TWI487543B - 梳狀結構高分子、醫療裝置的改質方法及醫療裝置 - Google Patents
梳狀結構高分子、醫療裝置的改質方法及醫療裝置 Download PDFInfo
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Description
本發明係有關於一種功能性高分子及其於醫療裝置之應用，特別是有關於一種梳狀結構高分子及其於醫療用敷料與醫療導管產品上的應用。
多數醫療裝置或生醫材料表面，接觸傷口滲出液(exudate)、尿液(urine)、或血液(blood)...等體液時，體液中之蛋白質會產生非特異性(nonspecific)地沉積。如果發生於於傷口部位，滲出液內大量蛋白質吸附於一般醫療裝置或生醫材料表面後，會開始吸引傷口處新生游離細胞與之結合；大量新生細胞不斷地累積在敷料基質之間隙中，形成新生組織與基質交錯之結構，即所謂之傷口沾黏現象；當發生於於泌尿道系統，尿液中蛋白質或細菌吸附於一般醫療裝置或生醫材料表面後，細菌會開始大量增生繁殖進而形成生物膜，可能引發感染與醫療裝置(導管)產生礦化(encrustation)致使阻塞；當發生於血管系統時，血液中蛋白質附於與血液接觸之醫療裝置或生醫材料表面後，非特異性蛋白會引發血液中血小板吸附與活化，進而產生血栓。
聚乙二醇(polyethylene glycol,PEG)是目前已知最具抑制蛋白質吸附功能之親水性材料，因此一般會以電漿、臭氧、電暈等方式將惰性之醫療裝置或生醫材料表面活化再施以化學接枝聚乙二醇分子親水分子。然而，對於不規則形狀、具厚度、或是多孔隙結構之醫療裝置或生醫材料而言，上述手段卻無法達到最均勻之親水化介面與最佳之親水化效果。
有鑑於此，業界亟需一種能夠達到表面均勻親水化，及抑制非特異性蛋白質吸附的多功能高分子材料組成。
本發明提供一種梳狀結構高分子，包括：線性高分子主鏈；以及梳狀側鏈結構，包括：疏水性分子鏈段，以及親水性分子鏈段及/或抑制生物膜/或抗菌之分子鏈段，其中上述線性高分子主鏈係以羥基與上述梳狀側鏈結構的各種鏈段之間之反應性官能基形成共價鍵結相互連接，其中上述反應性官能基包括：異氰酸酯、羧基、或環氧基。
本發明更提供一種醫療裝置的改質方法，包括：提供前述之梳狀結構高分子；將該梳狀結構高分子溶解於一溶液中；以及將上述含有上述梳狀結構高分子的溶液以塗佈或含浸方式，經過一乾燥程序，貼附於一醫療裝置表面。
本發明尚提供一種醫療裝置，其表面貼附及/或內部混摻有前述之梳狀結構高分子。
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細說明如下：
以下係藉由特定的具體實施例說明本發明之實施方式，熟習此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之優點及功效。本發明亦可藉由其它不同之實施方式加以施行或應用，本說明書中的各項細節亦可基於不同觀點與應用，在不悖離本發明所揭示之精神下賦予不同之修飾與變更。
第1圖係依據本發明之實施例，說明梳狀結構高分子之組成，本發明之梳狀高分子主要包括(a)線性高分子主鏈以及(b)梳狀側鏈結構。(a)線性高分子主鏈例如是含羥基之線性結構主鏈11。(b)梳狀側鏈結構包括：(b1)疏水性分子鏈段12，以及(b2)親水性分子鏈段13及/或抑制生物膜/或抗菌之分子鏈段14。上述線性高分子主鏈與上述梳狀側鏈結構之間，係上述線性高分子主鏈以羥基與上述梳狀側鏈結構之反應性官能基所形成之共價鍵結相互連接，其中上述反應性官能基包括：異氰酸酯、羧基、或環氧基。在本發明之梳狀結構高分子中，疏水性鏈段12可藉由物理性吸附方式，使得梳狀結構高分子結合於一疏水性醫療裝置表面，而親水性鏈段13可以提高被處理醫療裝置表面親水程度、降低摩擦係數、抑制蛋白質吸附、抑制活體細胞貼附、以及避免生物組織沾黏。此外，抑制細菌繁殖分子14具有抑制細菌繁殖、抗菌、以及抑制生物膜形成功能。在一實施例中，梳狀結構高分子結構更可富含有自由羥基，以供做為其他化學修飾之官能基，使上述醫療裝置表面處理技術性能大增，更能符合梳狀高分子材料於醫療裝置表面處理應用之實用性。
第2a圖係根據本發明之實施例，顯示一梳狀結構高分子101a之組成包括：線性高分子主鏈11，以及包括疏水性分子鏈段12與親水性分子鏈段13的梳狀側鏈結構之示意圖。
第2b圖係根據本發明之實施例，顯示一梳狀結構高分子101b之組成包括：線性高分子主鏈11，以及包括疏水性分子鏈段12、親水性分子鏈段13與抑制生物膜/或抗菌之分子鏈段14的梳狀側鏈結構之組成示意圖。
第2c圖係根據本發明之實施例，顯示一梳狀結構高分子101c之組成包括：線性高分子主鏈11，以及包括疏水性分子鏈段12與抑制生物膜/或抗菌之分子鏈段14的梳狀側鏈結構之組成示意圖。
第2d圖係根據本發明之實施例，顯示一梳狀結構高分子101d之組成包括：線性高分子主鏈11，以及包括疏水性分子鏈段12、親水性分子鏈段13與抑制生物膜/或抗菌之分子鏈段14的梳狀側鏈結構之組成示意圖，其中抑制細菌繁殖之分子鏈段14以共價鍵接枝於親水性分子鏈段13上，且親水性分子鏈段13接枝於線性高分子主鏈11上。
第2e圖係根據本發明之實施例，顯示一梳狀結構高分子101e之組成包括：線性高分子主鏈11，以及包括疏水性分子鏈段12、親水性分子鏈段13與抑制細菌繁殖之分子鏈段14的梳狀側鏈結構之組成示意圖，其中親水性分子鏈段13以共價鍵接枝於抑制生物膜/或抗菌之分子鏈段14上，且抑制生物膜/或抗菌之分子鏈段14接枝於線性高分子主鏈11上。
在本發明之梳狀高分子材料中，上述線性高分子主鏈且具有羥基者，可選自線性或含有支鏈之合成高分子與天然高分子，而較佳為線性之合成高分子與天然高分子，最佳為線性合成高分子，其中上述線性合成高分子主鏈可包括但不限於：聚乙烯醇(polyvinyl alcohol,PVA)、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)、多醣高分子(polysaccharide)、或上述之組合。上述天然高分子可為多醣類高分子(polysaccharide)，其中上述多醣類高分子可包括但不限於：透明質酸(hyaluronic acid)、纖維素(cellulose)、葡聚糖(dextran)、幾丁質(chitin)、幾丁聚醣(chitosan)、褐藻膠(alginate)、角叉藻膠(carrageenan)、澱粉(starch)、果膠(pectin)、阿拉伯樹膠(gum Arabic)、關華豆膠(guar gum)、普路蘭(pullulan)、硬葡聚糖(scleroglucan)、結蘭膠(gellan)、軟骨素(chondroitin sulfate)、肝素(heparin)、硫酸角蛋白(keratin sulfate)、上述衍生物或上述之組合。上述線性高分子主鏈的重量平均分子量介於約500~2000000，較佳介於約5000~1000000。
在本發明之梳狀高分子材料中，上述疏水性分子鏈段包括但不限於：含有胺基甲酸酯(urethane)之重複單元所構成高分子鏈段、含有聚氧化丙烯(poly propylene oxide,PPO)之重複單元所構成高分子鏈段、含有乙烯(Ethylene)之重複單元所構成高分子鏈段、含有丙烯基(Propylene)之重複單元所構成高分子鏈段、含有苯乙烯(Styrene)之重複單元所構成高分子鏈段、含有碸(Sulfone)之重複單元所構成高分子鏈段、或上述組成之共聚合物所構成高分子鏈段，其中上述含有胺基甲酸酯之重複單元所構成高分子鏈段包括：脂肪族聚胺基甲酸酯、芳香族聚胺基甲酸酯、或上述之組合，且上述疏水性分子鏈段之重量平均分子量介於約500至50,000道爾頓(Dalton)之間。
在本發明之梳狀高分子材料中，上述親水性分子鏈段包括但不限於：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)、或上述之組合，其中較佳之親水性分子鏈段包括：聚乙二醇(polyethylene glycol,PEG)、聚氧化乙烯(polyethylene oxide,PEO)、聚乙烯吡咯烷酮(polyvinylpyrrolidone,PVP)、或上述之組合。上述親水性分子鏈段之重量平均分子量介於約500至100,000道爾頓(Dalton)，較佳可介於約500至50,000道爾頓(Dalton)，最佳介於約500至30,000道爾頓(Dalton)。
在本發明之梳狀高分子材料的另一實施例中，更可以化學鍵結或物理吸附方式接上抑制生物膜/或抗菌分子鏈段，其中上述抑制生物膜/或抗菌之分子包括但不限於：法尼醇(Farnesol)、木糖醇(xylitol)、乳鐵蛋白(Lactoferrin)、乙二胺四醋酸(ethylene diamine tetraacetic acid,EDTA)、鎵(Gallium)、PNAG-分解酵素(PNAG-degrading enzyme)、RNA-III抑制胜肽(RNA-III inhibiting peptide)、呋喃酮C30(Furanone C30)、銀、碘、鋅、銅、抗生素、藥物或上述之組合，較佳包括：法尼醇(Farnesol)或木糖醇(Xylitol)，最佳為法尼醇(Farnesol)。
上述抑制生物膜/或抗菌之分子鏈段可直接以化學鍵結或物理吸附方式接到本發明之線性高分子主鏈上，亦可以化學鍵結或物理吸附方式接於前述之親水性分子鏈段或疏水性分子鏈段。
上述親水性分子鏈段、疏水性分子鏈段、或抑制生物膜/或抗菌分子鏈段與上述線性高分子主鏈的官能基，例如羥基，可利用本身或經改質後之反應官能基，例如異氰酸酯、羧基、或環氧基等，形成共價鍵結而相互連接，進而形成本發明之梳狀高分子結構。舉例而言，當線性高分子主鏈具有-OH基，而梳狀側鏈結構具有-NCO基時，兩者之間的共價鍵係為胺基甲酸酯鍵結(Urethane Linkage;-O(C=O)NH-)；當線性高分子主鏈具有-OH基，而梳狀側鏈結構具有羧基(-COOH)時，兩者之間的共價鍵係為酯基鍵結(Ester Linkage)；當線性高分子主鏈具有-OH基，而梳狀側鏈結構具有環氧基時，兩者之間的共價鍵係為醚基鍵結(Ether Linkage)。
參閱第3圖，本發明另提供一種醫療裝置之表面改質方式：提供前述之梳狀結構高分子材料101，透過將梳狀結構高分子材料101溶解於溶液中，以塗佈或含浸等方式，並經過一乾燥程序吸附於醫療裝置表面23而達到表面改質目的。如第3圖中所示，梳狀結構高分子101之疏水性鏈段12是以物理性吸附方式結合於疏水性的醫療裝置表面23。另一方面，親水性分子鏈段13則排列成纖毛結構。上述溶解溶液可包括但不限於：N,N-二甲基甲醯胺(N,N-dimethylformamide,DMF)、N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)、二甲基亞碸(Dimethyl sulfoxid,DMSO)、四氫呋喃(Tetrahydrofuran,THF)、醇類(Alcohols)、酮類(Ketones)、水(Water)、或上述之組合，較佳包括：N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)、酮類(Ketones)、水(Water)、或上述之組合，更佳者包括下列溶劑組合(a)丁酮及水、(b)丙酮及N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)、或(c)丙酮、水及N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)。
在一實施例中，上述梳狀結構高分子材料溶解於溶液中之固含量可介於約0.01%至50%(重量百分比)，較佳介於約0.1%至30%(重量百分比)，最佳介於約0.1%至20%(重量百分比)。
在一實施例中，上述梳狀結構高分子溶液以塗佈或含浸等方式處理於一醫療裝置或基材後，可以熱風或真空方式進行乾燥，且溫度介於室溫至200℃，較佳為約30℃至100℃。
除上述以溶液溶解後利用塗佈或含浸等方式進行醫療裝置或基材表面處理外，亦可以混摻方式混合於與高分子材料內，而上述梳狀結構高分子與高分子材料混摻方式可包括但不限於：熔融混摻或溶劑共溶解混摻，其中上述高分子材料包括：熱塑性聚胺基甲酸酯(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(polyvinyl chloride,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)、聚碸(Polysulfone)、聚醚碸(poly ether sulfone)、上述之衍生物或上述之組合。
因此，上述梳狀結構高分子材料可溶解於溶液中，以物理性方式吸附於疏水性材料或醫療裝置表面；或可以混摻方式分佈於疏水性材料內部或醫療裝置內部及表面。梳狀高分子材料之親水性鏈段裸露於醫療裝置表面後，親水鏈段除了可提升醫療裝置或生醫材料表面親水程度外，親水鏈段分子鏈更可於表面形成之空間障礙，且親水鏈段分子鏈熵斥力(entropic repulsion)會使親水鏈段分子排列成纖毛(cilia)結構，將靠近之蛋白質分子排開，因此可抑制了蛋白質與基材之吸附外，醫療裝置表面親水程度提升後可降低醫療裝置或材料之摩擦係數，與抑制活體細胞貼附，並可避免生物組織沾黏，抑制細菌貼附。此外，本發明中之梳狀高分子材料側鏈亦可以共價鍵結引入抑制生物膜/或抗菌分子，使改質後之醫療裝置或生醫材料表面具有抑制細菌繁殖、抗菌、以及抑制生物膜形成功能。
綜合本發明，梳狀結構高分子材料無論以物理性吸附或以混摻方式分佈於疏水性材料內部或醫療裝置內部及表面，上述醫療裝置可為敷料(Wound dressing)、導管(Catheter)，血管通路裝置(Vascular access devices)，血液透析裝置(Hemodialyzer)、血管支架(Stent)、膽道支架(Biliary stent)、或植入式裝置(Implantable devices)等。
以下係藉由特定之具體實施例進一步說明本發明之特點與功效，但非用於限制本發明之範疇。
【實施例1】
疏水分子鏈段預聚合物(A)『mPU(BDO)
-NCO』
梳狀結構高分子材料中之疏水分子鏈段預聚合物(A)製備步驟如下，取1,4-丁二醇(1,4-butanediol,1,4-BDO)1.53g，置於圓底反應瓶並添加7.65ml N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)溶劑緩慢昇溫至60℃後混合均勻，繼之將溶解於42.35ml DMAc之8.47克二苯基甲烷4,4'-二異氰酸酯(Diphenylmethane-4,4'-diisocyanate,MDI)緩慢滴入反應瓶中以50℃反應3小時並通以氮氣，反應3小時候取樣進行分子量分析，以GPC測得重量平均分子量(Mw)約為2,243。接下來取0.12ml甲醇以0.6ml DMAc稀釋後緩慢滴入前述反應瓶中形成單側具有活性之疏水分子預聚合物。
【實施例2】
疏水分子鏈段預聚合物(B
)『mC8
PU8,000
-NCO』
梳狀結構高分子材料中之疏水分子鏈段預聚合物(B)製備步驟如下，取19.5 g聚四氫呋喃1000(PolyTetramethylene-ether-Glycol,PTMEG1000)加入36 ml DMAC於150 ml雙頸瓶，將2.325 g MDI加入4 ml DMAc，並使用用等壓漏斗緩慢滴入，混合均勻後升溫到65℃反應2小時，反應完得到預聚合物(prepolymer)。接下來取1.64 ml C8
-NCO加入4 ml DMAc，將前述預聚合物降到室溫後，將C8
-NCO加入預聚合物中，並加入Catalyst，混合均勻後升溫到65℃反應2小時，得到mC8
-預聚合物。
繼之，取2.325 g MDI加入4 ml DMAc，並緩慢加入前述mC8
-預聚合物中，混合均勻後升溫到60℃反應3小時，得到mC8
PU(PU)疏水分子鏈段預聚合物(B
)，以GPC測得重量平均分子量(Mw)約8,000。
【實施例3】
疏水分子鏈段預聚合物(C
)『mPPO2,500
-NCO』
取2.9 g mPPO(重量平均分子量2500)加入4 ml DMAc溶解，接下來並將0.275 g MDI加入2 ml DMAc於25 ml雙頸瓶溶解。於室溫下將前述mPPO(重量平均分子量2500)緩慢加入MDI溶液中，混合均勻後升溫到60℃反應2小時，反應完後得到mPPO2500
-NCO。
【實施例4】
疏水分子鏈段預聚合物(D
)『mPPU4,923
-NCO』
預先將使用之溶劑(DMAc)、1,4-丁二醇及mPPO(重量平均分子量2500)用分子篩除水一天。製備步驟如下，取5.32 g MDI加入26.6 ml DMAC於250 ml雙頸瓶中室溫攪拌至溶解，再將0.58 g之1,4-丁二醇加入2.9 ml DMAc中攪拌後加入前述MDI溶液中混合均勻後升溫到60±5℃反應3小時，反應完得到預聚合物(prepolymer)，GPC測得重量平均分子量為Mw=1,447。
取10.3 g mPPO(重量平均分子量2500)加入51.5 ml DMAc於150 ml單頸瓶中室溫搖晃至溶解，將此mPPO溶液置於等壓漏斗緩慢滴入前述60±5℃之預聚合物溶液中，此滴入過程約30分鐘，待mPPO溶液全部加入後於60±5℃下攪拌反應2.5小時，得到mPPO2,500
-b
-PU1,447
-NCO(mPPU-NCO)之預聚合物，GPC測得重量平均分子量為Mw=4,923(mPPU4,923
-NCO)。
【實施例5】
疏水分子鏈段預聚合物(E
)『mPPU9,764
-NCO』
預先將使用之溶劑(DMAc)、1,4-丁二醇及mPPO(重量平均分子量2500)用分子篩除水一天。製備步驟如下，取25.16 g MDI加入126 ml DMAC於250 ml雙頸瓶中室溫攪拌至溶解，再將5.44 g之1,4-丁二醇加入27 ml DMAc中攪拌後加入前述MDI溶液中混合均勻後升溫到60±5℃反應3小時，反應完得到預聚合物(prepolymer)。GPC測得重量平均分子量為Mw=4581。
取10.22 g mPPO(重量平均分子量2500)加入51.1 ml DMAc於150 ml單頸瓶中室溫搖晃至溶解，並取103ml前述之預聚合物溶液後將此mPPO溶液置於等壓漏斗緩慢滴入前述60±5℃之預聚合物溶液中，此滴入過程約30分鐘，待mPPO溶液全部加入後於60±5℃下攪拌反應2.5小時，得到mPPO2,500
-b
-PU4,581
-NCO(mPPU-NCO)之預聚合物，反應計算重量平均分子量為Mw=9,764(mPPU9,764
-NCO)。
【實施例6】
親水分子鏈段預聚合物『mPEG5,000
-NCO』
製備親水分子鏈段預聚合物前，先將使用之溶劑(DMAc)用分子篩除水一天，並將mPEG(重量平均分子量5000)以真空乾燥24小時備用。取80 g mPEG5000
加入120 ml DMAc於500 ml雙頸瓶後預熱至60℃溶解，接下來取3.5 g MDI加入35 ml DMAc中溶解後降溫至40℃後，繼之將MDI溶液緩慢加入mPEG5000
中，混合均勻後緩慢升溫至60℃反應2小時，反應後得到親水性mPEG5000
-NCO預聚合物。
【實施例7】
抑制細菌繁殖之分子鏈段預聚合物(A)『Farnesol-HDI-NCO』
製備抑制細菌繁殖之分子鏈段預聚合物前，先將使用之溶劑DMAc用分子篩除水一天，並將法尼醇(3,7,11-Trimethyl-2,6,10-dodecatrien-1-ol,Farnesol)以70℃真空乾燥24小時備用。取5.818 g Farnesol加入80 ml DMAc於250 ml雙頸瓶後攪拌溶解，再將0.04 g之三乙亞二胺(1,4-Diazabicyclo-(2,2,2) Octane,DABCO)及0.02 g之Sn(Oct)2
(stannous octoate,Sn(II))加入Farnesol溶液中。接著取4.182 g之1,6-己二異氰酸酯(1,6-Diisocyanatohexane,HDI)加入20 ml DMAc攪拌溶解後，將HDI溶液緩慢加入Farnesol溶液中，混合均勻後緩慢升溫至55-60℃反應3小時，得到可抑制細菌繁殖之分子鏈段Farnesol-HDI-NCO預聚合物。
【實施例8】
抑制細菌繁殖之分子鏈段預聚合物(B)『Farnesol-IPDI-NCO』
製備前先將使用之溶劑DMAc用分子篩除水一天，取0.72 g Farnesol加入14 ml DMAc於500 ml雙頸瓶溶解，接著取0.68 g IPDI加入500 ml雙頸瓶中溶解後，取DABCO 0.1g以及0.05g Sn(Oct)2
加入2ml DMAc於20ml瓶中以超音波震盪30min溶解後，取0.056ml加入500 ml雙頸瓶中，均勻攪拌後加溫至55℃反應3小時，得到抑制細菌繁殖之分子鏈段預聚合物(B)『Farnesol-IPDI-NCO』。
【實施例9】
抑制細菌繁殖之分子鏈段預聚合物(C)『Farnesol-b
-PEG10,000
-NCO』
製備前先將使用之溶劑DMAc及PEG diol(重量平均分子量10,000)以真空乾燥24小時備用，取30.76g PEG diol10,000
加入307.6 ml DMAc於500 ml雙頸瓶溶解，倒入實施例8中含有Farnesol-IPDI-NCO預聚合物於500 ml雙頸瓶，均勻攪拌後加溫至65℃反應16小時，得到親水性抑制細菌繁殖之分子鏈段預聚合物(Farnesol-b
-PEG10,000
-NCO)。
【實施例10】
抑制細菌繁殖之分子鏈段預聚合物(D)『Farnesol-b
-PEG2,000
-NCO』
製備前先將使用之溶劑DMAc及PEG diol(重量平均分子量2,000)以真空乾燥24小時備用。取15.47g PEG2,000
加入154.7 ml DMAc於250 ml雙頸瓶溶解，倒入實施例8中含有Farnesol-IPDI-NCO預聚合物於250 ml雙頸瓶，均勻攪拌後加溫至65℃反應16小時，得到親水性抑制細菌繁殖之分子鏈段預聚合物(Farnesol-b
-PEG2,000
-NCO)。
【實施例11】
梳狀結構高分子材料(A)『PVA10,000
-g-(60%
PEG5,000
-co-30%
mC8
PU)』
取1 g聚乙烯醇(Polyvinyl alcohol,PVA；重量平均分子量10,000)加入19 ml DMAc於50 ml雙頸瓶中緩慢加熱到60℃溶解，繼之將前述PVA10,000
溶液降溫至室溫後加入實施例5之mPEG5,000
-NCO預聚合物中，混合均勻後緩慢升溫到60±5℃反應3小時，反應後得到PVA10,000
-g-PEG5,000
產物。
取實施例2之mC8
PU疏水分子鏈段預聚合物(B)56 ml添加至前述PVA10,000-g-mPEG5k產物，混合後升溫到60℃反應3小時，反應後得到PVA10,000
-g-(60%
PEG5,000
-co-30%
mC8
PU)，親水性鏈段(PEG)接枝率(鏈段中的單鍵莫耳數/羥基的總莫耳數)為60%，疏水性鏈段(mC8
PU)接枝率為30%。
上述梳狀結構高分子材料純化步驟為反應後產物於DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下來以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最後於水中以MWCO：12K-14K透析膜透析2天後將產物取出後進行冷凍乾燥。
【實施例12】
梳狀結構高分子材料(B)『PVA10,000
-g-(60%
PEG5,000
-co-10%
mC8
PU)』
取1 g聚乙烯醇(Polyvinyl alcohol,PVA；重量平均分子量10,000)加入19 ml DMAc於50 ml雙頸瓶中緩慢加熱到60℃溶解，繼之將前述PVA10,000
溶液降溫至室溫後加入實施例5之mPEG5,000
-NCO預聚合物中，混合均勻後緩慢升溫到60±5℃反應3小時，反應後得到PVA10,000
-g-PEG5,000
產物。
取實施例2之mC8
PU疏水分子鏈段預聚合物(B)56 ml添加至前述PVA10,000
-g-mPEG5,000
產物，混合後升溫到60℃反應3小時，反應後得到PVA10,000
-g-(60%
PEG5,000
-co-10%
mC8
PU)，親水性鏈段(PEG)接枝率為60%，疏水性鏈段(mC8
PU)接枝率為10%。
上述梳狀結構高分子材料純化步驟為反應後產物於DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下來以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最後於水中以MWCO：12K-14K透析膜透析2天後將產物取出後進行冷凍乾燥。
【實施例13】
梳狀結構高分子材料(C)『PVA10,000
-g-(30%
PEG5,000
-co-10%
mC8
PU)』
取1 g聚乙烯醇(Polyvinyl alcohol,PVA；重量平均分子量10,000)加入19 ml DMAc於50 ml雙頸瓶中緩慢加熱到60℃溶解，繼之將前述PVA10,000
溶液降溫至室溫後加入實施例5之mPEG5,000
-NCO預聚合物中，混合均勻後緩慢升溫到60±5℃反應3小時，反應後得到PVA10,000
-g-PEG5,000
產物。
取實施例2之mC8
PU疏水分子鏈段預聚合物(B)56 ml添加至前述PVA10,000
-g-mPEG5,000
產物，混合後升溫到60℃反應3小時，反應後得到PVA10,000
-g-(30%
PEG5,000
-co-10%
mC8
PU)，親水性鏈段(PEG)接枝率為30%，疏水性鏈段(mC8PU)接枝率為10%。
上述梳狀結構高分子材料純化步驟為反應後產物於DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下來以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最後於水中以MWCO：12K-14K透析膜透析2天後將產物取出後進行冷凍乾燥。
【實施例14】
梳狀結構高分子材料(D)『PVA10,000
-g-(60%
PEG5,000
-co-10%
mC8
PU)』
取1 g聚乙烯醇(Polyvinyl alcohol,PVA；重量平均分子量10,000)加入19 ml DMAc於50 ml雙頸瓶中緩慢加熱到60℃溶解，繼之將前述PVA10,000
溶液降溫至室溫後加入實施例5之mPEG5,000
-NCO預聚合物中，混合均勻後緩慢升溫到60±5℃反應3小時，反應後得到PVA10,000
-g-PEG5,000
產物。
取實施例2之mC8
PU疏水分子鏈段預聚合物(B)56 ml添加至前述PVA10,000
-g-mPEG5,000
產物，混合後升溫到60℃反應3小時，反應後得到PVA10,000
-g-(60%
PEG5,000
-co-10%
mC8
PU)，親水性鏈段(PEG)接枝率為60%，疏水性鏈段(mC8
PU)接枝率為10%。
上述梳狀結構高分子材料純化步驟為反應後產物於DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下來以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最後於水中以MWCO：12K-14K透析膜透析2天後將產物取出後進行冷凍乾燥。
【實施例15】
梳狀結構高分子材料(E)『PVA10,000
-g-(90%
PEG5,000
-co-10%
mC8
PU)』
取1 g聚乙烯醇(Polyvinyl alcohol,PVA；重量平均分子量10,000)加入19 ml DMAc於50 ml雙頸瓶中緩慢加熱到60℃溶解，繼之將前述PVA10,000
溶液降溫至室溫後加入實施例5之mPEG5,000
-NCO預聚合物中，混合均勻後緩慢升溫到60±5℃反應3小時，反應後得到PVA10,000
-g-PEG5,000
產物。
取實施例2之mC8
PU疏水分子鏈段預聚合物(B)56 ml添加至前述PVA10,000
-g-mPEG5,000
產物，混合後升溫到60℃反應3小時，反應後得到PVA10,000
-g-(90%
PEG5,000
-co-10%
PU)，親水性鏈段(PEG)接枝率為90%，疏水性鏈段(mC8
PU)接枝率為10%。
上述梳狀結構高分子材料純化步驟為反應後產物於DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下來以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最後於水中以MWCO：12K-14K透析膜透析2天後將產物取出後進行冷凍乾燥。
【實施例16】
梳狀結構高分子材料(F)『PVA10,000
-g-(30%
PEG5,000
-co-10%
PPO)』
取1 g聚乙烯醇(Polyvinyl alcohol,PVA；重量平均分子量10,000)加入19 ml DMAc於50 ml雙頸瓶中緩慢加熱到60℃溶解，繼之將前述PVA10,000
溶液降溫至室溫後加入實施例5之mPEG5,000
-NCO預聚合物中，混合均勻後緩慢升溫到60±5℃反應3小時，反應後得到PVA10,000
-g-PEG5,000
產物。接下來取取實施例3，mPPO2500
-NCO疏水分子鏈段預聚合物(C)添加至前述PVA10,000
-g-PEG5,000
產物中混合後升溫到60℃反應3小時，反應後得到PVA10,000
-g-(30%
PEG5,000
-co-10%
PPO)，親水性鏈段(PEG)接枝率為60%，疏水性鏈段(mPPO)接枝率為10%。
上述梳狀結構高分子材料純化步驟為反應後產物於DMAc溶液中以MWCO：12K-14K透析膜透析2天，接下來以DMSO溶液中以MWCO：12K-14K透析膜透析2天，最後於水中以MWCO：12K-14K透析膜透析2天後將產物取出後進行冷凍乾燥。
【實施例17】
梳狀結構高分子材料(G)『PVA10,000
-g-(PEG5,000
-co-PPU4,923
)』
步驟1. 親水分子鏈段預聚合物『mPEG
5,000
-NCO』
製備親水分子鏈段預聚合物前，先將使用之溶劑(DMAc)用分子篩除水一天，並將mPEG(重量平均分子量5,000)以真空乾燥24小時備用。預先分別取86.12 g mPEG5,000
加入856 ml DMAc於1000 ml雙頸瓶後預熱至60℃溶解，接下來分別取1.18 g、1.37g及1.54g之MDI加入13 ml、14ml及18ml DMAc於1000 ml雙頸瓶中室溫攪拌溶解後開始逐步升溫至60±5℃，同時並將mPEG5000
溶液分成320 ml、286ml及250ml三份置於等壓漏斗緩慢滴入MDI溶液中，此滴入過程約2小時，待mPEG5000
溶液全部加入後於60±5℃下反應1小時，得到親水性mPEG5000
-NCO預聚合物。
步驟2. 疏水分子鏈段預聚合物『PPO-
b
-PU-NCO,PPU-NCO』
預先將使用之溶劑(DMAc)、1,4-丁二醇及mPPO(重量平均分子量2500)用分子篩除水一天。製備步驟如下，取5.32 g MDI加入26.6 ml DMAC於250 ml雙頸瓶中室溫攪拌至溶解，再將0.58 g之1,4-丁二醇加入2.9 ml DMAc中攪拌後加入前述MDI溶液中混合均勻後升溫到60±5℃反應3小時，反應完得到預聚合物(prepolymer)，GPC測得重量平均分子量為Mw=1,447。
取10.3 g mPPO(重量平均分子量2500)加入51.5 ml DMAc於150 ml單頸瓶中室溫震盪至溶解，將此mPPO溶液置於等壓漏斗緩慢滴入前述60±5℃之預聚合物溶液中，此滴入過程約30分鐘，待mPPO溶液全部加入後於60±5℃下攪拌反應2.5小時，得到PPU-NCO之預聚合物，GPC測得重量平均分子量為Mw=4,923。
步驟3. 梳狀結構高分子材料
預先取三份0.3 g聚乙烯醇(Polyvinyl alcohol,PVA;重量平均分子量10,000)分別加入6 ml DMAc於20 ml樣品瓶中放置65℃烘箱溶解，繼之PVA10,000
溶液降溫至室溫後分別加入338 ml、300ml及263ml前述之親水分子鏈段mPEG5,000
-NCO預聚合物中，混合均勻後緩慢升溫到60±5℃反應3小時，反應後得到PVA10,000
-g-PEG5,000
產物。接下來取前述之疏水分子鏈段mPPO2,500
-NCO預聚合物13.5 ml、27ml及40.5ml分別添加至PVA10,000
-g-PEG5,000
產物中，並分別加入0.054g、0.01g及0.0016g之DABCO和0.027g、0.0054g及0.0008g之Sn(Oct)2
，混合後升溫到65℃反應16小時，得到PVA10,000
-g-(PEG5,000
-co-PPU)，親水性鏈段(PEG)接枝率為70%、80%及90%，疏水性鏈段(mPPU)接枝率為30%、20%及10%。上述梳狀結構高分子材料純化步驟為反應後產物於DMSO溶液中以MWCO：25K透析膜透析2天，接下來於DI-Water中以MWCO：25K透析膜透析2天後將產物取出後進行冷凍乾燥。
【實施例18】
梳狀結構高分子材料(H)『PVA-g-(PEG5,000
-co-PU9,764
)』
步驟1. 親水分子鏈段預聚合物『mPEG
5,000
-NCO』
製備親水分子鏈段預聚合物前，先將使用之溶劑(DMAc)用分子篩除水一天，並將mPEG(重量平均分子量5,000)以真空乾燥24小時備用。預先取86.12 g mPEG5,000
加入856 ml DMAc於1000 ml雙頸瓶後預熱至60℃溶解，接下來分別取1.18 g、1.37g及1.54g之MDI加入13 ml、14ml及18ml DMAc於1000 ml雙頸瓶中室溫攪拌溶解後開始逐步升溫至60±5℃，同時並將mPEG5000
溶液分成320 ml、286ml及250ml置於等壓漏斗緩慢滴入MDI溶液中，此滴入過程約2小時，待mPEG5000
溶液全部加入後於60±5℃下反應1小時，得到親水性mPEG5000
-NCO預聚合物。
步驟2. 疏水分子鏈段預聚合物『PPO-
b
-PU-NCO,PPU-NCO
』
預先將使用之溶劑(DMAc)、1,4-丁二醇及mPPO(重量平均分子量2500)用分子篩除水一天。製備步驟如下，取25.16 g MDI加入126 ml DMAC於250 ml雙頸瓶中室溫攪拌至溶解，再將5.44 g之1,4-丁二醇加入27 ml DMAc中攪拌後加入前述MDI溶液中混合均勻後升溫到60±5℃反應3小時，反應完得到預聚合物(prepolymer)，GPC測得重量平均分子量為Mw=4,581。
接下來取10.22 g mPPO(重量平均分子量2500)加入51.1 ml DMAc於150 ml單頸瓶中室溫搖晃至溶解，並取103ml前述之預聚合物溶液後將此mPPO溶液置於等壓漏斗緩慢滴入前述60±5℃之預聚合物溶液中，此滴入過程約30分鐘，待mPPO溶液全部加入後於60±5℃下攪拌反應2.5小時，得到PPU-NCO之預聚合物，GPC測得重量平均分子量為Mw=9,764。
步驟3. 梳狀結構高分子材料
預先分別取三份0.3 g聚乙烯醇(Polyvinyl alcohol,PVA;重量平均分子量10,000)分別加入6 ml DMAc於20 ml樣品瓶中放置65℃烘箱溶解，繼之PVA10,000
溶液降溫至室溫後分別加入338 ml、300ml及260ml實施例15之親水分子鏈段mPEG5,000
-NCO預聚合物中，混合均勻後緩慢升溫到60±5℃反應3小時，反應後得到PVA10,000
-g-PEG5,000
產物。接下來取前述之疏水分子鏈段PPU9,764
-NCO預聚合物25.6 ml、51.1ml及76.7ml分別添加至PVA10,000
-g-PEG5,000
產物中，並加入0.01g、0.02g及0.03g之DABCO和0.005g、0.01g及0.015g之Sn(Oct)2
，混合後升溫到65℃反應16小時，得到PVA10,000
-g-(PEG5,000
-co-PPU9,764
)，親水性鏈段(PEG)接枝率為70%、80%及90%，疏水性鏈段(mPPU)接枝率為30%、20%及10%。上述梳狀結構高分子材料純化步驟為反應後產物於DMSO溶液中以MWCO：25K透析膜透析2天，接下來於DI-Water中以MWCO：25K透析膜透析2天後將產物取出後進行冷凍乾燥。
【實施例19】
梳狀結構高分子材料(I)『PVA-g-(Farnesol-co-PPU4,923
)』
步驟1. 疏水分子鏈段預聚合物『PPO-
b
-PU-NCO,PPU-NCO』
預先將使用之溶劑(DMAc)、1,4-丁二醇及mPPO(重量平均分子量2,500)用分子篩除水一天。製備步驟如下，取5.32 g MDI加入26.6 ml DMAC於250 ml雙頸瓶中室溫攪拌至溶解，再將0.58 g之1,4-丁二醇加入2.9 ml DMAc中攪拌後加入前述MDI溶液中混合均勻後升溫到60±5℃反應3小時，反應完得到預聚合物(prepolymer)，GPC測得重量平均分子量為Mw=1,447。接下來取10.22 g mPPO(重量平均分子量2500)加入51.1 ml DMAc於150 ml單頸瓶中室溫搖晃至溶解，並取前述之預聚合物溶液後將此mPPO溶液置於等壓漏斗緩慢滴入前述60±5℃之預聚合物溶液中，此滴入過程約30分鐘，待mPPO溶液全部加入後於60±5℃下攪拌反應2.5小時，得到PPU-NCO之預聚合物，GPC測得重量平均分子量為Mw=4,923。
步驟2. 梳狀結構高分子材料『PVA-g-(Farnesol-co-PPU
4,923
)』
製備PVA-g-Farnesol預聚合物前預先將使用之溶劑(DMAc)用分子篩除水一天，PVA真空乾燥24小時備用。取1 g PVA加入2 ml DMAC於50 ml雙頸瓶中於60℃烘箱至溶解，取3.028 g實施例7之親水性抑制細菌繁殖之分子鏈段預聚合物加入63.6 ml DMAc中攪拌後加入前述PVA溶液混合均勻後，加入0.016g DABACO及0.008g Sn(Oct)2
升溫到60±5℃反應16小時，反應完得到預聚合物PVA-g-Farnesol(預聚合物)。
將PVA-g-Farnesol預聚合物加入前述13.5ml疏水分子鏈段預聚合物溶液中，混合均勻後，升溫至60±5℃反應6小時，反應完得到聚合物PVA-g-(Farnesol-co-PPU4,923
)，親水性鏈段(Farnesol)接枝率為30%、60%，疏水性鏈段(PU)接枝率分別為30%、30%。
【實施例20】
梳狀結構高分子材料(J)『PVA-g-(Farnesol-b
-PEG-co-PPU10,171
)』
步驟1. 疏水分子鏈段預聚合物『PPO-
b
-PU-NCO,PPU-NCO』
預先將使用之溶劑(DMAc)、1,4-丁二醇及mPPO(重量平均分子量2,500)用分子篩除水一天。製備步驟如下，取4.86 g MDI加入24.3 ml DMAC於250 ml雙頸瓶中室溫攪拌至溶解，再將0.34 g之1,4-丁二醇加入1.7 ml DMAc中攪拌後加入前述MDI溶液中混合均勻後升溫到60±5℃反應3小時，反應完得到預聚合物(prepolymer)，GPC測得重量平均分子量為Mw=2,254。接下來取5.77 g mPPO(重量平均分子量2500)加入28.83 ml DMAc於150 ml單頸瓶中室溫搖晃至溶解，並取前述之預聚合物溶液後將此mPPO溶液置於等壓漏斗緩慢滴入前述60±5℃之預聚合物溶液中，此滴入過程約30分鐘，待mPPO溶液全部加入後於60±5℃下攪拌反應2.5小時，得到PPU-NCO之預聚合物，GPC測得重量平均分子量為Mw=10,171。
步驟2.梳狀結構高分子材料『PVA-g-(Farnesol-
b
-PEG-co-PPU
10,171
)』
製備PVA-g-(Farnesol-b
-PEG200
)預聚合物前預先將使用之溶劑DMAc用分子篩除水一天，PVA真空乾燥24小時備用。製備步驟如下，取0.027 g PVA加入0.1 ml DMAC於50 ml雙頸瓶中於60℃烘箱至溶解，接著取0.814 g實施例8之抑制細菌繁殖之分子鏈段預聚合物加入49.73 ml DMAc中均勻攪拌後，加入前述PVA溶液混合均勻，再加入0.0034g DABACO及0.0017g Sn(Oct)2
升溫到65±5℃反應16小時，反應完得到預聚合物PVA-g-(Farnesol-b
-PEG200
)。
接著取前述1/3份量之預聚合物PVA-g-(Farnesol-b
-PEG200
)加入1.8ml前述之PPU-NCO疏水分子鏈段預聚合物溶液混合均勻後，升溫到60±5℃反應6小時，反應完得到聚合物PVA-g-(Farnesol-b
-PEG2,000
-co-PPU10,171
)，親水性鏈段(Farnesol-b
-PEG2,000
)接枝率為50%，疏水性鏈段(PPU)接枝率為30%。
製備PVA-g-(Farnesol-b
-PEG10,000
)預聚合物前預先將使用之溶劑DMAc用分子篩除水一天，PVA真空乾燥24小時備用。製備步驟如下，取0.08 g PVA加入0.8 ml DMAC於50 ml雙頸瓶中於60℃烘箱至溶解，取9.3 g實施例8之抑制細菌繁殖之分子鏈段預聚合物加入102.2 ml DMAc中均勻攪拌後，加入前述PVA溶液混合均勻後，再加入0.0038g DABACO及0.0019g Sn(Oct)2
升溫到65±5℃反應16小時，反應完得到預聚合物PVA-g-(Farnesol-b
-PEG10,000
)。
取前述1/3份量PVA-g-(Farnesol-b
-PEG10,000
)預聚合物加入2.52ml前述之PPU-NCO疏水分子鏈段預聚合物溶液混合均勻後，升溫到60±5℃反應6小時，反應完得到聚合物PVA-g-(Farnesol-b
-PEG10,000
-co-PPU)，親水性鏈段(Farnesol-b
-PEG10,000
)接枝率為50%，疏水性鏈段(PPU)接枝率為30%。
【實施例21】
疏水性基材含浸梳狀結構高分子溶液
疏水性基材含浸(dipping)梳狀結構高分子溶液程序為，取前述實施例11至實施例20中之梳狀結構高分子材料依照下表所列示溶劑組成與比例震盪溶解，溶解完成後將上述梳狀結構高分子溶液置入一玻璃容器中，將疏水性薄膜基材(熱可塑性聚胺基甲酸乙酯薄膜；Thermoplastic Polyurethane Film)浸入前述此梳狀結構高分子溶液20秒後取出，放置於65±5℃烘箱中移除溶液中之溶劑2小時後即完成。
表1、各樣品編號之材料組成及溶解比例與溶劑組成比例
表面接觸角測試(A)
表面接觸角測試時，分別取未做表面含浸處理之熱可塑性聚胺基甲酸乙酯薄膜(芳香族(aromatic type)，硬度(hardness)=shore 95A)以及以前述實施例20之梳狀結構高分子溶液含浸處理樣品同時進行測試，測試樣品為厚度0.3 mm，長寬分別為5×2公分之試樣進行測試，測試時取用二次水(Distilled De-ionized Water，DD Water)作為接觸角測試溶液，將二次水液滴接觸於測試樣品後30秒進行角度判讀，結果如表2所列(n=3)。
表2、材料組成及溶劑組成比例與水表面接觸角
表面接觸角測試(B)
表面接觸角測試時，分別取未做表面含浸處理之熱可塑性聚胺基甲酸乙酯薄膜(aromatic type,hardness=shore 95A)以及以前述實施例20之梳狀結構高分子溶液含浸處理樣品，測試前以二次水(DD Water)震盪清洗30分鐘後於室溫下風乾備用，接下來以生理緩衝液(phosphate buffer saline,PBS buffer)於37℃下浸泡3天及7天後取出，並以二次水(DD Water)沖洗乾淨後室溫下風乾進行測試(測試樣品尺寸為：厚度0.3 mm，長寬分別為5×2公分之試樣)，測試時取用二次水(DD Water)作為接觸角測試溶液，將二次水(DD Water)液滴接觸於測試樣品後30秒進行角度判讀，結果如第4圖所示(n=3)。
蛋白質吸附測試
表面以梳狀結構高分子溶液含浸處理之熱可塑性聚胺基甲酸乙酯薄膜(aromatic type,hardness=shore 85A及65D)蛋白質吸附測試前蛋白質標準液配製以及標準曲線繪製，配置方法為以二次水(DD Water)將2mg/ml纖維蛋白原溶液(Fibrinogen solution)稀釋成50、100、250、500、1000、2000μg/ml solution，接下來再以1% SDS將標準液稀釋為5、10、25、50、100、200μg/ml Fibrinogen solution。並以酵素免疫分析儀(ELISA reader)讀取各濃度點吸光值進行標準曲線繪製。
接下來將測試樣品裁切成2×1.5 cm大小放入15ml離心管，分別加入5 ml(4.5mg/m)纖維蛋白原溶液後置入37℃培養箱中吸附24小時。24小時候取出並移除蛋白質溶液，以PBS buffer浸泡清洗樣品2次。繼之，將樣品置入內含5ml(1.0%)SDS的微量離心管中，以超音波震盪20分鐘後收集萃取蛋白質的十二烷基硫酸鈉(Sodium dodecyl sulfate，SDS)溶液，以ELISA reader測量其750nm吸光值並對照已知之不同濃度纖維蛋白原溶液所繪製標準曲線，求得蛋白質濃度，結果如表3所示(n=3)。
表3、各實施例所得之樣品與蛋白質吸附量
體外細胞貼附測試
表面以梳狀結構高分子溶液含浸處理之熱可塑性聚胺基甲酸乙酯薄膜(aromatic type,hardness=shore 85A及65D)體外細胞貼附性能評估，測試前將樣品放入24 well培養盤中，並以玻璃管柱與無毒環將樣品平整固定。於放置樣品的培養孔內，分別加入小鼠纖維母細胞(L929)及人類皮膚纖維母細胞(CCD-966SK)細胞溶液(1*105
/well)並置入37℃培養箱中培養24及48小時後以PBS浸泡清洗樣品數次。繼之利用固定液(4% paraformaldehyde)將已經貼附的細胞固定，移除固定液後以PBS清洗樣品後，加入螢光染劑(DAPI,Phalloidine)，並於螢光顯微鏡下觀察細胞型態，並計算樣品上貼附的細胞量。體外細胞貼附測試結果如表4、表5所示。
表4、小鼠纖維母細胞(L929)體外細胞貼附測試結果
表5、人類皮膚纖維母細胞(CCD-966SK)體外細胞貼附測試結果
抗菌效能評估
表面以梳狀結構高分子溶液含浸處理之熱可塑性聚胺基甲酸乙酯薄膜(aromatic type,hardness=shore 95A)抗菌效能評估，評估菌種為綠膿桿菌(Pseudomonas aeruginosa)，測試前將各試驗樣品以UV照光20分鐘進行滅菌，評估之定性描述以對照組(TPU膜)樣品下方細菌生長程度相對於各梳狀結構高分子溶液含浸處理之TPU膜定性紀錄，抗菌效能如表6所列示。
表6、樣本之抗菌效能評估
雖然本發明已經以數個較佳實施例揭露如上，然其並非用以限定本發明。任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
11．．．線性高分子主鏈
12．．．疏水性分子鏈段
13．．．親水性分子鏈段
14．．．抑制生物膜/或抗菌之分子鏈段
101．．．梳狀結構高分子
101a．．．梳狀結構高分子
101b．．．梳狀結構高分子
101c．．．梳狀結構高分子
101d．．．梳狀結構高分子
101e．．．梳狀結構高分子
23．．．疏水性基材/醫療裝置
第1圖係根據本發明之實施例，顯示梳狀結構高分子之組成示意圖。
第2a至2e顯示本發明五種梳狀結構高分子之實施例。
第3圖係根據本發明之實施例，顯示利用梳狀結構高分子對醫療裝置基材表面進行改質之示意圖。
第4圖係根據本發明之實施例，顯示疏水性側鏈與基材附著的穩定性。
11．．．線性高分子主鏈
12．．．疏水性分子鏈段
13．．．親水性分子鏈段
14．．．抑制生物膜/或抗菌之分子鏈段
Claims (17)
- 一種梳狀結構高分子，包括：(a)線性高分子主鏈；以及(b)梳狀側鏈結構，包括：(b1)疏水性分子鏈段，其中該疏水性分子鏈段包括聚胺基甲酸酯，以及(b2)親水性分子鏈段及/或抑制生物膜/或抗菌之分子鏈段，其中該抑制生物膜/或抗菌之分子鏈段包括：法尼醇(Farnesol)、木糖醇(xylitol)、乳鐵蛋白(Lactoferrin)、乙二胺四醋酸(ethylene diamine tetraacetic acid,EDTA)、鎵(Gallium)、PNAG-分解酵素(PNAG-degrading enzyme)、RNA-III抑制胜肽(RNA-III inhibiting peptide)、呋喃酮C30(Furanone C30)、銀、碘、鋅、銅、抗生素、藥物或上述之組合，其中該線性高分子主鏈係以羥基與該梳狀側鏈結構之反應性官能基形成共價鍵結相互連接，其中該反應性官能基包括：異氰酸酯、羧基、或環氧基。
- 如申請專利範圍第1項所述之梳狀結構高分子，其中該線性高分子主鏈包括：聚乙烯醇(polyvinyl alcohol,PVA)、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)、多醣高分子(polysaccharide)、或上述之組合。
- 如申請專利範圍第1項所述之梳狀結構高分子，其中該疏水性分子鏈段包括：脂肪族聚胺基甲酸酯、芳香族聚胺基甲酸酯、或上述之組合。
- 如申請專利範圍第1項所述之梳狀結構高分子，其中該疏水性分子鏈段之重量平均分子量介於500至50,000道爾頓(dalton)之間。
- 如申請專利範圍第1項所述之梳狀結構高分子，其中該親水性分子鏈段包括：聚乙二醇(polyethylene glycol,PEG)、聚氧化乙烯(polyethylene oxide,PEO)、聚乙烯吡咯烷酮(polyvinylpyrrolidone,PVP)、聚丙烯酸(polyacrylic acid,PAA)及聚甲基丙烯酸(polymethacrylic acid,PMA)、或上述之組合。
- 如申請專利範圍第1項所述之梳狀結構高分子，其中該親水性分子鏈段包括：聚乙二醇(polyethylene glycol,PEG)、聚氧化乙烯(polyethylene oxide,PEO)、聚乙烯吡咯烷酮(polyvinylpyrrolidone,PVP)、或上述之組合。
- 如申請專利範圍第5至6項中任一項所述之梳狀結構高分子，其中該親水性分子鏈段之重量平均分子量介於約500至100,000道爾頓(dalton)之間。
- 如申請專利範圍第1項所述之梳狀結構高分子，其中該線性高分子主鏈以及該梳狀側鏈結構之間的共價鍵結包括胺基甲酸酯鍵結(Urethane Linkage)。
- 一種醫療裝置的改質方法，包括：提供申請專利範圍第1至8項中任一項所述之梳狀結 構高分子；將該梳狀結構高分子溶解於一溶液中；以及將上述含有該梳狀結構高分子的溶液以塗佈或含浸方式，經過一乾燥程序，貼附於一醫療裝置表面。
- 如申請專利範圍第9項所述之醫療裝置的改質方法，其中該溶液包括：N,N-二甲基甲醯胺(N,N-dimethylformamide,DMF)、N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)、二甲基亞碸(Dimethyl sulfoxid,DMSO)、四氫呋喃(Tetrahydrofuran,THF)、醇類(Alcohols)、酮類(Ketones)、水(Water)、或上述之組合。
- 如申請專利範圍第9項所述之醫療裝置的改質方法，其中該溶液包括：(a)丁酮及水、(b)丙酮及N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)、或(c)丙酮、水及N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)、或(d)丙酮、N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)、及二甲基亞碸(Dimethyl sulfoxid,DMSO)。
- 如申請專利範圍第9項所述之醫療裝置的改質方法，其中該乾燥程序係以熱風或真空方式進行，且溫度介於室溫至200℃。
- 如申請專利範圍第9項所述之醫療裝置的改質方法，其中該醫療裝置係由一高分子材料所構成，該高分子材料包括：熱塑性聚胺基甲酸酯(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(polyvinyl chloride,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)、聚碸(Polysulfone)、聚醚碸(poly ether sulfone)、或上述之組合。
- 如申請專利範圍第9項所述之醫療裝置的改質方法，其中該醫療裝置為敷料(Wound dressing)、導管(Catheter)，血管通路裝置(Vascular access devices)，血液透析裝置(Hemodialyzer)、血管支架(Stent)、膽道支架(Biliary stent)、或植入式裝置(Implantable devices)。
- 一種醫療裝置，其表面貼附及/或內部混摻有如申請專利範圍第1至8項中任一項所述之梳狀結構高分子。
- 如申請專利範圍第15項所述之醫療裝置，係由一高分子材料所構成，該高分子材料包括：熱塑性聚胺基甲酸酯(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(polyvinyl chloride,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)、聚碸(Polysulfone)、聚醚碸(poly ether sulfone)、或上述之組合。
- 如申請專利範圍第15項所述之醫療裝置，其中該醫療裝置為敷料(Wound dressing)、導管(Catheter)，血管通路裝置(Vascular access devices)，血液透析裝置(Hemodialyzer)、血管支架(Stent)、膽道支架(Biliary stent)、或植入式裝置(Implantable devices)。
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| US13/595,561 US8968765B2 (en) | 2011-12-12 | 2012-08-27 | Brush polymer and medical use thereof |
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