TWI376440B - Electrospinning compositions for the preparation of nanofibers and the applications thereof - Google Patents
Electrospinning compositions for the preparation of nanofibers and the applications thereof Download PDFInfo
- Publication number
- TWI376440B TWI376440B TW97141495A TW97141495A TWI376440B TW I376440 B TWI376440 B TW I376440B TW 97141495 A TW97141495 A TW 97141495A TW 97141495 A TW97141495 A TW 97141495A TW I376440 B TWI376440 B TW I376440B
- Authority
- TW
- Taiwan
- Prior art keywords
- weight
- cellulose acetate
- composition according
- solvent
- cellulose
- Prior art date
Links
Description
u/6440 六、發明說明： 【發明所屬之技術領域】 崎之輪及細度之方^ 發明縣—翻讀造以_赌之料_、域物，一 及一種酷酸纖u/6440 VI. Description of the invention: [Technical field of invention] The wheel of Kawasaki and the side of fineness ^ Inventing the county - reading the material of _ gambling, domain, one and one kind of cool acid fiber
【先前技掏J 已知’使賴統上製備醋酸纖維素纖纟[Previously known as J] to make cellulose acetate fibrils on Lai Tong
JO 15 之方法通常無法獲得纖維細度小1 ^醋&纖維素纖維) 具有抗菌性太平義、 咖的奈米纖維。以往製造 令仇圏f生不、木纖維一般會在奈米纖維 已定(chlorhexidine)，以提供纖維的浐结卜 + 口几* ’例如氯 利用靜電料枯淋制供太Γ就、、抗邊性’但是此種抗菌劑會影響 :=:、、.糸技捕備奈米纖維的效果，特別是例如以醋 如聚環氧乙烯，而使太米鏃维料t去係添加其他面分子，例 外為样-太止⑽丁…准成糸來達到形成奈米纖維之效果。此 卜導電度進而控娜電_的 :奈Γ於歸!’但此結果往往造成溶液分散性不佳== 物，、使紡爲堵基而影響靜電紡絲效果。 、 已知先前撕巾，絲：，，ultmfmepGrcusfib_le_punfr〇m cellulose triacetate» Seong Ok Han et al, Materials Letters 59 (2005), γρ 2998 3GG1 ’揭示以靜電紡絲技術製備三醋酸纖維素多孔纖維， 該文獻中針對不同比例的共溶細如二氯甲烧/酒精(比例為W至 1:9)對纖_備效果的影響進行比較。以共溶劑製備的三醋酸纖維 素《.截’准I獲知的纖維型態一般為不均勻，且細度分佈從微至次 微米。. 20 1376440 先前技術”Electrospun cellul〇se chlorhexidine as a bactericide» Liang Chen et al, P〇lymer 49 (2008), _266福，揭不在醋酸纖維素/聚環氧乙婦的高分子溶液中添加 抗菌劑’例如氣己定，之後進行靜電纺絲以獲得具有抗菌功能的夺 未纖維’然而此方式獲得的奈米纖維的可纺性並不佳，由於抗菌劑 (chbrhexidin咖添加會影響靜電纺絲醋酸纖維素的效果一般須添 加聚環氧乙烯方可改善此問題。 Ψ 15 ： -Antimicrobial cellulose acetate nanofibers containing w〇n Keun s〇n et ^ Carb〇hydrate ^ (2006)，PP43G-434，揭示在_纖維素高分子溶液中加入雜銀， 在進行靜電縣養奈__後，私χ w ^吏奈米銀於纖維中還原。此種方式雖可獲得具有抗菌 =銀，醋酸纖維素奈米纖維’但直接在高分子溶液中加人奈米銀容易 產生聚集的現象因而會影響纖維的可纺性。另一方面，於言於 液=添加石肖酸銀會形成銀離子，在靜電紡絲時不會因為粒=‘ ^==事後_ w财式使雜預原成奈米銀，但 而可能會對細胞造成直接的傷害。在習知 的先則的肋t ’為了戦奈米縣細辟靜電紡絲的可纺性， -般採_酸銀於高分子溶液t形成銀離子之方式，於靜電訪辦 传纖維後以歸UV絲原奈米銀的方式獲得 ^The method of JO 15 usually cannot obtain fiber fineness 1 ^ vinegar & cellulose fiber) Nanofiber with antibacterial Taipingyi, coffee. In the past, the manufacture of 圏 圏 生 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor chlor Edge's but this kind of antibacterial agent will affect: =:,,. The effect of capturing nanofibers, especially for example, using vinegar such as polyethylene oxide, and making the rice bran t Molecules, the exception is the sample - too (10) Ding ... quasi-forming into the effect of the formation of nanofibers. This conductivity is further controlled by the _ _ _ _ _ _ _ _ 但 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’! Known prior tears, silk:, ultmfmepGrcusfib_le_punfr〇m cellulose triacetate» Seong Ok Han et al, Materials Letters 59 (2005), γρ 2998 3GG1 ' reveals the preparation of cellulose triacetate porous fibers by electrospinning technique, The effects of different ratios of co-solvent fines such as methylene chloride/alcohol (ratio W to 1:9) on fiber preparation were compared. The fiber form of the cellulose triacetate prepared by the co-solvent is generally non-uniform, and the fineness distribution is from micro to sub-micron. 20 1376440 Prior art "Electrospun cellul〇se chlorhexidine as a bactericide» Liang Chen et al, P〇lymer 49 (2008), _266 Fu, Jie does not add antibacterial agent to the cellulose acetate / polyethylene oxide polymer solution 'For example, the gas is determined, and then electrospinning to obtain the fiber with antibacterial function'. However, the spinnability of the nanofiber obtained in this way is not good, due to the antibacterial agent (chbrhexidin coffee addition will affect the electrospinning acetic acid) The effect of cellulose generally requires the addition of polyethylene oxide to improve this problem. Ψ 15 : -Antimicrobial cellulose acetate nanofibers containing w〇n Keun s〇n et ^ Carb〇hydrate ^ (2006), PP43G-434, revealed in _ Adding miscellaneous silver to the cellulose polymer solution, after carrying out the static county y___, the private χ w ^ 吏 nano silver is reduced in the fiber. This method can be obtained with antibacterial = silver, cellulose acetate nanofiber' However, the addition of human nano silver directly to the polymer solution tends to cause aggregation, which affects the spinnability of the fiber. On the other hand, in the case of liquid = silver hexacylate, silver ions are formed. In the electrospinning, it is not because the grain = ' ^ = = after the _ w financial formula to make the miscellaneous into the nano silver, but may cause direct damage to the cells. In the conventional ribs t ' In order to clarify the spinnability of electrospinning in the county, the method of forming silver ions in the polymer solution t is obtained in the way of electrostatically visiting the fiber and returning it to the original nano silver of the UV wire.
銀醋酸纖維素奈米_臈。 n果U X^ ： »Vitamin,oaded electrospun celluJose acetate nano iber mats as transdermal and dermal therapeutic agents of vitamin Λ a〇ld and V1tamin E, Pattama Taepaib〇〇n et ^ ^ ^ 〇f 20 1376440Silver acetate cellulose nano _ 臈. n Fruit U X^ : »Vitamin,oaded electrospun celluJose acetate nano iber mats as transdermal and dermal therapeutic agents of vitamin Λ a〇ld and V1tamin E, Pattama Taepaib〇〇n et ^ ^ ^ 〇f 20 1376440
Pharmaceutics and Biopharmaceutics 67 (2_，pp387 397，揭示在醋 酸纖維素溶液f加入維生素A酸及維生素E，及以靜電纺絲方式製 成奈米纖维薄膜’該薄膜可用於藥物釋放之用途。基本上，添加5重 量％的維生素A酸/維生素E於高分子溶液中，對控制醋酸纖 的細度並沒有幫助。 ’、 10 為了改善先前技術悄為加入(例如)奈米銀等類的添加物而產 生聚集的_及影__可雛，本發贿供—齡有四環徵素 化合物的靜電_域物，肋改善醋酸纖維素高分子溶液的導電 度’及同触韻維餘轉得紐較細且_縣更為均—的〆 米，截、’隹膜本發明又提供—種可降低奈#纖維粒徑之方法，其 善醋酸纖維素之靜電紡絲效果。 ^ 【發明内容】 本發明之-目的在於提供—麵於製造奈米_麟之靜電纺 絲組成物’其舰在於使用四環黴素化合物_麟麟素高分子 溶液的導電度，其中該組成物包含： A)含有醋酸纖維素與溶劑之均勻溶液，其中以溶液的重量為美 準，該醋酸纖維素的含量為_至2〇重量％，及該溶劑選自群= ，含二氣曱烧、二氣曱烧、二甲基亞颯、二曱基曱酿胺、乙醇、四 氫呋喃、醋酸及丙酮或上述至少二者的組合， Β)以上述均勻溶液的重量為基準，〇 〇1至i 〇〇重量％之式①四環 素化合物及其衍生物， 20Pharmaceutics and Biopharmaceutics 67 (2_, pp 387 397, discloses the addition of vitamin A acid and vitamin E in cellulose acetate solution f, and the production of nanofiber film by electrospinning]. The film can be used for drug release. Adding 5% by weight of vitamin A acid/vitamin E to the polymer solution does not help to control the fineness of the cellulose acetate. ', 10 In order to improve the prior art, it is added to the additives such as nano silver. And the accumulation of _ and shadow __ can be young, this bribe for the age-old tetracycline compound electrostatic _ domain, the rib improves the conductivity of cellulose acetate polymer solution 'and the same 〆 , , , , , , , , , , , , , , , , , , , , , , 截 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本The present invention is directed to providing a surface-to-surface electrospinning composition for the manufacture of nano-lin. The ship uses a conductivity of a tetracycline compound, a solution of a polymer solution, wherein the composition comprises: A ) contains acetate fiber a homogeneous solution of a solvent and a solvent, wherein the content of the cellulose acetate is _ to 2% by weight, and the solvent is selected from the group =, containing two gas smoldering, two gas smoldering, two Methyl hydrazine, dimercapto chelating amine, ethanol, tetrahydrofuran, acetic acid and acetone or a combination of at least two of the above, Β) based on the weight of the above homogeneous solution, 〇〇1 to i 〇〇% by weight of Formula 1 Tetracycline compounds and their derivatives, 20
〇H 〇 OH 〇 I OH II O〇H 〇 OH 〇 I OH II O
TU R5 (I) 式中TU R5 (I)
Ri為H或Cw院基，較佳H， =各自社地為H、OH或Ci 6域，触為H及CH3， 心各自獨立地為H或Cm燒基，較佳為CH3。 把:據本發明之一具體例，靜組成物中的醋酸纖維素選自 二、，=括早醋酸纖維素、二醋酸纖維素及三醋酸纖維素，其中以單 成纖維素及n娜素為触，m酸齡素為最佳。 本發明中使用的祕纖維素具有相對分子量範圍為2G，_至 35,000克/莫耳，較佳為25，_至3〇，_克/莫耳。 ^發明中使用的醋酸纖維素中的乙絲含量範圍，以醋酸纖維 素重里為基準’為20至80重;f%，較佳為30至70重量％，及最 佳為40至55重量％。 本發明中’明勻溶液的重量絲準，該醋酸纖維素的含量為 〇.01至20重量0/〇，較佳為0.〇1至15重量％，及更佳為〇·〇1至8重 量％。 根據本發明’ _纖維素係溶於溶劑中以形成均句溶液，其中 /备只丨ΊΓ為單’谷劑或一種以上溶劑組合的共溶劑混合物，該溶劑可 選自群組包含三氯曱烧、二氣甲烧、二甲基亞石風、二曱基曱酿胺、 1376440 為-二氯 _二_ 根據本發明之-具體例，溶劑較佳 颯的共溶劑或包含醋酸與丙酮的共溶 < '元/、一曱基亞 29:丨，較佳為…。至2。小及Ri is H or Cw, preferably H, = each of the H, OH or Ci 6 domains, H and CH3, and the cores are each independently H or Cm, preferably CH3. According to one embodiment of the present invention, the cellulose acetate in the static composition is selected from the group consisting of: second cellulose acetate, cellulose diacetate and cellulose triacetate, wherein the cellulose and the n-nagin are mono-cellulose. For the touch, m acidity is the best. The secret cellulose used in the present invention has a relative molecular weight in the range of 2G, _ to 35,000 g/mole, preferably 25, _ to 3 Å, _g/mole. The range of the content of the ethyl acetate in the cellulose acetate used in the invention is 20 to 80 weight based on the cellulose acetate weight; f%, preferably 30 to 70% by weight, and most preferably 40 to 55% by weight. . In the present invention, the weight of the clear solution is from 0.001 to 20% by weight, preferably from 0.1 to 15% by weight, and more preferably from 〇·〇1 to 8 wt%. According to the invention, the cellulose is dissolved in a solvent to form a homogenous solution, wherein the oxime is a single gluten or a solvent mixture of more than one solvent combination, the solvent may be selected from the group consisting of trichloropurine. Burning, dimethyl sulphur, dimethyl sulphur, dimercaptoamine, 1376440 is -dichloro-di-. According to the invention - the solvent is preferably a co-solvent of hydrazine or comprising acetic acid and acetone. Co-solvent < 'yuan /, one 曱 基亚29: 丨, preferably .... To 2. Small and
ΊΟ 15ΊΟ 15
根據本發明之較佳具體例，使用的溶劑為包含二 基頻之重量_為1 : 1的共溶劑。又，根據本發明之^：：^ 具體例，使用的溶劑為包含醋酸與丙酮之重量比例為8:2的= 本發明巾’所述，，四環素化合物，’及，，其衍生物，，進—步包括四環 素化合物及其衍生物之無機鹽類，例如鹽酸鹽等。根據本發明之一 具體例，靜電紡絲組成物中的式(1)四環素化合物及其衍生物具有提 南酉θ酸纖維素均勻溶液的導電度之功能，除此之外，四環素化合物 亦可進一步作為抗菌劑之用。根據本發明之一較佳具體例，式①所 示的環素化合物及其衍生物可選自下列式(π)至(VIII)所示的四環素 化合物及其衍生物， 多西環素(Doxycycline)According to a preferred embodiment of the invention, the solvent used is a cosolvent comprising a weight of two fundamental frequencies of 1:1. Further, according to the specific example of the present invention, the solvent used is a weight ratio of acetic acid to acetone of 8:2, as described in the present invention, tetracycline compound, 'and, its derivative, The further step includes inorganic salts of tetracycline compounds and derivatives thereof, such as hydrochlorides and the like. According to a specific example of the present invention, the tetracycline compound of the formula (1) and the derivative thereof in the electrospinning composition have a function of conductivity of a uniform solution of the cellulose of the sulphate θ acid, in addition to the tetracycline compound Further used as an antibacterial agent. According to a preferred embodiment of the present invention, the cyclic compound represented by Formula 1 and derivatives thereof may be selected from the group consisting of tetracycline compounds represented by the following formulas (π) to (VIII) and derivatives thereof, and doxycycline (Doxycycline) )
(Π) > 四環黴素(Tetracycline) 1376440(Π) > Tetracycline 1376440
(III)， 美諾環素(Minocycline)(III), Minocycline
氯四環素(Chlortetracy cline) 2Chlortetracycline 2 (Chlortetracy cline) 2
地美環素(Demeclocycline) (IV)， (V)， (VI)， 1376440Demeclocycline (IV), (V), (VI), 1376440
5 較佳為多西環素(Doxycycline)與四環黴素(Tetracycline)，又以多西環 素為最佳。 根據本發明，以醋酸纖維素均勻溶液的重量為基準，式①四環 素化合物及其衍生物的含量為_至〗⑽重量％，較佳為〇 〇1至 ⑽重量％ ’更佳為0.02至〇12重量％，及最佳為〇 〇2至〇 1〇重 量％。 贈酸tit發ΐΐ靜電纺絲組成物，其中使用四麵素化合物控制 在t纖r溶液的導電度及改善靜電紡絲的可紡性，再者， 維的対直接㈣雜細歧使奈米纖 奈米纖维之良好德之外’也賦予所獲得的醋酸纖維素 響醋酸纖較靜^雜祕可在不影 电、、万、，糸放果之情況下獲得纖維細度 1376440 小於500奈米的抗菌性醋酸纖維素奈米鐵维，以纖維細度為50至 500奈米為較佳’及以80至350奈米為最佳。 本發明中’靜電紡絲組成物中的醋酸纖維素之均勻溶液主要成 分選擇地可為醋酸纖維與另一種高分子所形成的複合材料，適合的 高分子實施例選自群組包含：聚己内酯(poly(s-caprolactone)、聚環 氧乙烯(p〇ly(ethylene oxide)、聚乙嫜醇(Poly(vinyl alcohol)、聚乳酸 (polylactic acid)、聚氨g旨(p〇iyUrethane)、聚經基乙酸（polyglycolic acid)、聚-β 經基丁酸酯(p〇ly (β-hydroxybutyrate)、纖維素(cellulose)、 缓甲基纖維素(Carboxymethyl Cellulose)、幾丁質(chitin)/幾丁聚· (chitosan)、膠原蛋白(collagen)、明膠(gelatin)、玻尿酸(Hyaluronic acid 或 Hyaluronan)、褐藻酸(alginate)、聚麵氨酸(y_p〇ly(glutamic add)。 本發明之靜電紡絲組成物可選擇性地添加表面接枝/固定化物 質或纖維添加物等類添加劑，諸如抗體、酵素'蛋白質、含 、 2 宮能基之高分子、細菌、細胞、界面活性劑、奈米金屬粒子、微膠 囊/奈米膠囊、藥物、活性碳、奈米碳管、鹽類、聚電解質、觸媒等 物質。 、 本發明之另一目的在於提供一種改善醋酸纖維素奈米纖維之導 電度及細度之方法，其步驟包含： 1)將0.01至20重量％，較佳為〇.〇1至15重量％及更佳為〇〇1 至8重量％之猶纖維素高分子加人—共溶射，以配製一 ，纖維素高分子溶液，其中共溶劑由選自包含二氣抵、二甲基^ =、醋酸及_之群組中的二種溶劑所構成，其重量比例為i :凶 B)將〇.(U至L00重量％，較佳為〇.〇1至〇Μ重量％，更佳為〇 Ο: 1376440 至0.12重量％及最佳為0.02至o.io重量％之四環素化合物添加至 步驟A)配製的高分子溶液中，以製得具有導電度介於1〇·3至 之間的醋酸齡素高分子溶液，其巾四環素化合物為式①之四 及其衍生物： 衣”5 Preferably, Doxycycline and Tetracycline, and doxycycline is preferred. According to the present invention, the content of the tetracycline compound and its derivative of the formula 1 is _ to 10% by weight, preferably 〇〇1 to (10)% by weight, more preferably 0.02 to 〇, based on the weight of the cellulose acetate homogeneous solution. 12% by weight, and most preferably 〇〇2 to 〇1% by weight. An acid-tit hairpin electrospinning composition is used, in which an tetrahedral compound is used to control the conductivity of the t-fiber solution and to improve the spinnability of the electrospinning, and further, the bismuth of the bismuth is directly (four) In addition to the good virtue of fiber nanofibers, it also gives the cellulose acetate to be obtained. The cellulose acetate fiber is more static and confusing. It can obtain fiber fineness of 1376440 and less than 500 without the shadow of electricity. The antibacterial cellulose acetate nano-iron of nanometer is preferably a fiber fineness of 50 to 500 nm and is preferably 80 to 350 nm. In the present invention, the main component of the uniform solution of cellulose acetate in the electrospinning composition may be a composite material formed by the cellulose acetate and another polymer. Suitable polymer examples are selected from the group consisting of: Lactone (poly(s-caprolactone), poly(ethylene oxide), poly(vinyl alcohol), polylactic acid, polyaluminum (p〇iyUrethane) , polyglycolic acid, poly-β-butylbutyrate, cellulose, carboxymethyl cellulose, chitin /chitosan, collagen, gelatin, hyaluronic acid or Hyaluronan, alginate, glutamic add. The present invention The electrospinning composition may selectively add an additive such as a surface graft/immobilized substance or a fiber additive, such as an antibody, an enzyme 'protein, a polymer containing 2 gongs, a bacterium, a cell, a surfactant, Nano metal particles, microcapsules / nano rubber , a drug, activated carbon, carbon nanotubes, salts, polyelectrolytes, catalysts, etc. Another object of the present invention is to provide a method for improving the conductivity and fineness of cellulose acetate nanofibers, the steps thereof The method comprises the following steps: 1) adding 0.01 to 20% by weight, preferably 〇1 to 15% by weight, and more preferably 〇〇1 to 8% by weight of the jujube polymer to human-co-solubilization to prepare a fiber a polymer solution, wherein the co-solvent is composed of two solvents selected from the group consisting of dioxins, dimethyl groups, acetic acid and _, and the weight ratio thereof is i: murder B) 〇. (U Up to L00% by weight, preferably 〇.〇1 to 〇Μ% by weight, more preferably 376: 1376440 to 0.12% by weight and most preferably 0.02 to o.io% by weight of the tetracycline compound is added to the step A) In the polymer solution, an acetic acid-inducing polymer solution having a conductivity of between 1 and 3 is obtained, and the tetracycline compound is a tetradentate compound and a derivative thereof:
Ri為Η或Ck院基， 化及&各自獨立地為Η、OH或CV6烷基， ^4及Rs各自獨立地為Η或Cy烷基， C)將步驟B)製得的高分子溶液通過包含紡嘴與電極Ri is Η or Ck, and each is independently Η, OH or CV6 alkyl, ^4 and Rs are each independently Η or Cy alkyl, C) the polymer solution obtained in step B) By including a nozzle and an electrode
J5 裝置，其操作電壓範圍介於5kV至80kV之間，以紡出且二^ 於50奈米至500奈米之間的奈米纖維。 、"有罝徑1 根據本發明方法之-具體例，醋酸纖維素選自群 =維素、二醋酸纖維素及三醋酸纖維素，其中以單醋酸纖：: 醋酸纖維素為較佳，又以三醋酸纖維素為最佳。 、/、- 本發明方种制的暖_素财姉分子量 至35,000克/莫耳’較佳為25，_至3〇，_克/莫耳。’、’、， 本發明方种使用的醋酸纖維素中的乙酿基含A J5 device operating at a voltage range of between 5 kV and 80 kV to spun and between nanometers of between 50 nanometers and 500 nanometers. And having a diameter of 1 according to the method of the present invention, the cellulose acetate is selected from the group consisting of a group of vitamins, cellulose diacetate and cellulose triacetate, of which cellulose acetate: cellulose acetate is preferred. Further, cellulose triacetate is preferred. The molecular weight of the warm-based protein of the present invention is preferably 3,5 g/mole, preferably 25, _ to 3 Å, _g/mole. ', ', the ethyl acetate in the cellulose acetate used in the invention
80重量％，較佳為3〇 $ 70會旦<ν η 圍為20 J 里雜為30至7〇重里〇/〇，及最佳為4〇至％重量％^80% by weight, preferably 3 〇 $70 meeting dan < ν η is 20 J, 30 to 7 〇 heavy 〇 / 〇, and most preferably 4 〇 to % by weight ^
1J/044U 醋酸纖維素重量為基準。 根據本義之方法，溶劑可為二_働 ==氯⑽二⑽的共溶劑或混：:二 重：雜10至20:卜更佳…錢:!及最佳 重量比例ιιαΓ月方法中使用的溶劑為醋酸與丙酮的共溶劑，其 8 2例較佳為1:10至20:1，更佳為1 : 1錢：！，及最佳為1J/044U cellulose acetate weight as a benchmark. According to the method of the present meaning, the solvent may be a co-solvent or a mixture of two _ 働 == chlorine (10) two (10):: two weight: miscellaneous 10 to 20: better bu ... money:! and the best weight ratio ιια used in the method The solvent is a co-solvent of acetic acid and acetone, and the 82 cases are preferably 1:10 to 20:1, more preferably 1:1:: And best
iO 5 祕祕絲(細卿_g)方式，藉高電壓(例如 =)辅_維素高分子均雜液帶有電荷，《噴出之太 =纖維乾燥與1H卜根據本發明之—具體例，方法中，在提供高^ =情況下，利用裝配有計量幫浦的注射器將高分子溶液喷出、，告 場強度後，姐職的毛崎尖端產生半球形流體表二 =形成圓錐狀(如所謂的泰勒圓錐形(Taylw c㈣))；繼續增加電場 雜界值，雜電财力超過越絲張力值時， 圓之帶電荷流體產生伽現象，在此過程中溶劑蒸發固化 於收集器上。於靜電纺絲裝置中，一電極連接喷出的 、…合液或熔融體’另-電極鱗接齡的或靜止的收集器。 纖= 據本發明之方法，醋酸纖維素為選自單醋酸纖維素、二醋酸 、’’:、或二醋賴維素’以單醋g_維素及三醋峨維素為較佳， 維素繼。根據本發明’可瓣咖形式的醋 物’方法巾的四繼合物及其衍生 予、自如上所速户西每素、四環姆、土黴素、美諾環素 20 又以多西環素為=加核素’其尹以多西環素及四環鐵素為較佳， 本發明之方法，除 其特徵在於使用本發明H於種醋酸鐵维素奈米纖維膜材， 有均勾細度且可纺性佳的靜電纺絲組成物作為材料製得具 又’根據本發明之方法制 可紡性的醋酸纖維素夺乎二^、有改善的導電性、均勻細度與 細度小於500奈米，以根據本發明，獲得的奈米纖維 米為最佳。 乂50至500奈米為較佳’及以8〇至350奈 奈嶋_備成 素等），因撕_纖維素奈米：^抗==«、四環徽 米纖H本纟㈣目6^冑㈣跑功能的奈 根據本發舊得的__維素奈雜賴材 · 3需的產品2，使用的加工方式例如包含：界面聚合、塗= ^在文質斗、接枝、固定化、交聯、親水化/疏水化、枯 合或在其他基材(如不織布、金屬薄片等)上纺絲等。 貼 本發明獲得的醋酸纖維素奈米纖維膜材可進—步加工而 需纖f型態J如實心型、多組份型、多孔型及中__斤 發魏付的^纖維騎可單獨仙或與其絲則如 布、聚合反應、貼合_等)_起組合，其可再進—步經加工，例二 、交聯、酵素固定化、樹脂塗佈、熱壓等，最後形成所需 崎，特別是醫 土血液淨化独卿响㈣/血液透析(Η_崎叫使用本發 =靜電紡絲絲纖_材應驗血液淨化可發揮清除錢中具有 内源性抗體'異常的血毁以及累積於體内的藥物或毒物 析膜作為半透二膜材可用於血液透 物貝產生!。合或反應之特性來達到生物感測之效果。 M^#^DmgDeliVeiy) ： 隹中加入樂劑(例如藥物微囊，藥物顆粒等形可經 =控制釋放_溫度、酸驗值、親水親油特性等)等方式= 用外，也可以複合纖維形式應用。 成伤减、准直接應 5.組織工程支架⑺咖吻職㈣卿細）： ^成物製成的奈米纖維作為組織工程支架之 電纺絲 直接應用外，也可以複合纖維形式應用。 示早成份纖維 【實施方式】 丄376440 本發明將藉由下述實施例更詳盡地說 何方式限制本發明細，雖然設於域 $實關*意欲以任 近似值，但儘可能精確地紀齡較的顚及參數範圍是 π只施例中的數值。 實施例 靜電纺絲裝置及操作條件如 本發明之實施例及比較例中使用的 下說明：iO 5 secret silk (fine _g) way, by high voltage (such as =) auxiliary _ weisu high polymer mixed liquid with charge, "spray out too = fiber drying and 1H according to the invention - specific examples In the method, in the case of providing high ^ =, the polymer solution is sprayed out using a syringe equipped with a metering pump, and after the intensity of the field is reported, the tip of the Maosaki of the sister's office produces a hemispherical fluid. For example, the so-called Taylor conical shape (Taylw c (4))); continue to increase the electric field heterocline value, when the financial power exceeds the wire tension value, the circular charged fluid generates a gamma phenomenon, in which the solvent evaporates and solidifies on the collector. In the electrospinning apparatus, an electrode is connected to the ejected, ... liquid or molten body. Fiber = According to the method of the present invention, cellulose acetate is selected from the group consisting of cellulose monoacetate, diacetic acid, '':, or diacetin', preferably vinegar g-vitamin and triacetin, vitamins Following. According to the invention, the tetra-compound of the 'vinegar-formed vinegar' method towel and the derivative thereof are as described above, and the above-mentioned Shouhususu, tetracycline, oxytetracycline, minocycline 20 and Dorsey Cyclin is = plus nuclide', Yin is preferably doxycycline and tetracycline, the method of the present invention, except that it is characterized by using the present invention H for ferric acetate nanofiber membrane, The electrospinning composition having the fineness and good spinnability as a material can be made with the cellulose acetate which can be made into the spinnability according to the method of the invention, has improved conductivity, uniform fineness and The fineness is less than 500 nm, and in accordance with the present invention, the obtained nanofiber rice is optimal.乂50 to 500 nm is preferred 'and 8 〇 to 350 奈奈嶋_备成素, etc.), due to tear _ cellulose nano: ^ anti == «, four-ring emblem rice fiber H 纟 (four) head 6 ^ 胄 (4) Run the function of the nai according to the old __Vai Nai Nai Lai material · 3 required product 2, the processing methods used include, for example, interfacial polymerization, coating = ^ in the text bucket, grafting, fixing , cross-linking, hydrophilization/hydrophobization, drying or spinning on other substrates (such as non-woven fabrics, metal foils, etc.). The cellulose acetate nanofiber membrane obtained by the invention can be further processed into a fiber type f, such as a solid type, a multi-component type, a porous type, and a medium-sized fiber. Xian or its silk is like cloth, polymerization, bonding _, etc.), which can be further processed - step 2, cross-linking, enzyme immobilization, resin coating, hot pressing, etc. Saki, especially the medical blood purification, the singularity of the singer (four) / hemodialysis (Η _ _ 叫 使用 使用 = = = = = = = = = = = = = = = = = = = = = 血液 血液 血液 血液 血液 血液 血液 血液 血液 血液 血液 血液And the drug or toxicant film accumulated in the body as a semi-permeable membrane can be used for the production of blood-transparent shells. The characteristics of the combination or reaction to achieve the effect of biological sensing. M^#^DmgDeliVeiy) : Adding music to the sputum Agents (such as drug microcapsules, drug particles, etc. can be controlled by = temperature, acid value, hydrophilic and lipophilic properties, etc.), etc., can also be applied in the form of composite fibers. Injury reduction, quasi-direct response 5. Tissue engineering support (7) Curry kiss (four) Qing fine): ^ Nanofiber made of adult material as a tissue engineering scaffold for electrospinning, can also be applied in the form of composite fiber. EMBODIMENTAL COMPONENT FIBER [Embodiment] 丄 376 440 The present invention will be more specifically described by the following examples in a more limited manner, although it is intended to be an approximation, but as accurate as possible. The range of parameters and parameters is the value in the π only example. EXAMPLES Electrospinning apparatus and operating conditions are as follows in the examples and comparative examples of the present invention:
i-0 1.靜電紡絲裝置(型號ESL-004，榜庐八___ 高分子溶液播出金屬針頭的推進裝置，，1) ·包3個使 Λ -支金屬針，-個電源供應器與—個收集纖維的基板。 2.操作條件：靜電纺絲操作的電壓為2〇 kv，推進壓力為〇 廳’金屬針規格25 gage，金屬針尖端至基板之距離為2〇公分 根據本發明之實施例及比較例獲得的醋酸纖維素奈米纖維靜電 紡絲組成物及其臈材之特性依據下述方法進行評估及測定： 1.奈米纖維結構/奈米纖維粒徑分佈 利用掃描式電子顯微鏡(SEM)裝置(型號j〇eL JSM-6700F， JOEL公司製造）’ 5,〇〇〇倍率，觀察奈米纖維結構及細度或粒徑分 佈情形。 2.高分子溶液導電度 利用電阻計(型號SC-SRT Surface Resistant，宏星電機股份有限 公司製造)檢測高分子溶液的導電度(1/Ω)。 1376440 3.抗菌效果 A)疋性抑 |j 性測試：使用標準 AATCC (American Association of Textile Chemists and Colorists) Test Method 147 定性測試奈米纖維膜 材的抑涵性，其操作流程如下所述： 拳 15I-0 1. Electrospinning device (Model ESL-004, 庐 庐 ___ Propelling device for metal needles for polymer solution, 1) · Packing 3 for Λ - Branch metal needle, - Power supply With a substrate for collecting fibers. 2. Operating conditions: the voltage of the electrospinning operation is 2 〇 kv, the pushing pressure is 25 gage of the metal needle of the 〇 hall, and the distance from the tip of the metal needle to the substrate is 2 〇 cm according to the examples and comparative examples of the present invention. The characteristics of the cellulose acetate nanofiber electrospinning composition and its coffin were evaluated and determined according to the following methods: 1. Nanofiber structure/nano fiber particle size distribution using a scanning electron microscope (SEM) device (model j〇eL JSM-6700F, manufactured by JOEL) '5, 〇〇〇 magnification, observe the structure of the nanofiber and the fineness or particle size distribution. 2. Conductivity of polymer solution The conductivity (1/Ω) of the polymer solution was measured using an electric resistance meter (Model SC-SRT Surface Resistant, manufactured by Hongxing Electric Co., Ltd.). 1376440 3. Antibacterial effect A) 疋 抑 | | j sex test: using the standard AATCC (American Association of Textile Chemists and Colorists) Test Method 147 qualitative test of the inhibition of nanofiber membrane, the operation process is as follows: 15
20 準備細囷培養基.均勻混合23.5克洋菜膠(Nutrient Agar)/1升 瘵餾水與8克營養培養基(Nutrient Broth)/l升蒸餾水，之後將形成 的培養基在咼溫高壓滅菌爸中殺崮，以製得細菌培養基； 菌液培養.將金育色葡萄球菌(staphyl0C0ccus aureus)(格蘭氏陽 性菌)加入該經滅菌的培養基中培養18至24小時； -測試樣品：準備尺寸2公分x 2公分之經過滅g的靜電纺絲 醋酸纖維素奈米纖維膜樣品； 式驗V驟.將經滅菌的培養基置於無菌操作台中’於未凝固前20 Prepare the fine media. Mix 23.5 grams of Nuttrient Agar / 1 liter of distilled water and 8 grams of Nutrient Broth / 1 liter of distilled water, and then form the medium to kill in the autoclave. To prepare a bacterial culture medium; culture liquid culture. Staphyl0C0ccus aureus (Gram-positive bacteria) is added to the sterilized medium for 18 to 24 hours; - Test sample: preparation size 2 cm x 2 cm of electrospun cellulose acetate nanofiber membrane sample after g-killing; test V. Place the sterilized medium in the aseptic table 'before coagulation
’以製成平板培養基；在平板培養基中接種g株並以L 均自塗佈’轉奈米纖賴與以塗佈方式製成的薄膜利用 小〜地放置於洋菜縣面及與平板培養基貼合，在37〇C溫 度培養箱中下培養24小時； 果丨、纖蝴綱抗· 疋置抗菌性測試:使用® (】叩齡In 準^進行測試，其操作流程如下所述： _i、δ式驗的生物：今龙 — 、任 t 、* 汽巴葡萄球菌（staphylococcus aureus) -準備細菌培養基：脾ς ± u 將5克牛肉汁(beef extract)、10克蛋白月| 1376440 (peptone)、5克氣化鈉、15克洋菜膠與1〇〇〇亳升 中均句混合；在沸水浴中加熱以充份溶解混合液的^置 合液的pH值調控至pH 7 〇 士 〇 2著， 迎後將此 以形成細菌培養基； 接者U…皿_滅菌爸殺菌， 1試樣品：準備尺寸4()総x4G絲之經 醋酸纖維素奈米纖維膜樣品； _ ”紡絲 -試驗步驟：'To make a plate medium; inoculate the g strain in the plate medium and self-coat the 'transfer nanofibers' and the film prepared by the coating method to the acacia county surface and the plate medium Fitting, cultivating in a 37 ° C temperature incubator for 24 hours; Antibacterial test of scorpion scorpion, scorpion scorpion anti - sputum: test using ® ( 叩 In , , , , , , , , , , : : : : : _ _ _ _ , δ-tested organisms: Iron -, t, * Staphylococcus aureus - preparation of bacterial culture medium: spleen ± u 5 grams of beef extract (beef extract), 10 grams of protein month | 1376440 (peptone ), 5 g of sodium sulphate, 15 g of acacia gum and 1 liter of medium-mixed sentence; the pH of the liquid in the boiling water bath to fully dissolve the mixture is adjusted to pH 7 〇士〇 2, after the welcome to form a bacterial culture medium; Receiver U... dish _ sterilization dad sterilization, 1 test sample: prepare size 4 () 総 x4G silk cellulose acetate nanofiber membrane sample; _ "spinning - experiment procedure:
Day 1 =化，將接人培養射在37。⑽ 養18至24小時；Day 1 = chemistry, and the training will be taken at 37. (10) raise 18 to 24 hours;
iO 15iO 15
Day 2 ··計算初始菌數，稀釋為每毫升！ χ ι〇5的菌液濃戶， 再將此液體均㈣在膜上直到膜材吸滿菌液即 ΓΓίΙΓΓ時茜菌液的膜材置於37°c的培養箱令培養 ^ 3 : f㈣2的膜置於20毫升的PBS中震盪i分鐘以 ’之後’賴得的賴稀釋至原有濃度的1〇5， 取此稀釋液體在洋菜平板上作塗佈，在坑的 相中培養18至24小時； 。養Day 2 ·· Calculate the initial number of bacteria and dilute to each ml! χ 〇 〇 的 的 的 的 的 的 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 The membrane was shaken in 20 ml of PBS for 1 minute, and then diluted to the original concentration of 1〇5, and the diluted liquid was applied to the acacia plate and cultured in the pit phase to 18 24 hours; . support
Day 4 :計算Day 3的結果； 外相轉得戦_奈錢狀㈣働抑菌值， 田权雜大於0時，較樣品具核 j值 2時，評定樣品具有抑菌作用。 料备抑函值大於 I. 醋酸纖維素靜電紡絲組成物配製及導電度測試 比較例A ' 20 u76440 照組配裳不含有四環素化合物之靜電纺絲單·鐵维素溶液作為對 驗，靖自 =:Γ)共溶劑'痛方式二二 ==蝴额★增細峨恤麵，結1: 實施例1 释取I5克單醋酸纖維素原料(相對分子量29，_ F1Uka公司)置入玻璃瓶中，於其中添加含有68克醋酸ϋ 3自 醋酸纖維素均句溶液。 J J以獲侍早 * 多二素加入上述獲得的單醋_素均勻溶液 中。口句⑽後件含有〇.〇2%多西環素之單赠 絲均勻溶液’測試該溶液的導電度，結果如表丨所示。、 實施例2 的之方式，惟於單醋酸纖維素靜電纺絲均勻溶液中 的夕衣素3里為4克，以獲得含有0.04%多西壤夸 辛靜雷紡絲>1、…产t 长素之早醋酸纖維 京静均勻减。接著測試該均勻溶液的Day 4: Calculate the result of Day 3; the external phase turns to 戦_奈钱状(四)働Antibacterial value, when Tianquan is greater than 0, the sample has a bacteriostatic effect when the sample has a nuclear j value of 2. The material preparation inhibition value is greater than I. Cellulose acetate electrospinning composition preparation and conductivity test comparison example A ' 20 u76440 according to the group with the electrospinning single iron solution containing tetracycline compound as a test, Jing From =: Γ) co-solvent 'pain mode two two == butterfly amount ★ thinning t-shirt face, knot 1: Example 1 Release 1 5 grams of monoacetate raw material (relative molecular weight 29, _ F1Uka company) placed in glass In the bottle, 68 g of a solution of cerium acetate 3 from cellulose acetate was added thereto. J J is added to the mono-acetin-uniform solution obtained above in order to obtain the early service. The latter part of the oral sentence (10) contains a single-filament homogeneous solution of 〇.〇2% doxycycline' to test the conductivity of the solution, and the results are shown in Table 。. The method of the second embodiment is only 4 g in the monosodium acetate electrospinning uniform solution in the smectin 3 to obtain a 0.04% polyclogan quenching static spinning > The early acetate fiber is evenly reduced. Next testing the homogeneous solution
所示。 电度、、口果如表1 比較例B 20 1376440 照组配製不含有四環素化合物之三醋酸纖維素靜電紡絲溶液作為對 祥取8克三醋酸纖維素原料(乙醯基含量幻至4 一乳曱炫，讓减簡在贼溫度下靜置—天後，再加 克 甲基亞颯，以震衫式使溶液混合均勻，以麟於二氯找 : 亞石風(1 · 1)共溶劑中之三醋酸纖維素均勾 ^ : 液之導電度檢測，結果如表！所示。 订上述獲钎的溶 10 15 20 實施例3 AL-mrs^rr^!,!43 ^49 ^ 購自Slgma-Aldnch)置入玻璃瓶中，於发令π ± 二氣甲貌，讓溶液保持在40t溫度下靜置一於h中添加42克 甲基亞昏以震盡方式使溶液 再加人42克二 溶液。 以獲件二醋酸纖維素均勻 秤取1.84克的彡西環素加人上麵得的三 中’混合均勻後，獲得含有〇 ^素句勻溶液 絲均句溶液，测試該溶液的導電/結纖維素靜電纺 實施例4 如同實施例3之方式，惟於二萨醅 的多西料含* 遍纖維素靜電紡絲均勻溶液中 、准素靜電紡絲均勻溶液。垃装 西裱素之二醋酸纖 示。 文接者測式各溶液的導電度，結果如表！所 20 137-6440 實施例5 結果如表1所 如同貫施例3之方式，惟於三雜纖維素靜 的多西環素含量為7.36克’以獲得含有_%多西考;^二二 維素靜電紡絲㈣溶液。接著測試各溶液的導電度 醋 示。 又 實施例6 如同實施例3之方式，惟於三醋酸纖維素靜電纺絲均勻溶液中 環素含量為9.2克’以獲得含有α職多西環素之三醋酸纖 、准素靜電_均勻雜。接相試各溶㈣導電度，結果如表i所 不0Shown. The electric energy and the fruit are as shown in Table 1. Comparative Example B 20 1376440 According to the group, a triacetyl cellulose electrospinning solution containing no tetracycline compound is prepared as a raw material of 8 g of cellulose triacetate (the content of ethyl acetate is 4 to 1).曱 曱 曱 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , — 在 — — — — — — — — — — — — — — — — — — — — — — — — The cellulose triacetate in the solvent is checked: the conductivity of the liquid is detected, and the results are shown in Table!. The above-mentioned solution for obtaining the solder 10 15 20 Example 3 AL-mrs^rr^!,!43 ^49 ^ Placed in a glass bottle from Slgma-Aldnch), the π ± two gas appearance is allowed to be released, and the solution is allowed to stand at 40t for a period of time. Adding 42 grams of methyl faint in h to shock the solution to add 42 Two grams of solution. The obtained diacetate cellulose was uniformly weighed and weighed 1.84 g of cilostatin and the above three succincts were uniformly mixed, and then a solution containing the sputum succinct solution was obtained, and the conductivity of the solution was tested/ Cellulose Electrospinning Example 4 As in the case of Example 3, only the doxantant of Disam has a uniform solution of the electrospinning uniform solution in the cellulose electrospinning uniform solution. Disintegrated with diacetyl acetate. The splicer measures the conductivity of each solution, and the results are as shown! 20 137-6440 Example 5 The results are as shown in Table 1 as in the case of Example 3, except that the content of doxycycline in the tri-hocleic cellulose is 7.36 g' to obtain _% doroxiw; Weiss electrospinning (four) solution. Next, the conductivity of each solution was tested. Further, Example 6 was carried out in the same manner as in Example 3 except that the content of cyclin in the triacetyl cellulose electrospinning homogeneous solution was 9.2 g' to obtain a triacetate containing α-doxcycline and a monodisperse. The phase is tested for each dissolved (four) conductivity, and the results are as shown in Table i.
表1 醋酸 〇/„ - tbfe例 A 15 势包例 1 1 5 魏例 2 _例 Β 你包例 3 势&例 4 獅例 5 實施例 6 ---- 三醋酸纖維 素，％ 1 15 8 8 8 8 8 夕曲5衣素，％ 0 0.02 0.04 0 0.02 0.04 0.08 卜 0.10 问分子溶液導 電度Cl/Ω) 10 6 10 ·5 10 .5 10 ·7 10 ·5 10"4 10 ·3 10 *3 如表1所示’與未含有多西環素的組成物(比較例A及比較例 相較T ’實_ 1至6所獲得的靜電紡雜成物的導電度有提高 的傾向。 1376440 絲絲纖轉備及_細度測試 將比較例Α獲得的未含有多 行靜電纺絲料。絲電_裝㈣抑f ㈣溶液進 該均勾溶議。在靜電_顧^=擠_針頭，將 固化，於收集器上分別形成奈米2。使禮中的溶劑蒸發及之後 圖la對上圖=2奈錢料行細歧分布的檢測，結果如表2及 實施例7 15 獲得置的針筒内農填由實施例工所 頭，將該均句溶液噴出。在^ = 進裝f將溶液擠出金屬針 及之後固化:於收集器上分卿：：使溶液中的溶劑蒸發 圖2a、圖 1 二::未纖維進行細度及分布的檢測’結果如表2及 實施例8 ‘程序，以形成奈米 义西^1?17知之靜電纺絲程序’將實施例2獲得之含有〇.〇4% 户西讀的早雜纖維素Μ溶液進行靜電纺絲： 纖維。 結果如表2及 對上述形成的奈米纖維進行細度及分布的檢测， 20Table 1 Barium acetate / „ - tbfe Example A 15 Potential package case 1 1 5 Wei case 2 _ Example Β Your package example 3 Potential & Example 4 Lion Case 5 Example 6 ---- Cellulose triacetate, % 1 15 8 8 8 8 8 夕曲5衣素,% 0 0.02 0.04 0 0.02 0.04 0.08 卜 0.10 The molecular solution conductivity Cl/Ω) 10 6 10 ·5 10 .5 10 ·7 10 ·5 10"4 10 ·3 10 *3 as shown in Table 1 'The tendency to increase the conductivity of the electrospun hybrid obtained from the composition containing no doxycycline (comparative example A and comparative example compared with T 'real _ 1 to 6) 1376440 Filament fiber transfer and _ fineness test will be compared with the sample obtained without containing multiple rows of electrospinning material. Silk electricity _ loading (four) f (four) solution into the Hook solution. In the static _ Gu ^ = squeeze _ needle, will solidify, form nano 2 on the collector respectively. Evaporate the solvent in the ritual and then check the distribution of the fineness distribution of the above figure = 2 nanometer. The results are shown in Table 2 and Example 7 15 The obtained syringe is filled in by the embodiment, and the homogenous solution is sprayed out. The solution is extruded into the metal needle and then solidified in the feed f: on the collector: Solvent evaporation Fig. 2a, Fig. 1 2:: Detection of fineness and distribution of unfibers' results as shown in Table 2 and Example 8 'to form an electrospinning procedure known as nano-Iss. The electrospinning of the early miscellaneous cellulose solution containing 〇.〇4% of the households was carried out: fiber. The results are shown in Table 2 and the fineness and distribution of the nanofibers formed as described above, 20
圖3a、圖3b所示。 比較例D 如同比較例C之靜電紡 ^ 環素之三紐齡素㈣ '、々’將比較例B獲得的未含有多西 維。 —'錢進行靜電紡絲程序，以形成奈米 圖纖維進行細度及分布的檢測， 10 貫施例9 如同實施例7之靜電纺絲程序，將實施例3獲得之含有議 ^環素的三麟纖維素均勻溶液進行靜電紡絲程序，以形成奈米 對上述形細奈米纖軸行細纽分布雜測，結果如表2及 圖5a、圖5b所示。Figure 3a, Figure 3b. Comparative Example D As in the case of Comparative Example C, the three-year-old (IV) ', 々' of the electrospun cyclocycline obtained in Comparative Example B did not contain doxevi. - 'Money electrospinning procedure to form nanograph fibers for fineness and distribution detection, 10 Example 9 As in the electrospinning procedure of Example 7, the cyclin obtained in Example 3 was obtained. The Sanlin cellulose homogeneous solution was subjected to an electrospinning procedure to form nanometers for the distribution of the fine-grained fine-grained fine-axis, and the results are shown in Table 2 and Figures 5a and 5b.
實施例10 如同實施例7之靜電紡絲程序，將實施例4獲得之含有〇 〇4% 20 纖 結果如表2及 多西環素的三醋酸纖維素均勻溶液進行靜電紡絲程序，以形成奈米 纖維。 對上述形成的奈米纖維進行細度及分布的檢測，結果如表2及 圖6a、圖6b所示。 實施例11 23 u/t)44〇 如同實施例7之靜電紡絲程序，將實施例5獲得 多西環素的三紐纖維素均勻溶液進行靜電_ ^ 纖維。 以形成奈米 對上述形成的奈米纖維進行細度及分布的檢測，結果如 圖7所示。 表2及 貧施例12 夕如同實施例7之靜電纺絲程序，將實施例6獲得之含有〇 1〇% 多西環素的三醋酸纖維素均勻溶液進行靜電紡絲程序，以形成卉0 纖維。 不〆、 對上述形成的奈米纖維進行細度及分布的檢測，結果如 圖8所示。 ——-_ 衣/ th|交例 C 銳例 7 额例 8 交例 D 實施例 9 魏例 10 魏例 11 實施 1〇 早醋酸纖維 > % 0 15 15 —醋酸纖維 0 8 8 8 8 _£西環素，〇/〇 0 0.02 0.04 0 0.02 0.04 0.08 010 纖維平均直徑 521.47 —441.50 35936 1186.03 49029 150.92 105.48 96.70 -—-—1 L墙38 Ϊ267.58 ±61.84 ±81229 士 123.13 ±6654 ±33.73 ±3237 由實施例結果顯示隨著多西環素的含量增加，奈米纖維的粒徑 降低及細度均句分布的效果更佳。如表2所示，與未含有多西環素 之醋酸纖維素靜電紡絲組成物(比較例C及比較例D)相較下，使用 本發明之错酸纖維素靜電紡絲組成物(實施例7至12)經過靜電紡絲 24 1376440 令的多西環素含量增加時，其教徑變=:顯示’當奈米纖維 十，又以含有〇.G2至丨〇%多西 二=。在上述實施例 物形成的奈米織維在細度及均句性上具靜電紡絲組成 6a、7及8所示。 顯者的效果’如圖5a、Example 10 As in the electrospinning procedure of Example 7, the uniform solution of cellulose triacetate obtained in Example 4 containing 〇〇4% 20 fiber results as shown in Table 2 and doxycycline was subjected to an electrospinning procedure to form Nanofiber. The fineness and distribution of the above-formed nanofibers were examined, and the results are shown in Table 2 and Figs. 6a and 6b. Example 11 23 u/t) 44 〇 As in the electrospinning procedure of Example 7, Example 5 obtained a uniform solution of doxycycline in a three-cell cellulose to carry out electrostatic _ ^ fibers. Formation of Nanoparticles The fineness and distribution of the above-described nanofibers were examined, and the results are shown in Fig. 7. Table 2 and Example 12: As in the electrospinning procedure of Example 7, the uniform solution of cellulose triacetate containing 〇1〇% of doxycycline obtained in Example 6 was subjected to an electrospinning procedure to form a plant 0. fiber. The fineness and distribution of the above-formed nanofibers were examined without fail, and the results are shown in Fig. 8. ——-_ Clothes/th|Cross-counter C Sharp example 7 Example 8 Example D Example 9 Wei case 10 Wei case 11 Implementation of 1 〇 early acetate fiber > % 0 15 15 - acetate fiber 0 8 8 8 8 _ £xicycline, 〇/〇0 0.02 0.04 0 0.02 0.04 0.08 010 Average fiber diameter 521.47 —441.50 35936 1186.03 49029 150.92 105.48 96.70 -—-—1 L wall 38 Ϊ267.58 ±61.84 ±81229 ±123.13 ±6654 ±33.73 ± 3237 The results of the examples show that as the content of doxycycline increases, the effect of particle size reduction and fineness distribution of nanofibers is better. As shown in Table 2, the acid-group cellulose electrospinning composition of the present invention was used in comparison with the cellulose acetate electrospinning composition (Comparative Example C and Comparative Example D) containing no doxycycline (implementation) Examples 7 to 12) When the doxycycline content of the electrospinning 24 1376440 is increased, the teaching diameter becomes =: when 'nine fiber ten, it contains 〇.G2 to 丨〇%多西二=. The nanowebs formed in the above examples have electrospinning compositions 6a, 7 and 8 in fineness and uniformity. The effect of the obvious' is shown in Figure 5a.
HI.奈米纖維膜材之抗菌性試驗 A)定性抑菌試驗 按照上述定性抑菌性試驗方法，取 _ 液靜電紡絲形成的奈米纖維膜(比較例心J= 1===：= 彻祕她~ 本試驗結果顯示’如圖9a所示’未添加多西環素的三酷酸纖維 :、不米纖雜在培養基上沒有抑菌圈形成，亦即不具有抑菌效果. 對照下’添加有_%多西環素的三醋酸纖維素奈米纖維膜由於能 有效地釋放出多西環素，在樣品周圍會形成抑菌圈’如圖％所示， 因而評定為具有抑菌能力。 20 Β)定量抗菌性測試 • 知^‘展上述疋里抗菌试驗方法’取樣含有0%(比較例D)、〇.〇2%(實 施例9)、〇.〇4°/。(實施例1〇)及〇.〇8%(實施例⑴之多西環素的三醋酸 纖維素溶液靜電紡絲形成的奈米纖維膜進行檢測殺菌值與抑菌值 以評估奈米纖維的抗菌能力，如表3所示。 25Antibacterial test of HI. nanofiber membrane A) Qualitative bacteriostatic test According to the above qualitative bacteriostatic test method, the nanofiber membrane formed by electrospinning of _ liquid was taken (Comparative Example J=1===:= Secretly her ~ The results of this test show that 'as shown in Figure 9a' is not added doxycycline three cool acid fiber: no rice fiber on the medium without the inhibition zone formation, that is, no bacteriostatic effect. The cellulose triacetate nanofiber membrane with _% doxycycline added can form an inhibitory zone around the sample due to the effective release of doxycycline, as shown in Fig.能力 能力 20 定量 定量 定量 定量 定量 定量 定量. (Example 1〇) and 〇.〇8% (the nanofiber film formed by electrospinning of the doxycycline cellulose triacetate solution of Example (1) was used to detect the bactericidal value and the bacteriostatic value to evaluate the nanofibers. Antibacterial ability, as shown in Table 3. 25
丄J 1----- 表3 ----~— 比較例D 實施例9 實施例10 實施例11 ^mmmr, 〇/〇 8 8 8 8 多西環素，％ -------- 0 0.02 0.04 0.08 殺菌值(>0) 1.42 2.02 2.02 抑菌值(>2) 4.19 4.79 4.79 沾夕由表上所矛:殺菌值(>。)與抑菌值(>2)顯示，含有。.㈣至_% 、夕西¥素的三__維素奈米纖雜顯示良好的抗菌作用。 由上述本發明之具體實施例得知，添力口 人 這類的導電度會有提高_向，而由 纺絲組成物所形成的奈米纖維的細度亦產生 分佈更均勻。再者，由於加人的四環素化合物或 /、何生物本身亦具有抗菌功能，上述實補結果亦證丄J 1----- Table 3 ----~- Comparative Example D Example 9 Example 10 Example 11 ^mmmr, 〇/〇8 8 8 8 Doxycycline, % ------ -- 0 0.02 0.04 0.08 Sterilization value (>0) 1.42 2.02 2.02 Antibacterial value (>2) 4.19 4.79 4.79 Spear on the table: Sterilization value (>.) and bacteriostatic value (>2 ) shows that contains. (4) to _%, Xixibusu's three __vitamin nanofibers show good antibacterial effect. From the above-described specific embodiments of the present invention, it is known that the conductivity of such a person is increased, and the fineness of the nanofiber formed by the spinning composition is more uniform. Furthermore, since the added tetracycline compound or /, the organism itself has an antibacterial function, the above-mentioned results are also proved.
明形成的奈雜細材啊可具錢異的抗驗果。χ X 1 上具體實施繼肋制本發批撕时及触，使 此項H賴之通常域者能瞭解本案之目的容以實 的改良或修倚的發明，仍應涵蓋在本發明範轉内/及精神所凡成 【圖式簡單說明】 圖la為含有0%多西環素之單醋酸纖維素(CA)奈米纖維離較 26 15 1376440 例C)之粒徑分佈。 圖lb為含有〇%乡西環素之單酷酸纖維素奈米織維較例 C)之SEM圖像。 圖2a為含有0.02%多西環素之單醋酸纖維素奈米纖維 5 例7)之粒徑分佈。 、 圖2b為含有〇·〇2%多西環素之單醋酸纖維素奈米纖維膜(實施 例C)之SEM圖像。 、 Φ 圖如為含有0.04%多西環素之單醋酸纖維素奈米纖維膜(實施 例8)之粒徑分佈。 ί〇 圖％為含有0.04%多西環素之單醋酸纖維素奈米纖維膜(實施 例8)之SEM圖像。 、 圖4a為含有〇%多西環素之三醋酸纖維素(TAC)奈米纖維膜(比 較例D)之粒徑分佈。 圖4b為含有〇%多西環素之三醋酸纖維素奈米纖維膜(比較例 15 D)之SEM圖像。 _ 圖5a為含有0.02%多西環素之三醋酸纖維素奈米纖維膜(實施 例9)之粒徑分佈。 圖5b為含有〇.〇2〇/。多西環素之三醋酸纖維素奈米纖維臈(實施 例9)之SEM圖像。 、、 20 圖知為含有0.04%多西環素之二醋酸纖維素奈米纖維膜(實施 . 例10)之粒徑分佈。 、、 圖6b為含有0.04%多西環素之二醋酸纖維素奈米纖維膜(實施 例10)之SEM圖像。 、 圖7為含有0.08%多西環素之三醋酸纖維素奈米纖維膜(實施例 27 1376440 11) 之粒徑分佈。 圖8為含有0.10%多西環素之三醋酸纖維素奈米纖維膜(實施例 12) 之粒徑分佈。 圖9a為含有0%多西環素之三醋酸纖維素奈米纖維膜(比較例 D)之定性抑菌測試結果。 圖9b為含有0.02%多西環素之三醋酸纖維素奈米纖維膜(實施 例9)之定性抑菌測試結果。 【主要元件符號說明】 益 <»*、The naphtha formed by the Ming Dynasty can have different anti-test results. χ X 1 is specific to the implementation of the ribs and tears, so that the general domain of this H can understand the purpose of the case to improve or repair the invention, should still cover the scope of the invention Internal/and Spirituality [Simplified Schematic] Figure la is the particle size distribution of cellulose monoacetate (CA) nanofibers containing 0% doxycycline compared to 26 15 1376440 C). Figure lb is an SEM image of a sample of a single acid cellulose nanoweb containing C. sinensis. Figure 2a shows the particle size distribution of 5 (7) of the cellulose acetate monocellulose containing 0.02% doxycycline. Figure 2b is an SEM image of a monocellulose cellulose nanofiber membrane containing 〇·〇 2% doxycycline (Example C). The Φ diagram is a particle size distribution of a monocellulose cellulose nanofiber membrane (Example 8) containing 0.04% of doxycycline. % Figure % is an SEM image of a monocellulose cellulose nanofiber membrane (Example 8) containing 0.04% doxycycline. Fig. 4a is a particle size distribution of a cellulose triacetate (TAC) nanofiber membrane containing 〇% doxycycline (Comparative Example D). Figure 4b is an SEM image of a cellulose triacetate nanofiber membrane containing 〇% doxycycline (Comparative Example 15 D). Fig. 5a is a particle size distribution of a cellulose triacetate nanofiber membrane containing 0.02% doxycycline (Example 9). Figure 5b contains 〇.〇2〇/. SEM image of doxycycline cellulose triacetate nanofiber raft (Example 9). 20, the figure shows the particle size distribution of cellulose diacetate nanofiber membrane (Example 10) containing 0.04% doxycycline. Figure 6b is an SEM image of a cellulose diacetate nanofiber membrane containing 0.04% doxycycline (Example 10). Figure 7 is a particle size distribution of a cellulose triacetate nanofiber membrane containing 0.08% doxycycline (Example 27 1376440 11). Figure 8 is a particle size distribution of a cellulose triacetate nanofiber membrane (Example 12) containing 0.10% of doxycycline. Figure 9a is a qualitative bacteriostatic test result of a cellulose triacetate nanofiber membrane containing 0% doxycycline (Comparative Example D). Fig. 9b is a qualitative bacteriostatic test result of a cellulose triacetate nanofiber membrane containing 0.02% doxycycline (Example 9). [Main component symbol description] Benefit <»*,
2828
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW97141495A TWI376440B (en) | 2008-10-29 | 2008-10-29 | Electrospinning compositions for the preparation of nanofibers and the applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW97141495A TWI376440B (en) | 2008-10-29 | 2008-10-29 | Electrospinning compositions for the preparation of nanofibers and the applications thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201016921A TW201016921A (en) | 2010-05-01 |
| TWI376440B true TWI376440B (en) | 2012-11-11 |
Family
ID=44830578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW97141495A TWI376440B (en) | 2008-10-29 | 2008-10-29 | Electrospinning compositions for the preparation of nanofibers and the applications thereof |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI376440B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI473646B (en) * | 2013-01-15 | 2015-02-21 | Univ Nat Yunlin Sci & Tech | Fibrous membrane and a method for using the fibrous membrane for wastewater treatment |
| US9761354B2 (en) | 2013-04-18 | 2017-09-12 | Industrial Technology Research Institute | Method of manufacturing a nano metal wire |
| WO2018132244A1 (en) * | 2017-01-13 | 2018-07-19 | Luna Innovations Incorporated | Dissolvable nanofiber materials and specimen recovery kits including the same for high efficiency specimen recovery |
| TWI738192B (en) * | 2020-01-22 | 2021-09-01 | 國立宜蘭大學 | Nanofiber and its preparation method and use |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI453312B (en) * | 2011-02-18 | 2014-09-21 | Univ Kun Shan | Preparation the polymer fiber for solar cells and light emitting device by directly electrospinning technique |
| US9259455B2 (en) * | 2011-04-11 | 2016-02-16 | University Of Massachusetts | Chemically modified cellulose fibrous meshes for use as tissue engineering scaffolds |
| GB201400990D0 (en) | 2014-01-21 | 2014-03-05 | British American Tobacco Co | Filter materials and filters made therefrom |
| CN113703086B (en) * | 2021-09-09 | 2022-07-26 | 武汉华星光电半导体显示技术有限公司 | Polarizer, manufacturing method thereof and display device |
-
2008
- 2008-10-29 TW TW97141495A patent/TWI376440B/en active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI473646B (en) * | 2013-01-15 | 2015-02-21 | Univ Nat Yunlin Sci & Tech | Fibrous membrane and a method for using the fibrous membrane for wastewater treatment |
| US9761354B2 (en) | 2013-04-18 | 2017-09-12 | Industrial Technology Research Institute | Method of manufacturing a nano metal wire |
| WO2018132244A1 (en) * | 2017-01-13 | 2018-07-19 | Luna Innovations Incorporated | Dissolvable nanofiber materials and specimen recovery kits including the same for high efficiency specimen recovery |
| TWI738192B (en) * | 2020-01-22 | 2021-09-01 | 國立宜蘭大學 | Nanofiber and its preparation method and use |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201016921A (en) | 2010-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI376440B (en) | Electrospinning compositions for the preparation of nanofibers and the applications thereof | |
| Alharbi et al. | Fabrication of core-shell structured nanofibers of poly (lactic acid) and poly (vinyl alcohol) by coaxial electrospinning for tissue engineering | |
| Tiwari et al. | Intelligent nanomaterials | |
| Aghamohamadi et al. | Preparation and characterization of Aloe vera acetate and electrospinning fibers as promising antibacterial properties materials | |
| Hang et al. | Preparation of regenerated silk fibroin/silk sericin fibers by coaxial electrospinning | |
| McKeon et al. | Electrospun poly (D, L‐lactide) and polyaniline scaffold characterization | |
| El-Newehy et al. | Nanospider technology for the production of nylon-6 nanofibers for biomedical applications | |
| Monticelli et al. | New stereocomplex PLA-based fibers: effect of POSS on polymer functionalization and properties | |
| Liu et al. | Regenerated cellulose micro-nano fiber matrices for transdermal drug release | |
| EP2133451B1 (en) | Antibacterial nanofiber | |
| Zhou et al. | Electrospinning of chitosan/poly (vinyl alcohol)/acrylic acid aqueous solutions | |
| CN106149203B (en) | A kind of medicament-carrying nano-fiber membrane and its application | |
| Zhou et al. | Photocrosslinked maleilated chitosan/methacrylated poly (vinyl alcohol) bicomponent nanofibrous scaffolds for use as potential wound dressings | |
| Ridolfi et al. | Electrospun poly (ethylene oxide)/chitosan nanofibers with cellulose nanocrystals as support for cell culture of 3T3 fibroblasts | |
| Sivan et al. | AC electrospinning: Impact of high voltage and solvent on the electrospinnability and productivity of polycaprolactone electrospun nanofibrous scaffolds | |
| Lian et al. | Fabrication and characterization of curcumin-loaded silk fibroin/P (LLA-CL) nanofibrous scaffold | |
| Yao et al. | Biodegradable nanofibrous membrane of zein/silk fibroin by electrospinning | |
| Eren Boncu et al. | Electrospinning of linezolid loaded PLGA nanofibers: effect of solvents on its spinnability, drug delivery, mechanical properties, and antibacterial activities | |
| Fan et al. | Preparation and characterization of electrospun polylactic acid (PLA) fiber loaded with birch bark triterpene extract for wound dressing | |
| Shokraei et al. | Fabrication and characterization of chitosan/kefiran electrospun nanofibers for tissue engineering applications | |
| Shan et al. | Electrospinning of chitosan/poly (lactic acid) nanofibers: the favorable effect of nonionic surfactant | |
| Xiaoqiang et al. | Fabrication and properties of core‐shell structure P (LLA‐CL) nanofibers by coaxial electrospinning | |
| Yang et al. | Thermal and mechanical performance of electrospun chitosan/poly (vinyl alcohol) nanofibers with graphene oxide | |
| Sazegar et al. | Preparation and characterization of water-absorbing gas-assisted electrospun nanofibers based on poly (vinyl alcohol)/chitosan | |
| Duygulu et al. | Electrospun drug blended poly (lactic acid)(PLA) nanofibers and their antimicrobial activities |