CA2049702A1 - One- or multi-layered layer elements applied to supports and their production - Google Patents
One- or multi-layered layer elements applied to supports and their productionInfo
- Publication number
- CA2049702A1 CA2049702A1 CA 2049702 CA2049702A CA2049702A1 CA 2049702 A1 CA2049702 A1 CA 2049702A1 CA 2049702 CA2049702 CA 2049702 CA 2049702 A CA2049702 A CA 2049702A CA 2049702 A1 CA2049702 A1 CA 2049702A1
- Authority
- CA
- Canada
- Prior art keywords
- layer
- ions
- support
- groups
- supports
- 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
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 39
- 239000011368 organic material Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 119
- 229910001868 water Inorganic materials 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 125000000524 functional group Chemical group 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 150000001450 anions Chemical class 0.000 claims description 15
- 229920000867 polyelectrolyte Polymers 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 claims 2
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000004375 physisorption Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229920000729 poly(L-lysine) polymer Polymers 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- -1 polyethylene Polymers 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 240000007839 Kleinhovia hospita Species 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000003010 ionic group Chemical group 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 108010090804 Streptavidin Proteins 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- YMXHPSHLTSZXKH-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 5-(2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl)pentanoate Chemical compound S1CC2NC(=O)NC2C1CCCCC(=O)ON1C(=O)CCC1=O YMXHPSHLTSZXKH-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- RDQVRMLSWFDZJP-UHFFFAOYSA-N 10-phosphonooxydecyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCCCCCCCCOP(O)(O)=O RDQVRMLSWFDZJP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 108010020346 Polyglutamic Acid Proteins 0.000 description 2
- 108010039918 Polylysine Proteins 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 208000016610 ataxia-hypogonadism-choroidal dystrophy syndrome Diseases 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000027455 binding Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000005591 charge neutralization Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000572 ellipsometry Methods 0.000 description 2
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- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 229960002897 heparin Drugs 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 229910052618 mica group Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000001338 self-assembly Methods 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 2
- YMXHPSHLTSZXKH-RVBZMBCESA-N (2,5-dioxopyrrolidin-1-yl) 5-[(3as,4s,6ar)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoate Chemical compound C([C@H]1[C@H]2NC(=O)N[C@H]2CS1)CCCC(=O)ON1C(=O)CCC1=O YMXHPSHLTSZXKH-RVBZMBCESA-N 0.000 description 1
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BTDPHFNCXHHFTD-UHFFFAOYSA-N 1-bromoundecan-1-ol Chemical compound CCCCCCCCCCC(O)Br BTDPHFNCXHHFTD-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
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- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
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- 229910006069 SO3H Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 150000001615 biotins Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-O cysteaminium Chemical compound [NH3+]CCS UFULAYFCSOUIOV-UHFFFAOYSA-O 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- YYUPXWUUUZXFHG-UHFFFAOYSA-N ethoxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)OCC YYUPXWUUUZXFHG-UHFFFAOYSA-N 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000005442 molecular electronic Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- PPPHYGCRGMTZNA-UHFFFAOYSA-N trifluoromethyl hydrogen sulfate Chemical compound OS(=O)(=O)OC(F)(F)F PPPHYGCRGMTZNA-UHFFFAOYSA-N 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/701—Langmuir Blodgett films
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31536—Including interfacial reaction product of adjacent layers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Theoretical Computer Science (AREA)
- Mathematical Physics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
One- or multi-layered layer elements applied to supports and their production Abstract One- or multi-layered layer elements applied to supports are described, which consist of a) a modified support having an even surface, in which modification means the application of ions or ionisable compounds of the same charge over the entire area, and b) one or more layers made of organic materials which in each layer contain ions of the same charge, the ions of the first layer having the opposite charge of the modified support and in the case of several layers each further layer having again the opposite charge of the previous layer.
Layer elements of this type applied to supports are produced by applying the individual layers from solutions of the organic materials in suitable solvents to modified supports by sequential physisorption (salt formation).
Le A 27 700 - US
Layer elements of this type applied to supports are produced by applying the individual layers from solutions of the organic materials in suitable solvents to modified supports by sequential physisorption (salt formation).
Le A 27 700 - US
Description
20a~97~)2 One- or Multi-layered Layer Elemen~s Applied ~o Suppor~s and ~heir Produc~ion -s BACKGROUND OF THE INVENTION
The invention relates to layer elements applied to supports, which elements can be one- or multi-layered.
The individual layers are first applied to a modified support from a solution of organic materials suitable for the layer formation and then applied on top of the previous layer in each case. Thuq, construction of these layer elements takes place by sequential physisorption (salt formation). Accordingly, the invention also relates to the production of these layer elements.
Coated supports have a variety of uses in industrial technology. For example, the frictional properties of materials can be adapted to a desired purpose by a suitable treatment of their surface. Furthermore, they can be a protective film for the supports underneath in order to preserve their special surface properties.
However, coated supports have recently found application in particular in structural components for optical communication technology and a~ electronic and optoelectronic information stores.
In particular for electronic and optical purpose~, it is necessary to produce extremely thin, defect-free multi-layered coatings whose layers have a high degree of order and an ad~ustable, substantially homogeneous layer thickness, it being desired of this high degree of order also to be maintained in the range of a large number of coating layers.
Le A 2Y 70Q-~S - 1 -20~97~2 Thus, the thin films produced from suitable organic material~ are the basis of ordered, defect-free systems on the molecular level, such as are required, for example, for - optical applications (guided transmission of low attehuation, for example optical waveguides having nonlinear optical properties), - electrical applications (electrical conductors of high anisotropy, for example one-dimensional or two-dimen~ional conductors in the area of molecular electronics), - ~host lattice~ for defined incorporation or specific binding of functional groups or molecules.
Further areas of application of such layer elements applied to supports are the modification of electrodes and their use in the catalysis of chemical reactions, and sensors, biosensors, surface treatments (for example coating of cationic surfaces, such as interior surfaces of tubings, with heparin to increase biocompatibility).
The invention relates to layer elements applied to supports, which elements can be one- or multi-layered.
The individual layers are first applied to a modified support from a solution of organic materials suitable for the layer formation and then applied on top of the previous layer in each case. Thuq, construction of these layer elements takes place by sequential physisorption (salt formation). Accordingly, the invention also relates to the production of these layer elements.
Coated supports have a variety of uses in industrial technology. For example, the frictional properties of materials can be adapted to a desired purpose by a suitable treatment of their surface. Furthermore, they can be a protective film for the supports underneath in order to preserve their special surface properties.
However, coated supports have recently found application in particular in structural components for optical communication technology and a~ electronic and optoelectronic information stores.
In particular for electronic and optical purpose~, it is necessary to produce extremely thin, defect-free multi-layered coatings whose layers have a high degree of order and an ad~ustable, substantially homogeneous layer thickness, it being desired of this high degree of order also to be maintained in the range of a large number of coating layers.
Le A 2Y 70Q-~S - 1 -20~97~2 Thus, the thin films produced from suitable organic material~ are the basis of ordered, defect-free systems on the molecular level, such as are required, for example, for - optical applications (guided transmission of low attehuation, for example optical waveguides having nonlinear optical properties), - electrical applications (electrical conductors of high anisotropy, for example one-dimensional or two-dimen~ional conductors in the area of molecular electronics), - ~host lattice~ for defined incorporation or specific binding of functional groups or molecules.
Further areas of application of such layer elements applied to supports are the modification of electrodes and their use in the catalysis of chemical reactions, and sensors, biosensors, surface treatments (for example coating of cationic surfaces, such as interior surfaces of tubings, with heparin to increase biocompatibility).
2, DESCRIPTION OF THE RELATED ART
The previously mo3t investigated method for producing ultra-thin films and multi-layered layers is the conventional Langmuir-Blodgett (LB) method. In thi~
method, the layer construction takes place by sequential transfer of monolayers from a water surface to a solid ~ubstrate. Thi~ method is distinguished by a relatively Le A 27 700 - 2 -Z0497~
high apparatus outlay, which nevertheless only allows small supports to be coated. The organic material for building up the layers must be sufficiently spreadable on the water surface.
Furthermore, the attempt has been made to take carboxyl-containing supports, as can be produced, for example, by oxidation of polyethylene supports, as the basis of uniform coating. To this end, for example, long-chain carboxylic acids were applied from a solution to the support described by means of calcium ions. The calcium ions provide an ionic bond between the carboxyl groups of the support and the carboxylic acid applied. Since dicarboxylic acids and calcium ions when applied from a solution would lead immediately to an insoluble and no longer usable salt precipitate, only monocarboxylic acids can be used. If it were decided to apply further layers onto this first layer, first the non-functionalised part of the carboxylic acid molecule which points away from the carboxyl group would have to be functionalised in order to allow the build up to continue. A still further attempt was made to produce a multi-layered layer construction by alternating reaction of 1,10-decanediol bisphosphate with its zirconium salt or by alternating reaction of 1,10-decanediol bisphosphate with zirconyl chloride. These attempts ended after about 8 layers, because by then the surface showed too severe a defect for an ordered further layer build up. In the case where zirconyl chloride was used, the change from the inorganic crystal lattice to the organic crystal combined therewith Le A 27 700 - 3 -2049~0~
can be assumed as the source of the defect formation.
Furthermore, it has been observed that where the attempt is made to coat an ionically modified support surface with organic molecules provided on both ~, ~ ends with ions, in which the ions have the opposite charge, defects were caused by the fact that many of the organic molecules provided on both sides with ions do not arrange themselves perpendicular to the support surface thus forming a bond with the support only with one ionic end of this molecule, but arrange themselves flat, i.e.
parallel to the support surface, and form a bond with the ionic support surface with both ionic ends of the molecule. Thus, on the one hand, no functional group (in this case the second ionic group of this organic molecule) remains for further build up of layers and, on the other hand, such an organic molecule adsorbed in an undesired manner parallel to the support surface covers the ionic groups of the support underneath which are present between the two binding sites formed and prevents these covered ionic groups from forming ordered layers.
Finally, organic monolayers can be formed by adsorption of organic mercapto compounds, for example on gold surfaces (self-assembly technique).
Accordingly, there was still a demand for layer elements applied to supports which have a high degree of order without the defects described. Such layer elements applied to supports should furthermore have a greater Le A 27 700 - 4 -204970,~
mechanical and thermal stability and a greater resistance to solvents than, for example, L~ films. In addition, it should be possible to produce new layer elements applied to supports in the form of fairly large areas.
S UMMARY OF THE I NVENT I ON
The disadvantages mentioned are overcome by the one- or multi-layered layer elements according to the invention applied to supports. The layer elements according to the invention form a highly ordered structure which is obtained by physisorption with the formation of salts and in each of which a uniformly charged surface is present which is coated in the subsequent layer with organic molecules having the opposite charge from that of the previous layer.
The invention relates to layer elements applied to a support, comprising a) a modified ~upport having an even surface, in which modification means the application of ions or ionisable compounds of the same charge over the entire area, and b) one or more layers made of organic materials which in each layer contain ions of the same charge, the ions of the first layer having the opposite charg~
of the modLfied support and in the case of several layers each further layer having again the opposite charge of the previous layer.
Le A 27 700 - 5 -20'1~'7~
The invention furthermore relateg to a process for the preparation of layer elements applied to ~upport3, characterised in that i) a support having a flat surface i9 modified such that it carries ions or ionisable compounds of the same charge over the entire area, and ii) one or more layers made of organic materials, which in each layer have ions of the same charge, are applied from a solution of such organic materials to the modified support, the organic material for the first layer having ions of the opposite charge relative to the charge of the ions of the modified support and, in the case of multiple layer~, alterna~ing further layers containing ions of the opposite charge in each case relative to the previous one are applied in the same manner as the first layer.
BRIEF DESCRIPTION OF THE DRAWINGS
The at~ached figures (Figure lA, lB and 2-12) illus~ra~e exemplary embodimen~s in addition ~o ~he Examples.
DETAILED DESCRIPTION OF THE INVENTION
Multi-layer systems of the type described comprise at least two materials having ionic groups of opposi~e charges. Thus, the simplest layer sequence is of the ABABAB.... type. However, the functionality of the layers can ~e selectively increased by using more than 2 materials. for example ABCBABABCB ... or ABCDCBADCBAC....
in which A and C and B and D carry the same charge. The layer sequence is a consequence of the selection of the dipplng bath used in each case for applying the individual layers.
Le A 27 700 - 6 -2(:)497~)2 The process according to the invention allows large-area highly ordered multi-layered layer elements on supports to be produced.
Suitable supports for the layer elements according to the invention are those having a surface which is flat and accessible to solvents, for example flat, cyliandrical, conical, spherical or other supports of uniform shape, which thus also include interior surfaces of bottles, tubings, and the like; supports having a flat surface are preferred. For various optical or electrical areas of application, the supports can be transparent, impermeable or reflecting as well as electrically conducting, semi-conducting or insulating. The chemical nature of these supports can be inorganic or organic. Examples of inorganic support materials are metals, semi-conductor materials, glasses or ceramic materials, such as gold, platinum, nickel, palladium, aluminium, chromium, steel and other metals, germanium, gallium arsenide, silicon and other semi-conductor materials, glas~es of a wide range of chemical composition, quartz glass, further glasses, and porcelain and further mixed oxides, which are understood to mean ceramic materials. Further inorganic substances which are suitable as supports are, for example, graphite, zinc selenide, mica, silicon dioxide, lithium niobate and further supports, if desired in the form of inorganic single crystals, such as are known to one skilled in LB technology.
Organic materials for the supports of the layer elements Le A 27 700 - 7 -204~3~70~
according to the invention are predominantly polymer materials, due to the dimensional stability and resistance to solvents. Examples which may be mentioned are: polyesters, such as polyethylene terephthalate, polybutylene terephthalate and others, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoro-ethylene, polycarbonate, polyamide, poly(meth)acrylate, polystyrene, polyethylene or ethylene/vinyl acetate copolymer. Organic supports of this type are also known to one skilled in LB technology.
The chemical nature of the support material plays a minor role, 80 that the above enumerations are only by way of example and are not exhaustive.
The 6upports to be used according to the invention have charged or ionisable surfaces or their surfaces are modified such that they are covered over the entire area with ions or ionisable compounds of the same charge. This application over the entire area can be a first monomolecular layer which is solidly attached to the support. However, the application of ions or ionisable compounds over the entire area can also be effected by a chemical reaction on the support itself, in which the surface is densely covered with ions or ionisable groups of the same charge to the extent of forming a monomolecular layer. Such a modification is known to one skilled in the art and working in the area of multi-layered thin films. Examples of these are self-assembly monolayers, for example comprising an ~ dithiol, Le A 27 700 - 8 -21a ~9~7i[~
cysteamine, amino-containing thiols and other thiols containing a further ionic or ionisable group, on metals, such as gold, silver, cadmium and others. In this case, the thiol group is -~olidly bound to the metallic surface and the second thiol group, a carboxyl group, an amino group or another ionic or ionisable group forms the ionic modification of the metallic support to be used. A
further important example is silanation of the surface with silanes containing alkoxy groups, which additionally contain a further ionic or ionisable group. This silanation is possible with all silicon-containing supports in a manner known to one skilled in the art. The ionic or ionisable group can be, for example, a sulphur qroup or an ionisable amino group. A still further example relates to the chemical modification of polymeric organic supports (polymer-analogous reaction). Thus, for example, polyethylene can be provided on the surface with carboxyl qroups by means of oxidising agents, such as chromic acid. (Meth)acrylate or (meth)acrylamides can also be provided on the surface with carboxyl groups by means of hydrolysis. Sulphonation of polystyrene resins on the surface also leads to a modification utilisable according to the invention. The last-mentioned modified polymers can also be called flat ion exchangers.
Furthermore, it is known to one skilled in the art that instead of anionic groups (carboxyl groups, sulpho groups) cationic groups, such as amino groups, can also be obtained by chloromethylation, followed by the introduction of an amino group. Reactions of this type are known as polymer-analogous reactions.
Le A 27 700 - 9 -20~9'782 Furthermore, freshly split mica may be mentioned, on which cationic compounds can be adsorbed directly.
Furthermore, on glass or quartz, it is also possible to adsorb cationic compounds, such as polyethyleneimine, after short dipping into sodium hydroxide solution.
In all cases mentioned and in further conceivable ones, it is immaterial which type the ions or ionisable groups on the surface of the support are; instead the dense covering with such groups over the entire area is decisive.
It is also important that it is always ions or ionisable groups of the same charge which constitute the modification of the support.
The organic materials for forming the individual layers on the modified support are either monomeric substances having two ionic or ionisable functional groups of the same charge (so-called bola amphiphiles) or polymers having a multiplicity of ionic or ionisable functional groups of the same charge (so-called polyelectrolytes or polyionenes). These organic materials always carry functional groups of the same charge (i.e. either ca~ions or groups which can be ionised to cations or anions or groups which can be ionised to anions). It is entirely conceivable in this case that different cations or different anions or groups which can be ionised thereto can be represented in the molecule. However, for reasons of accessibility and ease of producibility, it is Le A 27 700 - 10 -20~97C~;~
preferred that the two functional groups in the monomeric substances are identical and that the multiplicity of the functional groups in the polymers is also identical.
The low-molecular-weight bola amphiphiles contain in the S centre a hard segment, such as is also present in rod-like (calamitic) liquid crystals as mesogenic group.
Examples of such groups are biphenyl, terphenyl, stilbene, tolan, bis(aryl) ester, azobenzenes, or those compounds in which the aromatic ring is hydrogenated.
These and other mesogenic groups are known to one skilled in the art. In the general chemical formula (I) given below, the group in question is designated -X- and described in more detail by means of examples.
In the case where monomeric substances are used in the layer elements, preferably those of the formula ion_zl_ ( _y~_z2_ ) _X_Z3_y2_z4 ion (I) are used in which X represents -c-c-c-C-, ~3 CH
~ N=N ~ , ~ O_ Le A 27 700 - 11 -20497~)~
~I-C~;, ~CO-NH{~, ~NH - CO~, ~CH~
p CH <~
~N=CH~;, ~N=C ( CH3 )4~
~=CH~, ~;N=N ( CH3 )~, -~3 ~3-O O
_~, ~, O O
4~C N - N ~; or 4~ C,NH - C H 2 n --NH-CH2 m Le A 27 700 - 12 -Z049~2 in which the aromatic rings in these groups can be mono- to trisubstituted by methyl, fluorine or chlorine or can be hydrogenated to the cycloal~ane, yl and y2~ independently of one another, represent -(-CH2-)g-~ -(-Si(CH3~2-o-)q-~ ~(~CH=CH~)q~ or ~(C~C~)q~, it being possible for the hydrogen atoms in these groups to be substituted in part or completely by methyl, fluorine or chlorine, o Zl, Zz, Z3 and Z4, independently of one another, represent a single bond, -O-, -S-, -CO-, -SO-, -SO2-, -CO-O-, -O-CO-, SN-CO, -CO-N=, -NH- or -N~Cl-C4-alkyl)-, ion represents a cation or an anion or a group which can be ionised to the cation or the anion, m represents 0 or 1, preferably 1, n represents integral values from 0 to 7, o represents integral values from 1 to 3, p represents the value 1 or 2 and q represents integral values from 1 to 20.
Le A 27 700 - 13 -Z0~
X is preferably one of the groups n CH C~; ~-C~
{~N=N~ ' ~3 CO-~, ~3~-C~, The index n preferably adopts integral values from O to 3. The index o preferably adopts the value 1 or 2. The index p preferably adopts the value 1.
5 y1 and y2 preferably represent ~(CH2)q~t in which the hydrogen atoms can be replaced in part or completely by methyl, fluorine or chlorine. yl and y2~ independently of one another particularly preferably adopt the meaning ~(C~I2)q~, in which the hydrogen atoms are not substituted.
The index q preferably adopts integral values from 4 to 14, particularly preferably from 6 to 12. Z1 to Z4 preferably adopt the meaning -O-, -CH2-, -CO-NH-, single bond or -CO-O-.
Le A 27 700 - 14 -2[)a~97~
Suitable cations bound by Z1 and Z4 are those of the formulae e3,R 1 -N-R2 ( I I ) or `R3 (III) ,Rl or lonisable, such as ~R2 (IV) in which R1, R2 and R3, independently of one another, represent hydrogen, straight-chain or branched C1-C4-alkyl or C5-C6-cycloalkyl, in which R3 can furthermore represent phenyl or benzyl and in which furthermore two of the radicals R1 to R3 in (II) or (IV) together with the N atom, which they substitute, can form a pyridine ring, morpholine ring, piperidine ring or pyrimidine ring.
The radicals R1 to R3 preferably represent hydrogen or straight-chain or branched C1-C4-alkyl, it also being possible for R3 to represent benzyl and for two of the radicals R1 to R3 in (II) to form one of the abovementioned heterocyclic rings.
Such cations are combined for charge neutralisation with anions, such as chloride, bromide, iodide, fluoride, tetrafluoroborate, perchlorate, nitrate, sulphate, Le A 27 700 - 15 -21~49~2 hydrogen sulphate, tosylate, acetate, methylsulphate, trifluoromethylsulphate, higher alkylsulphonate or benzenesulphonate. Preferred anions for charge neutralisation are the monovalent ones, and of them the simple ones such as halides, perchlorate or acetate.
In the case where ion is an anion, it is, for example, carboxylate, sulphonate, phosphonate or alkylsulphate.
For charqe neutralisation, these anions are combined with cations of the alkali metals, alkaline earth metals, ammonium ion or ammonium ion which is completely or in part substituted; preferred cations are the monovalent ones, in particular those of the alkali metals and the unsubstituted ammonium ion and tetramethyl ammonium ion.
A functional group which can be ionised to an anion can be, for example, an incompletely dissociated carboxyl group.
A functional group which can be ionised to a cation is, for example, an amino group, which is only protonated by the acidity of the solvent or by an acidic group on the ionic support.
It is in principle possible to use mixtures of various substances of the formula (I), as long as the requirement of a content of ions of the same charge is met. However, in order to obtain layers of uniform thickness, it is preferred to use only one substance of the formula (I) per each layer.
Le A 27 700 - 16 -~o~
Polymers containing a multiplicity of ionic or ionisable functional groups are also called polyelectrolytes.
Examples of anionic or cationic or ionisable groups in such polymers are:
HO - P - , - CH2 - CH- , - CH2 - CH- , - CH2 - CH -. .- CH2 - CH -~3 ¢~ -CH2 - CH2~N-N(C2H5 )2 ~H3 -CH2-C,H- , -CH2-CH CH2 ICH , -CH2-CHz~NH~~
COOH . ~ OSO ~H
~SO3H
-CHz-ICH- , -CH2-ICH- ~ -CH2-CIH-NH2 ~ 3 0=C-O-(CHz)z-N(CH3)z ~N
S Examples of polyelectrolytes may be as follows:
polyacrylic acid, polymethacrylic acid, Le A 27 700 - 17 -2049~
polyethylenesulphonic acid, polyvinylsulphonic acid, polystyrenesulphonic acid, polyvinylphenylsulphuric acid (phenol ester), maleic acid/alkene copolymer, maleic acid/vinyl alkyl ether copolymer, polyglutamic acid, polylysine, and the corresponding copolymers with neutral amino acids, polyvinylamine, polyethyleneimine, polyvinyl-4-alkylpyridinium salt, poly(methylene)-N,N-dimethylpiperidinium salt, poly(vinylbenzyl-trimethyla~monium) salt.
Important and readily processable polyelectrolytes are especially:
1 -CH2-CH- , CH2-1CH- , -CH-CONH-, ¢~ ~3So3H 0503H I H2 Nl(c2Hs)2 lcH2 Dextran sulphate, heparin and polyallylamine.
Accordingly, the chain of the polymeric organic material for the layer elements can be a polyolefin, an acrylic polymer, a polyvinyl acetate, a polyester, a polyamide, a poly- or copolyamino acid, such as polylysine or polyglutamic acid, an ionic polysaccharide or another polymer known to one skilled in the art. The polymer can Le A 27 700 - 18 -; :0~9~7 carry the ions or the ionisable functional groups in the monomer unit and thus be water-soluble, but it can initially also be a hydrophobic and thus water-insoluble polymer, in which ions or ionisable groups are incorporated by polymer-analogous reactions.
Dyestuffs and active compounds which are important for the ultimate use of the layer elements according to the invention applied to supports can be applied to monomeric organic materials and also to polymeric organic materials by a covalent bond or integrated therewith. One example is one substance each from the pair antibody/antigen for purposes of sensory analysis, for example from the pair biotin/streptavidin.
In the case where monomeric organic materials are used with the starting mixture having the same molecular length but different molecular structures in the context of the formula (I), lateral crystallisation within a layer constructed therewith can be prevented, which makes this layer two-dimensionally amorphous and thus optically more homogeneous. By varying the composition of such a mixture of monomeric organic materials, it is possible to produce a tailored layer element for various optical requirements. When polymeric organic materials are used (polyelectrolytes), the amorphous character of a layer constructed therewith is in general ensured even without using a mixture of several polyelectrolytes.
While in the case of monomeric bola amphiphiles it is Le A 27 700 - 19 -20~7~:
always a complete monolayer of constant thickness which is applied, it is possible in the case of the poly-electrolytes to adjust additionally the thickness of the monolayer applied by ~arying the parameters of the molecular weight of the polymer, concentration and adsorption time. Thus, low molecular weights and/or small concentrations qive small layer thicknesses, while large molecular weights and/or high concentrations give large layer thicknesses.
Furthermore, a special variant of the invention is to apply initially only a layer comprising monomeric organic materials (bola amphiphiles) or a polymeric organic material (polyelectrolyte) to a sensitive modified support, so as to seal the support film sensitised by modification and thus to protect it. At this stage, the further layer formation can initially ~e halted only, to be resumed after some time (optional temporary storage).
Such a one-layer coated modified support thus represents a stable precursor for multi-layered layer elements according to the invention.
To produce the layer elements according to the invention applied to supports, the individual layers can be applied to the modified support from their solutions in a suitable solvent. In each application, a solution containing organic material whose functional groups have in each case the opposite charge is used. Between the individual applications, residual amounts of organic material which are not bonded or only loosely adsorbed Le A 27 700 - 20 -are removed from the previous application in each case by rinsing.
Suitable solvents are: water, aqueous solutions of salts (for example NaCl, MnCl2, (NH4)zS04) and water-miscible, non-ionic solvents, such as C1-C4-alkanols, C3-C~-ketones including cyclohexanone, tetrahydrofuran, dioxane, dimethyl sulphoxide, ethylene glycol, propylene glycol and oligomers of ethylene glycol and propylene glycol and ethers thereof and open-chain and cyclic amides, such as dimethylformamide,dimethylacetamide,N-methylpyrrolidone and others. Polar, water-immiscible solvents, such as chloroform or methylene chloride, which can contain a portion of the abovementioned organic solvents, insofar - as they are miscible with them, will only be considered in special cases. Water or solvent mixtures, one component of which is water, are preferably used. If permitted by the solubility of the monomeric or polymeric organic materials (bola amphiphiles and polyelectrolytes)~ only water is used as the solvent, since this simplifies the process.
It has been observed in many cases that monomeric organic materials (bola amphiphiles) arrange themselves in water as the solvent parallel to one another and form micelles, which facilitates an ordered, regular structure on the support. Furthermore, the bola amphiphiles can also be abqorbed at an angle other than 90 relative to the support surface or to the last-applied layer, as long as this is carried out in a regular manner throughout the Le A 27 700 - 21 -204976~
entire layer.
When polyelectrolytes are applied, they bind horizontally and thus prevent a loss of potential binding sites in the layer below. This is additionally favoured by the fact that no di~crete covalent bonds are formed, but, as a result of the electrostatic forces, a spatially fixed assignment of the ions on the various layers is not required.
The process according to the invention for producing the new layer elements applied to supports can easily be converted into a continuous procedure by passing the modified support to be coated in succession through various baths containing the organic materials to be applied alternately and through interposed baths containing washing liquids. This reduces the amount of work considerably, compared with the LB method. It is less because the demands on cleanliness between the application of two layers is not as high as in the LB
method.
The layer elements according to the invention applied to supports can be constructed by starting in all layers with monomeric organic materials having alternating charges from layer to layer.
Likewise, it is possible to start only with polyelectrolytes ha~ing alternating charges from layer to layer. However, it is likewise possible to use Le A 27 700 - 22 -204~7~
alternatingly bola amphiphiles and polyelectrolytes, ayain with alternating charge in each case.
Polyelectrolytes which carry both cationic and anionic groups and which have a similar absorption behaviour if one of the two groups is present in excess are likewise suitable.
It has been possible to apply up to 110 layers on a modified support as defined according to the invention.
The layer elements according to the invention were characterised by the following analytical methods:
The transmission of the layer systems on quartz supports was measured by W/Vis spectroscopy as a function of the layer thickness. Neither in the case of bola amphiphiles (bands at 284 nm and 263 nm) nor in ~he case of polyelectrolytes (band at 225 nm) were shifts relative to the solution spectra observed. A uniform layer growth up to a layer number of 38 layers was detected ~y a constant increase of the optical absorption. Since absorption in even thicker layers exceeds 1.5 and thus moves outside the linear range, the method is inherently inappropriate for thicker layers.
It was shown by ellipsometry at a wavelength of 633 nm that up to a layer thickness of five layers, assuming a constant refractive index, a constant increase in layer thickness occurs with each layer. Using a sample containing 6 layers of bola amphiphiles, a layer Le A 27 700 - 23 -20~7~.~
thickness of 185 ~ 1.2 ~ at a refractive index of n = 1.55 was determined at five different measuring points on a support 2 cm2 in size.
Several samples were investigated by means of small-angle X-ray defraction, but in all cases no Bragg reflection was observed. This indicates poor crystallographic correlation of the individual layers despite the good constant layer thickness of the entire layer (see ellipsometry).
The good homogeneity of the layers was also tested via a light microscope. This showed a dependence of the layer quality on the substrate quality. Effects from the edge of the support on the layer persist to about 2 mm.
Under a light microscope, a lateral structure could not be resolved either by Normarski interference contrast nor by crossed polarisers. Uniform interference colours were observed over the entire coated area with the exception of the edge by direct-light microscopy on reflecting supports (Si-wafers).
The following exemplary embodiments illustrate the process acc~rding to the invention, without limiting it thereto. A series of exemplary embodiments are additionally illustrated by the attached figures (Figure lA, lB and 2-12).
Figures lA, lB and 2-8 show the modification of a support Le A 27 700 - 24 -20~9~70~
(for example Si or qlass) and possible constructions of multilayers by way of examples. The sym~ols [1] and [2]
indicate the process steps to be carried out in succession in each case. Figure lA contains five symbols which appear in the following figures (from top to bottom): the cation C2H5O-Si(CH3)2-(CH2)3-N-H3; the di-anion of compound (5) from Example 5; the di-cation of compound (7) from Example 7; the polymer containing a multiplicity of cations and having the formula - (CH2~CH)n 1 (polymer ammonium cation, for example as polyiodide salt;
`r' compound (8) in CH2 Example 12);
the polymer having a multiplicity of anions and the formula (CH2-CH~ - (polystyrenesulphonate, n for example as poly-~ sodium salt; compound ~ (9) in Example 10).
S03e Figure lB shows the modification of a support and possible constructions of multilayers by way of examples Le A 27 700 - 25 -2049~7~
(Example 8 and 9).
Figure 2 illustrates Example 10.
Figures 3 and 6 illustrate Example 11.
Figures 4 and 7 illustrate Example 12.
Figures 5 and 8 illustrate Example 13.
Figure 9 shows formulae and symbols for poly-l-lysine of MW 75,000 (top~ and biotin-modified poly-l-lysine (bottom); cf. Example 14.
Figure 10 shows a coated support having a poly-l-lysine topcoat in the upper picture (cf. Example 15); in the lower picture, a topcoat comprising biotin-modified poly-l-lysine has been applied (cf. Example 16).
Figure 11 represents a bio-specific recognition reaction of a biotin-modified support surface (lower picture) in comparison with a non-biotinylated support surface (upper picture, no recognition) by means of fluorescence-labelled streptavidin (FITC = fluorescein isothiocyanate).
Figure 12 shows the fluorescence spectrum of the two support surfaces of Figure 11, upper and lower picture.
Examples The reactions of Examples 1 to 7 can be represented by the following equations:
Example 1:
BrCH2-(CH2)9-COOH ~ HO-CH(CH3)2 BrCH2-(CH2)9-COO-CH(CH ) Le A 27 700 - 26 -49'~2 Example 2:
H ~ H + 2BrCH2-(CH2)9-COO-C~(CH3)2 (CH3~2CH-OOC-(cH2)lo ~ -(CH2)l0-coo-cH(cH3)2 ( 1 ) Example 3: Hydrolysis of (1) Hooc-(cH2)lo ~ tCH2)10 COOH (Z) Example 4:
(2) + 2 SOC12 ClCO-(CH2)10-o ~ ~ (CH2)10-(3) (3) + 2 H2N-(CH2)3-N(CH3)2 ~O-(CH2)lo-co-NH-(cH2)3-N(cH3)2)2 (4 Example 5:
The previously mo3t investigated method for producing ultra-thin films and multi-layered layers is the conventional Langmuir-Blodgett (LB) method. In thi~
method, the layer construction takes place by sequential transfer of monolayers from a water surface to a solid ~ubstrate. Thi~ method is distinguished by a relatively Le A 27 700 - 2 -Z0497~
high apparatus outlay, which nevertheless only allows small supports to be coated. The organic material for building up the layers must be sufficiently spreadable on the water surface.
Furthermore, the attempt has been made to take carboxyl-containing supports, as can be produced, for example, by oxidation of polyethylene supports, as the basis of uniform coating. To this end, for example, long-chain carboxylic acids were applied from a solution to the support described by means of calcium ions. The calcium ions provide an ionic bond between the carboxyl groups of the support and the carboxylic acid applied. Since dicarboxylic acids and calcium ions when applied from a solution would lead immediately to an insoluble and no longer usable salt precipitate, only monocarboxylic acids can be used. If it were decided to apply further layers onto this first layer, first the non-functionalised part of the carboxylic acid molecule which points away from the carboxyl group would have to be functionalised in order to allow the build up to continue. A still further attempt was made to produce a multi-layered layer construction by alternating reaction of 1,10-decanediol bisphosphate with its zirconium salt or by alternating reaction of 1,10-decanediol bisphosphate with zirconyl chloride. These attempts ended after about 8 layers, because by then the surface showed too severe a defect for an ordered further layer build up. In the case where zirconyl chloride was used, the change from the inorganic crystal lattice to the organic crystal combined therewith Le A 27 700 - 3 -2049~0~
can be assumed as the source of the defect formation.
Furthermore, it has been observed that where the attempt is made to coat an ionically modified support surface with organic molecules provided on both ~, ~ ends with ions, in which the ions have the opposite charge, defects were caused by the fact that many of the organic molecules provided on both sides with ions do not arrange themselves perpendicular to the support surface thus forming a bond with the support only with one ionic end of this molecule, but arrange themselves flat, i.e.
parallel to the support surface, and form a bond with the ionic support surface with both ionic ends of the molecule. Thus, on the one hand, no functional group (in this case the second ionic group of this organic molecule) remains for further build up of layers and, on the other hand, such an organic molecule adsorbed in an undesired manner parallel to the support surface covers the ionic groups of the support underneath which are present between the two binding sites formed and prevents these covered ionic groups from forming ordered layers.
Finally, organic monolayers can be formed by adsorption of organic mercapto compounds, for example on gold surfaces (self-assembly technique).
Accordingly, there was still a demand for layer elements applied to supports which have a high degree of order without the defects described. Such layer elements applied to supports should furthermore have a greater Le A 27 700 - 4 -204970,~
mechanical and thermal stability and a greater resistance to solvents than, for example, L~ films. In addition, it should be possible to produce new layer elements applied to supports in the form of fairly large areas.
S UMMARY OF THE I NVENT I ON
The disadvantages mentioned are overcome by the one- or multi-layered layer elements according to the invention applied to supports. The layer elements according to the invention form a highly ordered structure which is obtained by physisorption with the formation of salts and in each of which a uniformly charged surface is present which is coated in the subsequent layer with organic molecules having the opposite charge from that of the previous layer.
The invention relates to layer elements applied to a support, comprising a) a modified ~upport having an even surface, in which modification means the application of ions or ionisable compounds of the same charge over the entire area, and b) one or more layers made of organic materials which in each layer contain ions of the same charge, the ions of the first layer having the opposite charg~
of the modLfied support and in the case of several layers each further layer having again the opposite charge of the previous layer.
Le A 27 700 - 5 -20'1~'7~
The invention furthermore relateg to a process for the preparation of layer elements applied to ~upport3, characterised in that i) a support having a flat surface i9 modified such that it carries ions or ionisable compounds of the same charge over the entire area, and ii) one or more layers made of organic materials, which in each layer have ions of the same charge, are applied from a solution of such organic materials to the modified support, the organic material for the first layer having ions of the opposite charge relative to the charge of the ions of the modified support and, in the case of multiple layer~, alterna~ing further layers containing ions of the opposite charge in each case relative to the previous one are applied in the same manner as the first layer.
BRIEF DESCRIPTION OF THE DRAWINGS
The at~ached figures (Figure lA, lB and 2-12) illus~ra~e exemplary embodimen~s in addition ~o ~he Examples.
DETAILED DESCRIPTION OF THE INVENTION
Multi-layer systems of the type described comprise at least two materials having ionic groups of opposi~e charges. Thus, the simplest layer sequence is of the ABABAB.... type. However, the functionality of the layers can ~e selectively increased by using more than 2 materials. for example ABCBABABCB ... or ABCDCBADCBAC....
in which A and C and B and D carry the same charge. The layer sequence is a consequence of the selection of the dipplng bath used in each case for applying the individual layers.
Le A 27 700 - 6 -2(:)497~)2 The process according to the invention allows large-area highly ordered multi-layered layer elements on supports to be produced.
Suitable supports for the layer elements according to the invention are those having a surface which is flat and accessible to solvents, for example flat, cyliandrical, conical, spherical or other supports of uniform shape, which thus also include interior surfaces of bottles, tubings, and the like; supports having a flat surface are preferred. For various optical or electrical areas of application, the supports can be transparent, impermeable or reflecting as well as electrically conducting, semi-conducting or insulating. The chemical nature of these supports can be inorganic or organic. Examples of inorganic support materials are metals, semi-conductor materials, glasses or ceramic materials, such as gold, platinum, nickel, palladium, aluminium, chromium, steel and other metals, germanium, gallium arsenide, silicon and other semi-conductor materials, glas~es of a wide range of chemical composition, quartz glass, further glasses, and porcelain and further mixed oxides, which are understood to mean ceramic materials. Further inorganic substances which are suitable as supports are, for example, graphite, zinc selenide, mica, silicon dioxide, lithium niobate and further supports, if desired in the form of inorganic single crystals, such as are known to one skilled in LB technology.
Organic materials for the supports of the layer elements Le A 27 700 - 7 -204~3~70~
according to the invention are predominantly polymer materials, due to the dimensional stability and resistance to solvents. Examples which may be mentioned are: polyesters, such as polyethylene terephthalate, polybutylene terephthalate and others, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoro-ethylene, polycarbonate, polyamide, poly(meth)acrylate, polystyrene, polyethylene or ethylene/vinyl acetate copolymer. Organic supports of this type are also known to one skilled in LB technology.
The chemical nature of the support material plays a minor role, 80 that the above enumerations are only by way of example and are not exhaustive.
The 6upports to be used according to the invention have charged or ionisable surfaces or their surfaces are modified such that they are covered over the entire area with ions or ionisable compounds of the same charge. This application over the entire area can be a first monomolecular layer which is solidly attached to the support. However, the application of ions or ionisable compounds over the entire area can also be effected by a chemical reaction on the support itself, in which the surface is densely covered with ions or ionisable groups of the same charge to the extent of forming a monomolecular layer. Such a modification is known to one skilled in the art and working in the area of multi-layered thin films. Examples of these are self-assembly monolayers, for example comprising an ~ dithiol, Le A 27 700 - 8 -21a ~9~7i[~
cysteamine, amino-containing thiols and other thiols containing a further ionic or ionisable group, on metals, such as gold, silver, cadmium and others. In this case, the thiol group is -~olidly bound to the metallic surface and the second thiol group, a carboxyl group, an amino group or another ionic or ionisable group forms the ionic modification of the metallic support to be used. A
further important example is silanation of the surface with silanes containing alkoxy groups, which additionally contain a further ionic or ionisable group. This silanation is possible with all silicon-containing supports in a manner known to one skilled in the art. The ionic or ionisable group can be, for example, a sulphur qroup or an ionisable amino group. A still further example relates to the chemical modification of polymeric organic supports (polymer-analogous reaction). Thus, for example, polyethylene can be provided on the surface with carboxyl qroups by means of oxidising agents, such as chromic acid. (Meth)acrylate or (meth)acrylamides can also be provided on the surface with carboxyl groups by means of hydrolysis. Sulphonation of polystyrene resins on the surface also leads to a modification utilisable according to the invention. The last-mentioned modified polymers can also be called flat ion exchangers.
Furthermore, it is known to one skilled in the art that instead of anionic groups (carboxyl groups, sulpho groups) cationic groups, such as amino groups, can also be obtained by chloromethylation, followed by the introduction of an amino group. Reactions of this type are known as polymer-analogous reactions.
Le A 27 700 - 9 -20~9'782 Furthermore, freshly split mica may be mentioned, on which cationic compounds can be adsorbed directly.
Furthermore, on glass or quartz, it is also possible to adsorb cationic compounds, such as polyethyleneimine, after short dipping into sodium hydroxide solution.
In all cases mentioned and in further conceivable ones, it is immaterial which type the ions or ionisable groups on the surface of the support are; instead the dense covering with such groups over the entire area is decisive.
It is also important that it is always ions or ionisable groups of the same charge which constitute the modification of the support.
The organic materials for forming the individual layers on the modified support are either monomeric substances having two ionic or ionisable functional groups of the same charge (so-called bola amphiphiles) or polymers having a multiplicity of ionic or ionisable functional groups of the same charge (so-called polyelectrolytes or polyionenes). These organic materials always carry functional groups of the same charge (i.e. either ca~ions or groups which can be ionised to cations or anions or groups which can be ionised to anions). It is entirely conceivable in this case that different cations or different anions or groups which can be ionised thereto can be represented in the molecule. However, for reasons of accessibility and ease of producibility, it is Le A 27 700 - 10 -20~97C~;~
preferred that the two functional groups in the monomeric substances are identical and that the multiplicity of the functional groups in the polymers is also identical.
The low-molecular-weight bola amphiphiles contain in the S centre a hard segment, such as is also present in rod-like (calamitic) liquid crystals as mesogenic group.
Examples of such groups are biphenyl, terphenyl, stilbene, tolan, bis(aryl) ester, azobenzenes, or those compounds in which the aromatic ring is hydrogenated.
These and other mesogenic groups are known to one skilled in the art. In the general chemical formula (I) given below, the group in question is designated -X- and described in more detail by means of examples.
In the case where monomeric substances are used in the layer elements, preferably those of the formula ion_zl_ ( _y~_z2_ ) _X_Z3_y2_z4 ion (I) are used in which X represents -c-c-c-C-, ~3 CH
~ N=N ~ , ~ O_ Le A 27 700 - 11 -20497~)~
~I-C~;, ~CO-NH{~, ~NH - CO~, ~CH~
p CH <~
~N=CH~;, ~N=C ( CH3 )4~
~=CH~, ~;N=N ( CH3 )~, -~3 ~3-O O
_~, ~, O O
4~C N - N ~; or 4~ C,NH - C H 2 n --NH-CH2 m Le A 27 700 - 12 -Z049~2 in which the aromatic rings in these groups can be mono- to trisubstituted by methyl, fluorine or chlorine or can be hydrogenated to the cycloal~ane, yl and y2~ independently of one another, represent -(-CH2-)g-~ -(-Si(CH3~2-o-)q-~ ~(~CH=CH~)q~ or ~(C~C~)q~, it being possible for the hydrogen atoms in these groups to be substituted in part or completely by methyl, fluorine or chlorine, o Zl, Zz, Z3 and Z4, independently of one another, represent a single bond, -O-, -S-, -CO-, -SO-, -SO2-, -CO-O-, -O-CO-, SN-CO, -CO-N=, -NH- or -N~Cl-C4-alkyl)-, ion represents a cation or an anion or a group which can be ionised to the cation or the anion, m represents 0 or 1, preferably 1, n represents integral values from 0 to 7, o represents integral values from 1 to 3, p represents the value 1 or 2 and q represents integral values from 1 to 20.
Le A 27 700 - 13 -Z0~
X is preferably one of the groups n CH C~; ~-C~
{~N=N~ ' ~3 CO-~, ~3~-C~, The index n preferably adopts integral values from O to 3. The index o preferably adopts the value 1 or 2. The index p preferably adopts the value 1.
5 y1 and y2 preferably represent ~(CH2)q~t in which the hydrogen atoms can be replaced in part or completely by methyl, fluorine or chlorine. yl and y2~ independently of one another particularly preferably adopt the meaning ~(C~I2)q~, in which the hydrogen atoms are not substituted.
The index q preferably adopts integral values from 4 to 14, particularly preferably from 6 to 12. Z1 to Z4 preferably adopt the meaning -O-, -CH2-, -CO-NH-, single bond or -CO-O-.
Le A 27 700 - 14 -2[)a~97~
Suitable cations bound by Z1 and Z4 are those of the formulae e3,R 1 -N-R2 ( I I ) or `R3 (III) ,Rl or lonisable, such as ~R2 (IV) in which R1, R2 and R3, independently of one another, represent hydrogen, straight-chain or branched C1-C4-alkyl or C5-C6-cycloalkyl, in which R3 can furthermore represent phenyl or benzyl and in which furthermore two of the radicals R1 to R3 in (II) or (IV) together with the N atom, which they substitute, can form a pyridine ring, morpholine ring, piperidine ring or pyrimidine ring.
The radicals R1 to R3 preferably represent hydrogen or straight-chain or branched C1-C4-alkyl, it also being possible for R3 to represent benzyl and for two of the radicals R1 to R3 in (II) to form one of the abovementioned heterocyclic rings.
Such cations are combined for charge neutralisation with anions, such as chloride, bromide, iodide, fluoride, tetrafluoroborate, perchlorate, nitrate, sulphate, Le A 27 700 - 15 -21~49~2 hydrogen sulphate, tosylate, acetate, methylsulphate, trifluoromethylsulphate, higher alkylsulphonate or benzenesulphonate. Preferred anions for charge neutralisation are the monovalent ones, and of them the simple ones such as halides, perchlorate or acetate.
In the case where ion is an anion, it is, for example, carboxylate, sulphonate, phosphonate or alkylsulphate.
For charqe neutralisation, these anions are combined with cations of the alkali metals, alkaline earth metals, ammonium ion or ammonium ion which is completely or in part substituted; preferred cations are the monovalent ones, in particular those of the alkali metals and the unsubstituted ammonium ion and tetramethyl ammonium ion.
A functional group which can be ionised to an anion can be, for example, an incompletely dissociated carboxyl group.
A functional group which can be ionised to a cation is, for example, an amino group, which is only protonated by the acidity of the solvent or by an acidic group on the ionic support.
It is in principle possible to use mixtures of various substances of the formula (I), as long as the requirement of a content of ions of the same charge is met. However, in order to obtain layers of uniform thickness, it is preferred to use only one substance of the formula (I) per each layer.
Le A 27 700 - 16 -~o~
Polymers containing a multiplicity of ionic or ionisable functional groups are also called polyelectrolytes.
Examples of anionic or cationic or ionisable groups in such polymers are:
HO - P - , - CH2 - CH- , - CH2 - CH- , - CH2 - CH -. .- CH2 - CH -~3 ¢~ -CH2 - CH2~N-N(C2H5 )2 ~H3 -CH2-C,H- , -CH2-CH CH2 ICH , -CH2-CHz~NH~~
COOH . ~ OSO ~H
~SO3H
-CHz-ICH- , -CH2-ICH- ~ -CH2-CIH-NH2 ~ 3 0=C-O-(CHz)z-N(CH3)z ~N
S Examples of polyelectrolytes may be as follows:
polyacrylic acid, polymethacrylic acid, Le A 27 700 - 17 -2049~
polyethylenesulphonic acid, polyvinylsulphonic acid, polystyrenesulphonic acid, polyvinylphenylsulphuric acid (phenol ester), maleic acid/alkene copolymer, maleic acid/vinyl alkyl ether copolymer, polyglutamic acid, polylysine, and the corresponding copolymers with neutral amino acids, polyvinylamine, polyethyleneimine, polyvinyl-4-alkylpyridinium salt, poly(methylene)-N,N-dimethylpiperidinium salt, poly(vinylbenzyl-trimethyla~monium) salt.
Important and readily processable polyelectrolytes are especially:
1 -CH2-CH- , CH2-1CH- , -CH-CONH-, ¢~ ~3So3H 0503H I H2 Nl(c2Hs)2 lcH2 Dextran sulphate, heparin and polyallylamine.
Accordingly, the chain of the polymeric organic material for the layer elements can be a polyolefin, an acrylic polymer, a polyvinyl acetate, a polyester, a polyamide, a poly- or copolyamino acid, such as polylysine or polyglutamic acid, an ionic polysaccharide or another polymer known to one skilled in the art. The polymer can Le A 27 700 - 18 -; :0~9~7 carry the ions or the ionisable functional groups in the monomer unit and thus be water-soluble, but it can initially also be a hydrophobic and thus water-insoluble polymer, in which ions or ionisable groups are incorporated by polymer-analogous reactions.
Dyestuffs and active compounds which are important for the ultimate use of the layer elements according to the invention applied to supports can be applied to monomeric organic materials and also to polymeric organic materials by a covalent bond or integrated therewith. One example is one substance each from the pair antibody/antigen for purposes of sensory analysis, for example from the pair biotin/streptavidin.
In the case where monomeric organic materials are used with the starting mixture having the same molecular length but different molecular structures in the context of the formula (I), lateral crystallisation within a layer constructed therewith can be prevented, which makes this layer two-dimensionally amorphous and thus optically more homogeneous. By varying the composition of such a mixture of monomeric organic materials, it is possible to produce a tailored layer element for various optical requirements. When polymeric organic materials are used (polyelectrolytes), the amorphous character of a layer constructed therewith is in general ensured even without using a mixture of several polyelectrolytes.
While in the case of monomeric bola amphiphiles it is Le A 27 700 - 19 -20~7~:
always a complete monolayer of constant thickness which is applied, it is possible in the case of the poly-electrolytes to adjust additionally the thickness of the monolayer applied by ~arying the parameters of the molecular weight of the polymer, concentration and adsorption time. Thus, low molecular weights and/or small concentrations qive small layer thicknesses, while large molecular weights and/or high concentrations give large layer thicknesses.
Furthermore, a special variant of the invention is to apply initially only a layer comprising monomeric organic materials (bola amphiphiles) or a polymeric organic material (polyelectrolyte) to a sensitive modified support, so as to seal the support film sensitised by modification and thus to protect it. At this stage, the further layer formation can initially ~e halted only, to be resumed after some time (optional temporary storage).
Such a one-layer coated modified support thus represents a stable precursor for multi-layered layer elements according to the invention.
To produce the layer elements according to the invention applied to supports, the individual layers can be applied to the modified support from their solutions in a suitable solvent. In each application, a solution containing organic material whose functional groups have in each case the opposite charge is used. Between the individual applications, residual amounts of organic material which are not bonded or only loosely adsorbed Le A 27 700 - 20 -are removed from the previous application in each case by rinsing.
Suitable solvents are: water, aqueous solutions of salts (for example NaCl, MnCl2, (NH4)zS04) and water-miscible, non-ionic solvents, such as C1-C4-alkanols, C3-C~-ketones including cyclohexanone, tetrahydrofuran, dioxane, dimethyl sulphoxide, ethylene glycol, propylene glycol and oligomers of ethylene glycol and propylene glycol and ethers thereof and open-chain and cyclic amides, such as dimethylformamide,dimethylacetamide,N-methylpyrrolidone and others. Polar, water-immiscible solvents, such as chloroform or methylene chloride, which can contain a portion of the abovementioned organic solvents, insofar - as they are miscible with them, will only be considered in special cases. Water or solvent mixtures, one component of which is water, are preferably used. If permitted by the solubility of the monomeric or polymeric organic materials (bola amphiphiles and polyelectrolytes)~ only water is used as the solvent, since this simplifies the process.
It has been observed in many cases that monomeric organic materials (bola amphiphiles) arrange themselves in water as the solvent parallel to one another and form micelles, which facilitates an ordered, regular structure on the support. Furthermore, the bola amphiphiles can also be abqorbed at an angle other than 90 relative to the support surface or to the last-applied layer, as long as this is carried out in a regular manner throughout the Le A 27 700 - 21 -204976~
entire layer.
When polyelectrolytes are applied, they bind horizontally and thus prevent a loss of potential binding sites in the layer below. This is additionally favoured by the fact that no di~crete covalent bonds are formed, but, as a result of the electrostatic forces, a spatially fixed assignment of the ions on the various layers is not required.
The process according to the invention for producing the new layer elements applied to supports can easily be converted into a continuous procedure by passing the modified support to be coated in succession through various baths containing the organic materials to be applied alternately and through interposed baths containing washing liquids. This reduces the amount of work considerably, compared with the LB method. It is less because the demands on cleanliness between the application of two layers is not as high as in the LB
method.
The layer elements according to the invention applied to supports can be constructed by starting in all layers with monomeric organic materials having alternating charges from layer to layer.
Likewise, it is possible to start only with polyelectrolytes ha~ing alternating charges from layer to layer. However, it is likewise possible to use Le A 27 700 - 22 -204~7~
alternatingly bola amphiphiles and polyelectrolytes, ayain with alternating charge in each case.
Polyelectrolytes which carry both cationic and anionic groups and which have a similar absorption behaviour if one of the two groups is present in excess are likewise suitable.
It has been possible to apply up to 110 layers on a modified support as defined according to the invention.
The layer elements according to the invention were characterised by the following analytical methods:
The transmission of the layer systems on quartz supports was measured by W/Vis spectroscopy as a function of the layer thickness. Neither in the case of bola amphiphiles (bands at 284 nm and 263 nm) nor in ~he case of polyelectrolytes (band at 225 nm) were shifts relative to the solution spectra observed. A uniform layer growth up to a layer number of 38 layers was detected ~y a constant increase of the optical absorption. Since absorption in even thicker layers exceeds 1.5 and thus moves outside the linear range, the method is inherently inappropriate for thicker layers.
It was shown by ellipsometry at a wavelength of 633 nm that up to a layer thickness of five layers, assuming a constant refractive index, a constant increase in layer thickness occurs with each layer. Using a sample containing 6 layers of bola amphiphiles, a layer Le A 27 700 - 23 -20~7~.~
thickness of 185 ~ 1.2 ~ at a refractive index of n = 1.55 was determined at five different measuring points on a support 2 cm2 in size.
Several samples were investigated by means of small-angle X-ray defraction, but in all cases no Bragg reflection was observed. This indicates poor crystallographic correlation of the individual layers despite the good constant layer thickness of the entire layer (see ellipsometry).
The good homogeneity of the layers was also tested via a light microscope. This showed a dependence of the layer quality on the substrate quality. Effects from the edge of the support on the layer persist to about 2 mm.
Under a light microscope, a lateral structure could not be resolved either by Normarski interference contrast nor by crossed polarisers. Uniform interference colours were observed over the entire coated area with the exception of the edge by direct-light microscopy on reflecting supports (Si-wafers).
The following exemplary embodiments illustrate the process acc~rding to the invention, without limiting it thereto. A series of exemplary embodiments are additionally illustrated by the attached figures (Figure lA, lB and 2-12).
Figures lA, lB and 2-8 show the modification of a support Le A 27 700 - 24 -20~9~70~
(for example Si or qlass) and possible constructions of multilayers by way of examples. The sym~ols [1] and [2]
indicate the process steps to be carried out in succession in each case. Figure lA contains five symbols which appear in the following figures (from top to bottom): the cation C2H5O-Si(CH3)2-(CH2)3-N-H3; the di-anion of compound (5) from Example 5; the di-cation of compound (7) from Example 7; the polymer containing a multiplicity of cations and having the formula - (CH2~CH)n 1 (polymer ammonium cation, for example as polyiodide salt;
`r' compound (8) in CH2 Example 12);
the polymer having a multiplicity of anions and the formula (CH2-CH~ - (polystyrenesulphonate, n for example as poly-~ sodium salt; compound ~ (9) in Example 10).
S03e Figure lB shows the modification of a support and possible constructions of multilayers by way of examples Le A 27 700 - 25 -2049~7~
(Example 8 and 9).
Figure 2 illustrates Example 10.
Figures 3 and 6 illustrate Example 11.
Figures 4 and 7 illustrate Example 12.
Figures 5 and 8 illustrate Example 13.
Figure 9 shows formulae and symbols for poly-l-lysine of MW 75,000 (top~ and biotin-modified poly-l-lysine (bottom); cf. Example 14.
Figure 10 shows a coated support having a poly-l-lysine topcoat in the upper picture (cf. Example 15); in the lower picture, a topcoat comprising biotin-modified poly-l-lysine has been applied (cf. Example 16).
Figure 11 represents a bio-specific recognition reaction of a biotin-modified support surface (lower picture) in comparison with a non-biotinylated support surface (upper picture, no recognition) by means of fluorescence-labelled streptavidin (FITC = fluorescein isothiocyanate).
Figure 12 shows the fluorescence spectrum of the two support surfaces of Figure 11, upper and lower picture.
Examples The reactions of Examples 1 to 7 can be represented by the following equations:
Example 1:
BrCH2-(CH2)9-COOH ~ HO-CH(CH3)2 BrCH2-(CH2)9-COO-CH(CH ) Le A 27 700 - 26 -49'~2 Example 2:
H ~ H + 2BrCH2-(CH2)9-COO-C~(CH3)2 (CH3~2CH-OOC-(cH2)lo ~ -(CH2)l0-coo-cH(cH3)2 ( 1 ) Example 3: Hydrolysis of (1) Hooc-(cH2)lo ~ tCH2)10 COOH (Z) Example 4:
(2) + 2 SOC12 ClCO-(CH2)10-o ~ ~ (CH2)10-(3) (3) + 2 H2N-(CH2)3-N(CH3)2 ~O-(CH2)lo-co-NH-(cH2)3-N(cH3)2)2 (4 Example 5:
(4) + 2 CH3J -- --(cH2)lo-co-NH-(cH2)3-N(cH3)3)l 2J
( S ) Le A 27 700 - 27 -Z~4~
Example 6:
H ~ H ~ 2 BrCH2-(CH2)9-CH20H
HO-(CH2)l1 ~ o (CH2)11-OH (6) Example 7:
( 6 ) + a ) 2 H2S04 ~ b ) 2 KOH
K~eO35-o-(cH2)l~ (CH2)1l-O-sO3 K
(7) Example 1 Preparation of isopropyl ll-bromo-undecanoate 40.3 g (0.67 mol) of isopropanol, 3.8 g (0.022 mol) of p-toluenesulphonic acid and 100 ml of CHC13 were added to 35.6 g (0.13 mol) of ll-bromoundecanoic acid, and the mixture was heated to reflux in a water separator until no more water had separated. After the reaction was complete, the mixture was allowed to cool, washed with water, aqueous sodium bicarbonate solution, and again with water, and the solvent was then distilled off.
Le A 27 700 - 28 -20~97i~.~
Distillation of the yellow oily residue gave 37.8 g (92%
of the theoretic yield) of a colourless, clear, somewhat viscous substance.
Identification: IR and NMR spectrum Example ? Preparation of compound (1) of the above equation 10.4 g (0.06 mol) of 4,4'-dihydroxybiphenyl, 9.4 g (0.18 mol) of KOH and a spatula tip of KI were dissol~ed in 640 ml of ethanol. The solution was heated to boiling, and then, while boiling was continued, a solution of 42.9 g (0.14 mol) of isopropyl ll-bromoundecanoate in 60 ml of ethanol was then quickly added. This immediately gave a milky cloudy solution, which became still more cloudy with time. After 64 hours, the white precipitate formed was filtered off, washed in portions with 100 ml of hot 10% strength KOH solution and with H2O until the filtrate gave a neutral reaction. After drying, 25.8 g (73% of the theoretical yield) of a white powder-like substance was obtained.
Identification: IR and NMR spectrum Example 3 Preparation of compound (2) 22.5 g (35 mmol) of compound (1) were suspended in 300 ml of dioxane. The reaction mixture was heated to boiling, and 10 ml of conc. ~Cl was then added dropwise, leading Le A 27 700 - 29 -2049~
to the formation of a clear solution. The reaction mixture was then heated under reflux overnight, as a result of which two non-miscible phases were formed. Upon cooling the reaction mixture, a white precipitate formed in the upper organic phase. The precipitate was isolated by filtration and washed with H20 until free of acid.
Recrystallisation from ethanol/dioxane (2/1) gave 18.0 g (92% of the theoretical yield) of a white powder-like substance.
Melting point: 170 to 171C
Identification:
1. Elemental analysis:
Found C 73.76% H 9.00% 0 17.27%
Calculated C 73.61% H 9.08~ 0 19.31 2. IR and NMR spectrum.
Example 4 Preparation of compound (3) and (4) 4 g (7.2 mmol) of (2) were introduced into a 100 ml three-neck flask equipped with a reflux condenser, dropping funnel and gas inlet valve. 10 ml of thionyl chloride were then added dropwise over a period of 10 minutes with thorough stirring. The reaction mixture was heated under reflux at 110C for 2 hours, leading to the formation of a brown clear solution. After the reaction was complete, excess thionyl chloride was removed under a weak water pump vacuum, and the reaction vessel was then aerated with argon. The compound (3) formed was diluted twice with 25 ml each of dried dioxane; the Le A 27 700 - 30 -20~9~7~)2 solvent was distilled off in each case at atmospheric pressure.
Thereafter (3) was again dissolved in 25 ml of dry dioxane, and the mixture was brought to about 10 to 15C
by means of an ice bath, during which (3) remained in solution. After addition of 1.8 g (18 mmol) of triethylamine, 1.6 g (15.5 mmol) of 3-dimethylamino-1-propylamine in 5 ml of dioxane were slowly added dropwise to the reaction mixture with thorough stirring, immediately resulting in a yellow precipitate. The reaction,mixture was then stirred at room temperature for 40 hours under an argon atmosphere and then heated to reflux for about 10 minutes. It was allowed to cool to room temperature and then further cooled using an ice bath. The resulting precipitate was isolated by filtration and washed several times with 100 ml of cold acetone. Two recrystallisations from dioxane/acetone gave 2.6 g (50% of the theoretical yield) of the slightly yellowish compound (4).
Identification: IR and NNR spectrum ,Example 5 Preparation of compound (5) 2.0 g (28 mmol) of (4) were suspended in 100 ml of dimethylformamide (DMF); 1.8 g (12 mmol) of methyl iodide were added to the mixture, which led to the dissolution of (4) in a few minutes. The reaction mixture was stirred overnight with the exclusion of light and under an argon Le A 27 700 - 31 -9'~
atmosphere. After the reaction was complete, the residue was separated off by filtration. The yellowish product was then isolated by precipitating it twice with CHCl3/ether (1/9), washed in portions with 100 ml of CHCl3/ether (1/9) and then with a small amount of ether.
Recrystallisation from ethanol gave 2.5 g (89% of the theoretical yield) of a yellowish substance.
Identification: NMR spectrum.
Example 6 Preparation of compound (6) 7.5 g (40 mmol) of 4,4'-dihydroxybiphenyl, 9.9 g (177 mmol) of ROH, a spatula tip of KI and 100 ml of ethanol/H2O (1/1) were initially introduced into a 500 ml three-neck flask, and the mixture was heated. 24.8 g (99 mmol) of bromoundecanol, dissolved in 200 ml of ethanol/HzO (3/1), were added dropwise to the boiling reaction mixture over a period of 20 minutes with vigorous stirring. The mixture was then heated under reflux for two days, resulting in a thick brown precipitate. The precipitate was isolated by means of an ultracentrifuge and recrystallised from CHCl3/ethanol (1/2.5). 12.0 g (57~ of the theoretical yield) of colourless silvery flake-like crystals were obtained.
Identification:
1. Elemental analysis:
Found C 77.42% H 10.29% O 12.29%
Calculated C 77.52~ H 10.33% O 12.15%
Le A 27 700 - 32 -20a~9~
2. IR and NNR spectrum.
ExamPle 7 Preparation of compound t7) 2.0 g (3.8 mmol) of (6) were suspended in freshly distilled DMF under a nitrogen atmosphere. 7.8 g (37.8 mmol) of dicyclohexylcarbodiimide in 5 ml of DMF
were added. 0.8 g (8.4 mmol) of sulphuric acid in 2 ml of DMF were then 810wly added dropwise to the reaction mixture; during this time, the temperature was kept below 25C by ice cooling. The mixture was stirred at room temperature under a nitrogen atmosphere and with the exclusion of light for 2 days, resulting in a white precipitate. After the reaction was complete, 0.7 ml of H2O was added to the mixture with ice bath cooling and vigorous stirring. The precipitate was then separated off by filtration. The filtrate containing the product was then brought to a pH of 8.5 with 10~ strength KOH
solution. The solvent was distilled off, and the residue was chromatographed through 500 ml of silica gel using warm DNF as the eluent. This gave 1.2 g (45% of the theoretical yield) of a white powder-like ~ubstance.
Identification: NMR spectrum.
Le A 27 700 - 33 -:~0~970Z
~P~ Silanation of the support The support used was quartz glass or silicon wafer. The wafer was treated with HzO in an ultrasound bath for l minute and carefully dried with N2 gas, which cleaned the surfaces and made them dust-free. The wafer was then placed in Caro's acid (conc. H2SO~/H2O2 = 7/3) to prepurify and treated therein at 80C in an ultrasound bath for l hour. After cooling to room temperature, the wafer was treated three times in H2O in an ultrasound bath for 60 seconds each time and washed free of acid with H2O. The wafer was then placed into H2O~H2O2/NH3 (5:1:1) solution and treated therein at 80C for 5 minutes. The wafer was then placed in H2O and carefully washed free of salt.
Finally, the wafer was treated before the silanation reaction in methanol, methanol/toluene and toluene for 2 minutes each tLme to remove traces of water. The wafer thus obtained was placed in 5~ strength 3-amino-~propyldimethylethoxysilane solution in toluene under an N2 atmosphere. The silanation reaction was carried out under an N2 atmosphere for 15 hours. After the reaction was complete, the wafer was first treated twice with toluene under an N2 atmosphere for 30 minutes each.
Finally, the wafer was treated with toluene, toluene/dimethyl sulphoxide (DMSO) and DMSO in an ultrasound bath for 1 minute each tLme. This gave a homogeneous hydrophobic surface.
Le A 27 700 _ 34 _ 20'1L9~702 Exam~le 9 Preparation of a support having a monomolecular interlayer according to Figure lB
The quartz glass or Si wafer was treated according to Example 8. This wafer which then contained ionisable amino groups on the surface was treated with a solution of 4 to 5 mg of (5), 0.3 ml of 0.1 N HCl, 1.7 ml of H2O
and 8 ml of DMSO at 0C for 20 minutes, during which the negatively charged anions (5) in ~he solution were adsorbed at the positively charged surface of the wafer with salt formation of the type of ammonium sulphate. The wafer was then first treated in ice-cold H2O and twice in H2O at room temperature for 20 seconds each time. This wafer having a monomolecular interlayer was made available to the further preparation of multilayer systems.
Exam~le 10 Preparation of a support having a polymer interlayer according to Figure 2 To this end, the quartz glass or Si wafer was treated according to Example 8. This wafer which then contained ionisable amino groups on the surface was treated with a solution of 20 mg of polystyrene polysulphonic acid sodium salt (9), 0.3 ml of 0.1 N HCl and 9.7 ml of HzO at room temperature for 20 minutes, during which the negatively charged anions (9) in the solution were adsorbed at the positively charged surface of the wafer with salt formation on the type of ammonium sulphate.
Le A 27 700 - 35 -20497~
This wafer having a polymer interlayer was made available to the further preparation of multilayer systems.
Example 11: Preparation of a physisorbed monomolecular multilayer on the monomolecular and polymer interlayer according to Figure 3 and Figure 6 The supports prepared according to Example 9 and Example 10, i.e. the support having the monomolecular or polymer interlayer, were used.
The wafer was treated with a solution of 10 mg of (7) in 10 ml of H20 at room temperature for 20 minutes. This was followed by three rinsing operations in H20 at room temperature for 20 seconds each time. This wafer was then treated with a solution of 4 to 5 mg of (5), 2 ml of H20 and 8 ml of DMS0 at room temperature for 20 minutes. The wafer was then first treated in ice-cold H20 and twice in H20 at room temperature for 20 seconds each time. The multilayer was constructed by repeating these adsorption processes alternately with (5) or with (7).
Exam~le 12: Preparation of a physisorbed polymer multilayer on the monomolecular- and polymer interlayer according to Figure 4 and Figure 7 The cupport was prepurified and silanised, as described in detail in Example 8. The supports were then treated to Le A 27 700 - 36 -;~04~3~7~
give the stable charged surface according to Example 9 and Example 10. The wafer was first placed in a solution of 30 mg of the polymer ammonium salt (8) described above and 10 ml of H2O and treated therein at room temperature for 20 minutes. The wafer was then washed in 10 ml of H2O
at room temperature three times for 20 seconds each time.
The wafer was then placed in a solution of 30 mg of the polystyrene sulphonate (9) described and 10 ml of H2O and treated therein at room temperature for 20 minutes. The wafer was then treated three times in 10 ml of H2O at room temperature again for 20 seconds each time. The polymer multilayer was constructed by continuing this process in the manner described in Example 11.
Example 13: Preparation of an alternating multilayer comprising a monomolecular di-anion and the polymer ammonium salt described in the above scheme on the monomolecular and polymer interlayer according to Figure S
and Figure 8 The support was prepurified and silanised, such as was described in detail Ln Example 8. The supports were then treated to give the stable charged surface according to Example 9 and Example 10.
The wafer was first placed in a solution of 30 mg of the polymer ammonium salt (8) described in the above reaction scheme and 10 ml of H2O and treated therein at room Le A 27 700 - 37 _ 204970~
temperature for 20 minutes. The wafer was then washed in 10 ml of H2O at room temperature three times for 20 seconds each time. The wafer was then placed in a solution of 4 to 5 mg of (5), 2 ml of H20 and 8 ml of DMS0 and treated therein at room temperature for 20 minutes.
The wafer was then first treated in ice-cold HzO and twice in H2O at room temperature for 20 seconds each time.
The alternating multilayer was constructed by continuing this process in the manner described in Example 11 and Example 12.
Example 14: Preparation of ~-biotinylated poly-l-lysine (compound 8) Compound 8 was prepared by reaction of poly-l-lysine (SERVA, Nn = 50,000-100,000) with the activated biotin active ester (biotin N-hydroxysuccinimide BNHS). 50 mg (0.5 mmol) of poly-l-lysine and 30 mg (0.5 mmol) of triethylamine were initially introduced into a 100 ml flask and dissolved in 30 ml of methanol. 40 mg (0.024 mmol) of BNHS, dissolved in 10 ml of CHCl3/isopropanol ~1:1), were then slowly added dropwise to the reaction mixture, which was then heated to reflux for one hour with stirring and then stirred at room temperature overnight. The resulting yellowish precipitate was isolated by filtration. It was suspended in 30 ml of methanol, stirred under reflux for 20 minutes, and again cooled to room temperature. The solid was again separated off by filtration and washed in Le A 27 700 - 38 -204'3~7~)~
portions three times with 20 ml of methanol each time, again suspended in 10 ml of CHCl3/isopropanol (1:1), again stirred under reflux for 20 minutes and again cooled to room temperature. After filtering, the solid was washed in portions three times with 20 ml of CHCl3/isopropanol (1:1) each time. The residue thus isolated was dried under an oil pump vacuum, dissolved in a small amount of distilled water and freed from low-molecular-weight by-products by gel permeation chromatography. ~he pure colourless copolymer was obtained from an aqueous solution by freeze drying. The yield was 25~ of theory.
The biotinylated poly-l-lysine was characterised by IR
and NMR spectroscopy. According to lH NMR, the composition of the copolymer tl-lysine/Nc-biotinyllysine) is 1:1 (formulae shown in Figure 9).
Exam~le 15: Preparation of a physisorbed multilayer having a poly-l-lysine topcoat The support was prepurified and silanised, as described in detail in Example 8. The support was then provided according to Example 9 with a negative surface by adsorption of the low-molecular-weight dianion.
The wafer was treated at room temperature with a solution of 2 mg of poly-l-lysine in a mixture of 2.8 ml of H2O and 0.2 ml of 0.1 N HCl for 20 minutes. The wafer was then washed three times in 10 ml f H20 at room temperature for one minute each time (diagram in Figure 10, upper picture).
Le A 27 700 - 39 _ 2~ 7~3 Example 16: Prepara$ion of a physisorbed multilayer having a topcoat comprising biotinylated poly-l-lysine (compound 8) The support was prepurified and silanised, as described in detail in Example 8. The support was then provided according to Example 9 with a negative surface by adsorption of the low-molecular-weight dianion.
The wafer was treated at room temperature with a solution of 2.3 mg of the biotinylated poly-l-lysine prepared in Example 14 in a mixture of 2.8 ml of H2O and 0.2 ml of 0.1 N HCl for 20 minutes. $he wafer was then washed three times in 10 ml of H2O at room temperature for one minute each time (diagram in Fi~lre 10, lower picture).
Example 17: ~iospecific recognition reaction of a biotinylated support surface in comparison with a non-biotinylated support surface by means of fluorescence-labelled streptavidin The multilayer systems prepared in Example 15 and Example 16 were dipped simultaneously into a solution of 0.02 mg of streptavi~in labelled with fluorescein isothiocyanate in 4.0 ml of 0.15 M NaCl solution at room temperature.
After 20 minutes, both supports were washed three times in 10 ml of H2O at room temperature for one minute each time and then analysed by fluorescence microscopy and spectroscopy. The support prepared in Example 15 having Le A 27 700 - 40 -Z0~L9~702 a surface comprising pure poly-l-lysine showed very little fluorescence under the fluorescence microscope, which was due to a few adsorbed fluorescent particles.
The support prepared in Example 16 having a surface comprising biotinylated poly-l-lysine showed an evenly distributed very intensive fluorescence under the fluorescence microscope (diagram in Figure 11). The relative fluorescence intensity at the fluorescence maximum found for the support from Example 16 by fluorescence spectroscopy was 100 scale divisions. The support from Example 15 showed a relative fluorescenc~
intensity of 8 scale divisions.
The fluorescence spectrum for Example 17 is shown in Figure 12.
Le A 27 700 - 41 -
( S ) Le A 27 700 - 27 -Z~4~
Example 6:
H ~ H ~ 2 BrCH2-(CH2)9-CH20H
HO-(CH2)l1 ~ o (CH2)11-OH (6) Example 7:
( 6 ) + a ) 2 H2S04 ~ b ) 2 KOH
K~eO35-o-(cH2)l~ (CH2)1l-O-sO3 K
(7) Example 1 Preparation of isopropyl ll-bromo-undecanoate 40.3 g (0.67 mol) of isopropanol, 3.8 g (0.022 mol) of p-toluenesulphonic acid and 100 ml of CHC13 were added to 35.6 g (0.13 mol) of ll-bromoundecanoic acid, and the mixture was heated to reflux in a water separator until no more water had separated. After the reaction was complete, the mixture was allowed to cool, washed with water, aqueous sodium bicarbonate solution, and again with water, and the solvent was then distilled off.
Le A 27 700 - 28 -20~97i~.~
Distillation of the yellow oily residue gave 37.8 g (92%
of the theoretic yield) of a colourless, clear, somewhat viscous substance.
Identification: IR and NMR spectrum Example ? Preparation of compound (1) of the above equation 10.4 g (0.06 mol) of 4,4'-dihydroxybiphenyl, 9.4 g (0.18 mol) of KOH and a spatula tip of KI were dissol~ed in 640 ml of ethanol. The solution was heated to boiling, and then, while boiling was continued, a solution of 42.9 g (0.14 mol) of isopropyl ll-bromoundecanoate in 60 ml of ethanol was then quickly added. This immediately gave a milky cloudy solution, which became still more cloudy with time. After 64 hours, the white precipitate formed was filtered off, washed in portions with 100 ml of hot 10% strength KOH solution and with H2O until the filtrate gave a neutral reaction. After drying, 25.8 g (73% of the theoretical yield) of a white powder-like substance was obtained.
Identification: IR and NMR spectrum Example 3 Preparation of compound (2) 22.5 g (35 mmol) of compound (1) were suspended in 300 ml of dioxane. The reaction mixture was heated to boiling, and 10 ml of conc. ~Cl was then added dropwise, leading Le A 27 700 - 29 -2049~
to the formation of a clear solution. The reaction mixture was then heated under reflux overnight, as a result of which two non-miscible phases were formed. Upon cooling the reaction mixture, a white precipitate formed in the upper organic phase. The precipitate was isolated by filtration and washed with H20 until free of acid.
Recrystallisation from ethanol/dioxane (2/1) gave 18.0 g (92% of the theoretical yield) of a white powder-like substance.
Melting point: 170 to 171C
Identification:
1. Elemental analysis:
Found C 73.76% H 9.00% 0 17.27%
Calculated C 73.61% H 9.08~ 0 19.31 2. IR and NMR spectrum.
Example 4 Preparation of compound (3) and (4) 4 g (7.2 mmol) of (2) were introduced into a 100 ml three-neck flask equipped with a reflux condenser, dropping funnel and gas inlet valve. 10 ml of thionyl chloride were then added dropwise over a period of 10 minutes with thorough stirring. The reaction mixture was heated under reflux at 110C for 2 hours, leading to the formation of a brown clear solution. After the reaction was complete, excess thionyl chloride was removed under a weak water pump vacuum, and the reaction vessel was then aerated with argon. The compound (3) formed was diluted twice with 25 ml each of dried dioxane; the Le A 27 700 - 30 -20~9~7~)2 solvent was distilled off in each case at atmospheric pressure.
Thereafter (3) was again dissolved in 25 ml of dry dioxane, and the mixture was brought to about 10 to 15C
by means of an ice bath, during which (3) remained in solution. After addition of 1.8 g (18 mmol) of triethylamine, 1.6 g (15.5 mmol) of 3-dimethylamino-1-propylamine in 5 ml of dioxane were slowly added dropwise to the reaction mixture with thorough stirring, immediately resulting in a yellow precipitate. The reaction,mixture was then stirred at room temperature for 40 hours under an argon atmosphere and then heated to reflux for about 10 minutes. It was allowed to cool to room temperature and then further cooled using an ice bath. The resulting precipitate was isolated by filtration and washed several times with 100 ml of cold acetone. Two recrystallisations from dioxane/acetone gave 2.6 g (50% of the theoretical yield) of the slightly yellowish compound (4).
Identification: IR and NNR spectrum ,Example 5 Preparation of compound (5) 2.0 g (28 mmol) of (4) were suspended in 100 ml of dimethylformamide (DMF); 1.8 g (12 mmol) of methyl iodide were added to the mixture, which led to the dissolution of (4) in a few minutes. The reaction mixture was stirred overnight with the exclusion of light and under an argon Le A 27 700 - 31 -9'~
atmosphere. After the reaction was complete, the residue was separated off by filtration. The yellowish product was then isolated by precipitating it twice with CHCl3/ether (1/9), washed in portions with 100 ml of CHCl3/ether (1/9) and then with a small amount of ether.
Recrystallisation from ethanol gave 2.5 g (89% of the theoretical yield) of a yellowish substance.
Identification: NMR spectrum.
Example 6 Preparation of compound (6) 7.5 g (40 mmol) of 4,4'-dihydroxybiphenyl, 9.9 g (177 mmol) of ROH, a spatula tip of KI and 100 ml of ethanol/H2O (1/1) were initially introduced into a 500 ml three-neck flask, and the mixture was heated. 24.8 g (99 mmol) of bromoundecanol, dissolved in 200 ml of ethanol/HzO (3/1), were added dropwise to the boiling reaction mixture over a period of 20 minutes with vigorous stirring. The mixture was then heated under reflux for two days, resulting in a thick brown precipitate. The precipitate was isolated by means of an ultracentrifuge and recrystallised from CHCl3/ethanol (1/2.5). 12.0 g (57~ of the theoretical yield) of colourless silvery flake-like crystals were obtained.
Identification:
1. Elemental analysis:
Found C 77.42% H 10.29% O 12.29%
Calculated C 77.52~ H 10.33% O 12.15%
Le A 27 700 - 32 -20a~9~
2. IR and NNR spectrum.
ExamPle 7 Preparation of compound t7) 2.0 g (3.8 mmol) of (6) were suspended in freshly distilled DMF under a nitrogen atmosphere. 7.8 g (37.8 mmol) of dicyclohexylcarbodiimide in 5 ml of DMF
were added. 0.8 g (8.4 mmol) of sulphuric acid in 2 ml of DMF were then 810wly added dropwise to the reaction mixture; during this time, the temperature was kept below 25C by ice cooling. The mixture was stirred at room temperature under a nitrogen atmosphere and with the exclusion of light for 2 days, resulting in a white precipitate. After the reaction was complete, 0.7 ml of H2O was added to the mixture with ice bath cooling and vigorous stirring. The precipitate was then separated off by filtration. The filtrate containing the product was then brought to a pH of 8.5 with 10~ strength KOH
solution. The solvent was distilled off, and the residue was chromatographed through 500 ml of silica gel using warm DNF as the eluent. This gave 1.2 g (45% of the theoretical yield) of a white powder-like ~ubstance.
Identification: NMR spectrum.
Le A 27 700 - 33 -:~0~970Z
~P~ Silanation of the support The support used was quartz glass or silicon wafer. The wafer was treated with HzO in an ultrasound bath for l minute and carefully dried with N2 gas, which cleaned the surfaces and made them dust-free. The wafer was then placed in Caro's acid (conc. H2SO~/H2O2 = 7/3) to prepurify and treated therein at 80C in an ultrasound bath for l hour. After cooling to room temperature, the wafer was treated three times in H2O in an ultrasound bath for 60 seconds each time and washed free of acid with H2O. The wafer was then placed into H2O~H2O2/NH3 (5:1:1) solution and treated therein at 80C for 5 minutes. The wafer was then placed in H2O and carefully washed free of salt.
Finally, the wafer was treated before the silanation reaction in methanol, methanol/toluene and toluene for 2 minutes each tLme to remove traces of water. The wafer thus obtained was placed in 5~ strength 3-amino-~propyldimethylethoxysilane solution in toluene under an N2 atmosphere. The silanation reaction was carried out under an N2 atmosphere for 15 hours. After the reaction was complete, the wafer was first treated twice with toluene under an N2 atmosphere for 30 minutes each.
Finally, the wafer was treated with toluene, toluene/dimethyl sulphoxide (DMSO) and DMSO in an ultrasound bath for 1 minute each tLme. This gave a homogeneous hydrophobic surface.
Le A 27 700 _ 34 _ 20'1L9~702 Exam~le 9 Preparation of a support having a monomolecular interlayer according to Figure lB
The quartz glass or Si wafer was treated according to Example 8. This wafer which then contained ionisable amino groups on the surface was treated with a solution of 4 to 5 mg of (5), 0.3 ml of 0.1 N HCl, 1.7 ml of H2O
and 8 ml of DMSO at 0C for 20 minutes, during which the negatively charged anions (5) in ~he solution were adsorbed at the positively charged surface of the wafer with salt formation of the type of ammonium sulphate. The wafer was then first treated in ice-cold H2O and twice in H2O at room temperature for 20 seconds each time. This wafer having a monomolecular interlayer was made available to the further preparation of multilayer systems.
Exam~le 10 Preparation of a support having a polymer interlayer according to Figure 2 To this end, the quartz glass or Si wafer was treated according to Example 8. This wafer which then contained ionisable amino groups on the surface was treated with a solution of 20 mg of polystyrene polysulphonic acid sodium salt (9), 0.3 ml of 0.1 N HCl and 9.7 ml of HzO at room temperature for 20 minutes, during which the negatively charged anions (9) in the solution were adsorbed at the positively charged surface of the wafer with salt formation on the type of ammonium sulphate.
Le A 27 700 - 35 -20497~
This wafer having a polymer interlayer was made available to the further preparation of multilayer systems.
Example 11: Preparation of a physisorbed monomolecular multilayer on the monomolecular and polymer interlayer according to Figure 3 and Figure 6 The supports prepared according to Example 9 and Example 10, i.e. the support having the monomolecular or polymer interlayer, were used.
The wafer was treated with a solution of 10 mg of (7) in 10 ml of H20 at room temperature for 20 minutes. This was followed by three rinsing operations in H20 at room temperature for 20 seconds each time. This wafer was then treated with a solution of 4 to 5 mg of (5), 2 ml of H20 and 8 ml of DMS0 at room temperature for 20 minutes. The wafer was then first treated in ice-cold H20 and twice in H20 at room temperature for 20 seconds each time. The multilayer was constructed by repeating these adsorption processes alternately with (5) or with (7).
Exam~le 12: Preparation of a physisorbed polymer multilayer on the monomolecular- and polymer interlayer according to Figure 4 and Figure 7 The cupport was prepurified and silanised, as described in detail in Example 8. The supports were then treated to Le A 27 700 - 36 -;~04~3~7~
give the stable charged surface according to Example 9 and Example 10. The wafer was first placed in a solution of 30 mg of the polymer ammonium salt (8) described above and 10 ml of H2O and treated therein at room temperature for 20 minutes. The wafer was then washed in 10 ml of H2O
at room temperature three times for 20 seconds each time.
The wafer was then placed in a solution of 30 mg of the polystyrene sulphonate (9) described and 10 ml of H2O and treated therein at room temperature for 20 minutes. The wafer was then treated three times in 10 ml of H2O at room temperature again for 20 seconds each time. The polymer multilayer was constructed by continuing this process in the manner described in Example 11.
Example 13: Preparation of an alternating multilayer comprising a monomolecular di-anion and the polymer ammonium salt described in the above scheme on the monomolecular and polymer interlayer according to Figure S
and Figure 8 The support was prepurified and silanised, such as was described in detail Ln Example 8. The supports were then treated to give the stable charged surface according to Example 9 and Example 10.
The wafer was first placed in a solution of 30 mg of the polymer ammonium salt (8) described in the above reaction scheme and 10 ml of H2O and treated therein at room Le A 27 700 - 37 _ 204970~
temperature for 20 minutes. The wafer was then washed in 10 ml of H2O at room temperature three times for 20 seconds each time. The wafer was then placed in a solution of 4 to 5 mg of (5), 2 ml of H20 and 8 ml of DMS0 and treated therein at room temperature for 20 minutes.
The wafer was then first treated in ice-cold HzO and twice in H2O at room temperature for 20 seconds each time.
The alternating multilayer was constructed by continuing this process in the manner described in Example 11 and Example 12.
Example 14: Preparation of ~-biotinylated poly-l-lysine (compound 8) Compound 8 was prepared by reaction of poly-l-lysine (SERVA, Nn = 50,000-100,000) with the activated biotin active ester (biotin N-hydroxysuccinimide BNHS). 50 mg (0.5 mmol) of poly-l-lysine and 30 mg (0.5 mmol) of triethylamine were initially introduced into a 100 ml flask and dissolved in 30 ml of methanol. 40 mg (0.024 mmol) of BNHS, dissolved in 10 ml of CHCl3/isopropanol ~1:1), were then slowly added dropwise to the reaction mixture, which was then heated to reflux for one hour with stirring and then stirred at room temperature overnight. The resulting yellowish precipitate was isolated by filtration. It was suspended in 30 ml of methanol, stirred under reflux for 20 minutes, and again cooled to room temperature. The solid was again separated off by filtration and washed in Le A 27 700 - 38 -204'3~7~)~
portions three times with 20 ml of methanol each time, again suspended in 10 ml of CHCl3/isopropanol (1:1), again stirred under reflux for 20 minutes and again cooled to room temperature. After filtering, the solid was washed in portions three times with 20 ml of CHCl3/isopropanol (1:1) each time. The residue thus isolated was dried under an oil pump vacuum, dissolved in a small amount of distilled water and freed from low-molecular-weight by-products by gel permeation chromatography. ~he pure colourless copolymer was obtained from an aqueous solution by freeze drying. The yield was 25~ of theory.
The biotinylated poly-l-lysine was characterised by IR
and NMR spectroscopy. According to lH NMR, the composition of the copolymer tl-lysine/Nc-biotinyllysine) is 1:1 (formulae shown in Figure 9).
Exam~le 15: Preparation of a physisorbed multilayer having a poly-l-lysine topcoat The support was prepurified and silanised, as described in detail in Example 8. The support was then provided according to Example 9 with a negative surface by adsorption of the low-molecular-weight dianion.
The wafer was treated at room temperature with a solution of 2 mg of poly-l-lysine in a mixture of 2.8 ml of H2O and 0.2 ml of 0.1 N HCl for 20 minutes. The wafer was then washed three times in 10 ml f H20 at room temperature for one minute each time (diagram in Figure 10, upper picture).
Le A 27 700 - 39 _ 2~ 7~3 Example 16: Prepara$ion of a physisorbed multilayer having a topcoat comprising biotinylated poly-l-lysine (compound 8) The support was prepurified and silanised, as described in detail in Example 8. The support was then provided according to Example 9 with a negative surface by adsorption of the low-molecular-weight dianion.
The wafer was treated at room temperature with a solution of 2.3 mg of the biotinylated poly-l-lysine prepared in Example 14 in a mixture of 2.8 ml of H2O and 0.2 ml of 0.1 N HCl for 20 minutes. $he wafer was then washed three times in 10 ml of H2O at room temperature for one minute each time (diagram in Fi~lre 10, lower picture).
Example 17: ~iospecific recognition reaction of a biotinylated support surface in comparison with a non-biotinylated support surface by means of fluorescence-labelled streptavidin The multilayer systems prepared in Example 15 and Example 16 were dipped simultaneously into a solution of 0.02 mg of streptavi~in labelled with fluorescein isothiocyanate in 4.0 ml of 0.15 M NaCl solution at room temperature.
After 20 minutes, both supports were washed three times in 10 ml of H2O at room temperature for one minute each time and then analysed by fluorescence microscopy and spectroscopy. The support prepared in Example 15 having Le A 27 700 - 40 -Z0~L9~702 a surface comprising pure poly-l-lysine showed very little fluorescence under the fluorescence microscope, which was due to a few adsorbed fluorescent particles.
The support prepared in Example 16 having a surface comprising biotinylated poly-l-lysine showed an evenly distributed very intensive fluorescence under the fluorescence microscope (diagram in Figure 11). The relative fluorescence intensity at the fluorescence maximum found for the support from Example 16 by fluorescence spectroscopy was 100 scale divisions. The support from Example 15 showed a relative fluorescenc~
intensity of 8 scale divisions.
The fluorescence spectrum for Example 17 is shown in Figure 12.
Le A 27 700 - 41 -
Claims (8)
1. A layer element applied to a support, comprising a) a modified support having an even surface, in which modification means the application of ions or ionisable compounds of the same charge over the entire area, and b) one or more layers made of organic materials which in each layer contain ions of the same charge, the ions of the first layer having the opposite charge of the modified support and in the case of several layers each further layer having again the opposite charge of the previous layer.
2. A process for the preparation of a layer element applied to a support, wherein i) a support having a flat surface is modified such that it carries ions or ionisable compounds of the same charge over the entire area, and ii) one or more layers made of organic materials, which in each layer have ions of the same charge, are applied from a solution of such organic materials to the modified support, the organic material for the first layer having ions of the opposite charge relative to the Le A 27 700 - 42 -charge of the ions of the modified support and, in the case of multiple layers, alternately further layers containing ions of the opposite charge in each case relative to the previous one are applied in the same manner as the first layer.
3. The layer element of claim 1, in which the modified support is selected from the group comprising - the metal surfaces covered with a single layer of thiol, in which the thiol carries a further ionic or ionisable functional group, - the supports treated with a silane and containing silicon, in which the silane carries an ionic or ionisable functional group, and - the polymers carrying ionic or ionisable functional groups on the surface as a result of polymer-analogous reaction.
4. The layer element of claim 1, in which the organic material is a monomeric substance having two ionic or ionisable functional groups of the same charge or polymers having a multiplicity of ionic or ionisable functional groups of the same charge (polyelectrolytes).
Le A 27 700 - 43 -
Le A 27 700 - 43 -
5. The layer element of claim 4, in which the two fuctional groups in the monomeric substances or the multiplicity of the functional groups in the polymers are in each case identical.
6. The layer element of claim 4, in which the monomeric substance is one of the formula ion-Z1-(-Y1-Z2-)a-X-Z3-Y2-Z4-ion (I) in which X represents -C?C-C?C, , , , , , , , , , , Le A 27 700 - 44 -,, ,, , , or in which the aromatic rings in these groups can be mono- to trisubstituted by methyl, fluorine or chlorine or can be hydrogenated to the cycloalkane, Y1 and Y2, independently of one another, represent -(-CH2-)q-, -(-Si(CH3)2-O-)q-, -(-CH=CH-)q- or -(C?C-)q-, Le A 27 700 - 45 -it being possible for the hydrogen atoms in these groups to be substituted in part or completely by methyl, fluorine or chlorine, Z1, Z2, Z3 and Z4, independently of one another, represent a single bond, -O-, -S-, -CO-, -SO-, -SO2-, -CO-O-, -O-CO-, =N-CO, -CO-N=, -NH- or -N(C1-C4-alkyl)-, ion represents a cation, or an anion or a group which can be ionised to the cation or the anion, m represents 0 or 1, preferably 1, n represents integral values from 0 to 7, o represents integral values from 1 to 3, p represents the value 1 or 2 and q represents integral values from 1 to 20.
7. The layer elements of claim 6, wherein X represents one of the groups , , , Le A 27 700 - 46 - , , .
8. The process of claim 2, wherein the solvent used for the preparation of the organic materials carrying functional groups is water or a mixture of water with a water-miscible, nonionic organic solvent.
Le A 27 700 - 47 -
Le A 27 700 - 47 -
Applications Claiming Priority (2)
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DE19904026978 DE4026978A1 (en) | 1990-08-25 | 1990-08-25 | Coated substrates for electro=optical applications, etc. |
DEP4026978.7 | 1990-08-25 |
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US (1) | US5208111A (en) |
EP (1) | EP0472990B1 (en) |
JP (1) | JP3293641B2 (en) |
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JPS5630609B2 (en) * | 1973-11-02 | 1981-07-16 | ||
FR2287754A1 (en) * | 1974-10-08 | 1976-05-07 | Commissariat Energie Atomique | DIELECTRIC MATERIAL WITH MONOMOLECULAR LAYERS AND CAPACITORS USING THIS MATERIAL |
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US5057339A (en) * | 1988-12-29 | 1991-10-15 | Matsushita Electric Industrial Co., Ltd. | Metallized polyacetylene-type or polyacene-type ultralong conjugated polymers and process for producing the same |
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1990
- 1990-08-25 DE DE19904026978 patent/DE4026978A1/en not_active Withdrawn
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1991
- 1991-08-12 EP EP19910113464 patent/EP0472990B1/en not_active Expired - Lifetime
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- 1991-08-15 US US07/745,572 patent/US5208111A/en not_active Expired - Fee Related
- 1991-08-20 JP JP23106791A patent/JP3293641B2/en not_active Expired - Fee Related
- 1991-08-22 CA CA 2049702 patent/CA2049702A1/en not_active Abandoned
- 1991-08-22 FI FI913973A patent/FI103981B1/en active
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US5208111A (en) | 1993-05-04 |
FI913973A0 (en) | 1991-08-22 |
FI913973A (en) | 1992-02-26 |
EP0472990A3 (en) | 1993-01-07 |
EP0472990A2 (en) | 1992-03-04 |
JP3293641B2 (en) | 2002-06-17 |
FI103981B1 (en) | 1999-10-29 |
DE59105840D1 (en) | 1995-08-03 |
JPH05154433A (en) | 1993-06-22 |
DE4026978A1 (en) | 1992-02-27 |
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