TWI330657B - Super-low fouling carboxybetaine materials and related methods - Google Patents

Description

!33〇657 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a sulfobetaine and a slow-sweet sweetness adhered to an ultra-low biomolecule

A method for preparing a surface of a base and a sulfhydryl beet test material, and a device having an ultra-low biomolecule adhesion surface. [Prior Art] The surface resistance t〇pr〇tdn ads〇rpti〇n is very important in many applications. For example, it can be applied to hull coating, implanted biomaterials, biomedical linings and organisms. System II, biological separation and secret transfer. For example, the ship's biofouling can cause problems including propulsion fuel loss due to increased drag and the reduction in ship speed and capacity. Many hydrophilic surfaces reduce protein adsorption. However, this silk is often used to prevent unwanted cells, bacteria or other micro-organisms. That is, the presence of a small amount of egg on the silk surface can also cause unwanted dirt adhesion and proliferation. For example, in order to exhibit good blood compatibility, the adsorption of retinoin is less than 5_1 ng/cm2 to inhibit platelet adhesion, and the surface or material to which the substance adheres is environmentally friendly, lacquer, and has excellent compatibility. Material, to some applications f to super masculine molecules _ surface. The non-polluting material ship makes it impossible for the surface coated with the material to be used for the eggs. The development of anti-egg (4) and anti-cell/micro-vibrators is very important. 'Anti-fouling or non-polluting marine oils and bio-sensing anti-fouling coatings with high specificity are unconventional for tributyltin (TBT) oil-sea estuary and dock low water exchange area, the best protection for ships Stained paint. With the increase in the number of TBTs in the TBT in particular, for example, coastal, 'TBT antifouling coatings have been included in the target marine biological effects, 1330657 US is restricted. The anti-stain paints on the market today are mainly composed of tin-free biocides such as copper particles or cuprous oxide. Because these paints filter out copper into the water, and these biocides are harmful to the marine environment, their use is highly limited. Non-toxic decontaminants (f〇uling_rdease) of oxane and fluorinated coatings developed in this case. However, these coatings are only effective for high speed moving yarns. However, the dirt coat is easy to produce on the static (four) structure, or on the slow movement of the sea towel near the land, _ the application of these faces

Restricted. There is still a need for environmentally friendly, non-polluting coatings that prevent microbes from adhering to them. Various polymers have been used as biocompatible materials in biomedical applications. In the absence of a few alternatives, it is considered to be “non-polluting material” ultra-low biomolecular adhesion material'. Polyethylene glycol (PEG) materials are generally used to make (4) non-polluting materials. The surface modification of PEG or oligoethylene glycol (coffee) has been discriminated against non-specific protein absorption. It is believed that lang repulsive efficacies are a cause of PEG polymers against protein adsorption. The study of self-assembled m〇n〇layers (SAMs) is obvious, if the surface is resistant and resistant; the white matter absorbs _ ability, the financial needs to have the age of the shot, and surrounds The water layer that is closely combined with dereliction of duty is mainly responsible for strong hydration repulsion. However, the contact or defamation group can rapidly auto-oxidize, especially in the presence of oxygen and transition metal ions. The biochemical-related solution contains transition metal ions. In addition, the grafted PEG brush polymer showed anti-protein resistance at room temperature, and the extension was lost on the 35th _(10) repellent. Therefore, the dirt (four) except for it is meaningful. A choline (PC)-based polymer or surface has been shown to reduce protein uptake by 1330657^. They are considered biomimetic antifouling materials because they contain a phosphorylcholine head group found in the outer layer of the cell membrane. Much of the work involved in phosphorylcholine-based materials. On the side of the chain of methacryloxyethylphosphocholine (tearing (:)-type copolymers, such as methacrylic acid oxime Copolymer of oxyethylphosphocholine and n-butyl methacrylate (BMA). Commercially, mpc-based copolymers have been used in contact lenses. Another method is to form phosphorylcholine-capped self-assembly on gold. Monolayer. The methyl-terminated self-assembled monolayer has been reported to have a low adsorption of fibrinogen of 18% of the monolayer. The hydration of phosphorylcholine materials is also considered to be the cause of hindering protein adsorption repair. However, the phosphate group is sensitive to the hydrolysis reaction, and the phosphorylcholine monomer such as 2-methacryloxyethylphosphocholine is sensitive to humidity and thus inconvenient to synthesize and handle. Therefore, we hope to develop phosphoric acid in addition to A new material other than choline for applications requiring long-term material stability. Similar to phosphorylcholine polymers, 'sulfobetaine polymers are polybetaine polymers in which cationic and anionic groups are present. All of them are on the same monomer residue. Compared with MPC, sulfobetaine methacrylate (SBMA) is easier to synthesize and process. However, the anti-fouling ability of sulphur-based acryl-based vinegar polymer is It is considered to be lower than the bismuth phthalocyanine polymer because most of the previous studies on the county sweet thiol acrylate polymer focused on their copolymers with other hydrophobic monomers in order to test the sulfo bene methacrylic acid. The vinegar is attached to the substrate or provides mechanical strength, while the potential to test the sulphur beet as a non-contaminating or biocompatible material is underestimated. Due to the excellent mechanical month b of segmented polyurethanes (SPU) , thus making it a widely used biomaterial, especially for use in cardiovascular devices. - Series of studies report by surface grafting, poly blending, or interpenetrating polymer (interpenetratingp) 〇lymer 7 1330657 networks, IPNs), can improve the biocompatibility of interstage polyesters with ]UPC polymers. Ishihara and colleagues conducted extensive research on MPC/inter-segment polyurethane films. • Compared with the original inter-segment polyurethane, the MPC/inter-block polyurethane film forms a stable '乂 network structure' and effectively reduces platelet adhesion. . See Morimoto, K. et al. 'Biomaterials 23:4881-87, 2002; Morimoto, K. et al., Biomaterials 25:5353-61, 2004. Because MPC monomers are sensitive to humidity, it is desirable to develop new interstage polyurethanes with ultra-low biomolecular adhesion properties other than MPC/inter-segment polyurethane films. • There is therefore a need for ultra-low biomolecular adhesion materials. Ultra-low biomolecular adhesion materials can be used to prepare ultra-low biomolecular adhesion surfaces for hulls, implantable biomaterials, biomedical diagnostic sensors, and drug delivery coatings. The object of the present invention will be explained below. SUMMARY OF THE INVENTION The present invention provides an ultra-low biomolecule-attached sulfobetaine and carboxyl beet test material; an ultra-low biomolecule adhesion surface and preparation of an ultra-low biomolecule-attached yellow-based beet test and an enemy beet test a method of surface; and a farm with an ultra-low biomolecule adhesion surface. The square Φ, the present invention provides a substrate coated with a continuous beet test or a tick beet test material. On the surface of the county, there is a county sweet or reduced beet test. The silk surface has no defects greater than about i nm2, and the adsorption of fibrinogen is less than about 30 ng/cm2. In one embodiment, the surface has a fibrinogen adsorption system of less than about 1 Or^g/cm2. In one embodiment, the surface fibrinogen adsorption system is less than about $ ng/cm. In one embodiment, the surface fibrinogen adsorption system is below the contact ng/cm ° 1330657. In one embodiment, the sulfobetaine material is polysulfo sweetener. The sulfobetaine material may be derived from one or more selected from the group consisting of sulfobetaine acrylates, sulfobetaine acrylamides, ore based beetyl compounds, sulphur beet epoxides, and mixtures thereof Body preparation. In one embodiment, the beet test material is a polyphenol beet test. The mercapto betain base material can be prepared from one or more monomers selected from the group consisting of carboxybetaine acrylate, carboxybetaine acrylamide, vinyl beet vinyl compound, rhodamine ben oxide, and mixtures thereof. In one embodiment, the sulfobetaine material is a two-block copolymer comprising a polysulfobetaine. In one embodiment, the diblock copolymer comprises polypropylene oxide. In one embodiment, the sulfobetaine material is an interpenetrating network polymer. In one embodiment, the carboxybetaine material is an interpenetrating network polymer. The interpenetrating network polymer may comprise a polymer selected from the group consisting of polyurethane, oxalate, polyester, polyethylene, and polyamidamine. In one embodiment, the sucrose beet test material is a polymer blench comprising at least one polysulfone beet test or poly phthalocyanine test. In another aspect, the invention provides a surface coated with sulfobetaine Or a substrate of a carboxyl beet polymer, and the polymer is attached to a monolayer covalently conjugated to the surface. In one embodiment, the sulfobetaine or carboxybetaine polymer is covalently bonded. Connected to a single layer. In one embodiment, the single layer is a self-assembled monolayer. In one embodiment, the polymer is a polysulfobetaine. In another embodiment, the polymer is a polycarboxybetaine. In embodiments, the surface of the substrate comprises a sulfobetaine or a carboxybetaine polymer' and the sulfobetaine or carboxybetaine polymer is covalently bonded to a fixed compound that forms a monolayer on the surface. 9 A In another aspect, the present invention provides a crosslinked polymer hydrogel. In one embodiment, the 'keng gum is a crosslinked copolysaccharide hydrogel. In another embodiment , hydrogel is cross-linked poly-sweet beet In still another aspect, the present invention provides a method of preparing an ultra low biomolecular adhesion surface. In one embodiment, the method comprises (4) forming a free radical initiator capped monolayer on a surface of the substrate; and (b) The monomer is polymerized on a single layer of a free radical initiator capping. The monomer is a sucrose beet test or a sulphur based beet test. The monomer may be selected from the group consisting of sulfonate beet and acrylic acid. Beet test for gynecamine, succinyl betaine, sulphate, sulphate, and mixtures thereof, or may be selected from the group consisting of silk betaine propylene In the amine, the silk beet test compound, the hetero sweet grade Weilu, and the ageing embodiment thereof, the single layer is a self-assembled monolayer. In one embodiment, the method comprises (8) on the substrate Forming a base-terminated flat layer on the surface; (b) converting the reduced-end monolayer into a free-radical-terminated monolayer; and (C) polymerizing a monomer on the free radical initiator monolayer. The body may be a % based beet test or a rebel test as described above, and the single layer may be a self-assembled single In another embodiment, the method comprises (8) forming a silk-terminated monolayer on the surface of the substrate; treating the parent-capped monolayer with the first-type diblock copolymer; and (6) copolymerizing the second two-bond with the second The silk-terminated monolayer is treated. In one embodiment, the first-type diblock copolymer includes a [hydrophobic monomer] Γ 段 segment [[hydrophilic substance. [Epoxy group] [renewed betaine methacrylate] m copolymer. In one embodiment, the second diblock copolymer includes [hydrophobic monomer] Γ _ [hydrophilic monomer ] n copolymer. In one embodiment, the 'second diblock copolymer includes [epoxypyrene] 丨·years _[renering beet 1330657 test 3 methyl propyl _n copolymer. For these polymerizations物····, 1 is an integer of .1G to 3G, m is an integer from 10 to just, an integer of 岐(10), and m is greater than n. At the same time, the present invention provides a novel block copolymer for the preparation of low biomolecule adhesion surfaces. In other aspects, the present invention provides devices and materials having ultra-low biomolecular adhesion surfaces. The surface of the device and material includes a single layer of county beet test-based beet test material 'where the surface is not greater than about! Defects of dish 2, and wherein the surface has an adsorption to fibrinogen of less than about 30 ng/cm2. Representative devices and materials include implantable i1 raw materials, (4) glasses, live shivering, hulls, tissue scaffolds, implantable medical devices, touch, non-viral gene delivery vehicles, granules, and paints. In one embodiment the invention provides a hull coated with a paint comprising particles having an ultra-low biomolecule adhesion surface, wherein the surface comprises a layer of beet test or a rebel test material, wherein the surface is absent A defect greater than about [fine 2], and wherein the surface has a fibrinogen adsorption system of less than about 30 ng/cm2. [Embodiment] The present invention provides an ultra-low biomolecule_surface; a material for preparing an ultra-low biomolecule adhesion surface; a preparation method of a low biomolecule adhesion surface; and a method of adhering a surface using an ultra-low biomolecule. The ultra low biomolecular adhesion surface comprises a contiguous betaine and a carboxybetaine material. The present invention provides an ultra low biomolecular adhesion surface. The term "ultra-low biomolecular adhesion surface" as used herein refers to a surface that is resistant to protein adsorption. The anti-protein adsorption ultra-low biomolecules have a fine surface which is resistant to cell fineness, anti-fine g and other microbial adhesion, and formation of anti-biofilm. The ultra-low biomolecular adhesion surface of the present invention is treated with one or more materials and is ultra-low on both sides. The material that is treated to provide a fine surface for ultra low biomolecules includes zwitterionic materials. Zwitterionic materials are electrically neutral materials, which read positive and negative charges. Representative zwitterionic materials useful in the preparation of the ultra low biomolecules of the present invention include heterobetaine materials (sulfate negative and positive domain charge) and several base beet test material negative charge and positive k-charge. (4) 1 side 'The present invention provides a surface coated with a contiguous betaine or a few beet substrate. The surface of the substrate has a single layer (four) based beet test or Lin beet test material. The monolay er) is covered by the beet test or the slow-base sweet base material. The single layer can be a self-assembled monolayer. The advantage of the surface of the invention is that the density control of the dibasic coating of the polyglycoline or the silk beet test material is well characterized by the present invention. If the coating is well controlled, the surface can be low in bio-molecular viscosity. In this context, "good" means that the surface is coated with at least a completely single layer of coating nm2. It is qualitatively/defective (ie, no defect is greater than about 1 benefit, and at least 9 defects), definition In the case of a non-contaminating coating material (for example, a surface area, in general, when the defect of the surface material layer is related to the ability, the smaller the defect size, the better the density control of the present invention is __ pin attached surface C. There is no _A_ln trap in the surface which is lower than about lrnn2. U! The parental lack of the ultra-low biomolecule adhesion surface of the invention contains dense, or beet paint. The table of this turn* has chalky adsorption. Γ. Two protein-adsorbing-Nagan is called rugged molecular viscosity = 1330657 The weight of fibrinogen adsorbed per unit area on the surface. The fibrinogen adsorption system on the surface of the present invention is less than about 30 ng/cm2. In one embodiment, the surface has a fibrinogen adsorption system of less than about 10 ng/cm<2 > In one embodiment, the surface has a fibrinogen adsorption system of less than about 5 ng/cm<2>. In one embodiment, the surface fibrinogen The adsorption system is less than about 0.3 ng/cm2 °'. The present invention The fibrinogen adsorption system of the representative ultra-low biomolecule adhesion surface is less than about 30 ng/cm. In one embodiment, the adsorption of fibrinogen to the surface coated with the sulfobetaine material is less than about 30 ng/cm2. In another embodiment, on the surface of the coated fine-grained material, the adsorption system of the egg-origin is less than about IGng/on2. In another implementation, the material is coated with Wei beet. On the surface, its adsorption to fibrinogen is less than about 5 ng/cm2. In another embodiment, the adsorption of fibrinogen to the surface of the coating-based sweetener material is less than about 0.3 ng/ Cm2. In one embodiment, the adsorbent to fibrinogen is less than about 3 ng/cm2 on the surface coated with the reneke beet test material. In another embodiment, the carboxy beet is coated. On the surface of the alkali material, its adsorption to fibrinogen is less than about 10 ng/cm2. In another embodiment, on the surface coated with the county beet test material, the fiber is lightly self-made. In another embodiment In the adsorption of fibrinogen on the surface of the coated beet test material The system is less than about 0.3 ng/cm2. "In one embodiment, the contiguous beet test material is a poly gin beet test. The ore-based beet test material may be selected from - or a variety of vinegar vinegar selected from the group The base beet test propylene, the bribery test compound, the devil test epoxy dimer wood and a mixture thereof are prepared as a group of monomers. In one embodiment, the enemy beet test material is Polyester betaine. Mercapto sweet 1330657 Vegetable test material can be one or more selected from the group consisting of thiol beet, acrylic acid, ruthenium betaine acrylamide, carboxybetaine vinyl compound, carboxybetaine epoxide, and The mixture is prepared as a group of monomers. In one embodiment, the sulfobetaine material is a diblock copolymer comprising a polysulfobetaine. In one embodiment, the diblock copolymer comprises polyglycidazole. In one embodiment, the zeolitic beet test material is an interpenetrating network polymer. In one embodiment, the carboxybetaine material is an interpenetrating network polymer. The interpenetrating network polymer may comprise a polymer selected from the group consisting of polyurethane, terracotta, polyester, polyethylene, and polyamine. In one embodiment, the sulfobetaine material is a polymer blend comprising at least one polysulfo sweet or polydecyl sweet test. A variety of ultra low biomolecularly adhered surfaces can be provided using the materials and methods described herein. Representative surfaces that can be rendered ultra-low fouling include metal and metal oxide surfaces, ceramic surfaces, synthetic and natural, polymeric surfaces, glass surfaces, fiberglass surfaces, gutta percha, and granules. Silky natural polymer surfaces include prefectures, secrets, and other surfaces that are suitable for use in the hydration process. Representative carbon-based materials include carbon fibers, nanotubes, and bulky ball surfaces. Another aspect 'The present invention provides a material for preparing an ultra-low biomolecule adhesion surface. Suitable for the package of fine (four), # its burning office (for example, with the stove key lightly in the table shouting __ training surface), the neon surface has anti-egg attachment. In this paper, (4) Deflections ’ County’s two kinds of different structures or structures are different. The two or more compounds are mixed by a compound c S ) 1330657 to form a polymer. . Representative zwitterionic materials include polymers derived from zwitterionic monomers. Suitable materials for use in the present invention include sulfobetaine polymers and carboxybetaine polymers. The sulphate-based betaine polymer includes a sulfobetaine unit and can be formed by polymerizing a suitable reactive sucrose beet monomer. The county beet (tetra) compound includes a silk beet test unit and can be produced by polymerizing a suitable reactive carboxybetaine monomer. The surface of the present invention is coated with a continuous beet test and a carboxyl beet polymer material. The sulfobetaine polymer is grafted onto the initiator-terminated hydrophobic layer by atom transfer radical polymerization (Station 111 tmnsfer* mdieal polymerization, ATRP). The surface of the substrate is coated with an aqueous layer that is terminated by an initiator. The contiguous betaine monomer is then polymerized on the monolayer to form a sulfobetaine polymer coating on the surface of the substrate. The atom transfer free radical polymerization is initiated by a free radical initiator at the end of the monolayer. In one embodiment, the 'sulfobetaine polymer is grafted onto the initiator-terminated self-assembled monolayer by atom transfer radical polymerization. The surface of the substrate is coated with a self-assembled monolayer capped with a free radical initiator. The sulfobetaine monomer is then polymerized on the self-assembled monolayer to form a primate beet polymer coating on the surface of the substrate. The atom transfer free radical polymerization is initiated by a free radical initiator at the end of the self-assembled monolayer. The free-radically terminated self-assembled monolayer can be formed by a one-step (two-step) or two-step method. In a one-step process, a free-radical-terminated molecule is attached to the surface via covalent bonding or non-covalent bonding to form an initiator-terminated self-assembled monolayer. In a two-step process, a 15 1330 657 f-energy-terminated molecule is attached to the county via a covalent bond or a non-covalent bond to form a self-assembled monolayer of the capped end. Subsequently, the chemical reaction rfij converts the functional group __ self-assembled monolayer into an initiator-terminated self-assembled monolayer. A continuous beet polymer layer is formed on the surface by a polymerization of a beet monomer on a surface using a fixed initiator. The synthesis of the self-assembled monolayers of the representative initiator-terminated self-assembled layer and the capped end will be found in the actual _1. Grafting the sugar beet test polymer from the Dessert County to the surface of the trigger cap will be described in Example 2 and please refer to the second figure. Ultra low biomolecules - silk surface can be obtained after the well-controlled initiator formation and by the use of living polymerization techniques to grow polymer bonds from the surface of the substrate. Although the method of Dyna's method draws a specific group, it is understood that the surface of the substrate of the present invention may be various surfaces, and the self-assembled layer of the functional group = may be any functional group suitable for conversion to a radical initiator. The initiator-terminated self-assembled monolayer on the surface can be a variety of free radical initiators, and the coatings of the present invention can include a variety of base betaine polymers. Used on this date _ surface includes gold coated substrate surface and rough surface. In general, you can understand other surfaces and listen to the _ method as the hair _ surface. Two methods can be used to immobilize the initiator of the atom transfer radical polymerization to the substrate, as shown in the figure. One method is to prepare a thiol-terminated initiator, Λ, '; after the thiol is connected to the substrate (4) the self-assembled monolayer capped by the hair styling agent. Another method is to connect the base alcohol to the surface of the substrate to form a self-assembled monolayer which is terminated by the base, and the post-initiation of the weave is grafted to the substrate by the reaction of the base tooth with the base. On the surface. The beet test monomer on the surface of the self-assembled monolayer capped by a free radical initiator, N-(3-石黄propyl) gu (methyl propyl-oxyethyl) oxa-dimethyl ketone (S) 1330657 The test (SBMA) 'polymerization can be carried out at room temperature, and the reaction medium can be water or other polar solvent, and the molecular weight of the sulfone beet polymer product can be controlled. After polymerization of SBMA by atom transfer radical polymerization, the protein adsorption of the large towel field is reduced to below 0.02 nm (0.1% ml or 〇 3 ng/cm 2 of fibrinogen adsorption X, see Figure 5A). Surface plasma resonance technology (surface pias_

reS〇nance, SPR) was used to measure the adsorption of lysozyme and bovine serum albumin (BSA), and it was found to be similar to the adsorption of fibrinogen. Using the above method, it is possible to obtain an ultra-low biomolecular adhesion surface covered with a well-controlled poly(SBMA) brush. The poly(SBMA) grafted substrate is stable, and it can be placed in air or impregnated in water for more than one month at room temperature without damaging the poly(SBMA) coated surface. The fact that the substrate has ultra-low fouling properties has been confirmed. The amount of initiator self-assembled monolayer is important for subsequent surface polymerization and protein adsorption. The unbonded initiating dose on the surface affects the adsorption of fibrinogen (Fig. 3). Self-assembled monolayers of the initiator treated with a suitable solvent are necessary to obtain an ultra-low biomolecular axis surface. In the real-purpose towel, the self-assembled monolayer is prepared by carefully immersing the surface of the gold-coated substrate in a pure mercaptan in ethanol at room temperature, and the percentage of the complex bonding (4) and the concentration of the 5 deuterium solution are Zheng Er Xi 2 self-assembled monolayers. If the bow I hair agent self-assembled single layer only uses pure county bonding two molecules. Since the solvent is good for taking the two molecules (see the figure), if the initiator is washed with THF from the early layer of the electric charge, it can be completely removed. Atomic force microscopy (AFM) map, σ = ~ knife and region outside, gold on (four) (four) from Mdan County recorded a defect on the gold surface of the plume on the monolayer without unbonded two molecules (the first: second, its table is not c : s ) 17 After surface polymerization, the thickness of the polymer is too thick and accurate from the 12 nm ellipsometry. Figure 8 shows the surface plasma resonance wavelength shift difference for fibrinogen adsorption on two polymeric surfaces with different polymer thicknesses. The thicker polymer layer initiated by the surface with unbonded thiols will have some fibrinogen adsorption (wavelength shift 〇.9 nm), which corresponds to 6% ml of fibrinogen adsorption. The polymer layer initiated by the absence of a surface with unbonded thiols has only very low protein adsorption. Unbonded thiol molecules can initiate the formation of thick polymer films. It is generally believed that strong intermolecular interactions between zwitterionic groups via ionic contact between the interior of the chain and between the chains result in dehydration of the thick polymer film and thus adsorption of the protein. The sulfobee polymer brush grows fast. Figure 8 shows the polymer thickness as a function of polymerization time for different SBMA waves. The density of the reaction is 〇"μ, and the thickness of the polymer film rapidly increases at the beginning of the reaction, flattening at about 8 nm, at which point the reaction may terminate. The SBMA concentration of the reaction was 〇_3 M and the thickness was flattened at about 12 nm (Fig. 8). The higher concentration of the opposite age results in the formation of a thick and uniform (tetra) film on the fine. The long-term anti-lining can turn the gelation of the entire solution, which makes it difficult to measure the film thickness by surface photometry. Copper bromide pyridine (CuBr/BpY) complex is used to catalyze the "combination reaction. The eighth figure details fibrinogen as measured by spR on the surface of the poly(10) ancestral layer. This shows that the surface having a polymer film thickness of Η mn can be highly resistant to fibrinogen adsorption. - The substitute monomer used in the beet assay of the f county of the present invention comprises a sequel beet test methyl acrylate vinegar (SBMA), a sucrose beet test acryl vinegar, a scutellaria beet test acrylonitrile, a county Sweet and secret compound, miscellaneous epoxide, and /, "mystery, isocyanate, amino or silk (4) fine vegetables. 1330657 Representative polymerization method is atom transfer radical polymerization, reversible addition In-segment 4-strand transfer (RAFT) polymerization, and free radical polymerization. Any conventional free radical initiator used in the polymerization can be used to carry out the invention. Representative for standard thermal or photochemical free radical polymerization Sex initiators include benzammonium peroxide, 2,2, azo-bisindole methyl propyl carbonitrile, and benzoin decyl ether. Representative initiators for atom transfer radical polymerization include yards. Halogens, for example, derivatized isoindole (ΒΙΒβ). Representative initiators for reversible addition-splitting chain transfer polymerization (ie, free radical initiators with chain reversible reagents (CTA)) include sulfur storage sulfur Base compound. In a real _ towel, containing the base of sweetness The fraction (for example, poly(10)-based beet-tested f-acrylic acid vinegar) and the hydrophobic portion (for example, poly(glycidyl)) are defined by the two-block copolymer. On the surface of a single layer (such as a methyl (CH3)-capped self-assembled monolayer). In this embodiment, the hydrophobic polymeric link is attached to the hydrophobic surface and the hydrophilic heterobetaine is partially exposed to dissolution. The synthesis of the diblock copolymer of the well-defined betaine-containing betaine is illustrated in the actual _3, and please refer to the ninth figure. ...There is a surface suitable for the self-assembled monolayer, coated with other hydrophobic The surface of the material (or the aqueous surface of the claw) can be used to adhere the copolymer of the present invention. The adhesion surface of the post-parameter molecule is attached to the surface of the substrate by the diblock copolymer, and the surface of the branch is generally made. The surface of the substrate of π r may be various surfaces, and the surface-positive-capped self-assembly is a self-assembled monolayer of various hydrophobic groups, and the length of the diblock ugly hand of the present invention is determined by the hydrophilic portion of the sugar beet and Any part of the water-repellent part, and the diblock copolymer can be s ) 1330657 As shown in the ninth figure, the copolymerization of the diblock copolymer is a reversible redox step, via which the transition metal compound is sequentially attached to the non-functional monomer using a carrier as a functional atom. a macroinitiator of a base. In this synthesis, a poly(propylene oxide) having a macroinitiator (poly(propylene oxide)-Br) is obtained by reacting a monohydroxy group (propanol) with a 2-bromo group. The reaction of butyl bromide with bromine is carried out. For the polymerization of sulfobetaine methacrylate (SBMA) having a molecular weight of 11,200, the contiguous betaine monomer (SBMA) is based on propylene oxide and catalyst. The copolymer was obtained by polymerization in the presence of QiBr. The structure of the di-recorded copolymer formed by poly(epoxypropane) and poly(SBMA) was characterized by a magnetic resonance (NMR) spectrum. The typical epoxidized post-stage _ _ base beet test methyl acrylate 35 spectrum see the tenth figure. The clean gold-coated substrate was immersed in a solution of HS(CH2)8CH3 to form a methyl-terminated self-assembled monolayer on a gold-coated glass. The two-copolymer formed by the weaving (glycidyl) and the poly(supply betaine methyl (10)_) is dissolved on the surface of the substrate, and is washed with the buffer solution to remove the copolymer which is not adsorbed. In this example, the protein-based protein was adsorbed on the surface by a physical adsorption copolymer. The amount of protein adsorption is defined as the difference between the two baselines before and after protein adsorption. The tenth-figure shows a typical SPR-induced SPR induction map, followed by an in situ assessment of fibrinogen adsorption. The physical adsorption of the hydrophobic CHr self-assembled monolayer surface to the definition of the green diblock copolymer poly(glycidyl)-block-poly (renering beet methyl acrylate) was carried out. In order to control the surface accumulation density of the physically adsorbed copolymer, three different miscellaneous beet methacrylic acid lysate block copolymers were synthesized (referred to as propylene-propylene-segment-sequence beet methacrylic acid S) 2Q, ring Oxypropyl propylene 2. _ block - contiguous beet 曱 丙烯酸 acryl vinegar", and propylene cyanate 2. _ 段 segment · continued base beet test methyl acrylate vinegar 5.). The length of the bond of c S ) 20 1330657 is kept constant, and the chain length of poly(Ginebetaine thiol acrylate) is the monomer of sequential addition by atom transfer radical polymerization at ambient temperature. Control. The synthetic parameters and average molecular weights of the three poly(ethylene oxide) cascading-poly(trans-betaine thioglycolic acid vinegar) copolymers are summarized in Table 1.

Table 1, three kinds of poly(epoxypropanol XPPO)-block-poly(renering betaines methyl propylene vinegar) (P (SBMA) copolymer reaction conditions and average molecular weight solvent [SBMA] [PPOBr] reaction Time--(hr) Mi,gpc c MJMn 6490 1.232 11183 1.255 15114 1.353

ABC composition (DPn6) P〇20~SBMA20 PO20-SBMA35 P〇20-SBMASn (10 ml) (g) sterol 2.0 methanol 2.0 sterol 2.0 358.0 143.2 71.6 24 24 24 β initiator ratio: Cu(I)Br : bpy ratio is 1: l : 2 ΔDPn is the degree of polymerization. It is an average molecular weight, and Mw/Mn is the dispersibility of the degree of polymerization of the prepared copolymer.

The higher the chain length ratio of the poly(SBMA)/PP〇 when the poly(SBMA) chain is longer, the more asymmetric the structure of the two-block copolymer. The two-step reaction pathway (Fig. 9) provides a pp〇_block-poly(SBMA) copolymer with controlled molecular weight (from n) and polydispersity from =! 2 to 1.35). Low polydispersity means controlling excellent polymerization accuracy. Figure 12 shows that the three polymers having a molecular weight of 6500 to 15000 have low polydispersity. In the fifteenth graph, the copolymers A, B and C copolymers represent p〇2〇_block·δΒΜΑ2〇, ρ〇2, respectively. - Block-SBMA35 and ΡΟμ block-Sbma%. It is expected that the three SBMA-like block co-t species have different accumulation densities and protein adsorption behaviors. The amount of 21 1330657 adsorption of copolymers and proteins was obtained from SPR. .* The effect of the concentration of 0.005 to h^APPO-block-poly(SBMA) solution on the surface bulk density and the adsorption of the protein were determined. From the thirteenth figure, it can be seen that the 'extracted' protein adsorption system depends on the chemical nature and structure of the copolymer layer (ie SBMA surface stimuli and (SBMA) ZPPO ratio) and the SBMA surface density and ratio are determined by (8) PPQH poly( SBMA) is determined by the frontal touch (Cpp_part_) and (b) poly (SBMA) volume fraction (ν〇1_ ―). A PPO-SBMA diblock copolymer of higher f-poly-ββμα} at low Cpp〇_block-poly(SBMA) (eg, Cppo-grade poly{sbma} below 0.〇2 mg/mL) Protein adsorption is reduced due to higher SBMA surface coverage. Conversely, at higher (ship-to-face), protein adsorption on PPO-block-poly(SBMA) diblock copolymers with lower /^sbma} is rapidly reduced. For the lower molecular weight copolymer A, protein adsorption was very low (3 ng/cm2) when Cp_.__ was greater than 0.03 mg/ml. For the copolymer c and s, in the relatively 觅 range Cppo-block p. In the sputum, protein adsorption is maintained at a high level (2〇·3 ng/cm2). Although not intended to be limited by assumptions, it is generally believed that this is because larger φ WSBMA fragments create voids between themselves and thus do not adequately cover the surface, resulting in adsorption of proteins. The surface-accumulation density of PPO-block-poly(SBMA) plays an important role in surface anti-protein adsorption capacity. Figure 14 shows the spR subtraction of fibrinogen adsorbed on various PP〇_block_poly(SBMA) coatings (CPPO negative-poly(SBMA) = 1 .〇 mg/mi). Fibrinogen has a very low adsorption on the surface coated with copolymers A and B, and a higher adsorption on the surface coated with copolymer c. This is due to an increase in surface packing defects formed by the macromolecular size copolymer c. When the surface coated with copolymer c is backfilled with a smaller molecular weight copolymer A (see Figure 15), the adsorption of the protein is also 22 C S ) 1330657 ^ very low. According to the hybrid yarn, the higher lining of the lining of the lining of the higher numerator will result in a more vacant surface vacancy, and these cavities can be backfilled with a smaller molecular weight copolymer. Silk containing SBMA, if the surface is high density, the protein is ideal for adsorption. The adsorption of various proteins against the adsorption of various proteins can be further evaluated by measuring the adsorption of proteins (fibrinogen, BSA and lysozyme) on three different molecular weights (10) milk ~ (10) and vitamins 8 to 10.9). Copolymer. Figure 16 shows that the adsorption of all three proteins on copolymer A is less than 〇·25 nm (about 3.7 ng/cm2) ° For block copolymers, some of the representative monomers of sulfobetaine include sulfobetaine A. Acrylic vinegar (SBMA), sucrose beet, acrylic acid, sulphur beetamine, sulfobetaine vinyl compound, sulfobetaine epoxide, and others with hydroxyl, isocyanate A sulfobetaine compound of an amino group or a carboxyl group. Any hydrophobic polymer chain can be used as the hydrophobic portion of the copolymer of the present invention. Representative hydrophobic moieties include polyepoxypropylene (PPO), polymethacrylic acid vinegar, polyacrylic acid vinegar, polyacrylamide, polyester, polyether, polyurethane, and polyamine. In one embodiment, the preparation of a poly(SBMA) coating will be illustrated in Example 5. This example illustrates the preparation of polySBMA, which can be used alone or in standard paints to reduce biofouling or improve biocompatibility. The polymer was prepared by reacting SBMA with AIBN' followed by the addition of lauryl methacrylate. The product was filtered and dispersed in a weight of 99 g/L. The enzyme-binding immunosorbent assay (ELISA) showed a decrease in the adsorption of protein on the surface of the poly-SBMA coating by more than 8% (the results are shown in Figure 17). Marine biofouling analysis showed that the polySBMA coating significantly reduced the precipitation of marine microorganisms (see Figures 19 to 21). 23 1330657 Poly SBMA prepared by the method described in Example 5 in an epoxy-based paint can reduce biofouling. Table 2 lists the components of a representative formula. Table 2, representative poly coating waste formula

The polySBMA dispersion was polySBMA dispersed in diphenylbenzene at a concentration of 99 g/L, the epoxy resin was 70-80% epoxy resin solution, and Ti〇2, Fe2〇3 and carbon black were pigments. In this formulation, the 'additive is composed of an organic clay structuring agent) and a vermiculite thixotropic agent. The crosslinker is a polyamine which reacts with the epoxy resin at ambient temperature. A liquid, non-contaminating coating is applied to the epoxy primer substrate by brushing or spraying. Enzyme-bound immunosorbent measurements showed a significant decrease in fibrinogen adsorption and a 50% reduction in Helegan nematode deposition. Interpenetrating mesh 缉 厶 Another aspect The present invention provides an ultra low biomolecular adhesion surface coated with an interpenetrating network polymer (IpN). The term "interpenetrating network polymer" as used herein refers to a polymer comprising two or more network structures which are at least partially parental at the molecular level. (Interlace), but not bonded to each other by a covalent bond and cannot be separated unless the chemical bond is broken. In one embodiment, the interpenetrating network polymer containing the % based beet polymer is obtained by making the sulfobetaine The monomer is penetrated into the second material matrix and the monomer is polymerized. The second material may be the same as or different from the penetrating compound. The sulfobetaine polymer and the interstage polyurethane (SPU) A representative interpenetrating network polymer will be described in Example 6, and please refer to the third figure. An interpenetrating network polymer having anti-protein adsorption and high mechanical strength is crosslinked by The sulfobetaine thiol acrylate (SBMA) polymer is modified by modifying the interstage polyamine oxime. The SPU is used as a matrix component to enhance the mechanical strength of the interpenetrating network polymer film. Poly (SBMA) is used to reduce Protein adsorption of the network structure polymer film. As shown in the third figure, the SPU film was prepared by solvent evaporation method. Then, the SPU film was immersed in the SBMA monomer, 2-ethylhexyl acrylate (EHMA). In a culture solution of a monomer, a glycerol 1,3-diglycerolate diacrylate (GDGDA) crosslinking agent and a photoinitiator. SBMA is polymerized by photopolymerization by visible light irradiation to produce an interpenetrating network polymer. Membrane. Adjust the total concentration (or culture concentration) of the culture solution for best results. The SBMA monomer ratio (mol%) is defined as the number of SBMA monomer moles divided by the total number of SBMA and EHMA monomers in the culture solution. In this example, the SBMA monomer ratio is adjusted between 〇 and 100 mol% to optimize the preparation conditions of the interpenetrating network polymer, and the GDGDA is fixed at 1.0xl (T2m〇l/L. To eliminate side reactions, light The initiator (for example, camphorquinone and ethyl 4-(N,N-didecylamino)benzoate) is added to the culture solution under the protection of nitrogen in the dark. For photopolymerization, visible light (λ=4) 〇〇_5〇〇25 1330657 nm) illuminating the SPU film to form an interpenetrating network junction Polymer film. The interpenetrating network polymer film is then cleaned according to well-established post-treatment methods known to those skilled in the art to remove unreacted monomers. The chemical composition of the interpenetrating network polymer film The depth profile is determined by confocal Raman microscopy. The amount of protein adsorbed on the interpenetrating network polymer membrane is determined by enzyme-bound immunosorbent assay (ELISA). The process of interpenetrating network polymer can generally be It is divided into two stages. The first stage is related to the incubation time of the New Zealand. In this stage, the amount of poly(SBMA) diffused from the culture solution into the spu matrix is mainly controlled by the SPU swelling degree. The second phase is related to longer incubation times. The amount of poly(SBMA) in the 'SPU matrix at this stage is determined by the solubility of SBMA in the spu film. Therefore, it is expected that the solvent polarity plays a very important role in the preparation of the interpenetrating network polymer, and the solvent polarity has a trade-off (trade_〇ff) property. Initial incubation in a less polar solvent will result in higher spu swelling (or SBMA diffusion into the matrix or reduced protein adsorption). However, after long-term incubation, it will also reduce SBMA solubility in the SPU membrane (or reduce SBMA enrichment in the SPU matrix or higher protein adsorption). The culture solution should be capable of swelling the hydrophobic φ SPU and dissolving the hydrophilic poly(SBMA), requiring a suitable solvent polarity to obtain the most effective interpenetrating network polymer film. The amount of protein adsorbed on the interpenetrating network polymer film depends on the culture conditions, including the solvent polarity, the culture time, the SBMA monomer ratio, and the culture concentration. The interpenetrating network polymer prepared in a longer polarity culture time in a higher polarity mixed solvent has a very low protein adsorption, which means that the poly(SBMA) interpenetrating network is included when the distribution of the SBMA unit in the SPU film is well controlled. The structural polymer has high resistance to non-specific protein adsorption. The protein adsorption system on each of the prepared interpenetrating network polymer crucibles used poly 26 1330657 ethylene (ps) as a reference substrate and was evaluated by enzyme-bound immunosorbent assay. The twenty-second graph is a plot of protein adsorption for various samples relative to polystyrene. Referring to Figure 22, protein adsorption on the interpenetrating network polymer film is significantly reduced compared to PS or unmodified spu films. The human Fg adsorbed on the unmodified S PU membrane was 82% on the PS. Protein adsorption on interpenetrating network polymer membranes is similar to or even lower than poly(HEMA) hydrogels, while interpenetrating network polymer membranes have more properties than poly(HEMA) Good mechanical properties. The lowest protein-adsorbed interpenetrating network polymer membrane was obtained by culturing SPU membrane (TECOFLEX 60) in a solution containing 95v〇1% methanol and 5 vol% water for 24 hours at 2〇〇c, SBMA in solution. The percentage of monomeric moie is 7〇m〇i% ' and the culture concentration is 2 〇111〇丨. Poly (SBMA) hydrogels were also used for comparison. It can be seen that the protein shell adsorbed on poly(SBMA) is only 1.5%, indicating that poly(SBMA) can have high resistance to non-specific protein adsorption. The results show that the interpenetrating network polymer comprising poly(SBMA) and SPU has low protein adsorption while maintaining its mechanical strength. The anti-non-specific protein adsorption capacity of interpenetrating network polymers is strongly dependent on the polarity of the solvent used in their preparation. The anti-non-specific protein adsorption of the interpenetrating network polymer sample is determined by the balance between SH; the degree of swelling and the solubility of SBMA in the SPU film. After a long incubation period, the anti-non-specific protein adsorption of the interpenetrating network polymer is primarily determined by the solubility of SBMA in the SPU membrane. It is preferred to prepare a lower protein adsorbed interpenetrating network polymer sample in a more polar solvent. After swelling the SPU(R) by a higher polarity solvent containing highly polar SBMA during long incubation times, more SBMA can penetrate into the SPU membrane to form an SBMA-enriched region within the SPU matrix. For shorter incubation times, the reduction in protein adsorption on the interpenetrating network polymer is primarily determined by the degree of SPU swelling. The lower polar solvent swells the 27 &lt;S) SPU membrane more, while allowing more SBMA to diffuse into the membrane resulting in a reduction in initial protein adsorption. The effect of the solvent polarity on the protein absorption on the prepared interpenetrating polymer structure membrane. The main solution of the three-sided culture solution (the polarity is sequentially reduced) is used for research: methanol is greater than ethanol/ Sterol, the latter being larger than isopropanol/methanol. , as shown in Figure 23A, the interpenetrating network polymer film cultured in a higher polarity solvent (i.e., methanol) was observed after 24 hours compared to a lower polarity mixed solvent (i.e., ethanol).

Membranes prepared with /methanol and isopropanol/methanol), the former has less protein adsorption. It is generally believed that in the longer culture shots, the more sinister units can be partitioned into the SHJ membrane because of the better dissolution of the SBMA monomer in the polar solvent (methanol), resulting in SBMA-enrichment of the Qing matrix. The formation of the region thus provides better resistance to protein adsorption. The incubation time is long enough to achieve a balance between the swollen SPU membrane and the culture solution, resulting in higher SBma monomer distribution within the SPU membrane. Therefore, if the culture time is long, it is preferable to obtain the formation of the SPU film squeezing and enriching region in a higher polar environment to reduce protein absorption. This also explains why by adding a stronger polar solvent

(ie, 5 vd%·Prepared silk 峨 骑 合物 合物 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) In the succinct pure methanol, the clothing is tight. Because of the domain Linneng PU film, = pure water is not prepared for interpenetrating _ _ _ good hearing agent. A solvent containing % ν〇ι% A ==% water is clearly a good compromise between spu swell and s job solubility. , Yi 7 ^ SPU ^ on the turn _ change side system. The results show that the most traced B-transformation is different.) Kona is more rapid, teeth, and the swelling ratio (%) of the structural polymer in the preparation process towel is defined as the preparation of the 28 1330657 interpenetrating network structure fine and unchanged. Straightness between the SPU films (iv) Diameter of the film. It can be seen &amp;, when the SPU membrane is immersed in ethanol/methanol (or propylene glycol/intimidation solution for 2 hours, it can swell rapidly to the maximum. The spu membrane is also immersed in the methanol solution for 24 hours, but also obtained the job, however, This surface behavior is related to the reduction of protein adsorption. As shown in Fig. 23A, it is 'immersed in ethanol/nonanol (or isopropanol/methanol) solution compared with SPU membrane soaked in methanol solution. In the first 2 hours, the amount of protein adsorption decreased more rapidly. However, compared with the sample prepared in methanol solution, the interpenetrating network structure prepared in ethanol/alcohol (or isopropanol/information) solution The reduction in protein adsorption on the polymer sample is not apparent after 24 hours. Even if a less polar solvent (such as isopropanol) can quickly penetrate into the SPU matrix, isopropyl alcohol is enriched in the SPU membrane. The degree of solution is not good. This level indicates that the touch _ degree is important for making the sbma infiltrate into the SPU, and the SPU_^_ polar album plays an important role in the SPU matrix. After the higher polarity of the solvent can finally cause SBMA to infiltrate the SPU, but they are in the kinetics The spu membrane is slowed to swell. g) This is a suitable kiln with a towel lining as an interpenetrating network polymer to improve the kinetics of the interpenetrating network polymer process. A balance is reached between thermodynamics. The total concentration of the culture solution can also affect the dispersion of the SBMA unit within the SPU membrane. In this example, the concentration was varied between 0.1 and 3. Gm () l / L, and the adsorption of various interpenetrating network structures prepared at different culture concentrations was evaluated without protein adsorption. As shown in Fig. 24, protein f adsorption was effectively reduced when the concentration of Gmol/L was observed. For lower-wave cultures (less than 0.5 mol/L), the lack of SBMA in the interpenetrating network polymer film is higher in the polymer film (S &gt 29 1330657 Protein bribe. Trans-through mesh, Her film, green interpenetrating (greater than 2 G md / L) towel, interpenetrating network polymer film resistance to protein adsorption has not improved 'The behavior of the solvent in the highly concentrated culture solution containing highly charged SBMA has changed. As shown in Figure 25A, because in the case of the heart solution, less solvent molecules can be used to swell the SPU film and promote infiltration. In the spu film, compared with the interpenetrating network polymer film prepared from the 0.5 mol/L solution, the interpenetrating structure of the interpenetrating structure is obtained from the total concentration of 1 〇m〇l/L _ in the first hour. Reducing the adsorption of protein is slower. However, after 24 hours of culture, it is observed that the mol/L solution is more effective in reducing protein adsorption. In the preparation of interpenetrating network polymer, the change of the lysate and the change of the self-quality of the egg The weight gain is important for interpenetrating network structure polymerization (4) preparation process towel weight increase (%) The dry weight of the interpenetrating network structure prepared by the fixed material and the unmodified SPU is divided by the dry weight of the unmodified SPU film. From the twenty-fifth, it can be seen that the interpenetrating network structure is prepared. The swelling ratio, weight increase, and protein absorption of the film were clearly shown. The results show that the increase in swelling ratio and the weight increase in the twenty-fifth B chart correspond to a decrease in protein adsorption in the twenty-fifth with increasing culture time. The results also indicate that the monomer component actually diffuses the human spu film and polymerizes in the interpenetrating structure __ into the sbm^_ 畐 region. The twenty-sixth graph shows that the ratio of different SBMA monomers is in the 2 〇 culture solution. The effect of protein adsorption on the interpenetrating network polymer film, the incubation time is 1 mol / L. With the increase of the SBMA monomer ratio in the culture solution towel, the white matter absorption is low. When the molar ratio is When SBMA/E is 7:3, the protein absorption is less than the maximum. The results show that the culture solution with higher SBMA monomer ratio leads to more anti-protein adsorption polymerization in the interpenetrating network polymer film. 30 &lt; S ) 1330657 (SBMA) - enrichment area. The results also indicate that some methyl methacrylate ethyl hexyl vinegar (EHMA) units are included in the solution to increase the affinity between SPU and poly(SBMA). Therefore, it is important to optimally control the molar ratio of SBMA to EHMA for the dispersion of the SBMA_rich region in the spu film and the formation of an excellent interpenetrating network structure with very low protein adsorption. Confocal Raman spectroscopy is used to characterize interpenetrating network polymer films. A typical spectrum is shown in Figure 27, where the s_c chemical bond in poly(SBMA) is observed at a Raman shift of 605 cm 1 , which occurs on the surface of the interpenetrating network polymer film 0 and 20 The micron depth 'but does not appear in the unmodified spu film, which is why the t (SBMA) actually penetrates into the SPU film. As described above, the decrease in protein adsorption shows time-dependent behavior (Twenty-third A and twenty-fifth a), and there is a correlation between the swelling ratio and the change in weight and the change in protein adsorption (first ten) Figure 5B). For small molecule SBMA with 1M excitation, SBMA physical adsorption should occur quite rapidly. These facts and Raman spectroscopy show that SBMA is not simply adsorbed onto the surface of the SPU membrane but penetrates into the SPU matrix. Representative monomers for the preparation of the sulfobetaine polymer of the interpenetrating network polymer include succinyl betaine methacrylate (SBMA), zeal beet acrylate, reneke beet acrylamide, The beet beet test vinyl compound, the term beet test epoxide and other sulfobetaines having a hydroxyl group, an isocyanate group, an amino group or a carboxyl group. Representative substrates include polyurethanes, decanes, polyesters, polyethylenes, polyamines, and Teflon. Carboxyl Betaine Polymers In addition to sulfobetaine polymers, carboxybetaine polymers are also used to prepare ultra low biomolecular adhesion surfaces. 1330657 Mountain County? &lt;Combination of the domain is transferred to the hydrophobic layer of the initiator capping free silk reaction. The surface of the substrate is coated with an aqueous layer that is terminated by an initiator. Then, the substrate and the monomer are subjected to polymerization on the monolayer to form a confirmatory sweet layer on the surface of the substrate. The atom transfer free silk fission reaction is initiated by a free radical initiator at the end of the monolayer. In one embodiment, the present invention provides a coating material such as poly(carboxy bene) (i.e., poly(CBMA)) carboxybetaine polymer. In one method, the base 峨 甜菜 based beet polymer is grafted onto the fine surface by surface-initiated atom transfer free radical polymerization. In another method,

The double-acting test material for the sulfhydryl beet compound is a silk sweetener hydrogel. A representative non-staining-based sweetener polymerization with a reactive functionality (iv) preparation will be illustrated in Example 7, and see the fourth figure. The zwitterionic polycarboxybetaine material is obtained by grafting a polycarboxybetaine polymer onto a surface or by preparing a polycarboxy beet test hydrogel. Surfaces or hydrogels coated with polycarboxybetaine have high protein resistance or high cell adhesion. The surface of the ultra-low biomolecules adhering to the carboxybetaine can be obtained by controlled polymerization from the surface-grown polyphenol beet test polymer chain by living polymerization techniques. In this embodiment, the ultra-low biomolecule adhesion surface is grafted onto the substrate coated with the initiator by surface-initiated atom transfer radical polymerization. Made from the surface. Omega-decylundecyl bromide isobutyrate is synthesized by the reaction of bromoisobutyl bromo and decyl undecyl alcohol. The initiator was fixed to the gold substrate by self-assembly by immersing the gold substrate in a solution containing ω-mercapto undecyl bromoisobutyrate. A CBMA monomer '2-amino-indole, Ν·dimethyl-indole-(2'-methyl propylene methoxyethyl) ethylamine inner salt by making 2_(ν, Ν, - Dimethylamino)mercaptoacrylic acid

32 1330657 Acetone was synthesized by reaction with propylene glycol. The CBMA monomer U is grafted by a free radical initiator-bound self-assembled monolayer by atom transfer radical polymerization. , dipyridine (BPY) fractional sideing agent and ligand. Reverse rotation was carried out at room temperature under mild conditions in a mixed solution of methanol and water. Code_Atom Transfer Free Silky Reaction Polymerization After the average (four) secret beet county compound hit the New County. The thickness of the polymer layer was determined to be about 1 〇 to 15 am according to the roundness photometry. Two different proteins: human fibrinogen (34〇kD, pI=5 5), lysozyme (14kD, PI=12), and human chorionic gonadotropin (hCG, 37k〇, pl=45) The adsorption on the (CBMA) graft surface was shown to be reduced below 〇3 ng/cm2 (or the wavelength shift was below 0.02 nm, which is the detection limit of the SPR sensor), as shown in Figure 28. Thus the 'CBMA' grafted surface is highly resistant to protein adsorption. Representative monomers for use in the preparation of the carboxybetaine polymers of the present invention include carboxybetaine methacrylates, such as 2-carboxy-yttrium-2-methylideneoxyethyl)ethylamine inner salt; Beet test acrylic acid; silk beet test (four) decylamine; ruthenium betaine vinyl compound; carboxybetaine epoxide; and other carboxy betaine with hydroxyl, isocyanate, amino or carboxyl group. The carboxybetaine polymer can be produced by a polymerization method including atom transfer radical polymerization, reversible addition-split chain transfer polymerization, and radical polymerization. Any conventional free radical initiator for polymerization can be used. Poly(CBMA) or poly(SBMA) can be coated on the surface of the glass by surface initiated atom transfer radical polymerization. The standard glass substrate is a clean substrate which is then immersed in a solution containing 2_溪_2·曱----((tridecyloxyfluorenyl)propyl]-propanamide. The substrate is removed from the impregnation solution, rinsed and dried. SBMA (or CBMA) is polymerized by atom transfer radical polymerization initiated by the surface of Table 1330657 on the two substrates of the fixed initiator in the presence of CuBr and 2,2,-dipyridine. Example 9 describes and in the twenty-ninth figure illustrates the preparation of polySBMA (or polyCBMA) by surface initiated atom transfer radical polymerization on a glass slide. Enzyme-binding immunosorbent assays showed a significant decrease in protein adsorption on the surface of poly-SMB A (or poly-CBMA) grafts. The fibrinogen adsorbed on the polymer grafted glass sample was less than 4% adsorbed on the standard glass sample. On the poly-SBMA grafted surface, after incubation with Chlorella spores for 6 hours, no algal spores or algae adhesion was observed. The glass sample of the control was covered with green algae. In another aspect, the invention provides a crosslinked polymer hydrogel. In one embodiment, the invention provides a crosslinked poly(83-) hydrogel. In another embodiment, the invention provides a crosslinked poly(CBMA) hydrogel. The crosslinked poly(SBMA) hydrogel was prepared as described in Example 4. The transparent hydrogel was prepared by adding SBMA monomer to tetraethylene glycol dimethacrylate (Tegdma) followed by initiation of free radical polymerization by sodium metabisulfite and ammonium persulfate. After polymerization, the gel is prepared according to procedures defined in the art to remove residual chemicals. The poly(SBMA&gt;K gel as described above has low protein adsorption and low endothelial cell adhesion. The crosslinked poly(CBMA) hydrogel was prepared as described in Example 8. The transparent hydrogel was added to the CBMA monomer by four. Glycol dimercapto acrylate (TEGDMA) is subsequently prepared by free radical polymerization initiated by sodium metabisulfite and ammonium persulfate. After polymerization, the gel is prepared according to well-established procedures known in the art to remove residual chemicals. The pellets were cultured in the adhesion protein solution and cultured with bovine aortic endothelial cells (B^ECs). The results showed that the poly(CBMA) hydrogel itself is highly resistant to cell adhesion and is easily modified to introduce Proteins for Cell Adhesion. In another aspect, the present invention provides a method of preparing a low biomolecular adhesion surface. In one embodiment, 34 1330657, the method comprises (a) forming a free radical initiator capping on the surface of the substrate. a single layer, and (b) a monomerization reaction on a single layer of a free radical initiator capping wherein the monomer is a sulfobetaine or a carboxybetaine. The monomer may be selected from the group consisting of a contiguous betaine acrylate, Sulfo sweet Alkali acrylamide, sulphobetaine vinyl compound, sulphate betaine epoxide and mixtures thereof, or may be selected from the group consisting of carboxybetaine acrylate, carboxybetaine acrylamide, carboxybetaine ethylene The base compound, the carboxybetaine epoxide, and mixtures thereof are grouped together. In one embodiment, the monolayer is a self-assembled monolayer. In a practice, the method includes (8) forming a silk seal on the surface of the substrate. a single layer of the end; (b) converting the hydroxyl-terminated monolayer into a monolayer capped with a free radical initiator; and (the monomer is subjected to a polymerization reaction on the free radical initiating fresh layer. The monomer may be as described above) The performance of the base beet test or the slow-based beet test, the single layer may be a self-assembled single layer. In another - a real towel, the financial method includes (8) forming a single layer at the recording end of the yarn; (b) using the second type The segment copolymer treats the alkyl terminated monolayer; and (4) treats the clathrin-capped monolayer with a second diblock copolymer. In one embodiment, the 'first-type three-copolymer includes a hydrophobic number Body] a large enemy segment _ [hydrophilic monomer] m ^ material. In an embodiment, The first diblock copolymer comprises [epoxy propylene] [continued beet test methyl propyl phthalate copolymer. In one embodiment, the second copolymer includes [hydrophobicity Monomer block [hydrophilic monomer]. Copolymer. In the first example, the first monoblock copolymer includes [epoxypropane] "segment [sequential betaine methyl acrylate) η copolymer. For these polymers, set an integer of ~3〇, m is an integer of Κ)~, „is an integer of 1()~5(), and the claw is larger than η. The surface of the fine surface of the molecule, the surface of the material provides the surface of the ultra-low-staining material treatment or the surface of the ultra-low biomolecular adhesion surface of the surface of the 35 1330657 coating, a method to provide ultra-low-stained surface Treatment (eg compound or polymer): This material provides ultra-low surface contamination. In this method, the table _ a certain amount of material is processed / provides surface ultra-low fouling. A material that provides an ultra-low-surface effect on the surface is applied to the surface of the silky surface (4) on the covalent side or by covalently co-operating ions, electrostatic, coordination compounds formed by the bond. In one embodiment of the method, the surface of the substrate is washed and cleaned, and then soaked in an ultra-low-stained coating material/liquid towel. Qian, the surface of the substrate of the ultra-low-filt material of the silk is washed and dried. This method can be repeated several times. Another implementation of the method, the surface of the substrate is silked and cleaned, and then immersed in a mercaptan thiol spray. • The second-stage filament is dissolved on the surface of the substrate coated with a hydrophobic material (e.g., a self-assembled monolayer) and subsequently rinsed with a buffer solution to remove the less adsorbed copolymer. The second diblock copolymer solution is then cast onto the surface of the substrate coated with the second-stage copolymer, followed by rinsing with a buffer solution to remove the less adsorbed copolymer. • In another method, an ultra-low-stained surface is treated with one or more materials and processes to form a surface coating that provides adhesion to ultra-low biomolecules on the surface. In this method, the polymer coating is grafted onto the surface by living polymerization techniques, and the polymer chain is grown from the surface under controlled conditions to provide an ultra-low biomolecular adhesion surface. Further, the bond of the polymer material on the surface of the substrate can be completed by any conventional polymerization method such as atom transfer radical polymerization, reversible addition-split bond transfer reaction and radical polymerization. The self-assembled monolayer on the surface of the New Zealand is an excellent surface polymerization platform. Other hydrophobic materials (or hydrophobic surfaces) are also suitable. In one embodiment, the &apos;polymer oxime is grafted from the self-calling 35 of the gangue. Substrate surface 36 End-capped self-assembled monolayer. Then, the monomer in the self-assembled monolayer of the ultra-low biomolecule adhesion surface and material can be used for marine applications, providing the following device Na, = called this n-face, the present invention adhesion material H*&quot;, rice granules Modifying the surface to include the ultra-low biomolecular binder of the present invention, or preparing the surface thereof by the present invention; adhering paint: modifying the surface to include the ultra-low biomolecular adhesive material of the present invention 或' The method of the invention prepares the surface thereof; the hull of the paint of the county: the surface of the (4) super enchanting adhesive material is modified, or the surface is modified by the original money; modified, or: ==;: r biological Molecular adhesion _ its table m measured 111 trees _ do things Weiqing or prepared by the method of the present invention; separation == biological separation device 'for example, for microbial suspension, hormone fractionation (four) ^ and cell knife, Wastewater treatment, oligosaccharide bioreactor, egg process thinner: y, surface modification by the ultra-low biological classification material of the present invention, or preparation of the surface thereof by the present invention; implantable sensing n: Turning over low biomolecules _ materials change their surface to 37 1330657 sex, or by The method of the invention prepares its surface; subcutaneous sensor: the surface of the ultra-low biomolecule of the invention or recorded by the invention; H surface modification, implant, such as breast filling, 埚-shaped implant == bio-score Gam (four) 嶋 delete, (four) (four) method H hair tissue stent · · The invention of the ship biomolecule axis Xie from the present invention green t prepared its silk;,,,,,, or medical medical coffin, such as human side, artificial heart.. _, left ventricular assistive medical device (_), arterial grafting and fine, or the surface prepared by the method, and J treatment f set 'two ear drainage tube, artificial breast tube, glaucoma drainage tube, hydrocephalus Keratoprostheses, nerve conduits, catheters, tissue scavengers, wound dressings, and X-ray guides: surface-modified with the ultra-low biomolecular adhesion materials of the present invention, or prepared by the method of the present invention The following examples are intended to illustrate the objectives of the present invention. The present invention is directed to a representative single-layer self-assembled monolayer Dini mi. Assembly monolayer: fixed SPR from neodymium layer preparation and initiator Glass section or Shixi tablet by electron beam evaporation under vacuum with a layer of chromium 38 1330657* that promotes adhesion (thickness 2_ and surface cytoplasmic genomic active gold layer (48 (iv) coating. Self-planting - single layer preparation, substrate Wash with pure ethanol, clean under UV light, and wash with water and pure ethanol/V, self-assembled monolayer. After cleaning the surface at room temperature, the gold coated substrate is immersed in a pure ethanol solution cap of mercaptan. Cheng. The implementation of the financial, two self-assembly The layer is formed on the substrate: the initiator is substituted with isobutyric acid ω • silk eleven base (1) self-assembled monolayer (initiator self-assembled monolayer or Br-self-assembled monolayer) and Un_undeol (2 Self-assembled monolayer (OH-self-assembled monolayer) (see the first figure). In order to prepare the initiator self-assembled layers on the gold surface and compare their effects on polymerization and protein _ limbs, the test of each Wei degree 1 side and cleaning method. Even if the pure ethanol solution of '1 mM 1 is not used to soak the substrate for 24 hours. The substrate is rinsed with ethanol' followed by THF rinsing and drying under a nitrogen stream. To prepare a hydroxyl-terminated self-assembled monolayer, The gold substrate was immersed in an ethanol solution of 1111 River 2 for 24 hours, and then the substrate was rinsed with ethanol and dried under a nitrogen stream. The self-assembled single-layer gold wire through the base end was fine and the reaction was anhydrous (the first figure). In this reaction, the gold substrate coated with the self-assembled monolayer was incubated in 251 dry ΤΗρ and 2.1 mL pyridine (26.5 mmol), and then 3 丨BIBB (25 mmo1) was added dropwise with gentle stirring. It may be the bite of hydrogenate in the initial stage of the reaction. After the reaction, the substrate is used. The alcohol and the sub-water were sequentially washed with sodium and dried under a nitrogen stream. Example 2 The surface SB_MA of the representative hair-based polymer was coated with a right hair spray in a dry box, and QiBr under nitrogen protection. And a substrate with a fixed initiator was placed in the reaction tube. The tube sealed with a rubber gasket plug was taken out. Then a degassing solution containing SBMA and Βργ (pure water and decyl alcohol in a 1:1 volume) was used using a syringe. 39 1330657 ratio) transferred to the tube under nitrogen protection. After the reaction, the substrate was removed and rinsed with ethanol and water, and the sample was kept in water overnight. Usually rinsed with ph〇sphate buffered saline (PBS), which Used to remove unbonded polymers prior to testing (see Figure 2). Adhesive protein adsorption was performed using a custom surface plasmon resonance (SPR) sensor based on the wavelength question mark (Interrogation). The SPR slice is attached to the prism substrate. Optical contact is determined using a refractive index matching solution (Cargille). In the experiment, a dual channel flow cell with two independent parallel flow cells was used to store the liquid sample. A spiral compression pump (Ismatec) is used to transfer liquid samples to a dual flow cell. A solution of fibrinogen in 1.0 mg / mL PBS (0.15 M, pH 7.4) was cast on the surface at a flow rate of mL 5 mL / min. A surface sensitive SPR detector is used to monitor the immediate interaction between protein and surface. In this embodiment, the wavelength shift is used to measure the change in surface concentration (quality per unit area). The amount of fibrinogen adsorbed on the HSiCHJ^CH3 self-assembled monolayer (15 postal length shift) was used as a single layer (ML). The wavelength shift caused by protein adsorption on the measurement surface is normalized to %ML by the shift on the HSiCHJbCH3 self-assembled monolayer. If the amount of protein adsorbed on the surface of the analysis is greater than the amount of adsorption on the self-assembled monolayer of HSfHAsCH3, %ML may be greater than 1〇〇〇/0. The line photoelectron spectroscopy (XPS) is combined with the SPR slice; the method of preparing the single layer is the same as the SPR slice. XPS analysis was performed using a Surface Science Instruments (SSI) S-Probe equipped with a monochromator Αι Κα X-ray source. The energy of the emitted electrons is measured in a range of 5 〇 to 丨 5 〇 ev using a hemispherical energy analyzer. The composition of the elements on the surface is determined by a survey scan. All information is concentrated at 55. Surface standard deviation angle. The binding energy (BE) calibration was set by the cis spectrum set at 285 〇 eV for the most 40 &lt; S &gt; 1330657 large peak reference. Multiple sample analyses were performed in each batch, with average values. The high resolution Cls spectra were correlated using Shirley background subtraction and a series of Gaussian peaks. Data Analysis Software from Service Physics, Inc, Inc.趟Circular photometry _ ellipsometry using a spectroscopic ellipsometer (Sentech SE-850, OmbH) 〇 sample preparation is the same as the xpS experiment. In the vis area, five separate points are measured at two different angles of incidence (5 〇 '60 and 70 degrees). The same batch of gold coated sections were cleaned by a UV-ozone cleaner for 2 minutes, washed with ethanol and Millipore water, and dried with air. Bare gold coated sections were used as a reference. The film thickness studied was determined using a Cauchy layer model using a refractive index of 1.45. The fatigue-mode atomic force mirror (TM-AFM) TM-AFM gold substrate was prepared by steam deposition of gold on a fresh liquid mica (Asheville-Schoonmaher Mica Co.) by a high vacuum evaporator (BOC Edwards Auto 306). Prior to deposition, the mica substrate was preheated by a radiator heater to 325 ° C for 2 hours. The evaporation rate is a predetermined thickness of the nm/s 'gold film of about 200 nm. The gold coated substrate was annealed in the frame for 1 minute before use. All TM-AFM images were obtained using a Nanoscope Iv (Veeco, CA) AFM equipped with an E scanner. Use a cantilever (TESP, DI) with a resonant frequency of approximately 270 kHz, a constant force of 20 to i 00 N/m, and a punch tip radius of 5 to (7). Example 3 The SBMA block 埒 碑 肀铷 肀铷 肀铷 肀铷 肀铷 肀铷 肀铷 该 该 该 该 该 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制The copolymerization of the diblock copolymer is a reversible redox process in which a transition metal compound is used as a carrier of a halogen atom to sequentially bond the monomer to a monofunctional macroinitiator. PPO with macroinitiator (PPO-Br) by monohydroxyl-type polypropylene glycol and 2_indolizine bromide in four

Synthesis of 1330657 in hydrogen furan. The product was purified by three extractions with brine. The 11200 molecular weight SBMA polymerization is SBMA (2.0g ' 6.77|11111〇1) used in 1〇1111^ methanol [SBMA] : [PPO-Br] : [CuBr] : [bpy] = 50:1:1:2 , 20T, polymerization under nitrogen. After 24 hours, the obtained reaction solution was passed through an oxidation column, ethanol, and water, and then dissolved, and the residue catalyst was repeatedly removed. After the solvent was evaporated, the copolymer was dried in a vacuum oven at room temperature to obtain a white powder. Characterization of the PP-b-poly(SBMA) diblock copolymer structure was characterized by ιΗ NMR resonance spectroscopy using a Bruker 300 MHz optical spectrum analyzer and d2® as a solvent. A typical PCVb-SBMA35 spectrum is shown in the tenth figure. The results show that a pure pp〇_b_poly(SBMA) diblock copolymer was obtained. The molecular weight and molecular weight distribution of the prepared diblock copolymer was determined by hydrogel permeation chromatography (GPC) using 2 supergel 1 〇〇〇 and supergel 250 columns (molecular weight range 586 Da~885 kDa). Waters is connected to the model \^358〇¥丨5(;(^1&lt;; differential refractive index detector. 〇? (1! In the experiment, the flow rate is 711.71111 / min and the column temperature is 25 ° C. Elution The agent is an aqueous solution of pH 8.0 consisting of 0.1 M NaHJO4 and 0.1 M Na2HPO4. The PEG standard purchased from Scientific Polymer Products (T., Ontario, NY) is used for calibration. The typical GPC water content of the three synthetic ppo seven-poly(SBMA) copolymers can be found. Twelfth Figure. Relocation · &amp; Level Attached by Surface Ray #4U After NPR) Sensors are based on wavelength question marks and Teflon double flow cell custom SPR biosensors for monitoring coated surfaces Protein adsorption. In this example, an optical glass substrate was used as a sensor slice coated with a 2 nm promoted adherent chromium layer and a 50 nm surface cytoplasmic genomic active gold formed by vacuum evaporation by electron beam evaporation. Layer cCH3_ capped self-assembled monolayer consisting of gold coated substrate coated with 1^ ozone cleansing in HS (CH2) 8CH3 is formed in 〇 mM ethanol solution overnight. The modified section is attached to the prism substrate, and the optical contact is used to refract the finger 42 1330657

• Number matching solution (CaiBllle) is determined. For protein adsorption measurements, SPR was first stabilized with 2 mM phosphate buffer solution. The PPO-b-poly(SBMA) diblock copolymer solution was then flowed into the SPR cell for 20 minutes and then rinsed with 2 mM PBS solution for 15 minutes to remove the unabsorbed copolymer. 1. 〇 mg/mL protein flow for 20 minutes, followed by rinsing with 2 mM PBS solution for 15 minutes. In the present study, fibrinogen was used as a model system to evaluate protein adsorption on the surface of a physically adsorbed copolymer coating. All s pR experiments were performed at room temperature (about 25 C) and a flow rate of 0_05 mL/min. The amount of protein adsorption is defined as the difference between the two baselines for which the protein is adsorbed as determined. The eleventh figure shows a typical SPR induction map adsorbed on copolymer A, followed by an in situ assessment of the adsorption of fibrinogen. Example 4 Representative thiol sweetine hydrogel adenosine (SBMAJ hydrogel and its white matter adsorption and cell-attached resistance P-(methacryloxy)ethyl] dimethyl (3 _ propyl) ammonium hydroxide (SBMA) ( j 〇g) dissolved in 400 μl of PBS buffer with 600 μl of ethylene glycol and 2 μl of microliter of tetra (ethylene glycol) diacrylate (TEGDA) Mixing. Then, 50 μl of 15% sodium metaruthenium solution and 50 μl of 40 〇/〇 ammonium persulfate solution were added. The mixture was poured into two sterilized glass slides separated by Teflon separator. The fixture was used on the edge of the glass to ensure a perfect seal. The film was cured overnight at 37 T, and the film was thoroughly immersed in DI water for 24 hours, 70% ethanol for 24 hours, and DI water before being punched into a wafer. The hydrogel disc remains in DI water. The poly(SBMA) hydrogel as described above has low protein adsorption and low endothelial cell adhesion as well as poly(hEma) (see Figures 30A through 30D) Example 5 43 ί S &gt; il elastomeric SRMA-layer 5BMA (U2g) and AIBN (0.05g) were dissolved in methanol solvent (5 〇ml), and the solution was flushed with 3G. Bell, weaving, the reaction mixture is searched for π in a nitrogen atmosphere, and then, the human is dissolved in 100% isopropanol methyl methacrylate, the laurel is j5, and the reaction mixture is continuously stirred in a nitrogen atmosphere at 60 CT '5 Hour. Filter the product and hide the benzene towel at 5 g of 99 g/L. The combination of the rhythm and the rhythm shows that the protein adsorption decreases on the surface of the poly-SBMA coating (Figure 18). The apparent SBMA coating can be reduced to reduce the microbial sediments to the 21st map.罘10 Poly SBMA type, polymer can be added to epoxy-based paint to reduce biofouling (poly SBMA / i sulphur coating). The representative polymer dispersion in a representative formulation is a poly-SBMA-based polymer as described above dissolved in a diterpene benzene towel, and the epoxy resin is a 70-80% Wei resin solution. Called, secret 3 and carbon black are suitable as pigments, and organic clay structuring agents and vermiculite thixotropic agents can also be added. The crosslinker is polyamine which reacts with the epoxy resin at ambient temperature. The liquid, non-contaminating coating is applied to the epoxy primer substrate by coating or spraying. Enzyme-linked immunosorbent assay showed a 90% reduction in fibrinogen adsorption. The nineteenth to twenty-first graphs show extremely low zoospores, very low spore growth, and very weak spore adhesion strength. The eleventh figure shows a low juvenile // role in nematode sedimentation. The results show that the poly(SBMA)/epoxy coating significantly reduces marine microbial biofouling. Example 6 Preparation of a representative interpenetrating network structure polymer containing a sugar beet test and a microfiber box with a SPU and a poly(SBMA) stone-penetrating network polymer film as shown in the third figure '100 micron A thick SPU film was prepared by solvent evaporation. The SPu solution was first prepared by dissolving 5. 〇 44 1330657 wt% SPU powder in dimethyl ethanoamine (DMA). The solution was cast on a glass slide which was heated to 35 ° C to dry the film. After the solvent body was evaporated overnight, the SPU film was placed in a 60 ° C water bath for 24 hours to remove traces of DMA, and then dried in a vacuum oven for 3 days. The SPU film was then immersed in a culture solution containing a cryptic monomer, an ehma monomer, a GDGDA crosslinking agent, and a photoinitiator for 24 hours at 2 °C. The polarity of the solvent in the culture solution can be varied by using water, mood, ethanol or isopropyl-mix (4) with decreasing polarity. Adjust the total concentration (or culture concentration) of the culture solution to 〇丨~3 〇111〇1. The sbma monomer ratio (mol%) is defined as the number of SBMA monomer moles divided by the total number of moles of sbma and EHMA monomers in the culture solution. In this example, the SBMA monomer ratio was adjusted between 〇 and 〇 〇 mol% to optimize the preparation conditions of the interpenetrating network structure polymer, while the GDGDA was immobilized at l.〇xi〇-2m〇1/L. To eliminate side reactions, a photoinitiator (e.g., glycerol and 4-(N,N-monomethylamino)benzoic acid ethyl acetate) (1) is added to the culture solution in the dark under nitrogen. For photopolymerization, the spu film was placed between two mica sheets and irradiated with visible light (λ = 4 〇〇 _ 5 〇〇 nm). After 12 〇〇c irradiation for 12 minutes, the mica flakes were removed from the interpenetrating network polymer crucible in water, and the unreacted monomers were extracted by soaking ethanol and methanol several times, and the interpenetrating network structure was polymerized. The film was dried under vacuum. Interpenetrating network structure Polymerization Fine chemical composition depth profile Characterization using a Raman microspectrometer that combines the Renishawin ViaRaman Spectroscope and the reverse Leica DMIRBe Microscope. The 78s (10) laser is used as an excitation source, and a spot of about 丨 micron is focused on the surface of the sample by a 4 〇χ objective lens. The scattered light on the surface of the sample is focused by the same objective. Raleigh scattered light is cut off by holographic step screening. Raman light passes through a 65 micron open entrance slit and a 1200 L/mm diffracted optical thumb&apos; and is measured by a CCD camera. For the distribution depth (S) 45 1330657 d-plane of the SBMA unit in the SPU film, the Raman spectrum is obtained from the focal plane of the membrane surface and enters the membrane over an increment of micrometers. The enzyme adsorption immunosorbent assay was used to evaluate the adsorption of human fibrinogen (Fg) on the membrane of the fluorescein-attached interpenetrating polymer structure using enzyme-binding immunosorbent assays according to the standard protocol briefly described below. First, a bile membrane with a surface area of 2 mm2 was placed in each well of a 24-well tissue culture plate, and each well was cultured at room temperature with 5 μL of pBs. The interpenetrating network polymer film was then immersed in 5 μl of a 1 mg/ml Fg PBS solution. After incubation at 37 ° C for 90 minutes, the membrane was rinsed 5 times with 500 μl of pBS and then in bovine serum egg (BSA) towel 37. &lt;: Incubate for 90 minutes to fill the pgs area. The interpenetrating network polymer membrane was rinsed again with PBS 5 times and transferred to a new plate, in a pBS solution containing 5 々g/ml horseradish peroxidase (hrp) conjugated anti-Fg (us bio) Train in 37T for 3 minutes. The sample was rinsed 5 times with PBS and transferred to a clean well followed by the addition of 500 μl of 〇.1 Μ 檬 酸酯-phosphate containing img/mL o-phenylenediamine (〇Dp) and 〇〇3% hydrogen peroxide chromogen. Buffer solution (ρΗΐο). After 37 〇c incubation, the enzyme color reaction was induced by adding 5 〇〇 microliters of HjO4 from the Weihe River to each well solution, and finally the absorbance of light intensity was determined by a microplate reading mirror at 490 rnn. Protein adsorption on interpenetrating network polymer samples was normalized as a reference on a polystyrene (qua) plate. Due to the use of multiple anti-human binding sites, the amount of protein adsorbed can be higher than the actual amount. Example 7 - Representative non-contaminating carboxy-sweet test layer Human plasma fibrinogen and chicken lysozyme were from Sigma-Aldrich (Milwaukee, WI). Human plasmanectin was purchased from Chemicon International (Temecula, CA). Human chorionic gonadotropin 46 1330657 (hCG) and its monoclonal mouse antibody (heterotype IgGl) were purchased from Scripps Laboratories (San Diego, CA). Ethyl 2-(N,N'-didecylamino)decyl acrylate (DMAEM '98%) 'β-propiolactone (95%), copper (I) bromide (99.999%), bromoisobutyl醢Bromo (98%) '11-Weiyl 1-undecyl alcohol (97%), 2, 2, - II. Specific bite (ΒΡΥ99%) and tetrahydrofuran (THFHPLC grade), Ν-hydroxysuccinimide (NHS) and 1-ethyl-3_(3•didecylaminopropyl)-carbodiimide (EDC) Purchased from

Sigma-Aldrich (Milwaukee, WI). Phosphate buffer solution (〇.〇1 μ phosphate, 0.138 Μ gasification sodium ' 0.0027 Μ gasification clock ‘pH 7.4) is from Sigma Chemical Co. Ethanol (defined in absolute 200) was purchased from AAPER Alcohol and Chemical Co. The water used in the experiment was purified using a Millipore water purification system with a minimum resistivity of 18.0 ΜΩαη. The reaction and washing were dried with sodium before use with THF. ggMA synthesizes carboxybetaine methacrylate (CBMA) monomer, 2-mercapto-# has dimethyl-N-(2'-mercaptopropenyloxyethyl) inner salt by reaction 2_(N,N 'c曱-ylamino)mercaptoacrylic acid B g (DMAEM '98%) and β-propene g (95%) were synthesized. 〇_87 g (12 πυηο1) β-propiolactone dissolved in 10 mL of dry acetone was added dropwise to a solution of 1.57 g (10 mm 〇l) DMAEM dissolved in 5 Torr of dry acetone. The reaction was stirred at 丨5 ° C for about 5 hours under nitrogen. The white chamber was washed with 50 mL of dry acetone and 1 mL of dry ether. The product was dried under reduced pressure to obtain a CBMA monomer. The monomer is maintained at 2 to 8 C before polymerization. Yield: 91%. b NMR was recorded on a Bruker AV300 spectrum analyzer using heavy water as a solvent (Thirty-first graph). The upper surface of the detector is triggered. #肀4 §PR glass section is coated by electron beam evaporation under vacuum to promote adhesion of the chromium layer (thickness 2 (10)) and surface cytoplasmic genomic activity gold layer (48 nm). Prior to self-assembled monolayer preparation, the substrate was washed with pure ethanol, cleaned under UV light, and washed with water and pure ethanol. Initiator self-assembled monolayer by room temperature

47 1330657 The gold-coated substrate was formed by immersing it in a pure ethanol solution of 1 ΜηΜω-bromoisobutyrate decylundecyl ester for 24 hours. Prior to polymerization, the substrate was rinsed with pure ethanol, then rinsed with THF and dried under a stream of nitrogen. In a dry box, the substrate of CuBr and the fixed initiator was placed under a nitrogen atmosphere in a reaction tube. Remove the tube sealed with a rubber spat plug. Then, a degassed solution of CBMA and BPY (pure water and methanol in a 1:1 volume ratio) was transferred to the tube under a nitrogen atmosphere using a syringe. After the reaction, the substrate was removed and rinsed with ethanol and water, and the sample was kept in water and passed through. Rinsing with PBS buffer was also used to remove unbonded and polymer prior to testing. A typical polymerization is carried out by reacting a substrate with 7.5 mmol of CBMA, 2 mmol of BPY and 1 mm of Cui CuBr under nitrogen for 25 hrs in a CH3 〇H/l (1:1 volume ratio). After polymerization by a typical atom transfer radical polymerization, a homogeneous carboxybetaine polymer brush is grafted onto the gold surface of the SPR sensor. The thickness of the polymer layer is about 丨〇~丨5 and is determined by ellipsometry. White matter adsorption protein adsorption was determined using a custom surface plasma resonance (SPR) sensor based on the wavelength question mark. The sPR sections were attached to the prism substrate and the optical contact was determined using a refractive index matching solution (Cargille). In the experiment, four-fluid cells with four independent parallel flow cells were used to store liquid samples. A spiral compression pump (ISmatec) is used to transfer liquid samples to the four tanks of the flow cell. A 1.0 mg/mL solution of fibrinogen in PBS was cast on the surface of the sensor at a flow rate of 机.05 machine/min. The spR detector is used to instantly monitor protein-surface interactions. In this study, the wavelength shift was used to measure changes in surface concentration (or mass per unit area). The facelight ellipsometry method uses a spectroscopic ellipsometer (Sentech SE-850, GmbH). Sample preparation is the same as the chat experiment. In the Cong area, five separate points are measured at three different angles of incidence (5 〇, 60 and 70 degrees). The same batch of gold coated sections were washed with ethanol and Millipore water by &lt;, 5) 48 1330657 'cleaned by UV-ozone cleaner for 20 minutes' and dried with nitrogen. The bare gold plate was used as a reference. The film thickness studied was determined using a Cauchy layer • models with a refractive index of 1.45. - f Example 8 Representative Carboxyl Ester Sodium Hydrogel Poly(gg_MA) Hydrogel and a very good technique for adsorbing deductive viscous 柹CBMA hydrogel by mixing solution (ethylene glycol) /ethanol / h2 〇 = 3:1:1 volume ratio) Add 2.7 M CBMA monomer to tetraethylene glycol dimercapto acrylate (TEGDMA) (5.9 mol %) with sodium metabisulfite (丨.2 m Prepared by free radical polymerization initiated by 〇i 〇/〇) and ammonium persulfate (2.6 mol%). The reaction was carried out at 37 Torr for 12 hours. After the polymerization, the gel was immersed in a large amount of DI water for three days, and water was changed every day to remove residual chemicals. The gel is then equilibrated with a sterilized PBS solution which is changed daily or two days. The hydrogel was punched into a 5 mm diameter disc and stored in a sterilized buffer solution prior to use. The 'hydrogel discs were immersed in 2 mg/ml NHS in dioxane at room temperature and 2 mg/ml Lu EDC in dioxane/water (14:1) mixture for 1 hour. The hydrogel disc shrinks when soaked in the dioxane/water solution. The discs were removed from the solution, soaked into the water and swelled on the back, rinsed with Millipore water, and immersed in PBS buffer for another 30 minutes. The sample was immersed in a lOOpg/ml adhesion protein solution for 24 hours at 4 °C. Bovine aortic endothelial cells (BAECs) with a density of lxlO5 cells/mL were seeded on the gel surface. Samples of the loaded cells were incubated at 37 ° C in a humidified atmosphere of 51⁄4 C 〇 2 . Cell morphology between 2 and 3 days of culture was observed. ° f Example 9 A representative poly(SBMA) or poly(CBMA) coating was placed on a 20 wt% NaOH solution overnight in a 玻璃$辛今 49&lt;S) 1330657 standard glass substrate, washed with DI water and air dried. The cleaned substrate was immersed in a solution containing 0.5 g of 2-bromo-2-methyl-N-3-[(trimethoxymethylidene)propyl]-propanamide. After 2 hours, the substrate was removed from the impregnation solution &lt;slightly rinsed with ethanol. The substrate was held in a 100 °c vacuum box for 5 hours and evacuated by an oil-free vacuum pump.

Under the protection of the dry phase, the two substrates (^1^1' (143111 Lu, 1.〇111111〇1) and the fixed initiator were placed in a 50 mL flask, and the flask was removed from the drying oven. Rubber gasket plug seal. Then, SBMA (l.〇6 g, 3.8 mmol) or CBMA (874 mg, 3.8 111111〇1) and 2,2'-two bite (15611^'1 face 〇1) A gas solution (1:1 volume ratio of pure water and methanol, 10 ml) was transferred to the flask using a syringe under nitrogen. After the reaction, the substrate was removed and rinsed with ethanol, PBS buffer and water, and the sample was kept in water overnight. Prior to use, the substrate was dried with a stream of nitrogen. Enzyme-bound immunosorbent assay showed a decrease in protein on the surface of poly-SMBA (or poly-CBMA(see Figure 18). Suction on polymer-grafted glass samples_ _ Eggs work on 4% of fresh sampling samples. _ Sporeper's assimilating control glass samples were coated with green algae, and no algal spores or algae adhesions were observed on the surface of polysb nucleus (see twentieth) Changed to those who are familiar with this skill ^, this hair _ significant phase to make a variety of repairs and modifications and ^ separation of the spirit and system. Therefore, The invention includes the lesser cross-linking, and is included in the attached patent application. Circumference and its equal 50 &lt; S &gt; 1330657 [Simplified illustration] 'The first figure is prepared on the surface (gold) Schematic diagram of two methods (one-step and two-step method) of initiator-terminated self-assembled monolayer; 'Three-dimensional diagram is the preparation of representative polysulfonated beet by surface-induced transfer radical polymerization of the present invention Schematic diagram of the method for preparing the surface of the alkali material; a first diagram of the method for preparing the interdental network polymer (ipn) film of the present invention: (a) the inter-segment polyurethane (SPU) film is obtained by solvent evaporation method at 2〇挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发 挥发The medium is cultured in a decyl alcohol solution of a base vinegar (hema) monomer, a GDGDA cross-linking agent and a photoinitiator; (4) visible light-initiated photopolymerization; (available to agglomerate/post BMA); The invention prepares a representative poly-polymer by surface-initiated atom transfer radical polymerization A method of sounding the surface of a CBMA material; the fifth and fifth B are fibrinogen pairs obtained by surface ray resonance measurement (wavelength shift as a function of # time) Comparison chart of adsorption of representative surface of the invention (surface coated with beet test): Figure 5A shows that 1D proprotein in pBs buffer (0.15 Μ 'pH 7.4) on the bare gold surface (bare gold) Fixed initiator. Self-assembled monolayer) on the gold surface and poly(sbma) grafted surface (after polymerization) by immersing the Br_self-assembled monolayer surface with U mmol SBMA, 2 mmol ) adsorption on the bite (BPY > M mmd (10) ringing ^ ^ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .15M, pH 7.4) adsorption of tl mg/mL fibrinogen on a representative surface of the invention (poly&lt;S) 51 1330657 contiguous beet test coating surface; Figure 6 is a representative surface of the invention SPR induction map of fibrinogen adsorption on polyphosphorus-based beet test coating surface, wavelength shift as time letter , the surface has unbonded initiator (1) and no unbonded initiator (2) (both substrates are put into the same 'reactor, so that the specific substrate is 2.0 mmol SBMA, 0.1 mmol Βργ and 〇〇5 Mmoi CuBr is polymerized in 25 mL CH3〇H/H2〇 for π hours); Figure 7 is a plug-mode atomic force microscope (TM-AFM) image of the self-assembled monolayer of initiator 1 on a gold substrate (scan size: 1/ /mx丨Am), the surface is prepared by immersing in a 1 mM initiator 1 solution for 24 hours and then washing with ethanol and THF; the eighth figure is the polymer film thickness and the representative surface of the fibrin of the present invention. Comparison of original adsorption as a function of SBMA Hanta and polymerization time: poly (SBMA) thickness is determined by ellipsometry (solid symbol), fibrinogen adsorption is determined by surface plasma resonance technique (open symbol indicates χ01) MSBMA polymerization: 2 5 mmol SBMA, 1 mm 〇i BPY and 0.5 mmol CuBr in 25 mL CH30H/H20; 0.3 M SBMA polymerization: 7.5 mmol SBMA, 2 mmol BPY and 1 mmol CuBr in 25 mL CH3 Polymerization in 〇H/H2〇), % ML (monolayer) fibrinogen adsorption system CH3 self-assembled monolayer fibrinogen adsorption; ninth is a schematic diagram of the preparation of representative block copolymers of the invention: (a) monohydroxy terminated polyoxypropylene (PPO) Reacting with 2_bromoisobutylphosphonium bromide in THF at 2〇〇c; and (b) by atom transfer radical polymerization at 20 ° C to carry out oxime in 1 in sterol Block copolymerization; Figure 11 is a 1 H NMR spectrum of the representative block copolymer p〇2rSBMA35 diblock copolymer of the present invention (D2〇); t S ) 52 1330657 The eleventh figure is an SPR sensing diagram, The adsorption of the surface of the substrate by the representative copolymer P〇2〇-SBMA2() (copolymer A) of the present invention is described, and then the adsorption of fibrinogen is evaluated in situ; FIG. 12 is a representative copolymer of the present invention. Hydrogel permeation chromatography curve (GPC) (with polyethylene glycol as a reference), pp〇_block kSBMA) diblock copolymer prepared by atom transfer radical polymerization at 2〇〇c Copolymer A, Μί - 6490, Mw / Mn = 1.232; copolymer B, Mn = 11183, Mw / Mn = 1.255; and copolymer C ' Mn = 15114, Mw / Mn = 1. 353; Figure 13 is fibrinogen adsorption (SPR measurement) on the surface of physically adsorbed PP〇_block_poly(SBMA) at 25T as three representative copolymers of the present invention (copolymers A, B) A graph showing the relationship between the concentration of ΡΡΟ-b-poly(SBMA) solution (c_poly(face)) and C); the fourteenth figure is a representative copolymer of the present invention at 250 C (Cpp〇七聚(_) =1 〇mg /ml) (A: Copolymer A, B: Copolymer B, C: Copolymer C, C+A: SpR-sensitive map of fibrinogen adsorbed on the surface of copolymer ruthenium backfilled with copolymer A (The final SPR wavelength shift of each copolymer is marked in parentheses, and the spR retroreflection 丨nm wavelength shift corresponds to 15 ng/cm2 of protein adsorption); the fifteenth figure shows the self-assembly of copolymer C at CH3 capping Adsorption on the surface of the layer and backfilling with Copolymer A to obtain a schematic diagram of the increase in surface density and the increase in anti-protein adsorption capacity of the polyglycan beet; Figure 16 is a diagram showing several proteins (fibrinogen, bovine serum albumin (bsa) And lysozyme) adsorption on the representative surface of the invention (surface coated with copolymer A), the final wavelength shift of each protein Notes in parentheses, in response to the spR inm protein adsorption wavelength shift corresponds to 15ng / cm2 of;

53 1330657 The seventeenth® is a comparison of the secretive poly-weiding materials on the glass (respectively by the atom transfer radical polymerization to prepare (4) beet beet methyl acrylate (SBMAATrp), representative of the present invention Polysulfobetaine hydrogel (10) tender hydrogel), representative polyglycan beet coating (SBMA coating) and comparative epoxy primer coating on protein adsorption (determined by enzyme-linked immunosorbent assay) Bar graph; Figure 18 is a comparison of the uncoated glass, epoxy primer (four) (reference), coated with the representative of the present invention prepared by Example 5 beet test / epoxy resin The surface (glass XSBMA/epoxy coating), and the 4 spore deposits on the polysulfonated beet layer (SBMAATRP) prepared by atom transfer radical polymerization as a function of time (1, 3 and 6 hours) Bar graph; * Nineteenth A® and Nineteenth B®!;% comparison of sporeling growth on the surface of representative poly(neutral)/epoxy coatings of the present invention (thirteenth and in the ring) Growth on the surface of the oxygen primer coating (Fig. 19A); 曰10A to XXC in the respective slides Partially exposed to the water spray port after water spray at 2 〇〇 coffee water 'Comparative_glass (twentieth collapse), epoxy primer coating surface (20th B) and representative polysulfonate of the present invention Growth of the betaine/epoxy coated surface (苐10 C); 21st is a comparison of the representative polysulfobetaine/epoxy coating surface of the present invention (SBMA/Epoxy Coating) a bar graph of the average percentage of juvenile //. e/e妒 nematode on the biofilm (Bi〇film) as a reference, wherein each coating is exposed to 100 Pa wall shear stress The twenty-second figure is a comparison chart comparing the adsorption amount of each surface on the human fiber protease shoulder by using the polystyrene (PS) as a reference substance according to the enzyme binding-free &amp; adsorption method, wherein the measured surfaces are respectively SPU (unmodified), which is an interstage polyurethane film; IPN4, 54 (S) 1330657 is placed at 20 ° C by placing the interstage polyurethane film in a sterol solution containing % m〇i% sBMA monomer An interpenetrating network polymer film prepared by culturing for 24 hours at a concentration of 1 · 0 mol / L ' IPN-II The interpenetrating polymer membrane was prepared by incubating the interstage polyurethane film in a solution containing 70 mol% SBMA monomer at 2 ° C for 2 hours, and the culture concentration was 2.0 mol/L, and the mixed solvent was % v〇1% methanol and 5 vol% water '·HEMA hydrogel' is a methacrylic acid 2_base-based hydrogel; and SBMA hydrogel' is a representative poly(continued beet) of the present invention Hydrogel (sequential betaine methacrylate); Figure 12A is a comparison of the relative self-mass adsorption of eggs on a representative interpenetrating network polymer of the present invention using two different solvents. A plot of the function of the culture time, where 'the three solvents are sterol (6); (10) The mixture of ethanol/methanol (Δ); and ία volume ratio of isopropanol/methanol oxime, and the oxygen concentration is 〇5m〇i/L, ' and the percentage of SBMA monomer mole is 7〇 M〇1%, culture temperature is 2〇〇c; and twentieth

-B Figure 疋 疋 丨 丨 丨 f f f f f 网 网 网 聚合物 聚合物 聚合物 聚合物 聚合物 f f f X X X X X X X X X X X X X X X X X X X X Relative to the protein absorption-culture concentration function curve, (4) the nutrient solution is 7〇mol% SBMA monomer in methanol solution, the culture temperature is 2〇t&gt;c, and the culture is carried out; the twenty-fifth figure is compared in this A graph showing the relative protein adsorption and culture time on a representative interpenetrating network polymer. The culture solution is a methanol solution of 兀m〇1% SBMA monomer, the culture temperature is 2〇τ, and the culture is concentrated. Or the LGmH fifteen-graph is a graph of the ratio of swelling ratio and weight increase of the dry interpenetrating network = polymer film to the (four); 55 1330657. The twenty-sixth figure is a representative interpenetrating network polymer in the present invention. The relative protein adsorption and SBMA monomer ratio _%) as a function of the curve, while the culture concentration is 1 moI / L, and the culture system is carried out at 2 ° ° C for 24 hours; the twenty-seventh figure is to compare the IPN_j surface And the self-study surface of the 2 〇 division depth relative to the unmodified segment of the polyurethane film The twenty-eighth figure is a comparison of the adsorption of several hybrid white #(_proteinogen, lysozyme and hCG) on the representative surface of the present invention (the surface of the polyfilament sweet coating) measured by the surface plasma resonance method. Wavelength shift and time function curve · lmg / mL fibrinogen, 1 mg / mL lysozyme and adsorption in pBs (〗 〖5 〇 和 阳 7 4); The twenty-ninth figure is the preparation of the representative of the present invention Schematic diagram of a method for forming a surface, which shows that the surface of the decylated glass having an initiator is surface grafted by atom transfer radical polymerization to provide a polysulfobetaine or polycarboxybetaine coated surface; A to T30D are images comparing endothelial cell adhesion to tissue culture polystyrene (TCPS) (Thirty-eighth and King+b) and representative polyglycan beet water test of the present invention Gel (poly(SBMA) hydrogel) (p. 30c and 30th D) Graphs in 10% fetal bovine serum (FBS): Thirty a and thirty C are 1 day Thereafter, the twenty-B and thirty-third graphs are images after five days; and the thirty-first graph is used to prepare the polycarboxybetaine material of the present invention. Carboxybetaine methacrylate vinegar (the CBMA) the chemical structure of the monomer and its 1 H_NMR spectrum. [Main component symbol description] None 56

Claims (1)

X. Patent application scope: 1. - A substrate having a surface - wherein the surface comprises a single layer of _ silk sweet material, wherein the surface of the human chorionic gonadotropin adsorption system is lower than 03 ng / cm ' Let 'the carboxybetaine material be one or more selected from the group consisting of a carboxyl beet, a beetine acid, a slow beet, an alkaloid, a county beet, a tweed, a tetamine beet, and The mixture is prepared as a group of monomers. 2. If you apply for a patent scope! The substrate having a surface, the towel, and the carboxybetaine material is polycarboxybetaine. 3. If you apply for a patent scope! The substrate having a surface, wherein the silk betaine material is an interpenetrating network polymer. 4. The invention has a -substrate_substrate comprising: a secret beet polymer, the polymer being attached to the surface by a co-mussel bond to form a monolayer of a fixed compound, wherein the carboxybetaine The polymer is one or more selected from the group consisting of carboxybetaine thiol acrylate, carboxybetaine acrylate, carboxybetaine acrylamide, carboxybetaine vinyl compound, carboxybetaine epoxide, having hydroxyisocyanate &amp; The L-, amino or dithiol-based beet test, and mixtures thereof, are prepared as a group of monomers. 5. A parental polyphenolic beet hydrogel, adding carboxybetaine to tetraethylene glycol dimethacrylate (TEGDMA) in a solution consisting of ethylene glycol, ethanol and water followed by 15% It is prepared by initiating free radical polymerization of sodium metabisulfite and 4 〇〇/0 ammonium persulfate. 6. An implant material having an ultra-low biomolecule adhesion surface, which is a crosslinked polycarboxybetaine hydrogel as described in claim 5 of the patent application. 7. A method for preparing an ultra-low biomolecule adhesion surface comprising the steps of: 1330657 (8) forming an atom transfer radical initiator-terminated hydrophobic layer on a surface of the substrate; and (b) attaching a thiol betaine material The carboxybetaine material is prepared from the surface of the substrate coated with the atom transfer radical initiator, wherein the carboxybetaine material is selected from one or more selected from the group consisting of phenolic beet acrylate, carboxybetaine acrylamide, and carboxybetaine ethylene. The base compound, the carboxyl beet epoxide, and mixtures thereof are prepared as a group of monomers. 58