王葉香,閆星儒,王 璐,關(guān)國(guó)平

(東華大學(xué) a. 紡織學(xué)院;b. 紡織面料技術(shù)教育部重點(diǎn)實(shí)驗(yàn)室,上海 201620)

人工血管用海藻酸鈉-聚丙烯酰胺水凝膠的制備及性能

王葉香a,b,閆星儒a,王 璐a,b,關(guān)國(guó)平a,b

(東華大學(xué) a. 紡織學(xué)院;b. 紡織面料技術(shù)教育部重點(diǎn)實(shí)驗(yàn)室,上海 201620)

水凝膠應(yīng)用于生物材料領(lǐng)域已有多年,但是作為人工血管材料的研究較少. 一方面,水凝膠的力學(xué)性能有待提高,以符合人工血管性能要求； 另一方面,水凝膠在濕態(tài)環(huán)境下會(huì)發(fā)生體積溶脹而導(dǎo)致管腔減小,容易誘發(fā)血栓.以海藻酸鈉和丙烯酰胺為原材料,制備了力學(xué)性能滿足要求且低溶脹率的水凝膠. 結(jié)果表明: 該水凝膠的拉伸斷裂強(qiáng)度可達(dá)到306.87 kPa,拉伸斷裂伸長(zhǎng)率達(dá)到306.23%,壓縮正切模量為122.07 kPa. 當(dāng)海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%,丙烯酰胺質(zhì)量分?jǐn)?shù)為16.8%,CaCl2質(zhì)量分?jǐn)?shù)為0.42%時(shí),水凝膠溶脹率可低至128.16%,在12 h可達(dá)到溶脹平衡.

水凝膠;溶脹;海藻酸鈉;丙烯酰胺;生物材料;人工血管

隨著生物醫(yī)用材料研究的深入,水凝膠由于其結(jié)構(gòu)與細(xì)胞外基質(zhì)(ECM)類似,含水量高,能很好地分散氧氣和營(yíng)養(yǎng)物質(zhì)而備受關(guān)注[1-2]. 然而,力學(xué)性能不足限制了其在生物醫(yī)用材料領(lǐng)域的進(jìn)一步應(yīng)用[3-5]. 通過(guò)多種交聯(lián)方式結(jié)合及提高交聯(lián)密度可以提高水凝膠的韌性[6-11],且能夠在一定程度上降低溶脹率[12].

海藻酸是由β-D-古羅糖醛酸(G)和α-L-甘露糖醛酸(M) 依靠1,4-糖苷鍵連接的嵌段共聚物,包括G和M各自形成的均聚物和GM形成的交替聚合物. 由于其具有良好的生物相容性,在生物醫(yī)用材料領(lǐng)域的應(yīng)用潛力日益引起研究者的興趣[13-14]. 這種嵌段共聚物能通過(guò)離子相互作用在G和螯合離子(比如 Ca2+)間形成交聯(lián)[15-17]. 文獻(xiàn)[18]的研究表明,相對(duì)于純海藻酸鈉水凝膠,海藻酸鈉與聚丙烯酰胺互穿網(wǎng)絡(luò)水凝膠的韌性得到了顯著提高,且體內(nèi)外細(xì)胞相容性良好. 文獻(xiàn)[19]研究制備的殼聚糖與聚丙烯酰胺水凝膠細(xì)胞毒性小、血液相容性好,有望成為未來(lái)醫(yī)用生物材料. 由此可見(jiàn),海藻酸鈉-聚丙烯酰胺水凝膠具有與細(xì)胞外基質(zhì)類似的結(jié)構(gòu),柔韌性好,且生物相容性良好,故其可以作為人工血管材料研究.

提高水凝膠力學(xué)性能的研究已有較多的報(bào)道,但是控制水凝膠溶脹率的研究較少. 傳統(tǒng)水凝膠應(yīng)用目的是希望其能夠吸水溶脹,持水性好[20-22]. 但是,如果將水凝膠作為體內(nèi)管道器官的原材料,比如人工血管,在溶脹很大的情況下,就會(huì)導(dǎo)致管徑減小,造成凝血或血栓,影響血管遠(yuǎn)期通暢率. 而且溶脹會(huì)嚴(yán)重降低彈性模量和應(yīng)力松弛[23],從而降低整體力學(xué)性能,影響使用效果. 但是目前并無(wú)專門(mén)針對(duì)小口徑人造血管性能評(píng)價(jià)的標(biāo)準(zhǔn). ISO 7198—1998只是人造血管測(cè)試標(biāo)準(zhǔn),評(píng)價(jià)時(shí)需要在借鑒標(biāo)準(zhǔn)中提供的測(cè)試方法的基礎(chǔ)上,結(jié)合實(shí)際情況進(jìn)行綜合評(píng)價(jià). 因此,本文研究了海藻酸-聚丙烯酰胺水凝膠,期望獲得力學(xué)性能較好、溶脹率低且可控的水凝膠制備方法,為人工管道器官材料的應(yīng)用奠定基礎(chǔ).

1 材料與方法

1.1 試驗(yàn)材料

氯化鈣(CaCl2,分析純),購(gòu)自上海凌峰化學(xué)試劑有限公司;海藻酸鈉(化學(xué)純),丙烯酰胺(化學(xué)純),N,N,-亞甲基雙(丙烯酰胺)(MBAA,(化學(xué)純)),四甲基乙二胺(TEMED,生化試劑),過(guò)硫酸銨(APS,(分析純)),均購(gòu)自國(guó)藥集團(tuán)化學(xué)試劑有限公司.

1.2 水凝膠制備方法

稱取丙烯酰胺,溶解在水中,丙烯酰胺的質(zhì)量分?jǐn)?shù)為16.8%. 再稱取海藻酸鈉,緩慢加入丙烯酰胺溶液中,在室溫下攪拌,直至形成均一溶液. 隨后,往100 g均一溶液中加入0.01 g交聯(lián)劑MBAA、0.09 g催化劑TEMED和0.1 g熱引發(fā)劑APS,混合均勻[24]. 將100 g混合溶液倒入培養(yǎng)皿,再加氯化鈣粉末,靜置直至反應(yīng)完全,通過(guò)加入不同質(zhì)量分?jǐn)?shù)的海藻酸鈉和CaCl2制備不同的樣品. 具體試驗(yàn)方案如表1所示.

表1 水凝膠制備方案
Table 1 Experimental design of hydrogel

樣本編號(hào)海藻酸鈉質(zhì)量分?jǐn)?shù)/%CaCl2質(zhì)量分?jǐn)?shù)/%1#2.10.382#2.10.423#2.10.464#2.30.385#2.30.426#2.30.467#2.50.388#2.50.429#2.50.46

1.3 掃描電子顯微鏡(SEM)測(cè)試方法

取制備好的水凝膠,其大小為3 cm×2 cm×0.3 cm,經(jīng)冷凍24 h和干燥24 h后,用液氮進(jìn)行脆斷,將截面朝上貼在金屬臺(tái)上,對(duì)其噴金,采用TM 3000型掃描電子顯微鏡(日本日立公司)觀察截面結(jié)構(gòu),加速電壓為15 kV.

1.4 水凝膠溶脹率測(cè)試方法

將水凝膠用手術(shù)刀切成規(guī)則的長(zhǎng)方體,測(cè)量其長(zhǎng)(a)、寬(b)和厚度(h),計(jì)算初始體積V0=a×b×h. 然后,將樣品浸沒(méi)在室溫的蒸餾水中,分別在3,6,9,12,24,48和72 h時(shí)刻從水中取出,用濾紙吸干表面水分后再測(cè)量長(zhǎng)、寬和厚度,計(jì)算體積為V. 樣本重復(fù)數(shù)n=3,最后取平均值. 溶脹率Q=V/V0×100%.

1.5 力學(xué)性能測(cè)試方法

1.5.1 拉伸性能

根據(jù)GB/T 528—1998,采用大榮026G-500型織物強(qiáng)力機(jī)進(jìn)行拉伸性能測(cè)試. 試樣裁剪成50 mm×20 mm的長(zhǎng)條狀,隔距為25 mm,試樣拉伸速度由試樣厚度決定,本文采用的拉伸速度為(500±50)mm/min,每個(gè)試樣測(cè)試3次,取平均值. 預(yù)加張力為0.2 N,傳感器量程為500 N.

1.5.2 壓縮性能

采用LLY-06D 型人體內(nèi)生物管道壓縮彈性測(cè)試儀,進(jìn)行水凝膠的壓縮性能測(cè)試. 試樣裁剪成10 mm×10 mm的正方形,壓腳直徑為5 mm,每個(gè)試樣測(cè)試3次. 具體測(cè)試步驟: 將試樣放在試樣臺(tái)上,以10 mm/min 的速度將試樣壓縮至厚度的90%,停頓10 s,記錄最大壓縮強(qiáng)力； 以10 mm/min 的速度移除壓力,記錄外力完全移除后試樣的厚度. 壓縮正切模量選取應(yīng)變?yōu)?0%～30%處的模量值.

2 結(jié)果與討論

2.1 外觀與結(jié)構(gòu)

按照表1中水凝膠制備方案得到的水凝膠如圖1所示. 海藻酸鈉-聚丙烯酰胺水凝膠呈淡黃色透明膠體狀,手感柔軟,彈性較好,有韌性.

取5#水凝膠試樣進(jìn)行SEM測(cè)試觀察其截面結(jié)構(gòu),如圖2(a)和2(b)所示.孔徑分布如圖2(c)所示.由圖2(a)和2(b)可知,水凝膠為多孔結(jié)構(gòu),孔徑較均勻. 從圖2(c)可見(jiàn),孔徑主要分布在40～60 μm,孔徑最小為24.67 μm,最大為101.05 μm.

圖1 海藻酸鈉-聚丙烯酰胺水凝膠Fig.1 Alginate-polyacrylamide hydrogel

圖2 海藻酸鈉-聚丙烯酰胺水凝膠SEM圖像及孔徑分布Fig.2 SEM images and pore size distribution of alginate-polyacrylamide hydrogels

2.2 溶脹率

水凝膠內(nèi)、外部溶液存在濃度差,當(dāng)外部溶液濃度低于內(nèi)部溶液時(shí),水分子會(huì)進(jìn)入水凝膠. 兩者之間的濃度差越大,產(chǎn)生的滲透壓會(huì)越大,溶脹性越大[25]. 影響水凝膠溶脹率的因素較多,核心因素是交聯(lián)密度. 文獻(xiàn)[26]研究表明,加入納米管可增加交聯(lián)密度,網(wǎng)絡(luò)結(jié)構(gòu)中的空隙減小了,使得溶脹率下降.

本文對(duì)所制得的9種水凝膠進(jìn)行了溶脹率測(cè)試.不同質(zhì)量分?jǐn)?shù)海藻酸鈉的水凝膠溶脹率隨時(shí)間變化如圖3所示.由圖3可知,水凝膠在12 h內(nèi)達(dá)到溶脹平衡狀態(tài);且溶脹平衡后，CaCl2質(zhì)量分?jǐn)?shù)為0.42%和0.46%的水凝膠的溶脹率較接近,且均低于CaCl2質(zhì)量分?jǐn)?shù)為0.38%的水凝膠的溶脹率.

(a) 2.1%

(b) 2.3%

(c) 2.5%

溶脹12 h后,不同質(zhì)量分?jǐn)?shù)的海藻酸鈉對(duì)水凝膠溶脹率的影響如圖4所示,本文中*表示兩者之間有顯著性差異,p<0.05. 由圖4可知,海藻酸鈉質(zhì)量分?jǐn)?shù)為2.1%的水凝膠溶脹率顯著高于海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和2.5%的水凝膠溶脹率. 當(dāng)CaCl2質(zhì)量分?jǐn)?shù)為0.42% 和0.46%時(shí),海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和2.5%的水凝膠溶脹率之間無(wú)顯著性差異. 這可能是由于成膠過(guò)程中離子交聯(lián)起主要作用而共價(jià)交聯(lián)起次要作用. 故后續(xù)研究中選擇海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%,CaCl2質(zhì)量分?jǐn)?shù)為0.42%.

圖4 溶脹12 h后不同質(zhì)量分?jǐn)?shù)的海藻酸鈉對(duì)水凝膠溶脹率的影響Fig.4 Effect of alginate with different mass fractions on the swelling ratio of hydrogel after swelling for 12 hours

本文通過(guò)改變海藻酸鈉和CaCl2的質(zhì)量分?jǐn)?shù)來(lái)降低水凝膠溶脹率,從而控制其宏觀溶脹行為. 當(dāng)海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和CaCl2質(zhì)量分?jǐn)?shù)為0.42%時(shí),溶脹率可低至(128.16±0.99)%. 而文獻(xiàn)[24]研究表明,海藻酸鈉和聚丙烯酰胺復(fù)合水凝膠的最小溶脹率約為600%;文獻(xiàn)[27]研究的京尼平交聯(lián)的絲素蛋白和明膠復(fù)合水凝膠,其最小溶脹率約為843%.

2.3 力學(xué)性能

2.3.1 拉伸性能

CaCl2質(zhì)量分?jǐn)?shù)分別為0.38%,0.42%和0.46%時(shí),海藻酸鈉-聚丙烯酰胺水凝膠的拉伸斷裂強(qiáng)度及斷裂伸長(zhǎng)率如圖5所示.

(a) 斷裂強(qiáng)度

(b) 斷裂伸長(zhǎng)率圖5 不同質(zhì)量分?jǐn)?shù)的CaCl2對(duì)水凝膠拉伸斷裂強(qiáng)度和斷裂伸長(zhǎng)率的影響Fig.5 Effect of CaCl2 with different mass fractions on the breaking strength and elongation of hydrogel

由圖5(a)可知,當(dāng)CaCl2質(zhì)量分?jǐn)?shù)分別為0.42%和0.46%時(shí),拉伸斷裂強(qiáng)度沒(méi)有顯著性差異,且均高于CaCl2質(zhì)量分?jǐn)?shù)為0.38%時(shí)的拉伸斷裂強(qiáng)度. 而不同CaCl2質(zhì)量分?jǐn)?shù)時(shí),樣品的拉伸斷裂伸長(zhǎng)率均沒(méi)有顯著性差異,這說(shuō)明CaCl2質(zhì)量分?jǐn)?shù)的變化對(duì)拉伸斷裂伸長(zhǎng)率影響不大(圖5(b)).

不同海藻酸鈉質(zhì)量分?jǐn)?shù)的海藻酸鈉-聚丙烯酰胺水凝膠的拉伸斷裂強(qiáng)度及斷裂伸長(zhǎng)率如圖6所示. 由圖6(a)可知,當(dāng)海藻酸鈉質(zhì)量分?jǐn)?shù)分別為2.3%和2.5%時(shí),拉伸斷裂強(qiáng)度之間無(wú)顯著性差異,且高于海藻酸鈉質(zhì)量分?jǐn)?shù)為2.1%的結(jié)果,而本文所得海藻酸鈉-聚丙烯酰胺水凝膠的拉伸斷裂強(qiáng)度均值為307 kPa,高于文獻(xiàn)[24]的研究結(jié)果(250 kPa).由圖6(b)可知,海藻酸鈉質(zhì)量分?jǐn)?shù)分別為2.3%和2.5%的水凝膠,拉伸斷裂伸長(zhǎng)率之間也無(wú)顯著性差異,但均低于海藻酸鈉質(zhì)量分?jǐn)?shù)為2.1%時(shí)的斷裂伸長(zhǎng)率.

(a) 斷裂強(qiáng)度

(b) 斷裂伸長(zhǎng)率圖6 不同質(zhì)量分?jǐn)?shù)的海藻酸鈉對(duì)水凝膠拉伸斷裂強(qiáng)度和斷裂伸長(zhǎng)率的影響Fig.6 Effect of alginate with different mass fractions on the breaking strength and elongation of hydrogel

CaCl2質(zhì)量分?jǐn)?shù)為0.42%時(shí),不同海藻酸鈉質(zhì)量分?jǐn)?shù)的水凝膠拉伸應(yīng)力-應(yīng)變曲線如圖7所示. 由圖7可知,海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和2.5%的水凝膠拉伸至斷裂,其應(yīng)力大于海藻酸鈉質(zhì)量分?jǐn)?shù)為2.1%的水凝膠的應(yīng)力,但應(yīng)變較小,且海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和2.5%的水凝膠拉伸應(yīng)力和應(yīng)變無(wú)明顯差異.

圖7 水凝膠拉伸應(yīng)力-應(yīng)變曲線(CaCl2質(zhì)量分?jǐn)?shù)為0.42%)Fig.7 Tensile stress-strain curves of the hydrogel (CaCl2 mass fraction is 0.42%)

2.3.2 壓縮性能

CaCl2質(zhì)量分?jǐn)?shù)分別為0.38%,0.42%和0.46%時(shí),海藻酸鈉-聚丙烯酰胺水凝膠壓縮正切模量的測(cè)量結(jié)果如圖8所示. 由圖8可知,當(dāng)海藻酸鈉質(zhì)量分?jǐn)?shù)一定時(shí),CaCl2質(zhì)量分?jǐn)?shù)分別為0.38%,0.42%和0.46%時(shí),水凝膠壓縮正切模量依次減小,且兩兩均有顯著性差異.

圖8 不同質(zhì)量分?jǐn)?shù)的CaCl2對(duì)壓縮正切模量的影響Fig.8 Effect of CaCl2 with different mass fractions on compression modulus of hydrogel

海藻酸鈉質(zhì)量分?jǐn)?shù)分別為2.1%,2.3%和2.5%時(shí),海藻酸鈉-聚丙烯酰胺水凝膠的壓縮正切模量的測(cè)量結(jié)果如圖9所示. 由圖9可知,當(dāng)CaCl2質(zhì)量分?jǐn)?shù)一定時(shí),海藻酸鈉質(zhì)量分?jǐn)?shù)為2.1%時(shí),水凝膠壓縮正切模量顯著高于海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和2.5%的水凝膠. 海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和2.5%時(shí)的水凝膠壓縮正切模量沒(méi)有顯著性差異. 作為人工血管材料,控制溶脹率更為重要. 故當(dāng)海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%,CaCl2質(zhì)量分?jǐn)?shù)為0.42%時(shí),溶脹率得到了較好的控制. 壓縮正切模量為(122.07±3.77)kPa,能夠滿足人工血管的要求. 文獻(xiàn)[27]制備的京尼平交聯(lián)的絲素蛋白和明膠復(fù)合水凝膠壓縮正切模量約為475 kPa,然而溶脹率偏高.

圖9 不同質(zhì)量分?jǐn)?shù)的海藻酸鈉對(duì)水凝膠壓縮正切模量的影響Fig.9 Effect of alginate with different mass fractions on compression modulus of hydrogel

CaCl2質(zhì)量分?jǐn)?shù)為0.42%時(shí),海藻酸鈉質(zhì)量分?jǐn)?shù)為2.1%,2.3%和2.5%的水凝膠壓縮應(yīng)力-應(yīng)變曲線如圖10所示. 由圖10可知,海藻酸鈉質(zhì)量分?jǐn)?shù)為2.1%的水凝膠壓縮應(yīng)力接近600 kPa,大于海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和2.5%的水凝膠,且海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%和2.5%的水凝膠壓縮應(yīng)力無(wú)明顯差異.

圖10 水凝膠壓縮應(yīng)力-應(yīng)變曲線(CaCl2質(zhì)量分?jǐn)?shù)為0.42%)Fig.10 Compressive stress-strain curves of the hydrogel (CaCl2 mass fraction is 0.42%)

3 結(jié) 語(yǔ)

本文制備了低溶脹高彈性的海藻酸鈉-聚丙烯酰胺水凝膠,并分析了海藻酸鈉質(zhì)量分?jǐn)?shù)及CaCl2質(zhì)量分?jǐn)?shù)對(duì)水凝膠溶脹率及力學(xué)性能的影響. 當(dāng)海藻酸鈉質(zhì)量分?jǐn)?shù)為2.3%,丙烯酰胺質(zhì)量分?jǐn)?shù)為16.8%,CaCl2質(zhì)量分?jǐn)?shù)為0.42%時(shí),溶脹率可低至128.16%. 而拉伸斷裂強(qiáng)度仍可達(dá)到306.87 kPa,斷裂伸長(zhǎng)率達(dá)到306.23%,壓縮正切模量達(dá)到122.07 kPa. 隨著海藻酸鈉質(zhì)量分?jǐn)?shù)的增加,水凝膠斷裂強(qiáng)度增加,溶脹率、斷裂伸長(zhǎng)率和壓縮正切模量減小. 隨著CaCl2質(zhì)量分?jǐn)?shù)的增加,水凝膠拉伸斷裂強(qiáng)度增加,溶脹率和壓縮正切模量減小,但對(duì)斷裂伸長(zhǎng)率影響不大. 本文所得水凝膠力學(xué)性能良好,約在12 h達(dá)到溶脹平衡,可為開(kāi)發(fā)人工血管材料提供參考.

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Preparation of Alginate-Polyacrylamide Hydrogel for Vascular Prototype and Its Properties

WANGYe-xianga,b,YANXing-rua,WANGLua,b,GUANGuo-pinga,b

(a. College of Textiles;b. Key Laboratory of Textile Science &Technology,Ministry of Education,Donghua University,Shanghai 201620,China)

Hydrogels have been used in bio-materials field for many years,but few researches have been reported concerning being used as artificial blood vessels. On one hand,the mechanical properties of hydrogels need to be improved to meet the requirements of artificial blood vessels. On the other hand,the hydrogel swells in volume under wet environment and the swollen hydrogel will lead to reduced diameter and then cause thrombosis. Sodium alginate and acrylamide are selected to prepare hydrogels,which have satisfactory mechanical properties and low swelling ratio. The results show that tensile breaking strength of the hydrogel can reach 306.87 kPa,elongation at break is 306.23% and compressive tangent modulus is 122.07 kPa. When the mass fractions of sodium alginate,acrylamide and crosslinking agent are 2.3%,16.8% and 20%,the swelling ratio can fall down as low as 128.16%. The hydrogel reaches swelling equilibrium within 12 h.

hydrogel;swelling;alginate;acrylamide;biomaterial;vascular prototype

1671-0444 (2016)05-0647-07

2015-09-07

國(guó)家自然科學(xué)基金資助項(xiàng)目(11302154)；中央高?；究蒲袠I(yè)務(wù)費(fèi)專項(xiàng)資金資助項(xiàng)目(2232015A3-02)；上海市教育委員會(huì)科研創(chuàng)新資助項(xiàng)目(ZX201503000017)；紡織生物材料與技術(shù)創(chuàng)新引智基地資助項(xiàng)目(B07024)；2015研究生創(chuàng)新基金資助項(xiàng)目(EG2015045)

王葉香(1990—)，女，江蘇南通人，碩士研究生，研究方向?yàn)樯镝t(yī)用水凝膠. E-mail :wangyx624@163.com 關(guān)國(guó)平(聯(lián)系人)，男，副教授，E-mail :ggp@dhu.edu.cn

TS 101.3

A