AU752230B2 - Hydrophilic polymer coatings on hydrophobic or hydrophobized surfaces for biotechnological applications - Google Patents
Hydrophilic polymer coatings on hydrophobic or hydrophobized surfaces for biotechnological applications Download PDFInfo
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- AU752230B2 AU752230B2 AU20544/99A AU2054499A AU752230B2 AU 752230 B2 AU752230 B2 AU 752230B2 AU 20544/99 A AU20544/99 A AU 20544/99A AU 2054499 A AU2054499 A AU 2054499A AU 752230 B2 AU752230 B2 AU 752230B2
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Links
- 238000000576 coating method Methods 0.000 title claims description 40
- 230000002209 hydrophobic effect Effects 0.000 title claims description 24
- 229920001477 hydrophilic polymer Polymers 0.000 title description 5
- 125000001165 hydrophobic group Chemical group 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 32
- 150000004676 glycans Chemical class 0.000 claims description 25
- 229920001282 polysaccharide Polymers 0.000 claims description 25
- 239000005017 polysaccharide Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- -1 4- vinylbenzyl groups Chemical group 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 229920002307 Dextran Polymers 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 230000003993 interaction Effects 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000005661 hydrophobic surface Effects 0.000 claims description 3
- 238000001042 affinity chromatography Methods 0.000 claims description 2
- 150000001356 alkyl thiols Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 16
- 239000000463 material Substances 0.000 description 7
- 238000007306 functionalization reaction Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 238000001243 protein synthesis Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000014616 translation Effects 0.000 description 2
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 102000007562 Serum Albumin Human genes 0.000 description 1
- 108010071390 Serum Albumin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
Landscapes
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Chemical & Material Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
HYDROPHILIC POLYMER COATINGS ON HYDROPHOBIC OR HYDROPHOBICIZED SURFACES FOR BIOTECHNOLOGICAL
USES
t The invention under consideration refers to coatings made of hydrophilic, neutral polymers with hydrophobic groups on hydrophobic or hydrophobicized surfaces and methods for their production. More precisely, the invention refers to coatings of the aforementioned type for biotechnological uses, which prevent a nonspecific adsorption of organic, in particular, biological material on the surfaces of apparatuses, for example, sensors. If plastic parts are used in apparatuses or sensors which come into contact with organic material, a modification of the surfaces is necessary to prevent nonspecific adsorption, which up to now has been time and cost intensive. Among other things, the methods described in the following are known for this purpose. Polymer surfaces can be hydrophilicized by plasma treatment Chem. Phys. 97:12835 (1993)). The surfaces are oxidized thereby, wherein hydroxy and carboxyl groups are formed. These surfaces do not have very defined functionalization and are not suitable for preventing nonspecific adsorption without further treatment. In Biomaterials 18:845 (1997), polystyrene Ssurfaces are functionalized with carboxyl groups, in that first an adsorption of a salt of undecenoic acid takes place, which is followed by an argon plasma treatment. A charged surface is formed hereby which is hydrophilic, but which tends once again to nonspecific adsorption via electrostatic interactions. Another treatment possibility consists in the adsorption of polyelectrolytes (Macromolecules 30:1752- 1757 (1997)) on oxidatively pretreated surfaces. Here also, charged surfaces with *the disadvantages described above are formed. The adsorption of polyelectrolytes can take place without a previous surface treatment Colloid Interface Sci.
183:18-25 (1996), Chem. Mater. 8:1575-1578 (1996), J. Chem. Phys. 99:13065- 13069 (1995)). In this way, however, a charged surface with its inherent disadvantages is also produced. Furthermore, the resistance of such systems, which are adsorbed exclusively via hydrophobic interactions, is very limited, in comparison to various solvents, and does not ensure their mechanical stability (Macromol. Chem. Phys. 198:3239 (1997)). With the previous methods used, such as the dextranization of surfaces (Biosensors and Bioelectronics 11:579 (1996) -,ournal of Biomedical Materials Research 18:953 (1984)) it was not possible to coat untreated plastic surfaces. Nor was it possible to completely dispense with organic solvents in the methods, which, however, is a matter of concern with respect to environmental incompatibility of the methods and moreover generates costs. In functionalization by means of epoxy groups (Journal of Biomedical Materials Research 18:953 (1984)), the polymer solutions used must also have a very high concentration in order to arrive at satisfactory results. However, this leads, on the one hand, to hard-to-handle solutions because of their high viscosity and, on the other hand, to an increase in costs. In surface modification with aminodextran and EDC (Biosensors and Bioelectronics 11:579 (1996)), expensive additional reagents are required and the coating must contain amino groups, whose capacity for electrostatic interaction represents an inherent disturbance source. The problem of the invention under consideration is to produce hydrophobic or hydrophobicized objects which are modified by a coating such as those made of plastics, glass, quartz, silicon, silver, or gold, which are essentially not subjected to a nonspecific adsorption of hydrophobic or charged substances.
Pure glass, quartz, silicon, silver, or gold surfaces are, in fact, not hydrophobic when they are completely clean, but have the tendency, for example, to adsorb any organic impurities in the room air and thus to become hydrophobic. The object is to prevent this nonspecific adsorption. In addition, a nonspecific charge interaction is also to be prevented by an appropriate coating with glass, quartz, and silicon surfaces. Another problem of the invention is to make available coatings of the aforementioned type, which can be further functionalized and thus are suitable for use in biotechnological apparatuses. Receptors of biosensors on an affinity basis (affinity sensors) must, for example, be modified in such a manner that only one specific substance is adsorbed selectively on them from a complex multicomponent system. The adsorbed substance quantity can be measured via surface plasmon resonance. In affinity chromatography, the active Separation medium must be conditioned in such away that only the substance to be analyzed is selectively bound, whereas nonspecific adsorption is suppressed as much as possible using the coating in accordance with the invention. During the measurement of very small material quantities to be analyzed, for example, in the microliter range and below, it is of the greatest importance that the material to be analyzed does not adhere to vessel walls and the inside of hoses and that 4 J dnificant fractions are lost in this way. It is therefore desired that the adsorption of the material to be analyzed is minimized. Thus, nonspecific adsorption can be suppressed in vessels and hoses which are lined with the coating in accordance with the invention. Furthermore, the coating in accordance with the invention can also be used as a matrix for solid phase syntheses, after further functionalization.
Another problem is to make available a method which makes possible the application of these coatings on hydrophobic or hydrophobicized surfaces in a simple and low-cost, but environmentally friendly manner, and which leads to mechanically stable coatings which are also stable with respect to various solvents. The aforementioned problems are solved by the coating of hydrophobic or hydrophobicized surfaces with hydrophilic, neutral polymers, which have hydrophobic groups. In particular, the invention under consideration makes available an object with a hydrophobic or hydrophobicized surface and a coating which is applied on it and is made of a polysaccharide which has hydrophobic groups. Furthermore, a method of the production of the object is made available which is characterized in that a hydrophobic surface of the object which is to be coated is immersed in a solution of a polysaccharide with hydrophobic groups or a glass, quartz, silicon, or gold surface which is to be coated, is first hydrophobicied and then immersed into the solution of the polysaccharide. The objects of the invention with the surface modified by the applied coating can be used as a biotechnological matrix or instrument or as a matrix for biochemical solid phase synthesis, for example, solid phase protein synthesis. A polysaccharide which has hydrophobic groups is used for the coating. A polysaccharide made of glucose units is preferred. Dextran, pullulan or inulin are more preferable; dextran is particularly preferred. The hydrophobic groups of the polysaccharide essentially make possible, by means of their hydrophobic characteristic, the adsorption on the surfaces to be functionalized, in that a predominant number of the hydrophobic groups in the polymer point to the hydrophobic or hydrophobicized surface and thus hydrophobic interactions arise between the hydrophobic groups and the surface. The polymer is therefore predominantly bound to the surface via hydrophobic interactions. The hydrophobic groups can be crosslinked.
Hydrophobic groups which can be crosslinked by irradiation, for example, with UV light, are more preferable. A particularly preferred hydrophobic group is the 4vinylbenzyl group which, for example, can be introduced into it via the partial fiiherification of 4-vinylbenzyl chloride with hydroxy groups of the polymer. It can be crosslinked by irradiation with UV light of the wavelength 254 nm. If the coating consists of dextran, 1 to 20% of the available hydroxyl groups can be preferably substituted with 4-vinylbenzyl groups. Figure 1 shows a preferred embodiment of a polysaccharide. The ratio of m to n varies from 5:1 to 20:1. R is selected from hydrogen and a hydrophobic group, for example, the 4-vinylbenzyl group, provided that at least one R is a hydrophobic group. The polysaccharide in Figure 1 is a statistical copolymer--that is, the sequence of the monomeric units is random. The coating in accordance with the invention can be applied on various surfaces, wherein a distinction is made between hydrophobic and hydrophobicized surfaces.
The hydrophobic surfaces may be surfaces of plastic, for example, polyethylene, "***polypropylene, polycarbonate (for example, Makrolon®) and thermoplastic olefin polymers of anamorphous structure (for example, Topas®). The hydrophobicized surfaces may be silver, gold, glass, quartz, or silicon surfaces. If we are dealing with glass, quartz, or silicon surfaces, then they are hydrophobicized that is, the surfaces are subjected to a hydrophobicizing treatment. This can, for example, be carried out with a polycation which has hydrophobic groups. Only after hydrophobicizing does the adsorption of the polysaccharide then take place.
Alternately, other methods can be used for the hydrophobicization, for example, a treatment with alkoxyalkylsilanes. They are, however, mostly more complicated and more tedious than the adsorption of a polycation with hydrophobic groups.
With silver or gold surfaces, a hydrophobicization can be attained by treatment with an alkyl thiol or with a negatively charged thiol, such as mercaptopropyl sulfonate, onto which, in turn, a polycation with hydrophobic groups can then be applied. Preferably, a polycation is used for the hydrophobicization, which can be crosslinked via the hydrophobic groups. The crosslinking is preferably brought about by radiation. The hydrophobic groups of the polycation are preferably 4vinylbenzyl groups. A particularly preferred embodiment of the polycation with hydrophobic groups is poly(methacrylic acid-(3-dimethylaminopropylamide)), which was quaternized 100% with 4-vinylbenzyl chloride. A crosslinking of the coating via the hydrophobic groups of the polysaccharide and a crosslinking of any crosslinkable polycations present via the hydrophobic groups increases both the mechanical stability and also the solvent resistance of the coating. If the crosslinking is brought about by radiation, then it is also possible to crosslink only -oartial regions of the coating and the polycation. For this purpose, radiationimpermeable masks are used which cover the region which is not to be crosslinked. In addition, a functionalization of the coating is possible both via the hydroxyl groups and also via the hydrophobic groups which are not crosslinked.
o: Some of the hydroxyl groups can, for example, be brought to reaction with S..bromoacetic acid, wherein carboxyl groups are introduced into the coating which can be subjected to esterification or amidation in turn. This procedure can be useful, in particular with solid phase protein synthesis. Moreover, thio groups can be introduced on the noncrosslinked 4-vinylbenzyl groups via radical reactions. In particular, the functionalized coatings can be used-for the production of biosensors or for other uses in diagnosis or in screening methods. For the production of the coated object whose coated surface is essentially not subjected to a nonspecific adsorption of hydrophobic or charged substances, the hydrophobic or hydrophobicized surface of the object is merely immersed into a solution of a polysaccharide with hydrophobic groups. Preferably, it is an aqueous solution. The immersion time can be between 8 and 48 h and is, typically ca. 24 h. The method can be carried out in a temperature range of 1 to 50°C, preferably at room temperature. The concentration of the polysaccharide in the solution varies from 0.001 to 0.1 mol-L- 1 preferably from 0.01 to 0.05 mol-L 1 and, 0.02 mol-L- 1 is particularly preferred. If the polysaccharide contains crosslinkable hydrophobic groups, then a coating preferably follows wherein the groups are crosslinked and thus the mechanical stability of the coatings is increased. The type of surfaces to be used and the polysaccharide were already described in detail above. As additional investigations showed, this simple method is suitable for the application of the coating in accordance with the invention not only for polysaccharides, but very generally for neutral hydrophilic polymers with hydrophobic groups. The invention under consideration is thus to make available a method for the production of a coating which is essentially not subjected to nonspecific adsorption of hydrophobic substances, on a surface of an object which is characterized in that the surface, optionally after a previous hydrophobicization, is immersed in a solution of a neutral hydrophilic polymer with hydrophobic groups. The neutral hydrophilic polymer preferably refers to polymers with hydroxy or polyoxyalkylene groups. The hydrophobic groups and their preferred embodiments are those previously described. More preferred polymers with hydroxy groups are polysaccharides of the type described above. The type of polymers with polyoxyalkylene groups is not particularly limited. For example, polyalkylene derivatives_ such as polymethacrylic acid derivatives, for example, polymethacrylic amide or polymethacrylic acid ester, can be used. The polyoxyalkylene groups are optionally bound to the basic polymer structure via the carboxy or amide groups of the polymers as side chains. Polyoxyethylene groups are particularly well suited as polyoxyalkylene groups. Particularly preferred polymers are the compounds with the following formulas I, II, III, and IV.
0 0 0 oo S.
S.
S
.5
S
5.55 j* S S *IUSS S S S* 555.5 S S S S
S.
SSSS
S
S
5555
S
S. S S S
S.
5 0 0$
CH
NH
H-IC-N
I I)
S
S S
S.
*555
S
*SSS
S S
S
5S5~ 5555 N H
H
3
C-N
fl 0
(III)
(IV)
8 in which x:y varies from 20:1 to 5:1, and n varies from ca. 50 to ca.1000.
The invention is explained further by the following examples.
EXAMPLES
Reference example Synthesis of 4-vinylbenzyl-substituted dextran (VBD): 2.00 g Dextran (dextran T500 from Pharmacia, 37 mmol hydroxyl groups) are dissolved in a mixture of mL water and 10 mL dimethyl sulfoxide and mixed with 0.384 g potassium hydroxide (6.74 mmoi). When these are dissolved, 1.029 g 4-vinylbenzyl chloride and 2 drops nitrobenzene are added. The mixture is stirred at room temperature for 4 days. Subsequently, the polymer is precipitated in 400 mL acetone, wherein the work must be carried out with the exclusion of light.
Yield: 2.04 g (98%) *HNMR specrum 1 H-NMR spectrum (D 2 0): 0 0
U
0* 0* 0d r,u v xy= 181 CY -1 b c I H.o e
HO
I OH I t- x 6 [ppm]: 7.55 7.25 Harom), 6.85 6.65 Ha), 5.8 Hc), 5.3 Hb), 4.92 (He), 4.55 (Hd, partially masked by HDO), 4.2-3.3 (several m, H atoms of the polysaccharide backbone) Th sequence of the monomeric units is random; therefore it is a statistical :c lymer. The functionalization with the hydrophobic group is not carried out ."i exclusively on the 4-positions of the saccharide units, but rather, more or less statistically on all available hydroxyl groups.
*6 Example 1 .i Coating of plastics. In the first step, the plastic surface to be coated is cleaned by immersion in concentrated sulfuric acid for ca. 30 sec. Afterwards, rinsing is carried out with demineralized water three times, and subsequently the plastic is immersed in an aqueous solution VBD (2 x 10 2 mol-L-1) for 24 h. Afterwards, rinsing with demineralized water is carried out three times. Then, the photo crosslinking of the applied layer is undertaken by UV radiation at 254 nm for sec. Figure 2 shows UV spectra of a layer of the photoreactive polymer on •Topas®. The success of the photoreaction is documented by the decline of the absorption at 254 nm (broken-line measurement curve). Comparative measurements of nonspecific adsorption processes were carried out with a confocal microscope. The surface is hereby brought into contact with a solution of a fluorescence-label protein. With the aid of a microscope, the protein concentration is recorded as a function of the distance from the surface, in that the fluorescent intensity is determined in the individual focal plane. An almost uniform brightness profile is obtained as a function of the distance from the surface. This i: indicates that nonspecific adsorption does not take place on the functionalized surface. The surface depicted on the left in Figure 3 represents the concentration profile of a 500 nm fluorescence-label beef serum albumin (BSA-Texas Red) solution, on a coated Topas@ surface, recorded with a confocal microscope, wherein light areas correspond to BSA concentrations. To the right in Figure 3, the uncoated reference surface is depicted. The vertical area depicted corresponds to approximately 2 pm.
Example 2 Coating of silver, gold, glass, quartz, or silver surfaces. The surfaces are cleaned according to generally common methods (Ber. Bunsenges. Phys. Chem. 100:1033 (1996), Journal of Biomedical Materials Research 18:953 (1984)). The cleaned old or silver surfaces are then immersed for ca. 12 h in an aqueous 10 mercaptopropylsulfonate solution (2 x 10- 2 mol.L') and subsequently placed in a solution (2 x 10- 2 mol.L of poly(methacrylic acid-(3-dimethylaminopropylamide)), which was quaterized 100% with 4-vinylbenzyl chloride for min. Without previously treating with the mercaptopropylsulfonate solution, the cleaned glass, quartz, or silicon surfaces are placed in a solution (2 x 2 mol.L-1 of poly(methacrylic acid-3dimethylaminopropylamide)), which was quaternized 100% with 4-vinylbenzyl chloride for 20 min. After rinsing three times with an alytically pure water, the material is immersed in an aqueous solution VBD (2 x 10- 2 mol.L 1 for 24 h. Subsequently, rinsing with demineralized water is carried out three times. Then, the photocrosslinking of the applied layers is undertaken by means of UV irradiation at 254 nm for 60 sec. Figure 4 shows the structural formula of poly(methacrylic acid-(3dimethylaminopropylamide)), quaternized with 4-vinylbenzyl chloride.
In this specification, except where the context requires otherwise, the words "comprise", "comprises", and "comprising" mean "include", "includes", and "including", respectively, ie when the invention is described or defined as comprising specified features, various embodiments of the same invention may also include additional features.
H:\Shonal\Keep\Speci\20544-99 Speci 4/07/02
Claims (24)
1. Object with a hydrophobic or hydrophobicized surface and a coating made of a polysaccharide, which has hydrophobic groups applied on the surface, wherein the coating is crosslinked by radiation via the hydrophobic groups.
2. Object according to Claim 1, characterized in that the polysaccharide is bound to the surface via hydrophobic interactions.
3. Object according to one of Claims 1 or 2, characterized in that the polysaccharide is a dextran with 15 hydrophobic groups.
4. Object according to one of Claims 1 to 3, characterized in that the hydrophobic groups are 4- vinylbenzyl groups. "o
5. Object according to one of Claims 1 to 4, S" characterized in that the coating is made of a dextran in which 1 to 20% of the available hydroxyl groups are substituted with 4-vinylbenzyl groups.
6. Object according to one of Claims 1 to characterized in that the surface is made of a hydrophobic plastic.
7. Object according to one of Claims 1 to characterized in that the surface comprises glass, quartz, silicon, silver, or gold and is hydrophobicized before the Aapplication of the polysaccharide. H:\Shona1\Keep\Speci\20544-99 Speci 4/07/02 12
8. Object according to Claim 7, characterized in that the hydrophobicization of glass, quartz, or silicon surfaces is carried out by treatment with a polycation which has hydrophobic groups.
9. Object according to Claim 7, characterized in that the hydrophobicization of silver or gold surfaces is carried out by treatment with an alkyl thiol or with a negatively charged thiol on which a polycation with hydrophobic groups is then applied.
Object according to one of Claims 8 or 9, characterized in that the polycation is crosslinked via 15 the hydrophobic groups.
11. Object according to Claim 10, characterized in that the crosslinking is brought about by radiation. 20
12. Object according to one of Claims 8 to 11, characterized in that the hydrophobic groups are 4- vinylbenzyl groups.
13. Object according to one of Claims 8 to 12, characterized in that the polycation with hydrophobic groups is poly(methacrylic acid-3- dimethylaminopropylamide), which was quaternized, 100% with 4-vinylbenzyl chloride.
14. Object according to one of Claims 1 to 13, characterized in that the coating and optionally any crosslinkable polycation present is crosslinked in partial areas or on the entire surface.
H:\Shona1\Keep\Speci\20544-99 Speci 4/07/02 13 Object according to one of Claims 1 to 14, characterized in that some of the hydroxyl groups of the coating are functionalized.
16. Method for the production of a coating which is essentially not subjected to a non specific adsorption of hydrophobic or charged substances on a surface of an object, characterized in that the surface, optionally after a previous hydrophobicization, is immersed in a solution of polysaccharide with hydrophobic groups and subsequently the coating is crosslinked by radiation via hydrophobic groups. 15
17. Method according to Claim 16 for the production of a coated object according to one of Claims 1 to 14, charaeterized in that a hydrophobic surface of the object to be coated is immersed in a solution of a polysaccharide with hydrophobic groups, or a glass, quartz, silicon, 20 silver, or gold surface to be coated is first hydrophobicized and is subsequently immersed in the solution of the polysaccharide.
18. Method according to one of Claims 16 or 17, characterized in that the solution is an aqueous solution.
19. Method according to one of Claims 16 to 18, characterized in that any crosslinkable groups in the coating obtained are crosslinked in partial areas or on the entire surface. Use of an object according to one of Claims 1 to T as a biotechnological matrix or instrument.
H:\Shonal\Keep\Speci\20544-99 Speci 4/07/02 14
21.- Use of an object according to one of Claims 1 to as a matrix for the biochemical solid phase synthesis.
22. Use of an object according to one of Claims 1 to as a affinity sensor.
23. Use of an object according to one of Claims 1 to as an active separation medium in affinity chromatography in which x y varies from 20:1 to 5:1, and n varies from ca. 50 to ca. 1000.
24. Objects with a hydrophobic or hydrophobicized surface and a coating made of a polysaccharide, uses of 15 said objects or methods for the production of said coating, substantially as hereinbefore described with reference to the examples and/or drawings. 20 Dated this 4 t h day of July 2002 BIOTUL AG By their Patent Attorneys o GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia H,\Shona1\Keep\Speci\20544-99 Speci 4/07/02
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19756193 | 1997-12-17 | ||
| DE19756193A DE19756193A1 (en) | 1997-12-17 | 1997-12-17 | Hydrophilic polymer coatings on hydrophobic or hydrophobized surfaces for biotechnological applications |
| PCT/EP1998/008308 WO1999031189A1 (en) | 1997-12-17 | 1998-12-17 | Hydrophilic polymer coatings on hydrophobic or hydrophobized surfaces for biotechnological applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2054499A AU2054499A (en) | 1999-07-05 |
| AU752230B2 true AU752230B2 (en) | 2002-09-12 |
Family
ID=7852314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU20544/99A Ceased AU752230B2 (en) | 1997-12-17 | 1998-12-17 | Hydrophilic polymer coatings on hydrophobic or hydrophobized surfaces for biotechnological applications |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1098940B1 (en) |
| AU (1) | AU752230B2 (en) |
| DE (2) | DE19756193A1 (en) |
| WO (1) | WO1999031189A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314627C (en) * | 2005-11-29 | 2007-05-09 | 贵阳中化开磷化肥有限公司 | A kind of wrapping and cooling method of diammonium phosphate product |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2371304A (en) * | 2001-01-16 | 2002-07-24 | Suisse Electronique Microtech | Surface passivation of organic polymers and elastomers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0305346A1 (en) * | 1987-08-26 | 1989-03-01 | Astra Tech Aktiebolag | Articles exhibiting a blood-compatible surface layer and process for providing articles with such a surface layer |
| WO1994011411A1 (en) * | 1992-11-19 | 1994-05-26 | Case Western Reserve University | Nonthrombogenic implant surfaces |
| JPH08259470A (en) * | 1995-12-27 | 1996-10-08 | Nakarai Tesuku Kk | Reagent for optical resolution |
-
1997
- 1997-12-17 DE DE19756193A patent/DE19756193A1/en not_active Ceased
-
1998
- 1998-12-17 EP EP98965281A patent/EP1098940B1/en not_active Expired - Lifetime
- 1998-12-17 DE DE59805458T patent/DE59805458D1/en not_active Expired - Fee Related
- 1998-12-17 WO PCT/EP1998/008308 patent/WO1999031189A1/en active IP Right Grant
- 1998-12-17 AU AU20544/99A patent/AU752230B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0305346A1 (en) * | 1987-08-26 | 1989-03-01 | Astra Tech Aktiebolag | Articles exhibiting a blood-compatible surface layer and process for providing articles with such a surface layer |
| WO1994011411A1 (en) * | 1992-11-19 | 1994-05-26 | Case Western Reserve University | Nonthrombogenic implant surfaces |
| JPH08259470A (en) * | 1995-12-27 | 1996-10-08 | Nakarai Tesuku Kk | Reagent for optical resolution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314627C (en) * | 2005-11-29 | 2007-05-09 | 贵阳中化开磷化肥有限公司 | A kind of wrapping and cooling method of diammonium phosphate product |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19756193A1 (en) | 1999-07-01 |
| DE59805458D1 (en) | 2002-10-10 |
| EP1098940B1 (en) | 2002-09-04 |
| AU2054499A (en) | 1999-07-05 |
| WO1999031189A1 (en) | 1999-06-24 |
| EP1098940A1 (en) | 2001-05-16 |
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