CN108485259A - 一种具有层层组装结构的功能化一维纳米线/纳米链的制备方法 - Google Patents
一种具有层层组装结构的功能化一维纳米线/纳米链的制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有层层组装结构的功能化一维纳米线/纳米链的制备方法,首先将表面有疏水柱状微阵列的印章与DNA溶液或高分子量聚合物溶液接触后,利用分子梳法用剥离或提拉的方式制备长度可达厘米至分米级的一维纳米线/纳米链;之后在一维纳米线表面进行层层组装,制备层层组装的功能性纳米线/纳米链。由于可方便的将具有功能性的聚合物、生物大分子及纳米粒子组装到纳米线上,该自支持一维功能性纳米线/纳米链有望在集成电路、传感器、信息存储、化学催化等领域获得应用。该方法克服了传统一维纳米线层层组装时步骤繁琐的缺陷,也不需要昂贵的设备,为一维功能性纳米线/纳米链的广泛应用提供了更广阔的空间。
Description
技术领域
本发明属于功能材料技术领域,具体地说是一种具有层层组装结构的功能化一维纳米线/纳米链的制备方法。
相关背景
一维功能性纳米线在集成电路、传感器、信息存储、化学催化等领域有着广阔的应用前景。例如,在电子领域,一维功能性纳米线可制备二极管逻辑门、双极晶体管、场效应晶体管等;磁性纳米线可应用于信息存储材料,而其独特的一维结构更适合制备具有光电响应性的纳米线传感器。但传统的一维功能性纳米线制备方法或者制备繁复昂贵,制备后也存在着组装和图案化较为困难的为题,因此有必要进行一维功能性纳米线的制备研究。
传统的一维功能性纳米线制备方法既可以是自上而下“Top Down”的方法,也可以是自下而上“Bottom up”方法或是二者的组合。典型的“Top Down”的方法是刻蚀法,但即使是精度极高的光刻蚀法,也由于波长的限制,难以制备小于10纳米的纳米线。“Bottom up”方法很多,如汽-液-固生长法,激光辅助催化生长法,模板法等。模板法利用具有高长径比的材料为模板来制备功能性一维材料,而具有高长径比的天然高分子DNA是最典型的模板,利用DNA为模板进行金属纳米线、半导体纳米线的制备已有很多报道
DNA的取向可以用电泳拉伸、流体力学拉伸和分子梳法等。电泳拉伸法可以用电场强度、频率控制DNA的拉伸制备纳米线,流体力学拉伸可通过溶液粘度、流体速率控制DNA的拉伸制备DNA纳米线,但二者都需要将DNA进行修饰或固定后才能获得规整的DNA纳米线阵列。而分子梳法则是利用溶液液面退却时的表面张力拉伸DNA,无需对DNA进行修饰或固定就可获得纳米线。当在井状或柱状的图案化表面进行DNA分子梳法拉伸时,DNA可在柱状或井状图案化表面形成规整的纳米线阵列。
DNA纳米线的功能化已有很多报道。以DNA纳米线为模板直接进行蒸镀,或首先吸附功能性化合物的前驱体再进行还原、氧化、沉积等过程即可制得功能化的纳米线。也可以通过静电疏水作用等相互作用,将纳米材料等修饰在DNA纳米线上制备功能性纳米线/纳米链。但这些方法均存在以下问题:1)DNA难以进行多次修饰以具备多功能性,2)制得的功能性DNA纳米线难以图案化,3)难以制备沿链取向方向具有异质结构的一维纳米线/纳米链。
发明内容
本发明的目的为建立一种方便快捷的具有层层组装结构的图案化、功能化一维纳米线/纳米链的制备方法。
本发明的目的可以通过以下技术方案来实现:
本发明的具有层层组装结构的功能化一维纳米线/纳米链取向结构的制备方法,具体步骤包括:
(1)将图案化疏水印章的有柱状微阵列的一面与DNA溶液或高分子量的聚合物溶液接触后,用剥离或提拉的方式,采用分子梳法在柱状微阵列表面制备一维纳米线/纳米链阵列;
(2)干燥后将疏水印章上表面具有一维纳米线阵列的一面与另一种具有与纳米线具有较强相互作用的聚合物/生物大分子溶液或功能性粒子悬浮液接触,之后用剥离或提拉的方式制备聚合物/聚合物或聚合物/纳米粒子一维复合物纳米线/纳米链阵列;
(3)重复步骤(1)、(2)即可制得层层组装的一维复合物纳米线/纳米链阵列。
所述的图案化疏水印章包括聚二甲基硅氧烷(PDMS)、聚苯乙烯、聚甲基丙烯酸甲酯、经表面疏水化处理的金属、玻璃或陶瓷。
所述的高分子量的聚合物选自包括壳聚糖、海藻酸钠、胶原、蛋白质、聚苯乙烯磺酸钠、聚丙烯酸、聚甲基丙烯酸、聚乙烯亚胺、聚烯丙基胺在内的天然或合成高分子中的一种或两种以上。
所述的功能性纳米粒子选自包括无机物纳米粒子、有机物纳米粒子、囊泡或胶束,所述无机物纳米粒子包括金、银、铂纳米粒子,硅、硫、碳纳米粒子,氧化锌、二氧化钛、硫化锌、硒化镉纳米粒子;所述有机物纳米粒子包括8-羟基喹啉铝和四苯乙烯。
所述的层层组装驱动力包括经典相互作用力、氢键力、疏水相互作用、化学成键作用和特异性结合作用。
通过将层层组装纳米线/纳米链阵列与其它表面接触,便可将该纳米线/纳米链阵列转移到其它工作表面;也可以通过洗涤将纳米线/纳米链阵列转移到水相或有机相中,制备自支持的层层组装一维复合物纳米线/纳米链悬浮液。
本方法还可以通过只浸没部分即进行提拉的方法,方便快捷的制备沿链取向方向具有异质结构的一维纳米线/纳米链。例如,可首先制备DNA和金纳米粒子的(DNA/AuNPs)n层层组装纳米线,再用浸没到一半即提拉的方法,在纳米线的下半部用DNA和铂纳米粒子层层组装,制备沿链取向方向具有Au/Pt异质结构的图案化纳米线。
由于可方便的将具有功能性的聚合物、生物大分子及纳米粒子组装到纳米线上,该自支持一维功能性纳米线/纳米链有望在集成电路、传感器、信息存储、化学催化等领域获得应用。本发明的方法克服了传统一维纳米线层层组装时步骤繁琐的缺陷,也不需要昂贵的设备,为一维功能性纳米线/纳米链的广泛应用提供了更广阔的空间。
附图说明
图1显示了实施例1中组装层数与纳米线直径间的关系。左图为原子力三维形貌图,中间图为纳米线高度图,右图为组装层数与纳米线直径间的关系。
图2是实施例2制得的(Chi/PSS)n层层组装纳米线的荧光显微镜图。Chi用绿色荧光试剂染色(左图),PSS用红色荧光试剂染色(中间图),右图为叠加图。
图3是实施例3制得的(DNA/QDs)n层层组装纳米线的荧光显微镜图。DNA用YOYO-1修饰后显绿色(左图),QDs发红色荧光(中间图),右图为叠加图。
图4显示了实施例4中的(DNA/QDs)2层层组装纳米线在水相中的复合纳米链结构。DNA用YOYO-1修饰后显绿色(左图),QDs发红色荧光(中间图),右图为叠加图。
具体实施方式
实施例1:
(1)将表面有微型柱状阵列的图案化PDMS用刀切成2cm*1cm的长方形印章,将有图案化阵列的那一面用胶带除掉表面的灰尘与杂质;
(2)将λ-DNA用10mM Tris HCl/2mM EDTA缓冲液稀释至20μg/mL,如需荧光观察则用YOYO-1标记,将少量DNA溶液滴加到载玻片上;
(3)将PDMS印章有图案化阵列的一面盖在DNA溶液上,用手指轻压,使DNA溶液铺展后的面积大于PDMS印章面积。用食指固定住PDMS印章的一个短边,用拇指将另一短边以另一个固定边为轴向上翻转,即可在微型柱状阵列上制得一维的DNA纳米线,将有DNA纳米线的一面向上,干燥一段时间;
(4)将阳离子聚电解质聚乙烯亚胺(PEI,2mg/mL)溶液滴在另一个载玻片上,将PDMS印章有DNA纳米线的一面与PEI溶液轻轻接触后,用与步骤(3)相似的方法制备DNA/PEI纳米线。
重复步骤(3)和步骤(4),即可制得(DNA/PEI)n层层组装纳米线。组装层数与纳米线直径间的关系见图1。
实施例2:
(1)将表面有微型柱状阵列的图案化PDMS用刀切成2cm*1cm的长方形印章,将有图案化阵列的那一面用胶带除掉表面的灰尘与杂质;
(2)将壳聚糖(Chi)用0.5%的醋酸水溶液溶解制得10mg/mL的Chi溶液,将少量Chi溶液滴加到载玻片上;
(3)将PDMS印章有图案化阵列的一面盖在Chi溶液上,用手指轻压,使Chi溶液铺展后的面积大于PDMS印章面积,用食指固定住PDMS印章的一个短边,用拇指将另一短边以另一个固定边为轴向上翻转,即可在微型柱状阵列上制得一维的Chi纳米线,将有Chi纳米线的一面向上,干燥一段时间;
(4)将阴离子聚电解质聚苯乙烯磺酸钠(PSS,2mg/mL)溶液滴在另一个载玻片上,将PDMS印章有Chi纳米线的一面与PSS溶液轻轻接触后,用与步骤(3)相似的方法制备Chi/PSS纳米线。
重复步骤(3)和步骤(4),即可制得(Chi/PSS)n层层组装纳米线。其荧光显微镜图见图2,Chi用绿色荧光试剂染色,PSS用红色荧光试剂染色。
实施例3:
(1)将表面有微型柱状阵列的图案化PDMS用刀切成2cm*1cm的长方形印章,将有图案化阵列的那一面用胶带除掉表面的灰尘与杂质;
(2)将λ-DNA用10mM Tris HCl/2mM EDTA缓冲液稀释至20μg/mL,如需荧光观察则用YOYO-1标记,将少量DNA溶液滴加到载玻片上;
(3)将PDMS印章有图案化阵列的一面盖在DNA溶液上,用手指轻压,使DNA溶液铺展后的面积大于PDMS印章面积,用食指固定住PDMS印章的一个短边,用拇指将另一短边以另一个固定边为轴向上翻转,即可在微型柱状阵列上制得一维的DNA纳米线。将有DNA纳米线的一面向上,干燥一段时间;
(4)将电正性的硒化镉量子点(CdSe QDs,2mg/mL)悬浮液滴在另一个载玻片上,将PDMS印章有DNA纳米线的一面与QDs悬浮液轻轻接触后,用与步骤(3)相似的方法制备DNA/QDs纳米线;
重复步骤(3)和步骤(4),即可制得(DNA/QDs)n层层组装纳米线。其荧光显微镜图见图3,DNA显示绿色,QDs有红色荧光。
实施例4:
将表面有(DNA/QDs)2层层组装纳米线的PDMS印章表面全部用水润湿,10分钟后用移液枪将表面的水转移到载玻片上,盖上盖玻片用荧光显微镜观察。由于DNA用YOYO-1标记,QDs有红色荧光,可在488nm和543nm下观察到清晰的复合纳米链结构(图4)。
Claims (7)
1.一种具有层层组装结构的功能化一维纳米线/纳米链的制备方法,其特征在于,具体步骤包括:
(1)将图案化疏水印章的有柱状微阵列的一面与DNA溶液或高分子量的聚合物溶液接触后,用剥离或提拉的方式,采用分子梳法在柱状微阵列表面制备一维纳米线/纳米链阵列;
(2)干燥后将疏水印章上表面具有一维纳米线阵列的一面与另一种具有与纳米线具有较强相互作用的聚合物/生物大分子溶液或功能性粒子悬浮液接触,之后用剥离或提拉的方式制备聚合物/聚合物或聚合物/纳米粒子一维复合物纳米线/纳米链阵列;
(3)重复步骤(1)、(2)即可制得层层组装的一维复合物纳米线/纳米链阵列。
2.根据权利要求1所述的具有层层组装结构的功能化一维纳米线的制备方法,其特征在于:所述的图案化疏水印章包括聚二甲基硅氧烷(PDMS)、聚苯乙烯、聚甲基丙烯酸甲酯、经表面疏水化处理的金属、玻璃或陶瓷。
3.根据权利要求1所述的具有层层组装结构的功能化一维纳米线/纳米链的制备方法,其特征在于:所述的高分子量的聚合物选自包括壳聚糖、海藻酸钠、胶原、蛋白质、聚苯乙烯磺酸钠、聚丙烯酸、聚甲基丙烯酸、聚乙烯亚胺、聚烯丙基胺在内的天然或合成高分子中的一种或两种以上。
4.根据权利要求1所述的具有层层组装结构的功能化一维纳米线/纳米链的制备方法,其特征在于:所述的功能性纳米粒子选自包括无机物纳米粒子、有机物纳米粒子、囊泡或胶束,所述无机物纳米粒子包括金、银、铂纳米粒子,硅、硫、碳纳米粒子,氧化锌、二氧化钛、硫化锌、硒化镉纳米粒子;所述有机物纳米粒子包括8-羟基喹啉铝和四苯乙烯。
5.根据权利要求1所述的具有层层组装结构的功能化一维纳米线/纳米链的制备方法,其特征在于:所述的层层组装驱动力包括经典相互作用力、氢键力、疏水相互作用、化学成键作用和特异性结合作用。
6.根据权利要求1所述的具有层层组装结构的功能化一维纳米线/纳米链的制备方法,其特征在于:通过将层层组装纳米线/纳米链阵列与其它表面接触,将该纳米线/纳米链阵列转移到其它工作表面;或通过洗涤将纳米线/纳米链阵列转移到水相或有机相中,制备自支持的层层组装一维复合物纳米线/纳米链悬浮液。
7.根据权利要求1所述的具有层层组装结构的功能化一维纳米线/纳米链的制备方法,其特征在于:通过只浸没到一定高度即进行提拉的方法,制备沿链取向方向具有异质结构的一维纳米线/纳米链。
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