CN117050336B - 聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶及其制备方法和应用 - Google Patents
聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶及其制备方法和应用，首先合成EGCG修饰的聚多巴胺纳米颗粒PDA@EGCGNPs，再将PDA@EGCGNPs分散到聚乙烯醇/羧甲基壳聚糖共混溶液中，进行交联，得到聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶。其中，聚乙烯醇与羧甲基壳聚糖由于分子间氢键相互作用，在水凝胶形成过程中形成双网络。EGCG@NPs纳米颗粒的加入增强了复合水凝胶的力学性能和抗氧化性能，并且赋予水凝胶优异的光热性能，且本发明制备的水凝胶生物相容性良好，可广泛应用于生物医用材料领域中。
Description
技术领域
本发明属于生物高分子材料技术领域，特别涉及聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶及其制备方法和应用。
背景技术
皮肤作为人体最大、暴露在最外面的器官，在维持体内平衡和保护内部器官免受外界环境的影响方面起着至关重要的作用。且皮肤极易遭受各种创伤，各种急、慢性创伤千百年来一直困扰着人们。受损皮肤失去屏障保护作用。患者处理不当会导致皮肤感染，加重皮肤损伤，甚至导致死亡。
水凝胶作为一种软材料，是由亲水性高分子或聚合物借助氢键、共价键或范德华力等作用力物理、化学交联形成的三维网络材料，可以吸收大量溶液，并且能保持一定的力学强度。水凝胶具有与人体组织相似的结构和特性，能够保持伤口湿润的微环境，并且水凝胶还能吸收伤口组织的渗出液、透气、冷却伤口缓解疼痛等功能使伤口能够保持良好的愈合进程。
采用化学修饰和复合等技术可以设计与构建各种结构与功能的水凝胶。例如高强度水凝胶、抗菌水凝胶和可注射水凝胶等。聚乙烯醇是一种常见的合成高分子，可以很容易制成水凝胶，但是由于聚乙烯醇分子结构中不含功能性基团，导致水凝胶的抑菌、抗氧化、黏附等性能等明显不足，无法满足多功能材料的应用需求，因此必须对其进行化学修饰或复合，来赋予聚乙烯醇基水凝胶更广泛的生物医学用途。
发明内容
本发明的目的在于针对现有技术的不足，提供聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶及其制备方法和应用，该水凝胶具有优异的力学性能、抗氧化性能和光热性能，且生物相容性好，可广泛应用于生物医用材料领域中。
本发明的目的通过下述方案实现：
本发明提供了聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶的制备方法，包括：首先合成EGCG修饰的聚多巴胺纳米颗粒PDA@EGCGNPs，再将PDA@EGCGNPs分散到聚乙烯醇/羧甲基壳聚糖共混溶液中，进行交联，得到聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶。
进一步的，聚乙烯醇、羧甲基壳聚糖、PDA@EGCGNPs、硼砂的质量比为60：15：(0.5～2)：12。PDA@EGCGNPs在溶液中的质量百分浓度为0.05％～0.2％。
进一步的，PDA@EGCGNPs的合成方法具体如下：将EGCG溶解在水中，得到EGCG溶液；将多巴胺溶解在水中，调节溶液至碱性环境，得到聚多巴胺溶液；将EGCG溶液倒入到聚多巴胺溶液中，通氧搅拌24h后离心、真空冷冻干燥即可。
更进一步的，EGCG在水中的浓度为0.5mg/mL；多巴胺在水中的浓度为5mg/mL；和/或EGCG与多巴胺的质量比为1：10。
进一步的，聚乙烯醇/羧甲基壳聚糖共混溶液的配制方法如下：按比例将聚乙烯醇、羧甲基壳聚糖混合，再加入去离子水，所得混合物升温至90～95℃后充分搅拌均匀，使聚乙烯醇完全溶解。
更进一步的，聚乙烯醇/羧甲基壳聚糖共混溶液中聚乙烯醇的质量百分浓度(g/mL)为6％、羧甲基壳聚糖的质量百分浓度(g/mL)为1.5％。
进一步的，以硼砂水溶液作为交联剂。聚乙烯醇与硼砂之间以硼酸酯键作为物理交联点，组成水凝胶三维网状结构。
更进一步的，硼砂水溶液的质量百分浓度(g/mL)为6％。
进一步的，加入硼砂后在室温下迅速搅拌反应1～3分钟。
本发明制备方法先将EGCG对聚多巴胺进行修饰，PDA@EGCGNPs既保留了聚多巴胺纳米粒子的光热性能，又增强了聚多巴胺抗炎、抗氧化等生物活性。将合成的PDA@EGCG NPs加入到聚乙烯醇/羧甲基壳聚糖水凝胶中，加入交联剂硼砂，形成聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶。
本发明还提供上述方法制备得到的聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶。该水凝胶具有三维网络结构，同时具有良好的力学性能、抗氧化、自愈、光热和可塑性，且生物相容性好。
本发明又提供了上述聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶在生物医用材料领域中的应用。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明制备方法反应条件温和，制备所需时间短，操作简单且易于控制。
(2)本发明制备的PDA@EGCGNPs制备条件简单，合成的纳米粒子均匀，光热性能较好。
(3)本发明的制备方法为水凝胶体系提供高含量的PDA@EGCGNPs，聚多巴胺分子链上的酚羟基以及EGCG分子链上的酚羟基与水凝胶网络中的活性基团形成更多的动态非共价键，赋予水凝胶良好的自愈合性能。
本发明通过将合成的纳米粒子与凝胶体系共混的方式，构建集成多种功能组分的新型多功能抗氧化、光热、自愈合水凝胶。
本发明制备的聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶具有良好的生物相容性，具有广泛的生物医用材料应用前景。
附图说明
图1为实施例1聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶冷冻干燥后的断面微观扫描电镜图。
图2为测试例1中不同水凝胶的拉伸应力-应变图。
图3为测试例1中不同水凝胶的压缩应力-应变图。
图4为测试例2中不同水凝胶的DPPH清除率图。
图5为实施例3制得的聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶的流变测试图。
图6(a)、(b)为实施例3制得的聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶的光热性能图。
图7为测试例5中不同水凝胶的血液相容性图。
具体实施方式
下面结合实施例对本发明对本发明作进一步详细的描述，但本发明的实施例方式不限于此。下列实施例中涉及的物料均可从商业渠道获得。
本申请中，“w/v”的单位是“g/mL”，“室温”可以是20℃±5℃。
实施例1
(1)称取500mg盐酸多巴胺溶解在100mL去离子水中溶解，然后滴加1.5mL浓度为1mol/LNaOH溶液，调节溶液体系为碱性环境。再加入100mL浓度为0.05％(w/v)的EGCG溶液，混合物在室温下连续搅拌24小时。最后，离心、真空冷冻干燥48h得PDA@EGCG NPs。
(2)称取6g聚乙烯醇和1.5g羧甲基壳聚糖加入到100mL水中，95℃水浴搅拌4h直至完全溶解。将0.05g PDA@EGCGNPs加入到上述混合溶液中，超声分散20min，搅拌均匀。最后将20mL浓度为6％(w/v)硼砂溶液以加入到上述溶液中，搅拌1～3min，溶液发生交联反应生成聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶(PC-PDA@EGCG NPs-0.5)。
聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶冷冻干燥后进行断面扫描电镜观察，结果如图1所示。由图1可见，凝胶内部为规则多孔结构，该结构有利于为细胞的生长提供基质以及更好的透气性。
实施例2
(1)称取500mg盐酸多巴胺溶解在100mL去离子水中溶解，然后滴加1.5mL浓度为1mol/LNaOH溶液，调节溶液体系为碱性环境。再加入100mL浓度为0.05％(w/v)的EGCG溶液，混合在室温下连续搅拌24小时。最后，离心、真空冷冻干燥48h得PDA@EGCGNPs。
(2)称取6g聚乙烯醇和1.5g羧甲基壳聚糖加入到100mL水中，95℃水浴搅拌4h直至完全溶解。将0.1g PDA@EGCGNPs加入到上述混合溶液中，超声分散20min，搅拌均匀。最后将20mL浓度为6％(w/v)硼砂溶液以加入到上述溶液中，搅拌1～3min，溶液发生交联反应生成聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶(PC-PDA@EGCGNPs-1)。
实施例3
(1)称取500mg盐酸多巴胺溶解在100mL去离子水中溶解，然后滴加1.5mL浓度为1mol/LNaOH溶液，调节溶液体系为碱性环境。再加入100mL浓度为0.05％(w/v)的EGCG溶液，混合在室温下连续搅拌24小时。最后，离心、真空冷冻干燥48h得PDA@EGCGNPs。
(2)称取6g聚乙烯醇和1.5g羧甲基壳聚糖加入到100mL水中，95℃水浴搅拌4h直至完全溶解。将0.2g PDA@EGCGNPs加入到上述混合溶液中，超声分散20min，搅拌均匀。最后将20mL浓度为6％(w/v)硼砂溶液以加入到上述溶液中，搅拌1～3min，溶液发生交联反应生成聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶(PC-PDA@EGCGNPs-2)。对比例1聚乙烯醇/羧甲基壳聚糖水凝胶的制备
称取6g聚乙烯醇和1.5g羧甲基壳聚糖加入到100mL水中，95℃水浴搅拌4h直至完全溶解。再将20mL浓度为6％(w/v)硼砂溶液以加入到上述溶液中，搅拌1～3min，溶液发生交联反应生成聚乙烯醇/羧甲基壳聚糖水凝胶(PC)。
对比例2聚乙烯醇水凝胶的制备
称取6g聚乙烯醇加入到100mL水中，95℃水浴搅拌4h直至完全溶解。再将20mL浓度为6％(w/v)硼砂溶液以加入到上述溶液中，搅拌1～3min，溶液发生交联反应生成聚乙烯醇水凝胶(PB)。
对实施例1、实施例2、实施例3制备得到的水凝胶及对比例1、对比例2的水凝胶进行以下性能测试。
测试例1力学性能测试
将上述五种水凝胶各取三个相同大小的样品，用质构仪对五种水凝胶样品进行拉伸性能的测试，拉伸速率为2mm/s。取数据做应力-应变图，结果如图2所示。从图2可看出，本发明制备的聚乙烯醇/羧甲基壳聚糖/PDA@EGCGNPs水凝胶具有较好的拉伸性能，最大拉伸应变为550％，最大拉伸应力为035mP，能满足机械运动对水凝胶拉伸性能的要求。另外用质构仪对五种水凝胶样品进行压缩性能测试，压缩速率为0.5mm/s。取数据做应力-应变图，结果如图3所示。从图3可看出，本发明制备的聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶具有较好的抗压性能，在85％压缩应变下最大压缩应力为0.24mPa，符合生物医用材料对力学性能的要求。
测试例2抗氧化性能测试
DPPH清除能力测试：将15mg制备的水凝胶样品加入2mL新鲜备的DPPH/乙醇溶液(0.1mM)中，并将混合物在黑暗中保持1小时。通过在490nm处的吸光度来计算水凝胶的DPPH自由基清除能力，具体结果见图4。
图为抗氧化效果对比图，通过图可知，PC-PDA@EGCGNPs-2水凝胶具有良好的抗氧化性能，DPPH清除率为59.78％。
测试例3粘弹性和自愈合性能测试
粘弹性测试：将实施例3中制备的水凝胶圆片放到流变仪样品台上，设置温度为37℃，应变为0.1-1000％，角频率为6.28rad/s。如图5所示，在应变0.1-5％范围内该水凝胶处于线性粘弹区，
自愈合性能测试：将实施例3中制备的水凝胶圆片放到流变仪样品台上，设置温度为37℃，角频率为6.28rad/s，低应变为1％，时间200s，高应变为30％，时间200s。如图5所示，1％低应变时，样品处于凝胶状；当应变增到30％高应变时，样品处于溶液状态；回到1％低应变时，储能模量大于损耗模量，样品恢复凝胶状。此过程可重复多次，说明该水凝胶具有剪切变稀和自修复性能。
测试例4光热性能测试
将装有1mLPC-PDA@EGCGNPs-2水凝胶的2mL离心管在25℃室温下固定，用808NIR激光以1W/cm2的密度照射被测材料，每隔2min使用E6红外热像仪(美国FLIR)记录样品温度，结果如图6(a)。
图6(b)为水凝胶升温图，通过图可知，PC-PDA@EGCGNPs-2水凝胶具有优异的近红外光热性能，在低功率密度为1W/cm2时，10min最高能升温至57.1℃。满足近红外光热材料对温度的要求。
测试例5溶血率测试
将10mg水水凝胶浸没到500μL含有抗凝剂的大鼠血液中，37℃摇床中振荡1h，PBS和1％Triton X–100分别作为阴性和阳性对照组。将血液离心10min(1500rpm)，然后吸取200μL上清液加入到96孔酶标板中，使用UV–Vis光谱仪测试540nm处的吸光值。根据公式计算得到溶血率：溶血率(％)＝(A样品–A阴性)/(A阳性–A阴性)×100％，A表示540nm处的吸光值。每组实验重复5次。
测试结果如图7所示，与阳性对照组Triton X-100相比，PB、PC、PC-PDA@EGCG NPs-0.5、PC-PDA@EGCG NPs-1、PC-PDA@EGCG NPs-2组的大鼠溶血率均低于5％，符合生物医用材料对溶血率的要求。
显然，本发明的上述实施例仅仅是为更清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或变动，这里无法对所有的实施方法予以穷举，凡是属于本发明的技术方案所引申出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (8)
1.聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶的制备方法，包括：首先合成EGCG修饰的聚多巴胺纳米颗粒PDA@EGCG NPs，再将PDA@EGCG NPs分散到聚乙烯醇/羧甲基壳聚糖共混溶液中，最后加入硼砂水溶液进行交联，得到聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶，聚乙烯醇、羧甲基壳聚糖、PDA@EGCG NPs、硼砂的质量比为60：15：（0.5~2）：12；PDA@EGCG NPs的合成方法具体如下：将EGCG溶解在水中，得到EGCG溶液；将多巴胺溶解在水中，调节溶液至碱性环境，得到聚多巴胺溶液；将EGCG溶液倒入到聚多巴胺溶液中，通氧搅拌24h后离心、真空冷冻干燥即可。
2.根据权利要求1所述的制备方法，其特征在于，EGCG在水中的浓度为0.5mg/mL；多巴胺在水中的浓度为5mg/mL；和/或EGCG与多巴胺的质量比为1：10。
3.根据权利要求1所述的制备方法，其特征在于，聚乙烯醇/羧甲基壳聚糖共混溶液的配制方法如下：按比例将聚乙烯醇、羧甲基壳聚糖混合，再加入去离子水，所得混合物升温至90~95℃后充分搅拌均匀，使聚乙烯醇完全溶解。
4.根据权利要求3所述的制备方法，其特征在于，聚乙烯醇/羧甲基壳聚糖共混溶液中聚乙烯醇的质量百分浓度为6％、羧甲基壳聚糖的质量百分浓度为1.5%。
5.根据权利要求1所述的制备方法，其特征在于，硼砂水溶液的质量百分浓度为6%。
6.根据权利要求1所述的制备方法，其特征在于，加入硼砂后在室温下迅速搅拌反应1~3分钟。
7.聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶，由权利要求1~6任意一项所述的制备方法制得。
8.权利要求7所述的聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶在生物医用材料领域中的应用。
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