment, the agricultural chemical molecule used in forming the imprinted
polymer has a pyridine ring and is preferably selected from azoxystrobin, boscalid, diquat,
imidacloprid, iprodione, fluopyram, paraquat and thiabendazole.
In another embodiment, the agricultural chemical molecule used in forming the imprinted
polymer has an aromatic ring with two nitrogens, preferably a pyrimidine ring. Preferred
compounds include diazinon, imazalil, pirimicarb, pirimiphos-methyl, pyrimethanil and
trifloxystrobin.
A particularly preferred compound for imprinting polymers used in the invention is
pyrimethanil, a fungicide widely used in treating grapevines.
Other particularly preferred compounds include fluopyram, fluxapyroxad and pirimiphos-
methyl.
The compounds and groups of compounds specifically identified are preferred as imprinting
molecules and as target molecules to be removed in the methods of removal of agricultural
chemicals.
The molecules removed will not always only be identical to the imprinting molecule. Molecules
of similar structure to the imprinting molecule will bind to the imprinted polymer. The
invention contemplates use of an imprinted polymer where the imprinting is done with a
molecule that is sufficiently similar to the target agricultural chemical that it provides an
imprinted polymer that specifically binds the target agricultural chemical.
Whether a molecule of similar structure can be used to prepare an imprinted polymer that will
bind to a particular agricultural chemical can be checked by conducting a test similar to that
exemplified to assess whether the agricultural chemical binds to the imprinted polymer in a
clearly more specific manner than to the corresponding non-imprinted polymer.
In this specification where reference has been made to patent specifications, other external
documents, or other sources of information, this is generally for the purpose of providing a
context for discussing the features of the invention. Unless specifically stated otherwise,
reference to such external documents is not to be construed as an admission that such
documents, or such sources of information, in any jurisdiction, are prior art, or form part of the
common general knowledge in the art.
Certain preferred aspects of the invention will now be described in relation to the following
non-limiting examples.
BRIEF DESCRIPTIONS OF THE DRAWINGS
Figure 1 shows a comparison of the pyrimethanil concentrations in (1) a prewash of a cartridge
containing polymer particles (2) eluate after washing through test solution 15% ethanol spiked
with pyrimethanil, (3) water wash, (4) 0.1M HCl wash, (5) subsequent water wash for blank
and imprinted polymers.
Figure 2 shows the pyrimethanil concentrations of test solutions spiked with pyrimethanil
plotted against initial pyrimethanil concentrations after the test solutions have passed through
an empty cartridge, a cartridge containing particles of imprinted polymer and a
cartridge containing particles of blank polymer.
EXAMPLE 1 - Pyrimethanil
Preparation of polymers
The polymers were prepared by mixing 20 mg pyrimethanil with 11.5 mg bilirubin; 0.97 ml
ethylenedimethylacrylic acid (EDMA) and 5 ml methanol, then adding 20 mg 1,1’-azobis
(cyclohexanecarbonitrile) (ABCHC, initiator). The mixture was polymerized in a water bath at
65 degrees Celsius for 24 h. The polymer was ground, sieved, and particle sorted to give 30-
63 micrometer particles. The target molecule was removed by Soxhlet extraction with
methanol. Suspensions (100 mg/mL) were performed in 15% ethanol/water as the polymer
was tested mainly in this matrix. A blank polymer was made at the same time, treated the
same, but with no pyrimethanil used in its preparation.
Removal of pyrimethanil from test solutions
Polymer suspensions were loaded in 10 micron cut-off cartridges to give a packed volume of
500 mg polymer in each filter and the test solution was passed through. In a typical
experiment, the following fractions were passed through a cartridge:
- 30 mL water
- 50 mL test solution containing pyrimethanil
- 80 mL water
- 30 mL 0.1M HCl
- 100 mL water.
The test solution was between 0.1 and 10ppm, to match concentrations found in wine samples.
It was found that 50 mL HCl 0.1M was enough to remove the pyrimethanil bound to the
polymer particle and regenerate for a further test. Test solutions were either 15% ethanol-
water or wine spiked with known amounts of pyrimethanil.
The optimum speed of the pump was determined to be about 200 mL/min after each solution
was passed, air was flushed at 900 ml/min through the casing containing the polymer filter to
remove any solution trapped, then the speed was brought back down to approx. 200 mL/min.
For this polymer, at a rate of about 200 mL/min, we can define B/T (bound/total) as the
amount of analyte we are binding out of a known solution. Ideally an imprinted polymer will
bind all the analyte present and the blank polymer will bind a minimum amount. For this
speed, B/T of imprinted polymer was 0.75 and B/T for blank was 0.5. See Figure 1.
The B/T can be reflected in a lower concentration in the second point (concentration of test
solution after going through imprinted or blank polymer). A good rinse cycle should have a
higher peak in the fourth point; this is the HCl rinse (Figure 1). Figure 1 shows a comparison
of the pyrimethanil concentrations in (1) a prewash of a cartridge containing polymer particles
(2) eluate after washing through test solution 15% ethanol spiked with pyrimethanil, (3) water
wash, (4) 0.1M HCl wash, (5) subsequent water wash for blank and imprinted polymers.
If a mass balance is done on what the polymer has taken out from the test solution or the
wine, blank polymers usually yield slightly under or lower yields (due to non-specific binding)
and imprinted polymers are quite consistently accounting for the whole amount of pyrimethanil
that was passed through.
Figure 2 shows the pyrimethanil concentrations of test solutions spiked with a pyrithanil
plotted against initial pyrimethanil concentrations after the test solutions have passed through
an empty cartridge, a cartridge containing particles of imprinted polymer and a
cartridge containing particles of blank polymer.
Pyrimethanil is removed more effectively from the solutions when the imprinted polymer is
used, particularly at higher pyrimethanil concentrations.
Removal from wine
Pyrimethanil-imprinted polymer was placed in contact with wine (0.1 mL suspension and 0.9
ml wine) for 5 min, centrifuged, and supernatant was analysed via HPLC methods. 90% of the
pyrimethanil was removed. A large batch of wine was passed through a polymer bed and
pyrimethanil was completely removed from the wine.
With wine, negative B/T values were obtained and the blank leached previously trapped
pyrimethanil into the wine sample.
EXAMPLE 2 – Fluopyram
The polymer was made by mixing 0.1mmol fluopyram, 0.2mmol bilirubin, 2mmol EDMA, 15 mL
methanol and 20 mg ABCHC, followed by thermal polymerisation at 70degrees Celsius for 20h.
The resulting block of polymer was ground, sieved, sedimented, and the resulting 30-63
micrometer particles were subjected to Soxhlet extraction with methanol to remove the target
molecule, dried, then suspended in 15% ethanol at a 100 mg/mL suspension concentration.
This suspension was tested against a test solution containing fluopyram in 15% ethanol.
At the same time as the imprinted polymer a control polymer was developed that included the
same materials as above but no fluopyram. This was used to distinguish between adsorption
and specific binding in the polymer. Binding reported as specific binding is the difference
between binding in the imprinted polymer and the control as this is considered to be due to
interactions occurring in the active cavities of the polymer.
For fluopyram, tests were performed as following: 0.1 mL polymer suspension were placed in
contact with 0.9 mL test solution (25ppm fluopyram in 15% ethanol) in 1.5mL eppendorf
tubes. The tubes were mixed on an orbital shaker for 4h, the suspensions were then
centrifuged for 5min at 13000rpm and the supernatant was analysed by HPLC.
The imprinted polymer bound 85% of the analyte present in the test solution and the control
bound 43%, hence the specific binding was 42% overall. Tests at 24h showed complete
removal of fluopyram in the imprinted polymer and 45% in the control.
EXAMPLE 3 – Pirimiphos-methyl
The polymer was developed by mixing 0.2mmol template pirimiphos-methyl, 0.2mmol
bilirubin, mmol EDMA, 15 mL methanol, and 40 mg ABCHC followed by thermal polymerisation
at 70 degrees Celsius for 20h. The polymer was ground, sieved, sedimented, and the resulting
30-63 micrometer particles were subjected to Soxhlet extraction with methanol to remove the
target molecule, dried, and resuspended in 15% ethanol at a 100 mg/mL suspension
concentration. This suspension was tested against a test solution containing pirimiphos at 25
ppm in 15% ethanol.
At the same time the imprinted polymer was synthesized and processed a control polymer that
did not contain the template was subjected to the same process and specific binding is
reported as difference between binding in the imprinted and non-imprinted polymer.
Tests were performed as following: 0.1mL polymer suspension were placed in contact with 0.9
mL test solution in 1.5mL eppendorf tubes. The tubes were agitated on an orbital shaker for
24h, centrifuged at 13000rpm for 5 min and the supernatant was analysed. The binding in the
imprinted polymer was 67% of total test solution and binding in the control was 13%.
EXAMPLE 4 – Fluopyram
The polymers were prepared by mixing 63.51 mg fluopyram with 11.7 mg bilirubin; 717µl
ethylenedimethylacrylic acid (EDMA) and 2 ml methanol, then adding 80 mg 1,1’-azobis
(cyclohexanecarbonitrile) (initiator). The mixture was polymerized in a water bath at 70
degrees Celsius for 24 h. The polymer was ground, sieved, and particle sorted. The resulting
38-63 micrometer particles were subjected to Soxhlet extraction with methanol to remove the
target molecule, and dried. Suspensions (100 mg/mL) of the particles in 15% ethanol/water
were prepared. A blank polymer was made at the same time, treated the same, but with no
fluopyram used in its preparation. The suspensions were tested using fluopyram at 25ppm in
% ethanol. After 4 hours contact the imprinted polymer bound 96.99% of the fluopyram.
After 24 hours 97.81% was bound. The corresponding figures for the control were 27% and
29% respectively.
EXAMPLE 5 – Fluxapyroxad
The polymers were prepared by mixing 7.2 mg fluxapyroxad with 11.6 mg bilirubin; 717µl
ethylenedimethylacrylic acid (EDMA) and 5 ml methanol, then adding 80 mg 1,1’-azobis
(cyclohexanecarbonitrile) (initiator). The mixture was polymerized in a water bath at 70
degrees Celsius for 24 h. the polymer was ground, sieved, and particle sorted. The resulting
38-63 micrometer particles were subjected to Soxhlet extraction with methanol to remove the
target molecule, and dried. Suspensions (100 mg/mL) or the particles were prepared in 15%
ethanol/water. A blank polymer was made at the same time, treated the same, but with no
fluxapyroxad used in its preparation. The suspensions were tested using fluxapyroxad at
20ppm in 15% ethanol. After 4 hours contact the imprinted polymer bound 60.21% of the
polymer. After 24 hours 64.07% was bound. The corresponding figures for the control were
50.2% and 46.3% respectively.
The term “comprising” as used in this specification means ‘consisting at least in part of’, that is
to say when interpreting statements in this specification which include that term, the features,
prefaced by that term in each statement, all need to be present but other features can also be
present.
In the description in this specification reference may be made to subject matter which is not
within the scope of the claims of the current application. That subject matter should be readily
identifiable by a person skilled in the art and may assist in putting into practice the invention
as defined in the claims of this application.
It should be noted that the invention can be carried out with numerous modifications and
variations and that the above Examples are by way of illustration only. For example the
invention may be carried out using other molecules or ions and the polymers used may be
prepared using different monomers and/or proportions and/or crosslinkers.
Claims (33)
1. An imprinted polymer imprinted with an agricultural chemical molecule having a heterocyclic ring, wherein the matrix of said polymer has been prepared from one or more 5 monomers including bilirubin or a mono-or di-ester or amide thereof, and wherein the heterocyclic ring has 1-3 nitrogen atoms.
2. A polymer as claimed in claim 1 wherein the monomers include bilirubin. 10
3. A polymer as claimed in claim 1 or claim 2 wherein the monomers include one or more further alkenes having more than one alkene group.
4. A polymer as claimed in any one of claims 1 to 3 wherein the agricultural chemical molecule used in forming the imprinted polymer has a single nitrogen in a non-aromatic 5 or 6 15 membered heterocycle.
5. A polymer as claimed in claim 4 wherein the agricultural chemical molecule has a 5 membered heterocycle. 20
6. A polymer as claimed in claim 4 wherein the agricultural molecule is captan or procymidone.
7. A polymer as claimed in any one of claims 1 to 3 wherein the agricultural molecule used in forming the imprinted polymer has a heterocyclic ring with two nitrogens.
8. A polymer as claimed in claim 7 wherein the agricultural chemical molecule has a pyrazole ring.
9. A polymer as claimed in claim 7 wherein the agricultural chemical molecule is fipronil 30 or fluxapyroxad.
10. A polymer as claimed in any one of claims 1 to 3 wherein the agricultural chemical molecule used in forming the imprinted polymer has three nitrogens in a heterocyclic ring.
11. A polymer as claimed in claim 10 wherein the agricultural chemical molecule is selected from azaconazole, azinphos-methyl, flusilazole, imidacloprid, myclobutanil and thiabendazole. 5
12. A polymer as claimed in any one of claims 1 to 3 wherein the agricultural chemical molecule used in forming the imprinted polymer has a single nitrogen in an aromatic pyridine ring.
13. A polymer as claimed in claim 12 wherein the agricultural chemical molecule is 10 selected from azoxystrobin, boscalid, diquat, imidacloprid, iprodione, paraquat and thiabendazole.
14. A polymer as claimed in claim 1 wherein the agricultural chemical molecule used in forming the imprinted polymer has an aromatic ring with two nitrogens.
15. A polymer as claimed in claim 14 wherein the agricultural chemical molecule has a pyrimidine ring.
16. A polymer as claimed in claim 14 wherein the agricultural chemical molecule is 20 diazinon, imazalil, pirimicard, pirimiphos-methyl, pyrimethanil and trifloxystrobin.
17. A polymer as claimed in any one of claims 1 to 3 wherein the compound for imprinting the polymer is pyrimethanil.
18. A polymer as claimed in any one of claims 1 to 3 wherein the compound for imprinting the polymer is fluopyram.
19. A polymer as claimed in any one of claims 1 to 3 wherein the compound for imprinting 30 the polymer is pirimiphos-methyl.
20. A polymer as claimed in any one of claims 1 to 3 wherein the compound for imprinting the polymer is fluxapyroxad. 35
21. A method for preparing an imprinted polymer comprising polymerising one or more monomers including bilirubin or a mono- or di-ester or amide thereof in the presence of an agricultural chemical molecule to be imprinted, and subsequently at least partly removing the molecule to be imprinted, wherein the agricultural chemical has a heterocyclic ring with 1-3 nitrogen atoms.
22. A method as claimed in claim 21 wherein the bilirubin-containing polymers are 5 crosslinked in the presence of the agricultural chemical.
23. A method as claimed in claim 21 wherein in addition to bilibrubin, or mono- or di-ester or amide thereof, a mixture of bilirubin, or a mono- or di-ester or amide thereof, and one or more further alkenes having more than one alkene group is polymerised.
24. A method for the removal of an agricultural chemical having a heterocyclic ring from an aqueous liquid, comprising: a) contacting an imprinted polymer imprinted with the agricultural chemical molecule, wherein the matrix of the polymer has been prepared from one or more monomers 15 including bilirubin or a mono-or di-ester or amide thereof, with an aqueous liquid to remove at least a portion of the agricultural chemical, and b) separating the aqueous liquid with decreased agricultural chemical content from the polymer binding agricultural chemical, wherein the heterocyclic ring has 1-3 nitrogen atoms.
25. A method for removal of agricultural chemical having a heterocyclic ring from an aqueous liquid, comprising: a) contacting an imprinted polymer prepared by polymerising one or more monomers including bilirubin or mono-or di-ester or amide thereof in the presence of the 25 agricultural chemical molecule with the aqueous liquid, and subsequently at least partly removing the agricultural chemical molecule, and b) separating the aqueous liquid with decreased agricultural chemical content from the polymer binding agricultural chemical, wherein the heterocyclic ring has 1-3 nitrogen atoms.
26. A method as claimed in claims 24 or 25 wherein the aqueous liquid comprises up to 20% (w/v) ethanol.
27. A method as claimed in claim 26 wherein the aqueous liquid is wine and the agricultural 35 chemical is selected from pyrimethanil, fluopyram, pirimiphos-methyl and fluxapyroxad.
28. A method as claimed in claim 27 where the agricultural chemical is pyrimethanil.
29. A method as claimed in any one of claims 24-27 wherein the agricultural chemical is removed by filtration through a filter comprising or coated with the imprinted polymer.
30. A method as claimed in anyone of claims 24-26 and 28 wherein the aqueous liquid is a drink or a food ingredient.
31. A polymer as claimed in any one of claims 1-20, substantially as herein described with 10 reference to any example thereof.
32. A method as claimed in any one of claims 21, 24 or 25, substantially as herein described with reference to any example thereof.
33. A method as claimed in any one of claims 24-30 wherein the polymer is a polymer of claim 31.
Publications (1)
Publication Number | Publication Date |
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NZ615725B2 true NZ615725B2 (en) | 2015-06-30 |
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