CN107446581A - 一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝 - Google Patents

一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝 Download PDF

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CN107446581A
CN107446581A CN201710836622.1A CN201710836622A CN107446581A CN 107446581 A CN107446581 A CN 107446581A CN 201710836622 A CN201710836622 A CN 201710836622A CN 107446581 A CN107446581 A CN 107446581A
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Abstract

本发明公开了一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝，利用带负电的稀土掺杂上转换纳米材料与带正电的稀土掺杂上转换纳米材料之间的静电作用作为成膜推动力，赋予蚕丝上转换荧光性能。

Description

一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝
技术领域
本发明涉及一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝，属纤维材料领域。
背景技术
蚕丝是一种非常重要的纤维材料，它的应用已经不仅仅局限在纺织行业。天然蚕丝的颜色有白色和黄色，随着科学技术的发展，人们已经获得具有不同颜色的蚕丝，如红色、绿色、橙色等。此外，经过功能化后的蚕丝，还具有一些特殊功能，如荧光、防紫外、抗菌等，可用于纺织、生物医学、防伪领域。
目前制备荧光蚕丝方法，包括基因工程、喂食法、纳米材料结合方法以及双光子荧光技术等。例如采用喂食法制备彩色荧光蚕丝，具有操作简单、高效、环保等优点。但荧光染料在蚕体内的运输复杂，要使其有效进入蚕丝腺内，从而与蚕丝蛋白牢固结合，并保证荧光染料等物质对蚕无害和对丝产量无影响，仍是喂食法生产功能蚕丝所需克服的难点（曹丽薇,林乃波,刘向阳. 光学功能化蚕丝纤维材料[J]. 中国材料进展,2014,33(11):669-676+689）。
近几年来，纳米颗粒的应用受到广泛的关注，由于其粒径小，比表面积大，表现出尺寸效应、表面效应，具有光、电、磁等特殊的性能，被应用于医药、光电器件、生物传感器等领域。蚕丝作为一种天然的生物大分子，将蚕丝与无机纳米颗粒结合的潜在应用已经受到人们的关注。但是采用纳米颗粒结合的方法制备荧光蚕丝的局限性是蚕丝表面粘结的纳米颗粒稳定性不好，耐洗性较差。
稀土上转换纳米发光材料（UCNPs）能够通过双光子或多光子机制把低能量长波辐射转换成高能量短波辐射，其具备毒性低、化学稳定性高、光稳定性强、信噪比高、发射谱带窄、荧光寿命长、反斯托克斯位移大、较大的光穿透深度、无光漂白、无背景荧光以及对生物组织无损伤等诸多优点，在免疫分析、生物标记、生物传感、生物成像、药物载体、光动力治疗、光热治疗、光导开关、信息存储、食品安全检测、光催化以及太阳能电池等领域有着广泛的研究和应用。其中NaYF4:Yb,Er/Tm是发光效率最高的UCNPs之一。
目前已有将UCNPs与丝素蛋白复合的文献报道，Zhao以NaYF4:Yb,Er为例，将丝素蛋白作为柔性基底材料与Na YF4:Yb,Er复合制备了上转换荧光复合薄膜（上转换荧光丝素薄膜的制备及其性能研究[D].苏州大学,2016；Physical Chemistry Chemical Physics,2016, 18, 15289）。Song将UCNPs与丝素复合制备了丝素支架（Advanced FunctionalMaterials, 2017, 27(26): 1700628）。但是目前还未见将UCNPs组装到蚕丝纤维上的报道。
发明内容
本发明针对上述不足，提供一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝。
本发明通过下述技术方案予以实现：将端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm分别配制成0.1-5g/L的水溶液，随后将蚕丝织物浸渍在80℃的端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中10-60min，浴比1:10，取出后用去离子水反复冲洗，烘干；然后将上述蚕丝织物浸渍在80℃的端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中10-60min，浴比1:10，取出后用去离子水反复冲洗，烘干，至此已将一层NaYF4:Yb,Er/Tm组装到蚕丝织物的表面，随后依次在端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm整理液中重复上述操作，根据需要决定蚕丝织物表面NaYF4:Yb,Er/Tm组装的层数。
端氨基超支化聚合物的合成可参考下述公开文献：端氨基超支化聚合物及其季铵盐的制备与性能[J].高分子材料科学与工程, 2009, 25(8): 141-144；CN200710020794.8一种超支化活性染料无盐染色助剂；Coloration Technology, 2007, 123(6): 351-357；AATCC Review, 2010, 10(6): 56-60；Biomacromolecules, 2010, 11(1): 245-251；Chemical Research in Chinese Universities, 2005, 21(3): 345-354。
端羟基超支化聚合物的合成可参考下述公开文献：杨保平,张鹏飞,崔锦峰等.端羟基超支化聚合物的改性研究及其在涂料中的应用[J].中国涂料,2011,26(3):53-57；王学川,胡艳鑫,郑书杰等.端羟基超支化聚合物对Fe3+吸附行为研究[J].化工新型材料,2011,39(9):26-29,47；强涛涛,张国国,王学川等.端羟基超支化聚合物的合成与改性[J].日用化学工业,2012,42(6):413-417。
端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm制备步骤可参考文献：中国发明专利CN201410701945.6一种水溶性上转换纳米颗粒及其制备方法。
与现有技术相比，本发明的优点在于：利用带负电的端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm与带正电的端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm之间的静电作用作为成膜推动力。NaYF4:Yb,Er/Tm通过正负离子键的结合作用附着在蚕丝织物表面，避免了使用有害的化学交联剂，降低了对蚕丝织物强力的影响。改性后的蚕丝织物具有优异的上转换荧光性能和良好的耐洗、服用性能。
具体实施方式
下面结合具体实施方式，进一步阐述本发明。
实施例1
将端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm分别配制成0.1g/L的水溶液，随后将蚕丝织物浸渍在80℃的端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中10min，浴比1:10，取出后用去离子水反复冲洗，烘干；然后将上述蚕丝织物浸渍在80℃的端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中10min，浴比1:10，取出后用去离子水反复冲洗，烘干得到上转换荧光蚕丝。
实施例2
将端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm分别配制成1g/L的水溶液，随后将蚕丝织物浸渍在80℃的端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中30min，浴比1:10，取出后用去离子水反复冲洗，烘干；然后将上述蚕丝织物浸渍在80℃的端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中30min，浴比1:10，取出后用去离子水反复冲洗，烘干，至此已将一层NaYF4:Yb,Er/Tm组装到蚕丝织物的表面，随后依次在端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm整理液中重复四次上述操作，得到上转换荧光蚕丝。
实施例3
将端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm分别配制成5g/L的水溶液，随后将蚕丝织物浸渍在80℃的端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中60min，浴比1:10，取出后用去离子水反复冲洗，烘干；然后将上述蚕丝织物浸渍在80℃的端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中60min，浴比1:10，取出后用去离子水反复冲洗，烘干，至此已将一层NaYF4:Yb,Er/Tm组装到蚕丝织物的表面，随后依次在端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm整理液中重复七次上述操作，得到上转换荧光蚕丝。
显然，本发明的上述实施例仅仅是为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它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。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 (2)

1.一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝的制备方法，其特征在于：将端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm分别配制成0.1-5g/L的水溶液，随后将蚕丝织物浸渍在80℃的端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中10-60min，浴比1:10，取出后用去离子水反复冲洗，烘干；然后将上述蚕丝织物浸渍在80℃的端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm水溶液中10-60min，浴比1:10，取出后用去离子水反复冲洗，烘干，至此已将一层NaYF4:Yb,Er/Tm组装到蚕丝织物的表面，随后依次在端氨基超支化聚合物修饰NaYF4:Yb,Er/Tm和端羟基超支化聚合物修饰NaYF4:Yb,Er/Tm整理液中重复上述操作，根据需要决定蚕丝织物表面NaYF4:Yb,Er/Tm组装的层数。
2.按权利要求1制备方法得到的一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝。
CN201710836622.1A 2017-09-17 2017-09-17 一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝 Pending CN107446581A (zh)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN110367209A (zh) * 2019-06-26 2019-10-25 浙江大学 一种在近红外光照下发荧光桑蚕丝的制备方法及产品
CN111206414A (zh) * 2020-01-16 2020-05-29 南通纺织丝绸产业技术研究院 基于稀土掺杂上转换纳米材料的荧光纤维及其制备方法

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Publication number Priority date Publication date Assignee Title
CN104357931A (zh) * 2014-11-28 2015-02-18 赵兵 一种荧光沙柳再生纤维素纤维及其制备方法
CN104371715A (zh) * 2014-11-28 2015-02-25 赵兵 一种水溶性三氧化钼上转换纳米材料及其制备方法
CN105839404A (zh) * 2016-04-11 2016-08-10 武汉纺织大学 一种荧光颜色可调的蚕丝织物的制备方法

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Publication number Priority date Publication date Assignee Title
CN104357931A (zh) * 2014-11-28 2015-02-18 赵兵 一种荧光沙柳再生纤维素纤维及其制备方法
CN104371715A (zh) * 2014-11-28 2015-02-25 赵兵 一种水溶性三氧化钼上转换纳米材料及其制备方法
CN105839404A (zh) * 2016-04-11 2016-08-10 武汉纺织大学 一种荧光颜色可调的蚕丝织物的制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110367209A (zh) * 2019-06-26 2019-10-25 浙江大学 一种在近红外光照下发荧光桑蚕丝的制备方法及产品
WO2020259490A1 (zh) * 2019-06-26 2020-12-30 浙江大学 一种在近红外光照下发荧光桑蚕丝的制备方法及产品
CN111206414A (zh) * 2020-01-16 2020-05-29 南通纺织丝绸产业技术研究院 基于稀土掺杂上转换纳米材料的荧光纤维及其制备方法

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