CN103159958A - 梳状结构高分子、医疗装置的改质方法及医疗装置 - Google Patents
梳状结构高分子、医疗装置的改质方法及医疗装置 Download PDFInfo
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- CN103159958A CN103159958A CN2011104611814A CN201110461181A CN103159958A CN 103159958 A CN103159958 A CN 103159958A CN 2011104611814 A CN2011104611814 A CN 2011104611814A CN 201110461181 A CN201110461181 A CN 201110461181A CN 103159958 A CN103159958 A CN 103159958A
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Abstract
本发明提供一种梳状结构高分子，包括：线性高分子主链；以及梳状侧链，包括：疏水性分子链段；以及亲水性分子链段及/或抑制生物膜/或抗菌的分子链段，其中该线性高分子主链是以羟基与该梳状侧链的反应性官能基形成共价键结相互连接，其中该反应性官能基包括：异氰酸酯基、羧基、或环氧基。本发明也提供使用上述梳状结构高分子的医疗装置的改质方法及医疗装置。
Description
技术领域
本发明是涉及一种功能性高分子及其于医疗装置的应用，特别是涉及一种梳状结构高分子(brush polymer)及其于医疗装置的改质方法及医疗装置，所述医疗装置例如医疗用敷料与医疗导管等产品。
背景技术
多数医疗装置或生医材料表面(例如敷料)，接触伤口渗出液(exudate)、尿液(urine)、或血液(blood)...等体液时，体液中的蛋白质会产生非特异性(nonspecific)地沉积。如果发生于伤口部位，渗出液内大量蛋白质吸附于一般医疗装置或生医材料表面后，会开始吸引伤口处新生游离细胞与之结合；大量新生细胞不断地累积在敷料基质的间隙中，形成新生组织与基质交错的结构，即所谓的伤口沾粘现象；当发生于泌尿道系统，尿液中蛋白质或细菌吸附于一般医疗装置或生医材料表面后，细菌会开始大量增生繁殖进而形成生物膜，可能引发感染与医疗装置(例如导管)产生矿化(encrustation)致使阻塞；当发生于血管系统时，血液中蛋白质附于与血液接触的医疗装置或生医材料表面后，非特异性蛋白会引发血液中血小板吸附与活化，进而产生血栓。
聚乙二醇(polyethylene glycol，PEG)是目前已知最具抑制蛋白质吸附功能的亲水性材料，因此一般会以等离子体、臭氧、电晕等方式将惰性的医疗装置或生医材料表面活化再施以化学接枝聚乙二醇分子亲水分子。然而，对于不规则形状、具厚度、或是多孔隙结构的医疗装置或生医材料而言，上述手段却无法达到最均匀的亲水化界面与最佳的亲水化效果。
发明内容
本发明的目的在于提供一种能够达到表面均匀亲水化，及抑制非特异性蛋白质吸附的多功能高分子材料。
本发明提供一种梳状结构高分子，包括：线性高分子主链；以及梳状侧链，所述梳状侧链包括：疏水性分子链段，以及亲水性分子链段及/或抑制生物膜/或抗菌的分子链段；其中上述线性高分子主链是以羟基与上述梳状侧链的各种链段之间的反应性官能基形成共价键结相互连接，其中上述反应性官能基包括：异氰酸酯基、羧基、或环氧基。
本发明还提供一种医疗装置的改质方法，包括：提供前述的梳状结构高分子；将该梳状结构高分子溶解于一溶液中；以及将上述含有上述梳状结构高分子的溶液以涂布或含浸方式，经过一干燥程序，贴附于一医疗装置表面。
本发明还提供一种医疗装置，其表面贴附及/或内部混掺有前述的梳状结构高分子。
本发明的优点在于：本发明的梳状结构高分子材料可溶解于溶液中，以物理性方式吸附于疏水性材料或医疗装置表面；或可以混掺方式分布于疏水性材料内部或医疗装置内部及表面。由于本发明的梳状高分子材料的亲水性链段裸露于医疗装置表面后，亲水链段除了可提升医疗装置或生医材料表面亲水程度外，亲水链段分子链更可于表面形成空间障碍，且亲水链段分子链熵斥力会使亲水链段分子排列成纤毛结构，将靠近其的蛋白质分子排开，因此可抑制蛋白质与基材的吸附，医疗装置表面亲水程度提升后可降低医疗装置或材料的摩擦系数，与抑制活体细胞贴附，并可避免生物组织沾粘，抑制细菌贴附。此外，本发明中的梳状高分子材料侧链也可以共价键结引入抑制生物膜/或抗菌分子，使改质后的医疗装置或生医材料表面具有抑制细菌繁殖、抗菌、以及抑制生物膜形成功能。
为让本发明的上述和其它目的、特征和优点能更明显易懂，下文特举出较佳实施例，并配合所附附图，作详细说明如下：
附图说明
图1是根据本发明的实施例，显示梳状结构高分子的组成示意图；
图2a至2e显示本发明的五种梳状结构高分子的实施例；
图3是根据本发明的实施例，显示利用梳状结构高分子对医疗装置基材表面进行改质的示意图；
图4是根据本发明的实施例，显示疏水性侧链与基材附着的稳定性；
其中，主要元件符号说明：
11～线性高分子主链； 12～疏水性分子链段；
13～亲水性分子链段； 14～抑制生物膜/或抗菌的分子链段；
101～梳状结构高分子； 101a～梳状结构高分子；
101b～梳状结构高分子； 101c～梳状结构高分子；
101d～梳状结构高分子； 101e～梳状结构高分子；
23～疏水性基材/医疗装置。
具体实施方式
以下是藉由特定的具体实施例说明本发明的实施方式，熟习此技艺的人士可由本说明书所揭示的内容轻易地了解本发明的优点及功效。本发明也可藉由其它不同的实施方式加以施行或应用，本说明书中的各项细节也可基于不同观点与应用，在不悖离本发明所揭示的精神下赋予不同的修饰与变更。
图1是依据本发明的实施例，说明梳状结构高分子的组成，本发明的梳状高分子主要包括(a)线性高分子主链以及(b)梳状侧链。(a)线性高分子主链例如是含羟基的线性结构主链11。(b)梳状侧链包括：(b1)疏水性分子链段12，以及(b2)亲水性分子链段13及/或抑制生物膜/或抗菌的分子链段14。上述线性高分子主链与上述梳状侧链之间，是上述线性高分子主链以羟基与上述梳状侧链的反应性官能基所形成的共价键结相互连接，其中上述反应性官能基包括：异氰酸酯基、羧基、或环氧基。在本发明的梳状结构高分子中，疏水性链段12可藉由物理性吸附方式，使得梳状结构高分子结合于一疏水性医疗装置表面，而亲水性链段13可以提高被处理医疗装置表面亲水程度、降低摩擦系数、抑制蛋白质吸附、抑制活体细胞贴附、以及避免生物组织沾粘。此外，抑制生物膜/或抗菌的分子链段14具有抑制细菌繁殖、抗菌、以及抑制生物膜形成功能。在一实施例中，梳状结构高分子还可富含有自由羟基，以供做为其它化学修饰的官能基，使上述医疗装置表面处理技术性能大增，更能符合梳状高分子材料于医疗装置表面处理应用的实用性。
图2a是根据本发明的实施例，显示一梳状结构高分子101a的组成包括：线性高分子主链11，以及包括疏水性分子链段12与亲水性分子链段13的梳状侧链的示意图。
图2b是根据本发明的实施例，显示一梳状结构高分子101b的组成包括：线性高分子主链11，以及包括疏水性分子链段12、亲水性分子链段13与抑制生物膜/或抗菌的分子链段14的梳状侧链的组成示意图。
图2c是根据本发明的实施例，显示一梳状结构高分子101c的组成包括：线性高分子主链11，以及包括疏水性分子链段12与抑制生物膜/或抗菌的分子链段14的梳状侧链的组成示意图。
图2d是根据本发明的实施例，显示一梳状结构高分子101d的组成包括：线性高分子主链11，以及包括疏水性分子链段12、亲水性分子链段13与抑制生物膜/或抗菌的分子链段14的梳状侧链的组成示意图，其中抑制生物膜/或抗菌(抑制细菌繁殖)的分子链段14以共价键接枝于亲水性分子链段13上，且亲水性分子链段13接枝于线性高分子主链11上。
图2e是根据本发明的实施例，显示一梳状结构高分子101e的组成包括：线性高分子主链11，以及包括疏水性分子链段12、亲水性分子链段13与抑制生物膜/或抗菌(抑制细菌繁殖)的分子链段14的梳状侧链结构的组成示意图，其中亲水性分子链段13以共价键接枝于抑制生物膜/或抗菌的分子链段14上，且抑制生物膜/或抗菌的分子链段14接枝于线性高分子主链11上。
在本发明的梳状高分子材料中，上述线性高分子主链且具有羟基者，可选自线性或含有支链的合成高分子与天然高分子，而较佳为线性的合成高分子与天然高分子，最佳为线性合成高分子，其中上述线性合成高分子主链可包括但不限于：聚乙烯醇(polyvinyl alcohol，PVA)、聚醋酸乙烯酯(polyvinylacetate，PVAc)、乙烯醇-醋酸乙烯酯共聚合物(poly(vinyl alcohol-co-vinylacetate))、乙烯-乙烯醇共聚物(poly(ethylene vinyl-co-alcohol)，EVOH)、多糖高分子(polysaccharide)、或上述的组合。上述天然高分子可为多糖类高分子(polysaccharide)，其中上述多糖类高分子可包括但不限于：透明质酸(hyaluronic acid)、纤维素(cellulose)、葡聚糖(dextran)、壳质(chitin)、壳聚糖(chitosan)、褐藻胶(alginate)、角叉藻胶(carrageenan)、淀粉(starch)、果胶(pectin)、阿拉伯树胶(gum Arabic)、关华豆胶(guar gum)、普路兰(pullulan)、硬葡聚糖(scleroglucan)、结兰胶(gellan)、软骨素(chondroitinsulfate)、肝素(heparin)、硫酸角蛋白(keratin sulfate)、上述衍生物或上述的组合。上述线性高分子主链的重量平均分子量介于约500～2000000道尔顿，较佳介于约5000～1000000道尔顿。
在本发明的梳状高分子材料中，上述疏水性分子链段包括但不限于：含有胺基甲酸酯(urethane)的重复单元所构成高分子链段、含有聚氧化丙烯(poly propylene oxide，PPO)的重复单元所构成高分子链段、含有乙烯(Ethylene)的重复单元所构成高分子链段、含有丙烯(Propylene)的重复单元所构成高分子链段、含有苯乙烯(Styrene)的重复单元所构成高分子链段、含有砜(Sulfone)的重复单元所构成高分子链段、或上述重复单元组成的共聚合物所构成高分子链段，其中上述含有胺基甲酸酯的重复单元所构成高分子链段包括：脂肪族聚胺基甲酸酯、芳香族聚胺基甲酸酯、或上述的组合。上述疏水性分子链段的重量平均分子量介于约500至50,000道尔顿(Dalton)之间。
在本发明的梳状高分子材料中，上述亲水性分子链段包括但不限于：聚乙二醇(polyethylene glycol，PEG)、聚氧化乙烯(polyethylene oxide，PEO)、聚乙烯吡咯烷酮(polyvinylpyrrolidone，PVP)、聚丙烯酸(polyacrylic acid，PAA)及聚甲基丙烯酸(polymethacrylic acid，PMA)、或上述的组合，其中较佳的亲水性分子链段包括：聚乙二醇(polyethylene glycol，PEG)、聚氧化乙烯(polyethylene oxide，PEO)、聚乙烯吡咯烷酮(polyvinylpyrrolidone，PVP)、或上述的组合。上述亲水性分子链段的重量平均分子量介于约500至100,000道尔顿(Dalton)，较佳可介于约500至50,000道尔顿(Dalton)，最佳介于约500至30,000道尔顿(Dalton)。
在本发明的梳状高分子材料的另一实施例中，更可以化学键结或物理吸附方式接上抑制生物膜/或抗菌分子链段，其中上述抑制生物膜/或抗菌的分子包括但不限于：法尼醇(Farnesol)、木糖醇(xylitol)、乳铁蛋白(Lactoferrin)、乙二胺四醋酸(ethylene diamine tetraacetic acid，EDTA)、镓(Gallium)、PNAG-分解酵素(PNAG-degrading enzyme)、RNA-III抑制胜肽(RNA-III inhibitingpeptide)、呋喃酮C30(Furanone C30)、银、碘、锌、铜、抗生素、药物或上述的组合，较佳包括：法尼醇(Farnesol)或木糖醇(Xylitol)，最佳为法尼醇(Farnesol)。
上述抑制生物膜/或抗菌的分子链段可直接以化学键结或物理吸附方式接到本发明的线性高分子主链上，也可以化学键结或物理吸附方式接于前述的亲水性分子链段或疏水性分子链段。
上述亲水性分子链段、疏水性分子链段、或抑制生物膜/或抗菌分子链段与上述线性高分子主链的官能基，例如羟基，可利用本身或经改质后的反应官能基，例如异氰酸酯基、羧基、或环氧基等，形成共价键结而相互连接，进而形成本发明的梳状高分子结构。举例而言，当线性高分子主链具有-OH基，而梳状侧链具有异氰酸酯基(-NCO)基时，两者的间的共价键为胺基甲酸酯键结(Urethane Linkage；-O(C＝O)NH-)；当线性高分子主链具有-OH基，而梳状侧链具有羧基(-COOH)时，两者的间的共价键为酯基键结(EsterLinkage)；当线性高分子主链具有-OH基，而梳状侧链具有环氧基时，两者的间的共价键为醚基键结(Ether Linkage)。
参阅图3，本发明另提供一种医疗装置的表面改质方式：提供前述的梳状结构高分子材料101，通过将梳状结构高分子材料101溶解于溶液中，以涂布或含浸等方式，并经过一干燥程序吸附于医疗装置表面23而达到表面改质目的。如图3中所示，梳状结构高分子101的疏水性链段12是以物理性吸附方式结合于疏水性的医疗装置表面23。另一方面，亲水性分子链段13则排列成纤毛结构。上述溶解溶液可包括但不限于：N，N-二甲基甲酰胺(N，N-dimethylformamide，DMF)、N，N-二甲基乙酰胺(N，N-dimethylacetamide，DMAc)、二甲基亚砜(Dimethyl sulfoxid，DMSO)、四氢呋喃(Tetrahydrofuran，THF)、醇类(Alcohols)、酮类(Ketones)、水(Water)、或上述的组合，较佳包括：N，N-二甲基乙酰胺(DMAc)、酮类、水、或上述的组合，更佳者包括下列溶剂组合(a)丁酮及水、(b)丙酮及N，N-二甲基乙酰胺(DMAc)、或(c)丙酮、水及N，N-二甲基乙酰胺(DMAc)。
在一实施例中，上述梳状结构高分子材料溶解于溶液中的固含量可介于约0.01％至50％(重量百分比)，较佳介于约0.1％至30％(重量百分比)，最佳介于约0.1％至20％(重量百分比)。
在一实施例中，上述梳状结构高分子溶液以涂布或含浸等方式处理于一医疗装置或基材后，可以热风或真空方式进行干燥，且温度介于室温至200℃，较佳为约30℃至100℃。
所述医疗装置是由一高分子材料所构成，除上述以溶液溶解后利用涂布或含浸等方式进行医疗装置或基材表面处理外，也可以混掺方式混合于与医疗装置的高分子材料内，而上述梳状结构高分子与医疗装置的高分子材料混掺方式可包括但不限于：熔融混掺或溶剂共溶解混掺，其中上述组成医疗装置的高分子材料包括：热塑性聚胺基甲酸酯(Thermoplastic Polyurethane，TPU)、聚胺基甲酸酯(Polyurethane，PU)、聚乙烯醇(polyvinyl alcohol，PVA)、聚乙烯(Polyethylene，PE)、聚丙烯(Polypropylene，PP)、聚氯乙烯(polyvinylchloride，PVC)、聚苯乙烯(Polystyrene)、聚醋酸乙烯酯(polyvinyl acetate，PVAc)、乙烯醇-醋酸乙烯酯共聚合物(poly(vinyl alcohol-co-vinyl acetate))、乙烯-乙烯醇共聚物(poly(ethylene vinyl-co-alcohol)，EVOH)、聚砜(Polysulfone)、聚醚砜(poly ether sulfone)、上述的衍生物或上述的组合。
因此，上述梳状结构高分子材料可溶解于溶液中，以物理性方式吸附于疏水性材料或医疗装置表面；或可以混掺方式分布于疏水性材料内部或医疗装置内部及表面。梳状高分子材料的亲水性链段裸露于医疗装置表面后，亲水链段除了可提升医疗装置或生医材料表面亲水程度外，亲水链段分子链更可于表面形成空间障碍，且亲水链段分子链熵斥力(entropic repulsion)会使亲水链段分子排列成纤毛(cilia)结构，将靠近其的蛋白质分子排开，因此可抑制蛋白质与基材的吸附，医疗装置表面亲水程度提升后可降低医疗装置或材料的摩擦系数，与抑制活体细胞贴附，并可避免生物组织沾粘，抑制细菌贴附。此外，本发明中的梳状高分子材料侧链也可以共价键结引入抑制生物膜/或抗菌分子，使改质后的医疗装置或生医材料表面具有抑制细菌繁殖、抗菌、以及抑制生物膜形成功能。
综合本发明，梳状结构高分子材料无论以物理性吸附或以混掺方式分布于疏水性材料内部或医疗装置内部及表面，上述医疗装置可为敷料(Wounddressing)、导管(Catheter)，血管通路装置(Vascular access devices)，血液透析装置(Hemodialyzer)、血管支架(Stent)、胆道支架(Biliary stent)、或植入式装置(Implantable devices)等。
以下是藉由特定的具体实施例进一步说明本发明的特点与功效，但非用于限制本发明的范畴。
【实施例1】疏水分子链段预聚合物(A)『mPU(BDO)-NCO』
梳状结构高分子材料中的疏水分子链段预聚合物(A)制备步骤如下，取1，4-丁二醇(1，4-butanediol，1，4-BDO)1.53g，置于圆底反应瓶并添加7.65mlN，N-二甲基乙酰胺(DMAc)溶剂缓慢升温至60℃后混合均匀，继之将溶解于42.35ml DMAc的8.47克二苯基甲烷4，4′-二异氰酸酯(Diphenylmethane-4，4′-diisocyanate，MDI)缓慢滴入反应瓶中以50℃反应3小时并通以氮气，反应3小时候取样进行分子量分析，以GPC测得重量平均分子量(Mw)约为2,243道尔顿。接下来取0.12ml甲醇以0.6ml DMAc稀释后缓慢滴入前述反应瓶中形成单侧具有活性的疏水分子预聚合物。
【实施例2】疏水分子链段预聚合物(B)『mC8PU8,000-NCO』
梳状结构高分子材料中的疏水分子链段预聚合物(B)制备步骤如下，取19.5g聚四氢呋喃PTMEG1000(PolyTetramethylene-ether-Glycol，PTMEG，重量平均分子量1000道尔顿)加入36ml DMAC于150ml双颈瓶，将2.325gMDI加入4ml DMAc，并使用等压漏斗缓慢滴入，混合均匀后升温到65℃反应2小时，反应完得到预聚合物(prepolymer)。接下来取1.64ml正辛基异氰酸酯(Octyl isocyanate，简写C8-NCO)加入4ml DMAc，将前述预聚合物降到室温后，将C8-NCO加入预聚合物中，并加入1000ppm的辛酸亚锡(Stannous octoate)以及2000ppm的1，4-二氮杂二环[2.2.2]辛烷(1，4-Diazabicyclo-(2.2.2)octane)作为催化剂，混合均匀后升温到65℃反应2小时，得到mC8-预聚合物。
继之，取2.325g MDI加入4ml DMAc，并缓慢加入前述mC8-预聚合物中，混合均匀后升温到60℃反应3小时，得到mC8PU8,000-NCO(PU)疏水分子链段预聚合物(B)，以GPC测得重量平均分子量(Mw)约8,000道尔顿。
【实施例3】疏水分子链段预聚合物(C)『mPPO2,500-NCO』
取2.9g聚(丙二醇)单丁醚(Poly(propylene glycol)monobutyl ether，简称mPPO2500)(重量平均分子量2500道尔顿)加入4ml DMAc溶解，接下来并将0.275g MDI加入2ml DMAc于25ml双颈瓶溶解。于室温下将前述mPPO(重量平均分子量2500道尔顿)缓慢加入MDI溶液中，混合均匀后升温到60℃反应2小时，反应完后得到mPPO2500-NCO。
【实施例4】疏水分子链段预聚合物(D)『mPPU4,923-NCO』
预先将使用的溶剂DMAc、1，4-丁二醇及mPPO(重量平均分子量2500道尔顿)用分子筛除水一天。制备步骤如下，取5.32g MDI加入26.6ml DMAC于250ml双颈瓶中室温搅拌至溶解，再将0.58g的1，4-丁二醇加入2.9mlDMAc中搅拌后加入前述MDI溶液中混合均匀后升温到60±5℃反应3小时，反应完得到预聚合物(prepolymer)，GPC测得重量平均分子量为Mw＝1,447道尔顿。
取10.3g mPPO(重量平均分子量2500道尔顿)加入51.5ml DMAc于150ml单颈瓶中室温摇晃至溶解，将此mPPO溶液置于等压漏斗缓慢滴入前述60±5℃的预聚合物溶液中，此滴入过程约30分钟，待mPPO溶液全部加入后于60±5℃下搅拌反应2.5小时，得到mPPO2,500-b-PU1,447-NCO(mPPU-NCO)的预聚合物，GPC测得重量平均分子量为Mw＝4,923道尔顿(mPPU4,923-NCO)。
【实施例5】疏水分子链段预聚合物(E)『mPPU9,764-NCO』
预先将使用的溶剂DMAc、1，4-丁二醇及mPPO(重量平均分子量2500道尔顿)用分子筛除水一天。制备步骤如下，取25.16g MDI加入126ml DMAC于250ml双颈瓶中室温搅拌至溶解，再将5.44g的1，4-丁二醇加入27mlDMAc中搅拌后加入前述MDI溶液中混合均匀后升温到60±5℃反应3小时，反应完得到预聚合物(prepolymer)。GPC测得重量平均分子量为Mw＝4581道尔顿。
取10.22g mPPO(重量平均分子量2500道尔顿)加入51.1ml DMAc于150ml单颈瓶中室温摇晃至溶解，并取103ml前述的预聚合物溶液后将此mPPO溶液置于等压漏斗缓慢滴入前述60±5℃的预聚合物溶液中，此滴入过程约30分钟，待mPPO溶液全部加入后于60±5℃下搅拌反应2.5小时，得到mPPO2,500-b-PU4,581-NCO(mPPU-NCO)的预聚合物，反应计算重量平均分子量为Mw＝9,764道尔顿(mPPU9,764-NCO)。
【实施例6】亲水分子链段预聚合物『mPEG5,000-NCO』
制备亲水分子链段预聚合物前，先将使用的溶剂DMAc用分子筛除水一天，并将聚乙二醇单甲醚(Poly(ethylene glycol)monomethyl ether，简称mPEG5000)(重量平均分子量5000道尔顿)以真空干燥24小时备用。取80gmPEG5000加入120ml DMAc于500ml双颈瓶后预热至60℃溶解，接下来取3.5g MDI加入35ml DMAc中溶解后降温至40℃后，继之将MDI溶液缓慢加入mPEG5000中，混合均匀后缓慢升温至60℃反应2小时，反应后得到亲水性mPEG5000-NCO预聚合物。
【实施例7】抑制生物膜/或抗菌的分子链段预聚合物(A)『Farnesol-HDI-NCO』
制备抑制生物膜/或抗菌的分子链段预聚合物前，先将使用的溶剂DMAc用分子筛除水一天，并将法尼醇(3，7，11-Trimethyl-2，6，10-dodecatrien-1-ol，Farnesol)以70℃真空干燥24小时备用。取5.818g法尼醇加入80ml DMAc于250ml双颈瓶后搅拌溶解，再将0.04g的三乙亚二胺(1，4-Diazabicyclo-(2，2，2)Octane，DABCO)及0.02g的Sn(Oct)2(stannousoctoate，Sn(II))加入法尼醇溶液中。接着取4.182g的1，6-己二异氰酸酯(1，6-Diisocyanatohexane，HDI)加入20ml DMAc搅拌溶解后，将HDI溶液缓慢加入Farnesol溶液中，混合均匀后缓慢升温至55-60℃反应3小时，得到可抑制生物膜/或抗菌的分子链段Farnesol-HDI-NCO预聚合物。
【实施例8】抑制生物膜/或抗菌的分子链段预聚合物(B)『Farnesol-IPDI-NCO』
制备前先将使用的溶剂DMAc用分子筛除水一天，取0.72g法尼醇加入14ml DMAc于500ml双颈瓶溶解，接着取0.68g异佛尔酮二异氰酸酯(Isophorone diisocyanate，简称IPDI)加入500ml双颈瓶中溶解后，取DABCO0.1g以及0.05g Sn(Oct)2加入2ml DMAc于20ml瓶中以超音波震荡30min溶解后，取0.056ml加入500ml双颈瓶中，均匀搅拌后加温至55℃反应3小时，得到抑制生物膜/或抗菌的分子链段预聚合物(B)『Farnesol-IPDI-NCO』。
【实施例9】抑制生物膜/或抗菌的分子链段预聚合物(C)『Farnesol-b-PEG10,000-NCO』
制备前先将使用的溶剂DMAc及聚乙二醇(Polyethylene glycol，简称PEG diol10,000)(重量平均分子量10,000道尔顿)以真空干燥24小时备用，取30.76g PEG diol10,000加入307.6ml DMAc于500ml双颈瓶溶解，倒入实施例8中含有Farnesol-IPDI-NCO预聚合物于500ml双颈瓶，均匀搅拌后加温至65℃反应16小时，得到亲水性抑制生物膜/或抗菌的分子链段预聚合物(Farnesol-b-PEG10,000-NCO)。
【实施例10】抑制生物膜/或抗菌的分子链段预聚合物(D)『Farnesol-b-PEG2,000-NCO』
制备前先将使用的溶剂DMAc及聚乙二醇(Polyethylene glycol，简称PEGdiol2,000)(重量平均分子量2,000道尔顿)以真空干燥24小时备用。取15.47gPEG2,000加入154.7ml DMAc于250ml双颈瓶溶解，倒入实施例8中含有Farnesol-IPDI-NCO预聚合物于250ml双颈瓶，均匀搅拌后加温至65℃反应16小时，得到亲水性抑制生物膜/或抗菌的分子链段预聚合物(Farnesol-b-PEG2,000-NCO)。
【实施例11】梳状结构高分子材料(A)『PVA10,000-g-(60％PEG5,000-co-30％mC8PU)』
取1g聚乙烯醇PVA10,000(PVA；重量平均分子量10,000道尔顿)加入19ml DMAc于50ml双颈瓶中缓慢加热到60℃溶解，继之将前述PVA10,000溶液降温至室温后加入实施例6的mPEG5,000-NCO亲水分子链段预聚合物中，混合均匀后缓慢升温到60±5℃反应3小时，反应后得到PVA10,000-g-PEG5,000产物。
取实施例2的mC8PU8,000-NCO疏水分子链段预聚合物(B)56ml添加至前述PVA10,000-g-PEG5,000产物，混合后升温到60℃反应3小时，反应后得到PVA10,000-g-(60％PEG5,000-co-30％mC8PU8,000)，亲水性链段(PEG)接枝率(链段中的单键摩尔数/羟基的总摩尔数)为60％，疏水性链段(mC8PU)接枝率为30％。
上述梳状结构高分子材料纯化步骤为反应后产物于DMAc溶液中以分子量筛模法(molecular weight cut-off，简称MWCO)：12K-14K透析膜透析2天，接下来以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最后于水中以MWCO：12K-14K透析膜透析2天后将产物取出后进行冷冻干燥。
【实施例12】梳状结构高分子材料(B)『PVA10,000-g-(60％PEG5,000-co-10％mC8PU)』
取1g聚乙烯醇PVA10,000加入19ml DMAc于50ml双颈瓶中缓慢加热到60℃溶解，继之将前述PVA10,000溶液降温至室温后加入实施例6的mPEG5000-NCO亲水分子链段预聚合物中，混合均匀后缓慢升温到60±5℃反应3小时，反应后得到PVA10,000-g-PEG5,000产物。
取实施例2的mC8PU8,000-NCO疏水分子链段预聚合物(B)56ml添加至前述PVA10,000-g-PEG5,000产物，混合后升温到60℃反应3小时，反应后得到PVA10,000-g-(60％PEG5,000-co-10％mC8PU8,000)，亲水性链段(PEG)接枝率为60％，疏水性链段(mC8PU)接枝率为10％。
上述梳状结构高分子材料纯化步骤为反应后产物于DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下来以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最后于水中以MWCO：12K-14K透析膜透析2天后将产物取出后进行冷冻干燥。
【实施例13】梳状结构高分子材料(C)『PVA10,000-g-(30％PEG5,000-co-10％mC8PU)』
取1g聚乙烯醇PVA10,000加入19ml DMAc于50ml双颈瓶中缓慢加热到60℃溶解，继之将前述PVA10,000溶液降温至室温后加入实施例6的mPEG5,000-NCO预聚合物中，混合均匀后缓慢升温到60±5℃反应3小时，反应后得到PVA10,000-g-PEG5,000产物。
取实施例2的mC8PU8,000-NCO疏水分子链段预聚合物(B)56ml添加至前述PVA10,000-g-PEG5,000产物，混合后升温到60℃反应3小时，反应后得到PVA10,000-g-(30％PEG5,000-co-10％mC8PU8,000)，亲水性链段(PEG)接枝率为30％，疏水性链段(mC8PU)接枝率为10％。
上述梳状结构高分子材料纯化步骤为反应后产物于DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下来以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最后于水中以MWCO：12K-14K透析膜透析2天后将产物取出后进行冷冻干燥。
【实施例14】梳状结构高分子材料(D)『PVA10,000-g-(60％PEG5,000-co-10％mC8PU)』
取1g聚乙烯醇PVA10,000加入19ml DMAc于50ml双颈瓶中缓慢加热到60℃溶解，继之将前述PVA10,000溶液降温至室温后加入实施例6的mPEG5,000-NCO预聚合物中，混合均匀后缓慢升温到60±5℃反应3小时，反应后得到PVA10,000-g-PEG5,000产物。
取实施例2的mC8PU8,000-NCO疏水分子链段预聚合物(B)56ml添加至前述PVA10,000-g-PEG5,000产物，混合后升温到60℃反应3小时，反应后得到PVA10,000-g-(60％PEG5,000-co-10％mC8PU8,000)，亲水性链段(PEG)接枝率为60％，疏水性链段(mC8PU)接枝率为10％。
上述梳状结构高分子材料纯化步骤为反应后产物于DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下来以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最后于水中以MWCO：12K-14K透析膜透析2天后将产物取出后进行冷冻干燥。
【实施例15】梳状结构高分子材料(E)『PVA10,000-g-(90％PEG5,000-co-10％mC8PU)』
取1g聚乙烯醇PVA10,000加入19ml DMAc于50ml双颈瓶中缓慢加热到60℃溶解，继的将前述PVA10,000溶液降温至室温后加入实施例6的mPEG5000-NCO预聚合物中，混合均匀后缓慢升温到60±5℃反应3小时，反应后得到PVA10,000-g-PEG5,000产物。
取实施例2的mC8PU8,000-NCO疏水分子链段预聚合物(B)56ml添加至前述PVA10,000-g-PEG5,000产物，混合后升温到60℃反应3小时，反应后得到PVA10,000-g-(90％PEG5,000-co-10％mC8PU8,000)，亲水性链段(PEG)接枝率为90％，疏水性链段(mC8PU)接枝率为10％。
上述梳状结构高分子材料纯化步骤为反应后产物于DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下来以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最后于水中以MWCO：12K-14K透析膜透析2天后将产物取出后进行冷冻干燥。
【实施例16】梳状结构高分子材料(F)『PVA10,000-g-(60％PEG5,000-co-10％PPO)』
取1g聚乙烯醇PVA10,000加入19ml DMAc于50ml双颈瓶中缓慢加热到60℃溶解，继的将前述PVA10,000溶液降温至室温后加入实施例6的mPEG5,000-NCO预聚合物中，混合均匀后缓慢升温到60±5℃反应3小时，反应后得到PVA10,000-g-PEG5,000产物。接下来取实施例3，mPPO2500-NCO疏水分子链段预聚合物(C)添加至前述PVA10,000-g-PEG5,000产物中混合后升温到60℃反应3小时，反应后得到PVA10,000-g-(60％PEG5,000-co-10％PPO)，亲水性链段(PEG)接枝率为60％，疏水性链段(mPPO)接枝率为10％。
上述梳状结构高分子材料纯化步骤为反应后产物于DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下来以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最后于水中以MWCO：12K-14K透析膜透析2天后将产物取出后进行冷冻干燥。
【实施例17】梳状结构高分子材料(G)『PVA10,000-g-(PEG5,000-co-PPU4,923)』
步骤1.亲水分子链段预聚合物『mPEG5,000-NCO』
制备亲水分子链段预聚合物前，先将使用的溶剂DMAc用分子筛除水一天，并将mPEG5000以真空干燥24小时备用。预先分别取86.12g mPEG5,000加入856ml DMAc于1000ml双颈瓶后预热至60℃溶解，接下来分别取1.18g、1.37g及1.54g的MDI加入13ml、14ml及18ml DMAc于1000ml双颈瓶中室温搅拌溶解后开始逐步升温至60±5℃，同时并将mPEG5000溶液分成320ml、286ml及250ml三份置于等压漏斗缓慢滴入MDI溶液中，此滴入过程约2小时，待mPEG5000溶液全部加入后于60±5℃下反应1小时，得到亲水性mPEG5000-NCO预聚合物。
步骤2.疏水分子链段预聚合物『Poly propyleneglycol-b-polyurethane-isocyanate(PPO-b-PU-NCO)，简称PPU-NCO』
预先将使用的溶剂DMAc、1，4-丁二醇及mPPO2500用分子筛除水一天。制备步骤如下，取5.32g MDI加入26.6ml DMAC于250ml双颈瓶中室温搅拌至溶解，再将0.58g的1，4-丁二醇加入2.9ml DMAc中搅拌后加入前述MDI溶液中混合均匀后升温到60±5℃反应3小时，反应完得到预聚合物，GPC测得重量平均分子量为Mw＝1,447道尔顿。
取10.3g mPPO2500加入51.5ml DMAc于150ml单颈瓶中室温震荡至溶解，将此mPPO2500溶液置于等压漏斗缓慢滴入前述60±5℃的预聚合物溶液中，此滴入过程约30分钟，待mPPO2500溶液全部加入后于60±5℃下搅拌反应2.5小时，得到PPU-NCO的预聚合物，GPC测得重量平均分子量为Mw＝4,923道尔顿。
步骤3.梳状结构高分子材料
预先取三份0.3g聚乙烯醇PVA10,000分别加入6ml DMAc于20ml样品瓶中放置65℃烘箱溶解，继之PVA10,000溶液降温至室温后分别加入338ml、300ml及263ml步骤1的亲水分子链段mPEG5,000-NCO预聚合物中，混合均匀后缓慢升温到60±5℃反应3小时，反应后得到PVA10,000-g-PEG5,000产物。接下来取前述的疏水分子链段PPU-NCO预聚合物13.5ml、27ml及40.5ml分别添加至PVA10,000-g-PEG5,000产物中，并分别加入0.054g、0.01g及0.0016g的DABCO和0.027g、0.0054g及0.0008g的Sn(Oct)2，混合后升温到65℃反应16小时，得到PVA10,000-g-(PEG5,000-co-PPU)，亲水性链段(PEG)接枝率为70％、80％及90％，疏水性链段(mPPU)接枝率为30％、20％及10％。上述梳状结构高分子材料纯化步骤为反应后产物于DMSO溶液中以MWCO：25K透析膜透析2天，接下来于二次水中以MWCO：25K透析膜透析2天后将产物取出后进行冷冻干燥。
【实施例18】梳状结构高分子材料(H)『PVA-g-(PEG5,000-co-PPU9,764)』
步骤1.亲水分子链段预聚合物『mPEG5,000-NCO』
制备亲水分子链段预聚合物前，先将使用的溶剂DMAc用分子筛除水一天，并将mPEG5000以真空干燥24小时备用。预先取86.12g mPEG5,000加入856ml DMAc于1000ml双颈瓶后预热至60℃溶解，接下来分别取1.18g、1.37g及1.54g的MDI加入13ml、14ml及18ml DMAc于1000ml双颈瓶中室温搅拌溶解后开始逐步升温至60±5℃，同时并将mPEG5000溶液分成320ml、286ml及250ml置于等压漏斗缓慢滴入MDI溶液中，此滴入过程约2小时，待mPEG5000溶液全部加入后于60±5℃下反应1小时，得到亲水性mPEG5000-NCO预聚合物。
步骤2.疏水分子链段预聚合物『Poly propyleneglycol-b-polyurethane-isocyanate(PPO-b-PU-NCO)，简称PPU-NCO』
预先将使用的溶剂DMAc、1，4-丁二醇及mPPO2500用分子筛除水一天。制备步骤如下，取25.16g MDI加入126ml DMAC于250ml双颈瓶中室温搅拌至溶解，再将5.44g的1，4-丁二醇加入27ml DMAc中搅拌后加入前述MDI溶液中混合均匀后升温到60±5℃反应3小时，反应完得到预聚合物，GPC测得重量平均分子量为Mw＝4,581道尔顿。
接下来取10.22g mPPO2500加入51.1ml DMAc于150ml单颈瓶中室温摇晃至溶解，并取103ml前述的预聚合物溶液后将此mPPO溶液置于等压漏斗缓慢滴入前述60±5℃的预聚合物溶液中，此滴入过程约30分钟，待mPPO2500溶液全部加入后于60±5℃下搅拌反应2.5小时，得到PPU9,764-NCO的预聚合物，GPC测得重量平均分子量为Mw＝9,764道尔顿。
步骤3.梳状结构高分子材料
预先分别取三份0.3g聚乙烯醇PVA10,000分别加入6ml DMAc于20ml样品瓶中放置65℃烘箱溶解，继之PVA10,000溶液降温至室温后分别加入338ml、300ml及260ml实施例15的亲水分子链段mPEG5,000-NCO预聚合物中，混合均匀后缓慢升温到60±5℃反应3小时，反应后得到PVA10,000-g-PEG5,000产物。接下来取前述的疏水分子链段PPU9,764-NCO预聚合物25.6ml、51.1ml及76.7ml分别添加至PVA10,000-g-PEG5,000产物中，并加入0.01g、0.02g及0.03g的DABCO和0.005g、0.01g及0.015g的Sn(Oct)2，混合后升温到65℃反应16小时，得到PVA10,000-g-(PEG5,000-co-PPU9,764)，亲水性链段(PEG)接枝率为70％、80％及90％，疏水性链段(PPU)接枝率为30％、20％及10％。上述梳状结构高分子材料纯化步骤为反应后产物于DMSO溶液中以MWCO：25K透析膜透析2天，接下来于二次水中以MWCO：25K透析膜透析2天后将产物取出后进行冷冻干燥。
【实施例19】梳状结构高分子材料(I)『PVA-g-(Farnesol-co-PPU4,923)』
步骤1.疏水分子链段预聚合物『Poly propyleneglycol-b-polyurethane-isocyanate(PPO-b-PU-NCO)，简称PPU-NCO』
预先将使用的溶剂(DMAc)、1，4-丁二醇及mPPO2500用分子筛除水一天。制备步骤如下，取5.32g MDI加入26.6ml DMAC于250ml双颈瓶中室温搅拌至溶解，再将0.58g的1，4-丁二醇加入2.9ml DMAc中搅拌后加入前述MDI溶液中混合均匀后升温到60±5℃反应3小时，反应完得到预聚合物，GPC测得重量平均分子量为Mw＝1,447道尔顿。接下来取10.22g mPPO2500加入51.1ml DMAc于150ml单颈瓶中室温摇晃至溶解，并取前述的预聚合物溶液后将此mPPO2500溶液置于等压漏斗缓慢滴入前述60±5℃的预聚合物溶液中，此滴入过程约30分钟，待mPPO2500溶液全部加入后于60±5℃下搅拌反应2.5小时，得到PPU-NCO的预聚合物，GPC测得重量平均分子量为Mw＝4,923道尔顿。
步骤2.梳状结构高分子材料『PVA-g-(Farnesol-co-PPU4,923)』
制备PVA-g-Farnesol预聚合物前预先将使用的溶剂DMAc用分子筛除水一天，PVA10,000真空干燥24小时备用。取1g PVA10,000加入2ml DMAC于50ml双颈瓶中于60℃烘箱至溶解，取3.028g实施例7的亲水性抑制生物膜/或抗菌的分子链段预聚合物(A)加入63.6ml DMAc中搅拌后加入前述PVA10,000溶液混合均匀后，加入0.016g DABACO及0.008g Sn(Oct)2升温到60±5℃反应16小时，反应完得到预聚合物PVA-g-Farnesol(预聚合物)。
将PVA-g-Farnesol预聚合物加入步骤1的13.5ml疏水分子链段预聚合物溶液中，混合均匀后，升温至60±5℃反应6小时，反应完得到聚合物PVA-g-(Farnesol-co-PPU4,923)，亲水性链段(Farnesol)接枝率为30％、60％，疏水性链段(PPU)接枝率分别为30％、30％。
【实施例20】梳状结构高分子材料(J)『PVA-g-(Farnesol-b-PEG-co-PPU10,171)』
步骤1.疏水分子链段预聚合物『Poly propyleneglycol-b-polyurethane-isocyanate(PPO-b-PU-NCO)，简称PPU-NCO』
预先将使用的溶剂DMAc、1，4-丁二醇及mPPO2500用分子筛除水一天。制备步骤如下，取4.86g MDI加入24.3ml DMAC于250ml双颈瓶中室温搅拌至溶解，再将0.34g的1，4-丁二醇加入1.7ml DMAc中搅拌后加入前述MDI溶液中混合均匀后升温到60±5℃反应3小时，反应完得到预聚合物，GPC测得重量平均分子量为Mw＝2,254道尔顿。接下来取5.77g mPPO2500加入28.83ml DMAc于150ml单颈瓶中室温摇晃至溶解，并取前述的预聚合物溶液后将此mPPO溶液置于等压漏斗缓慢滴入前述60±5℃的预聚合物溶液中，此滴入过程约30分钟，待mPPO2500溶液全部加入后于60±5℃下搅拌反应2.5小时，得到PPU-NCO的预聚合物，GPC测得重量平均分子量为Mw＝10,171道尔顿。
步骤2.梳状结构高分子材料『PVA-g-(Farnesol-b-PEG-co-PPU10,171)』
制备PVA-g-(Farmesol-b-PEG200)预聚合物前预先将使用的溶剂DMAc用分子筛除水一天，PVA真空干燥24小时备用。制备步骤如下，取0.027gPVA10,000加入0.1ml DMAC于50ml双颈瓶中于60℃烘箱至溶解，接着取0.814g实施例8的抑制生物膜/或抗菌的分子链段预聚合物(B)加入49.73mlDMAc中均匀搅拌后，加入前述PVA10,000溶液混合均匀，再加入0.0034gDABACO及0.0017g Sn(Oct)2升温到65±5℃反应16小时，反应完得到预聚合物PVA-g-(Farnesol-b-PEG200)。
接着取前述1/3份量的预聚合物PVA-g-(Farnesol-b-PEG200)加入1.8ml步骤1的PPU-NCO疏水分子链段预聚合物溶液混合均匀后，升温到60±5℃反应6小时，反应完得到聚合物PVA-g-(Farnesol-b-PEG2,000-co-PPU10,171)，亲水性链段(Farnesol-b-PEG2,000)接枝率为50％，疏水性链段(PPU)接枝率为30％。
制备PVA-g-(Farnesol-b-PEG10,000)预聚合物前预先将使用的溶剂DMAc用分子筛除水一天，PVA真空干燥24小时备用。制备步骤如下，取0.08gPVA10,000加入0.8ml DMAC于50ml双颈瓶中于60℃烘箱至溶解，取9.3g实施例8的抑制生物膜/或抗菌的分子链段预聚合物(B)加入102.2ml DMAc中均匀搅拌后，加入前述PVA10,000溶液混合均匀后，再加入0.0038g DABACO及0.0019g Sn(Oct)2升温到65±5℃反应16小时，反应完得到预聚合物PVA-g-(Farnesol-b-PEG10,000)。
取前述1/3份量PVA-g-(Farnesol-b-PEG10,000)预聚合物加入2.52ml步骤1的PPU-NCO疏水分子链段预聚合物溶液混合均匀后，升温到60±5℃反应6小时，反应完得到聚合物PVA-g-(Farnesol-b-PEG10,000-co-PPU10,171)，亲水性链段(Farnesol-b-PEG10,000)接枝率为50％，疏水性链段(PPU)接枝率为30％。
【实施例21】疏水性基材含浸梳状结构高分子溶液
疏水性基材含浸(dipping)梳状结构高分子溶液程序为，取前述实施例11至实施例20中的梳状结构高分子材料依照下表所列示的溶剂组成与比例震荡溶解，溶解完成后将上述梳状结构高分子溶液置入一玻璃容器中，将疏水性薄膜基材(热可塑性聚胺基甲酸乙酯薄膜；TPU膜，ThermoplasticPolyurethane Film)浸入前述此梳状结构高分子溶液20秒后取出，放置于65±5℃烘箱中移除溶液中的溶剂2小时后即完成。
表1、各样品编号的材料组成及溶解比例与溶剂组成比例
表面接触角测试(A)
表面接触角测试时，分别取未做表面含浸处理的热可塑性聚胺基甲酸乙酯薄膜(芳香族(aromatic type)，TPU膜，硬度(hardness)＝shore 95A)以及以前述实施例20的梳状结构高分子溶液含浸处理样品同时进行测试，测试样品为厚度0.3mm，长宽分别为5×2厘米的试样进行测试，测试时取用二次水(Distilled De-ionized Water，DD Water)作为接触角测试溶液，将二次水液滴接触于测试样品后30秒进行角度判读，结果如表2所列(n＝3)。
表2、材料组成及溶剂组成比例与水表面接触角
表面接触角测试(B)
表面接触角测试时，分别取未做表面含浸处理的热可塑性聚胺基甲酸乙酯薄膜(芳香族，TPU膜，硬度＝shore 95A)以及以前述实施例20的梳状结构高分子溶液含浸处理样品，测试前以二次水震荡清洗30分钟后于室温下风干备用，接下来以生理缓冲液(phosphate buffer saline，PBS buffer)于37℃下浸泡3天及7天后取出，并以二次水冲洗干净后室温下风干进行测试(测试样品尺寸为：厚度0.3mm，长宽分别为5×2厘米的试样)，测试时取用二次水作为接触角测试溶液，将二次水液滴接触于测试样品后30秒进行角度判读，结果如图4所示(n＝3)。
蛋白质吸附测试
表面以梳状结构高分子溶液含浸处理的热可塑性聚胺基甲酸乙酯薄膜(芳香族，TPU膜，硬度＝shore 85A及65D)蛋白质吸附测试前蛋白质标准液配制以及标准曲线绘制，配置方法为以二次水将2mg/ml纤维蛋白原溶液(Fibrinogen solution)稀释成50、100、250、500、1000、2000μg/ml的溶液，接下来再以1％SDS(十二烷基硫酸钠，Sodium dodecyl sulfate)将标准液稀释为5、10、25、50、100、200μg/ml纤维蛋白原溶液。并以酵素免疫分析仪(ELISAreader)读取各浓度点吸光值进行标准曲线绘制。
接下来将测试样品裁切成2×1.5cm大小放入15ml离心管，分别加入5ml(4.5mg/m)纤维蛋白原溶液后置入37℃培养箱中吸附24小时。24小时候取出并移除蛋白质溶液，以PBS缓冲液浸泡清洗样品2次。继之，将样品置入内含5ml(1.0％)SDS的微量离心管中，以超音波震荡20分钟后收集萃取蛋白质的十二烷基硫酸钠溶液，以ELISA reader测量其750nm吸光值并对照已知的不同浓度纤维蛋白原溶液所绘制标准曲线，求得蛋白质浓度，结果如表3所示(n＝3)。
表3、各实施例所得的样品与蛋白质吸附量
体外细胞贴附测试
表面以梳状结构高分子溶液含浸处理的热可塑性聚胺基甲酸乙酯薄膜(芳香族，TPU膜，硬度＝shore 85A及65D)体外细胞贴附性能评估，测试前将样品放入24well培养盘中，并以玻璃管柱与无毒环将样品平整固定。于放置样品的培养孔内，分别加入小鼠纤维母细胞(L929)及人类皮肤纤维母细胞(CCD-966SK)细胞溶液(1*105/well)并置入37℃培养箱中培养24及48小时后以PBS浸泡清洗样品数次。继之利用固定液(4％多聚甲醛(paraformaldehyde))将已经贴附的细胞固定，移除固定液后以PBS清洗样品后，加入荧光染剂(DAPI，Phalloidine)，并于荧光显微镜下观察细胞型态，并计算样品上贴附的细胞量。体外细胞贴附测试结果如表4、表5所示。
表4、小鼠纤维母细胞(L929)体外细胞贴附测试结果
表5、人类皮肤纤维母细胞(CCD-966SK)体外细胞贴附测试结果
抗菌效能评估
表面以梳状结构高分子溶液含浸处理的热可塑性聚胺基甲酸乙酯薄膜(芳香族，TPU膜，硬度＝shore 95A)抗菌效能评估，评估菌种为绿脓杆菌(Pseudomonas aeruginosa)，测试前将各试验样品以UV照光20分钟进行灭菌，评估的定性描述以对照组(TPU膜)样品下方细菌生长程度相对于各梳状结构高分子溶液含浸处理的TPU膜定性记录，抗菌效能如表6所列示。
表6、样本的抗菌效能评估
虽然本发明已经以数个较佳实施例揭露如上，然其并非用以限定本发明。任何所属技术领域中具有通常知识者，在不脱离本发明的精神和范围内，当可作任意的更动与润饰，因此本发明的保护范围当视后附的权利要求书所界定的范围为准。
Claims (19)
1.一种梳状结构高分子，包括：
(a)线性高分子主链；以及
(b)梳状侧链，包括：
(b1)疏水性分子链段，以及
(b2)亲水性分子链段及/或抑制生物膜/或抗菌的分子链段，
其中所述线性高分子主链是以羟基与所述梳状侧链的反应性官能基形成共价键结相互连接，其中所述反应性官能基包括：异氰酸酯基、羧基、或环氧基。
2.如权利要求1所述的梳状结构高分子，其中所述线性高分子主链为：聚乙烯醇、聚醋酸乙烯酯、乙烯醇-醋酸乙烯酯共聚合物、乙烯-乙烯醇共聚物、多糖高分子、或上述的组合。
3.如权利要求1所述的梳状结构高分子，其中所述疏水性分子链段为：含有胺基甲酸酯的重复单元所构成高分子链段、含有聚氧化丙烯的高分子链段、含有乙烯的重复单元所构成高分子链段、含有丙烯的重复单元所构成高分子链段、含有苯乙烯的重复单元所构成高分子链段、含有砜的重复单元所构成高分子链段、或上述组成的共聚合物所构成高分子链段。
4.如权利要求3所述的梳状结构高分子，其中所述含有胺基甲酸酯的重复单元所构成高分子链段为：脂肪族聚胺基甲酸酯、芳香族聚胺基甲酸酯、或上述的组合。
5.如权利要求3所述的梳状结构高分子，其中所述疏水性分子链段的重量平均分子量介于500至50,000道尔顿之间。
6.如权利要求1所述的梳状结构高分子，其中所述亲水性分子链段为：聚乙二醇、聚氧化乙烯、聚乙烯吡咯烷酮、聚丙烯酸、聚甲基丙烯酸、或上述的组合。
7.如权利要求1所述的梳状结构高分子，其中所述亲水性分子链段为：聚乙二醇、聚氧化乙烯、聚乙烯吡咯烷酮、或上述的组合。
8.如权利要求6至7中任一项所述的梳状结构高分子，其中所述亲水性分子链段的重量平均分子量介于500至100,000道尔顿之间。
9.如权利要求1所述的梳状结构高分子，其中所述抑制生物膜/或抗菌的分子链段为：法尼醇、木糖醇、乳铁蛋白、乙二胺四醋酸、镓、PNAG-分解酵素、RNA-III抑制胜肽、呋喃酮C30、银、碘、锌、铜、抗生素、药物或上述的组合。
10.如权利要求1所述的梳状结构高分子，其中所述线性高分子主链以及所述梳状侧链之间的共价键结为胺基甲酸酯键结。
11.一种医疗装置的改质方法，包括：
提供权利要求1至10项中任一项所述的梳状结构高分子；
将所述梳状结构高分子溶解于一溶液中；以及
将上述含有梳状结构高分子的溶液以涂布或含浸方式，经过一干燥程序，贴附于一医疗装置表面。
12.如权利要求11所述的医疗装置的改质方法，其中所述溶液为：N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、二甲基亚砜、四氢呋喃、醇类、酮类、水、或上述的组合。
13.如权利要求11所述的医疗装置的改质方法，其中所述溶液为：(a)丁酮及水、(b)丙酮及N，N-二甲基乙酰胺、(c)丙酮、水及N，N-二甲基乙酰胺、或(d)丙酮、N，N-二甲基乙酰胺及二甲基亚砜。
14.如权利要求11所述的医疗装置的改质方法，其中所述干燥程序是以热风或真空方式进行，且温度介于室温至200℃。
15.如权利要求11所述的医疗装置的改质方法，其中所述医疗装置是由一高分子材料所构成，所述高分子材料为：热塑性聚胺基甲酸酯、聚胺基甲酸酯、聚乙烯醇、聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚醋酸乙烯酯、乙烯醇-醋酸乙烯酯共聚合物、乙烯-乙烯醇共聚物、聚砜、聚醚砜、或上述的组合。
16.如权利要求11所述的医疗装置的改质方法，其中所述医疗装置为敷料、导管，血管通路装置，血液透析装置、血管支架、胆道支架、或植入式装置。
17.一种医疗装置，其表面贴附及/或内部混掺有如权利要求1至10中任一项所述的梳状结构高分子。
18.如权利要求17所述的医疗装置，是由一高分子材料所构成，该高分子材料为：热塑性聚胺基甲酸酯、聚胺基甲酸酯、聚乙烯醇、聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚醋酸乙烯酯、乙烯醇-醋酸乙烯酯共聚合物、乙烯-乙烯醇共聚物、聚砜、聚醚砜、或上述的组合。
19.如权利要求17所述的医疗装置，其中所述医疗装置为敷料、导管，血管通路装置，血液透析装置、血管支架、胆道支架、或植入式装置。
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