CN116607336B - 一种自发热一氧化氮抗菌织物涂层及其制备方法和用途 - Google Patents
一种自发热一氧化氮抗菌织物涂层及其制备方法和用途 Download PDFInfo
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Abstract
本发明公开了一种自发热一氧化氮抗菌织物涂层及其制备方法和用途，涂层由以下方法制备得到：制备WS2量子点；将2‑巯基咪唑亚硝基化；将WS2量子点与亚硝基化后的2‑巯基咪唑配位制备WS2@ZIF‑SNO纳米颗粒；通过共混法制备WS2@ZIF‑SNO织物涂层液。本发明的自发热织物涂层具有聚氨酯类涂层丰满舒适的手感，弹性优异，其中包含的WS2部分为织物增加舒适安全的保暖效果；同时对细菌造成功能性障碍，诱导细菌死亡，增加WS2@ZIF‑SNO纳米颗粒的抗菌性能。本发明的自发热织物涂层可以实现发热织物在人体服装、保温材料、有效抗菌等领域的良好应用。
Description
技术领域
本发明涉及一种自发热抗菌织物涂层及其制备方法和用途。
背景技术
全国工业高速发展下，人们对织物的要求也不断在提高。保暖舒适、健康环保的织物涂层也越来越受到社会的关注。聚氨酯类(PU)、聚丙烯酸酯类(PA)、聚乙烯类(PE)、聚氯乙烯类(PVC)等涂层胶的品种越来越丰富，能够满足人们对织物涂层日益增长的需求。
聚氨酯类涂层柔然有弹性，强度高，通透性好，耐湿，奈干洗等诸多特点，可运用于各种很薄的涂层。若将自发热的纳米颗粒加入到聚氨酯中，人们保暖的衣物也将不再限制于棉袄、羽绒服等厚重宽大的衣物。
细菌感染及其引发的疾病也已经成为了社会关注的重点问题之一，并且其传染途径广泛多样常常让人防不胜防。一氧化氮(NO)，长期以来被认为是一种危害环境的有毒气体。在近些年的研究中发现，NO是生物中的一种内源性气体分子，在生理环境中起着重要作用。同时，外源性NO可以作为一种有效的杀菌剂，可以对细菌造成亚硝基化和氧化应激作用，破坏细菌的细胞膜并对细菌造成严重的细胞功能障碍。
因此，开发一种自发热一氧化氮抗菌的织物涂层具有很高的应用前景。
发明内容
本发明的目的在于提供一种具有良好自发热性能和一氧化氮抗菌性能的自发热一氧化氮抗菌织物涂层及其制备方法和用途。
本发明的技术解决方案是：
一种自发热一氧化氮抗菌织物涂层，其特征是：由以下方法制备得到：
步骤1：制备WS2量子点；
步骤2：用1.5当量亚硝酸叔丁酯将2-巯基咪唑亚硝基化；
步骤3：将WS2量子点与亚硝基化后的2-巯基咪唑配位制备WS2@ZIF-SNO纳米颗粒；
步骤4：通过共混法制备WS2@ZIF-SNO织物涂层液。
一种自发热一氧化氮抗菌织物涂层的制备方法，其特征是：包括下列步骤：
步骤1：制备WS2量子点；
步骤2：用1.5当量亚硝酸叔丁酯将2-巯基咪唑亚硝基化；
步骤3：将WS2量子点与亚硝基化后的2-巯基咪唑配位制备WS2@ZIF-SNO纳米颗粒；
步骤4：通过共混法制备WS2@ZIF-SNO织物涂层液。
步骤1制备WS2量子点的具体方法：
将1mmol的WCl6溶解在15mL的油酸和5mL的油胺混合溶液中，并在氩气保护下加热到150℃，搅拌30min；接着将1mmol的硫代苯甲酸加入到上述溶液中继续搅拌30min后，自然冷却到室温，然后转移到微波反应器中，在300℃下反应1h，即可得到油胺包裹的WS2量子点；进一步进行表面改性，将10mg的油胺包裹的WS2量子点和30mg的DSPE-PEG-COOH加入到20mL的氯仿溶剂中，磁力搅拌12小时后，在50℃下旋转蒸发以去除氯仿，加入去离子水分散得到表面亲水的WS2量子点。
步骤2的具体方法：
将2-巯基咪唑0.679mmol与1.5当量的亚硝酸叔丁酯溶解于10mL的甲醇中，搅拌3小时后，将搅拌好的液体用氮气缓慢吹干，使2-巯基咪唑充分亚硝基化。
步骤3的具体方法：将步骤1中的WS2量子点和步骤2中的亚硝基化后的2-巯基咪唑分散在氯仿中，搅拌5小时后，8000rpm离心，并用甲醇洗涤三次得到所述WS2@ZIF-SNO纳米颗粒。
步骤4的具体方法：将步骤3中制备的WS2@ZIF-SNO纳米颗粒1mg与聚氨酯20mg分别分散在3mL的氯仿中，超声15分钟后，室温条件下磁力搅拌2小时；然后将分散均匀的WS2@ZIF-SNO纳米颗粒和聚氨酯混合，继续搅拌2小时后，得到含WS2@ZIF-SNO纳米颗粒的涂层液。
一种所述的自发热一氧化氮抗菌织物涂层在制备自发热抗菌织物涂层织物中的应用，其特征是：将步骤4中的涂层液均匀涂抹在白色布料的表面，通过紫外灯照射2小时，涂层液固化在布料上，形成所述自发热抗菌涂层织物。
本发明用先制备WS2纳米球以及将2-巯基咪唑亚硝基化，利用咪唑结构与WS2配位形成新的WS2@ZIF-SNO纳米颗粒，再将聚氨酯参杂WS2@ZIF-SNO纳米颗粒，使得织物涂层同时具有自发热性能与抗菌性能。
本发明的自发热织物涂层具有聚氨酯类涂层丰满舒适的手感，弹性优异，其中包含的WS2部分可以利用自然光中的近红外辐射进行自发热，为织物增加舒适安全的保暖效果；同时温度的增高能够使得WS2@ZIF-SNO纳米颗粒释放出NO，通过亚硝基化和氧化应激扰乱细菌膜，对细菌造成功能性障碍，诱导细菌死亡，增加WS2@ZIF-SNO纳米颗粒的抗菌性能。本发明的自发热织物涂层可以实现发热织物在人体服装、保温材料、有效抗菌等领域的良好应用。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图1为实施例1中WS2的TEM图；
图2是WS2@ZIF-SNO纳米颗粒的SEM图。
图3为实施例1中WS2@ZIF-SNO纳米颗粒的紫外图。
图4是实施例1中WS2@ZIF-SNO纳米颗粒的红外图。
图5为WS2@ZIF-SNO纳米颗粒的NO释放性能示意图。
图6为实施例1中WS2@ZIF-SNO纳米颗粒的光热性能图。
图7为实施例1中WS2@ZIF-SNO织物涂层的红外热成像图。
图8是实施例1中WS2@ZIF-SNO织物涂层的抗菌效果图。
具体实施方式
实施例1
(1)、制备WS2量子点
将1mmol的WCl6溶解在15mL的油酸和5mL的油胺混合溶液中，并在氩气保护下加热到150℃，搅拌30min；接着将1mmol的硫代苯甲酸加入到上述溶液中继续搅拌30min后，自然冷却到室温，然后转移到微波反应器中，在300℃下反应1h，即可得到油胺包裹的WS2量子点；进一步进行表面改性，将10mg的油胺包裹的WS2量子点和30mg的DSPE-PEG-COOH加入到20mL的氯仿溶剂中，磁力搅拌12小时后，在50℃下旋转蒸发以去除氯仿，加入去离子水分散得到表面亲水的WS2量子点。
(2)、将2-巯基咪唑亚硝基化
将2-巯基咪唑(68mg，0.679mmol)与1.5当量的亚硝酸叔丁酯溶解于10mL的甲醇中，搅拌3小时后，将搅拌好的液体用氮气缓慢吹干，使2-巯基咪唑充分亚硝基化。
(3)、制备WS2@ZIF-SNO纳米颗粒
将上述步骤1中的50mg的WS2量子点和步骤2中100mg的亚硝基化后的2-巯基咪唑分散在氯仿中，搅拌5小时后，8000rpm离心，并用甲醇洗涤三次得到所述WS2@ZIF-SNO纳米颗粒。
(4)、制备WS2@ZIF-SNO织物涂层液
将上述步骤3中制备的ZIF-SNO@CuS纳米颗粒(1mg)与聚氨酯(20mg)分别分散在3mL的氯仿中，超声15分钟后，室温条件下磁力搅拌2小时。然后将分散均匀的WS2@ZIF-SNO纳米颗粒和聚氨酯混合，继续搅拌2小时后，得到含WS2@ZIF-SNO纳米颗粒的涂层液。
(5)、制备自发热抗菌涂层织物
将上述步骤四中的涂层液均匀涂抹在白色布料的表面，通过紫外灯照射2小时，涂层液固化在布料上，形成所述自发热抗菌涂层织物。
性能测试：
1.WS2@ZIF-SNO纳米颗粒的形貌测定
图1、图2为实施例1中WS2量子点TEM图和WS2@ZIF-SNO纳米颗粒的SEM照片，可以看到WS2量子点是直径10nm左右的纳米球，WS2@ZIF-SNO是直径110～200nm的球状物。
2.WS2@ZIF-SNO纳米颗粒的表征
通过图3中对WS2@ZIF-SNO纳米颗粒紫外光谱分析，WS2@ZIF-SNO纳米颗粒在1390nm处出现WS2的宽峰以及在280nm处出现了2-巯基咪唑中的咪唑结构特征峰。可以证明在WS2@ZIF-SNO纳米材料中同时含有WS2和亚硝基化后的2-巯基咪唑组成成分。
通过图4中对WS2@ZIF-SNO纳米颗粒和2-巯基咪唑的红外分析，2-巯基咪唑经过亚硝基叔丁酯的亚硝基化后，在2551cm-1处巯基的特征峰消失不见，由此判断2-巯基咪唑成功亚硝基化。
3.WS2@ZIF-SNO纳米颗粒的NO释放性能测定
将WS2@ZIF-SNO纳米颗粒均匀分散在水中，配置为0.1mg/mL的液体，加入一氧化氮检测试剂(Griess Reagent 1和Griess Reagent 2)，在1064nm激光照射下测定其不同时间的紫外吸收。通过图5可以发现在激光照射下，随着时间的推移，480nm处的吸收峰不断变高，而没有激光照射则没有NO的释放。这说明WS2@ZIF-SNO纳米颗粒可以通过近红外辐射实现可控NO的可控释放。
4.WS2@ZIF-SNO纳米颗粒的光热性能测定
将WS2@ZIF-SNO纳米颗粒分散在水中，分别配置0.2mg/mL、0.1mg/mL、0.05mg/mL的WS2@ZIF-SNO纳米颗粒水溶液，用1064nm的激光照射，记录实时温度，如图6。可以发现WS2@ZIF-SNO纳米颗粒溶液在激光照射下，随着时间的推移，温度逐渐升高；并且WS2@ZIF-SNO纳米颗粒溶液浓度越高，升温速率越快，这说明WS2@ZIF-SNO纳米颗粒有着优异的光热性能。
5.WS2@ZIF-SNO织物涂层的红外热成像
将实列1中配置好的涂层液紫外固化在布料上，用1064nm的激光照射，并用红外热成像仪实时记录温度变化。通过图7可以看到，普通布料在1064nm激光照射下，温度几乎没有变化；而涂有涂层液的布料在在1064nm激光照射下，随着时间的变化，温度逐渐升高。这说明WS2@ZIF-SNO织物涂层有着良好的光热性能。
6.WS2@ZIF-SNO纳米颗粒的抗菌性能测定
将普通布料和涂有WS2量子点涂层胶、WS2@ZIF-SNO纳米颗粒涂层胶的布料洗涤后对金黄色葡萄球菌和大肠杆菌进行检测，结果如图8。可以发现，在不加光照的情况下，布料在WS2纳米颗粒涂层胶和WS2@ZIF-SNO纳米颗粒涂层胶处理后，几乎没有降低；在加入1064nm激光照射后，产生光热效果，使得两者的产生抗菌效果，WS2量子点涂层胶处理后的布料上，金黄色葡萄球菌和大肠杆菌的存活率分别为20％和24％，并且温度的提升会使得WS2@ZIF-SNO纳米颗释放出NO，对细菌产生巨大杀伤性，金黄色葡萄球菌和大肠杆菌的存活率不足5％。这说明WS2@ZIF-SNO纳米颗粒涂层胶在没有光照的情况下，bu可以产生抗菌效果，而在光照情况下WS2@ZIF-SNO纳米颗粒涂层胶释放出NO，抗菌效果大大加强。
Claims (3)
1.一种自发热一氧化氮抗菌织物涂层，其特征是：由以下方法制备得到：
步骤1：制备WS2量子点；
步骤2：用1.5当量亚硝酸叔丁酯将2-巯基咪唑亚硝基化；
步骤3：将WS2量子点与亚硝基化后的2-巯基咪唑配位制备WS2@ZIF-SNO纳米颗粒；
步骤4：通过共混法制备WS2@ZIF-SNO织物涂层液；
步骤1制备WS2量子点的具体方法：将1mmol的WCl6溶解在15mL的油酸和5mL的油胺混合溶液中，并在氩气保护下加热到150℃，搅拌30min；接着将1mmol的硫代苯甲酸加入到上述溶液中继续搅拌30min后，自然冷却到室温，然后转移到微波反应器中，在300℃下反应1h，即可得到油胺包裹的WS2量子点 ；进一步进行表面改性，将10mg的油胺包裹的WS2量子点和30mg的DSPE-PEG-COOH加入到20mL的氯仿溶剂中，磁力搅拌12小时后，在50℃下旋转蒸发以去除氯仿，加入去离子水分散得到表面亲水的WS2量子点；
步骤4的具体方法：将步骤3中制备的WS2@ZIF-SNO纳米颗粒1 mg与聚氨酯20 mg分别分散在3 mL的氯仿中，超声15分钟后，室温条件下磁力搅拌2小时；然后将分散均匀的WS2@ZIF-SNO纳米颗粒和聚氨酯混合，继续搅拌2小时后，得到含WS2@ZIF-SNO纳米颗粒的涂层液。
2. 根据权利要求1所述的自发热一氧化氮抗菌织物涂层，其特征是：步骤2的具体方法：将2-巯基咪唑0.679 mmol与1.5当量的亚硝酸叔丁酯溶解于10 mL的甲醇中，搅拌3小时后，将搅拌好的液体用氮气缓慢吹干，使2-巯基咪唑充分亚硝基化。
3. 根据权利要求1所述的自发热一氧化氮抗菌织物涂层，其特征是：步骤3的具体方法：将步骤1中的WS2量子点和步骤2中的亚硝基化后的2-巯基咪唑分散在氯仿中，搅拌5小时后，8000 rpm离心，并用甲醇洗涤三次得到所述WS2@ZIF-SNO纳米颗粒。
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