CN111171807B - 一种兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料及其制备方法与用途 - Google Patents
一种兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料及其制备方法与用途 Download PDFInfo
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Abstract
本发明公开了一种兼具二阶、三阶非线性光学性能的染料/金属‑有机框架复合材料及其制备方法与自校准温度传感应用,化学式为[M(L)x(G)y]·(R)n,其中M为金属离子,L为含有羧酸基团的柔性对称有机配体,G为溶剂分子,R表示孔道内的染料分子。该材料在900~1300nm激发下,金属‑有机框架产生二次谐波,对温度不敏感;而染料产生的双光子荧光由于染料高温荧光淬灭,因此强度会随温度升高而下降。两个信号峰的比值与温度呈现线性关系,且循环性能好,能有效应用于生理温度传感。染料被装载后的量子效率、热稳定性有明显提高,并且在不同pH/温度的水溶液和PBS生理缓冲液的稳定性高,生物相容性好。这是首次报导的利用两种非线性光学信号实现生理温度传感。
Description
技术领域
本发明涉及一种兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料,该材料在900~1300nm激发下,金属-有机框架(MOFs)晶体可以产生二次谐波(SHG)与染料产生的双光子荧光的信号峰的强度比值随温度升高而变化,并存在一个线性关系,能有效应用于生理温度传感。且该材料具有优异的化学稳定性。
背景技术
与传统的传感方法相比,基于光学的传感器具有响应速度快、灵敏度高、对强电磁场干扰小等优点,受到了研究人员的广泛关注。基于光学强度的双发射荧光与单发射荧光相比具有许多优点,如不受探针浓度、中心荧光不均匀性、激发光源和探测器的光电漂移等影响,成为荧光传感的首选方法。虽然双发射荧光已经被广泛研究,但大多数研究集中在单光子激发和发射上,因此,多光子和非线性光学的发展具有重要意义。
双光子荧光属于三阶非线性光学,与单光子荧光相比,双光子荧光具有较强的穿透能力、微弱的光吸收和散射效应。此外,双光子技术可以减少近红外或红外光激发的光损伤、光毒性和光漂白问题。并且由于具有很高的空间选择性,这些因素使得它在生物传感领域有着非常广阔的应用前景。但是基于双发射的双光子荧光传感的研究还很少。倍频(SHG)也是一种非线性光学现象,在光信息技术、激光技术、纳米光子学技术和生物医学技术中已经显示出无穷的魅力。SHG信号在大多数情况下都是稳定的,除非材料晶体结构改变或激发功率不稳定。由于其稳定性,可被用做参考信号,能有效消除外界因素引起的测量误差,满足激发光源功率波动、荧光能量损失等多变的测量环境。具有SHG性能的绝大多数材料是无机化合物,且材料必须具有非对称中心,如氧化物晶体(磷酸二氢钾、磷酸二氢铵)和半导体晶体(碲)。但无机物具有潮解性,易受应用环境的限制,因此开发其他材料体系显得尤为重要。金属-有机框架(MOFs)由于其配体的多样性和结构的可设计性而成为典型的代表。MOFs是由金属团簇和有机配体通过配位键连接而成,具有稳定性好、生物相容性好、孔隙率高、发光位点多等优点,广泛应用于气体吸附分离、生物传感、药物负载和激光等领域,MOFs克服了许多无机化合物固有的缺点,并且由于其可变的有机配体,通过选择合适的配体并形成合适的配位结构来构建非中心对称结构是可行的;但是由于极化率、电子给体与受体之间电子传递的难易甚至π共轭长度对材料的SHG性能都起着至关重要的影响,因此如何构建一种具有良好SHG性能的MOFs材料值得重点研究。
温度是人们日常生活以及工业、军事、科学、生物等领域的一个重要参数。传统的热电偶和温度计不适用于高压、高速运动和电磁场等领域。基于上述原因,双发射非线性光学温度计以SHG信号为参考成为一种新的设计思路。为了实现双发射温度传感,除了引入SHG信号作为参考外,还必须引入随温度变化的传感信号。本发明将双光子荧光染料装载到MOFs孔中,不仅可以提供两个光学中心,而且可以解决上述问题。
发明内容
本发明的目的是提供一种兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料的制备方法,并将其非线性光学信号即二次谐波和双光子荧光应用于自校准生理温度传感上。
本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料,具有长程有序的晶体结构以及规则的孔道,其化学式为[M(L)x(G)y]·(R)n,其中M为金属离子,包括Zn、Cu、Cr、Co、Cd、或Zr;L为含有羧酸基团的柔性对称有机配体,包括4,4'-[[2,2-双[(4-羧基苯氧基)甲基]-1,3-丙二基]双(氧)苯甲酸,3,3'-[[2,2-双[[4-[(1E)-2-羧乙烯基]苯氧基]甲基]-1,3-丙二基]双(氧-4,1-苯撑)]2-丙烯酸,4',4”-[[2,2-双[(4'-羧基[1,1'-联苯]-4-基)氧基]甲基]-1,3-丙二醇]双(氧基)]-双-[1,1'-联苯]-4-羧酸,x=1~3;G表示与金属离子配位或在晶体孔道内的溶剂分子,为水、乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者N,N-二乙基甲酰胺;y=0~60;R表示孔道内的阳离子吡啶半菁类染料分子,包括4-(4-(二苯基氨基)苯乙烯基)-1-烷基吡啶、1-乙基-4-(4-(甲基(苯基)氨基)苯乙烯基)吡啶、4-(4-(二甲氨基)苯乙烯基)-1-乙基吡啶、4-(4-(二苯基氨基)苯基)偶氮-1-乙基吡啶或4-(4-(二乙氨基)苯乙烯基)-1-乙基吡啶,n=1~50。
本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料的制备方法,包括以下步骤:
将金属硝酸盐与含有羧酸基团的柔性对称有机配体,阳离子吡啶半菁类双光子染料一起加入去离子水和有机溶剂中,得到混合溶液,将得到的溶液放入反应釜内胆中,在120~160℃加热反应3~6天,离心、洗涤,得到兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料。
本发明中,金属硝酸盐为硝酸锌,硝酸铜,硝酸铬,硝酸钴,硝酸镉、或硝酸锆。
本发明中,含有羧酸基团的柔性对称有机配体是(a)4,4'-[[2,2-双[(4-羧基苯氧基)甲基]-1,3-丙二基]双(氧)苯甲酸;或(b)3,3'-[[2,2-双[[4-[(1E)-2-羧乙烯基]苯氧基]甲基]-1,3-丙二基]双(氧-4,1-苯撑)]2-丙烯酸;或(c)4',4”-[[2,2-双[(4'-羧基[1,1'-联苯]-4-基)氧基]甲基]-1,3-丙二醇]双(氧基)]-双-[1,1'-联苯]-4-羧酸。结构式分别如下:
本发明中,阳离子吡啶半菁类双光子染料结构式如下:(a)4-(4-(二苯基氨基)苯乙烯基)-1-烷基吡啶;(b)1-乙基-4-(4-(甲基(苯基)氨基)苯乙烯基)吡啶;(c)4-(4-(二甲氨基)苯乙烯基)-1-乙基吡啶;(d)4-(4-(二苯基氨基)苯基)偶氮-1-乙基吡啶;或(e)4-(4-(二乙氨基)苯乙烯基)-1-乙基吡啶。
本发明中,所用的有机溶剂为乙醇和N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者N,N-二乙基甲酰胺中任意一种。
本发明中,金属离子与含有羧酸基团的柔性对称有机配体摩尔比为1~3:1。
本发明中,有机溶剂和去离子水的体积比为2~5:1。
本发明中兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料,在红外/近红外光激发下,金属-有机框架(MOFs)晶体可以产生二次谐波(SHG)与染料产生的双光子荧光的信号峰的强度比值随温度升高而变化,并存在一个线性关系,可用于20~60℃生理温度传感。
本发明中兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料,在不同pH的水溶液和PBS生理缓冲液中,该材料都可以保持结构的稳定性。
本发明具体的有益效果在于:
1、本发明的方法用于兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料对生理温度的自校准传感,金属-有机框架(MOFs)晶体可以产生二次谐波(SHG)与染料产生的双光子荧光的信号峰的强度比值在生理温度范围内与温度成线性相关。利用SHG信号作为信号参照,这也是SHG信号与双光子荧光信号第一次同时被应用于生理温度传感。
2、生物相容性是评价一种材料能否被应用于生物医学领域的重要标准,本发明的染料/金属-有机框架复合材料生物相容性好,当其含量达到100μg·mL-1时,细胞的存活率还能达到80%以上。且与单纯的染料生物相容性相比,被装载进金属-有机框架材料后,生物相容性有显著增加。
3、与无机化合物、配合物或有机分子相比,金属-有机框架材料是一种具有有序微孔的晶态材料,具有长程有序的晶体结构和规则的孔道。染料分子能够均匀地分散在框架内,避免了分子团聚导致的荧光淬灭,从而提高了发光效率,由单纯染料的1.19%上升到复合材料中的58.46%。
4、双光子染料由于极易溶解,且热稳定性差,很难在生物组织中应用,被金属有机框架材料装载后可以提高染料的热稳定性,扩大其应用范围。
5、本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料可以重复利用,在多个温度循环内依然保持可回复的光学性能;经计算该材料的温度探测灵敏度可以达到1.1~1.8%·℃-1以上,分辨率可以达到0.018℃以下,完全可以应用于生物传感。
6、本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料可以在不同pH的水溶液中保持长时间的结构稳定。且在生物模拟溶液PBS中浸泡1天后结构也依然保持完好,保证了其在生物科学领域的应用。
附图说明
图1是本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料合成及结构示意图;
图2是本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料不同pH水溶液/PBS中稳定性表征;
图3是本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料a)光谱随温度的变化;b)二次谐波(SHG)与双光子荧光的信号峰的强度比值与温度的关系;
图4是本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料在5个循环变温周期中的二次谐波(SHG)与双光子荧光的信号峰的强度比值随温度的变化;
图5是本发明的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料与染料的生物相容性实验结果;
具体实施方式
下面将结合实例进一步阐明本发明的内容,但这些实例并不限制本发明的保护范围,在本发明的技术方案的基础上,本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
实施例1:
利用硝酸锌与4,4'-[[2,2-双[(4-羧基苯氧基)甲基]-1,3-丙二基]双(氧)苯甲酸,通过溶剂热方法合成金属-有机框架材料,其具体的合成路线如下:
将1mmol的硝酸锌和1mmol的4,4'-[[2,2-双[(4-羧基苯氧基)甲基]-1,3-丙二基]双(氧)苯甲酸,15mg阳离子染料4-(4-(二甲氨基)苯乙烯基)-1-乙基吡啶溶解于4mL DMF,4mL乙醇和4mL H2O混合溶剂中,随后将溶液封装于20mL聚四氟乙烯反应釜中,置于130℃烘箱中反应5天。冷却至室温,用DMF洗涤3次,得到含双光子染料的金属-有机框架材料,染料含量为8.45wt%。
该材料在1064nm激光激发下,所得到的发射光谱的峰值位于532,599nm,随着温度升高,其强度比值升高(图3)。可以用下面的公式拟合:
I532/599=0.01164T+0.3964
其中I为二次谐波(SHG)与双光子荧光的信号峰的强度比值。该含双光子染料的金属-有机框架材料在温度低时,其双光子荧光强度较强,随温度升高下降明显,而二次谐波随温度变化保持稳定。经计算该材料的探测灵敏度可以达到1.1~1.8%·℃-1,分辨率可以达到0.018℃,完全可以应用于生物传感。为了验证该材料在生理温度区间温度传感特性的精准度,我们研究了二次谐波(SHG)与双光子荧光的信号峰的强度比值随温度变化的重复可逆性。如图4所示,在5个周期的温度循环(20~60℃)中,该材料的信号随温度的变化是可逆的,这说明该材料可以重复使用。
对该材料的热稳定性进行了表征,装载进金属-有机框架材料的孔中后,染料的热稳定性提高了约140℃,由此扩大了染料的应用范围。
从图5中可以看出,该含双光子染料的金属-有机框架材料的细胞生物相容性较高,当其含量达到100μg·mL-1时,细胞的存活率还能达到80%以上,说明该材料有很好的生物相容性,有望应用于生物医学领域。此外,染料经过装载后,生物相容性比纯染料分子的增加很多。
将材料浸入pH=1/7/13的水溶液中1天后,其粉末X射线衍射图谱依然能够很好的能与其单晶模拟X射线衍射图谱较好吻合,证明其pH稳定性较好,能够在溶液中实现探测。用PBS溶液作为生物模拟溶液,该材料在浸泡1天后晶体结构依然保持完整,说明该材料可以适应生物环境。
染料在被装载后,发光的量子效率明显提高,由单纯染料的1.19%上升到复合材料中的58.46%,这也在一定程度上提高了材料温度探测的灵敏性。
实施例2:
利用硝酸锌与4',4”-[[2,2-双[(4'-羧基[1,1'-联苯]-4-基)氧基]甲基]-1,3-丙二醇]双(氧基)]-双-[1,1'-联苯]-4-羧酸,通过溶剂热方法合成金属-有机框架材料,其具体的合成路线如下:
将1mmol的硝酸锌和1mmol的6,6'-[[2,2-双[(6-羧基-2-萘基)氧]甲基]-1,3-丙二醇]双(氧)]-双-2-萘甲酸,15mg阳离子染料4-(4-(二甲氨基)苯乙烯基)-1-乙基吡啶溶解于4mL DMF,4mL乙醇和4mL H2O混合溶剂中,随后将溶液封装于20mL聚四氟乙烯反应釜中,置于130℃烘箱中反应5天。冷却至室温,用DMF洗涤3次,得到含双光子染料的金属-有机框架材料。
该材料在1064nm激光激发下,所得到的发射光谱的峰值位于532,599nm,随着温度升高,其强度比值升高。该含双光子染料的金属-有机框架材料在温度低时,其双光子荧光强度较强,随温度升高下降明显,而二次谐波随温度变化保持稳定。为了验证该材料在生理温度区间温度传感特性的精准度,我们研究了二次谐波(SHG)与双光子荧光的信号峰的强度比值随温度变化的重复可逆性。在5个周期的温度循环(20~60℃)中,该材料的信号随温度的变化是可逆的,这说明该材料可以重复使用。
对该材料的热稳定性进行了表征,装载进金属-有机框架材料的孔中后,染料的热稳定性提高了约150℃,由此扩大了染料的应用范围。
对该含双光子染料的金属-有机框架材料的细胞生物相容性进行表征,当其含量达到100μg·mL-1时,细胞的存活率还能达到80%以上,说明该材料有很好的生物相容性,有望应用于生物医学领域。此外,染料经过装载后,生物相容性比纯染料分子的增加很多。
将材料浸入pH=1/7/13的水溶液中1天后,其粉末X射线衍射图谱依然能够很好的能与其单晶模拟X射线衍射图谱较好吻合,证明其pH稳定性较好,能够在溶液中实现探测。用PBS溶液作为生物模拟溶液,该材料在浸泡1天后晶体结构依然保持完整,说明该材料可以适应生物环境。
另外,染料在被装载后,发光的量子效率明显提高,这也在一定程度上提高了材料温度探测的灵敏性。
Claims (3)
1.一种兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料,其特征在于,该材料利用两种非线性光学信号即二次谐波和双光子荧光,能用于20~60℃范围生理温度的探测;该材料具有长程有序的晶体结构以及规则的孔道,其化学式为[M(L)x(G)y]·(R)n,其中M为金属离子,为Zn;
L为含有羧酸基团的柔性对称有机配体,选自:(a)4,4'-[[2,2-双[(4-羧基苯氧基)甲基]-1,3-丙二基]双(氧)苯甲酸,(b)3,3'-[[2,2-双[[4-[(1E)-2-羧乙烯基]苯氧基]甲基]-1,3-丙二基]双(氧-4,1-苯撑)]2-丙烯酸,(c)4',4”-[[2,2-双[(4'-羧基[1,1'-联苯]-4-基)氧基]甲基]-1,3-丙二醇]双(氧基)]-双-[1,1'-联苯]-4-羧酸,其结构式分别如下:
G表示与金属离子配位或在晶体孔道内的溶剂分子,为水、乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者N,N-二乙基甲酰胺;y=0~60;
R表示孔道内的阳离子吡啶半菁类染料分子,选自:(a)4-(4-(二苯基氨基)苯乙烯基)-1-烷基吡啶、(b)1-乙基-4-(4-(甲基(苯基)氨基)苯乙烯基)吡啶、(c)4-(4-(二甲氨基)苯乙烯基)-1-乙基吡啶、(d)4-(4-(二苯基氨基)苯基)偶氮-1-乙基吡啶或(e)4-(4-(二乙氨基)苯乙烯基)-1-乙基吡啶,结构式如下:
所述材料的制备方法包括以下步骤:
将硝酸盐与含有羧酸基团的柔性对称有机配体,阳离子吡啶半菁类双光子染料一起加入去离子水和有机溶剂中,得到混合溶液,将得到的溶液放入反应釜内胆中,在120~160℃加热反应3~6天,离心、洗涤,得到具有非线性光学性能的染料装载的金属-有机框架材料。
2.根据权利要求1所述的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料,其特征在于,所述的混合溶液中有机溶剂为乙醇和N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者N,N-二乙基甲酰胺中任意一种;且其中有机溶剂和去离子水的体积比为2~5:1。
3.根据权利要求1所述的兼具二阶、三阶非线性光学性能的染料/金属-有机框架复合材料,其特征在于,硝酸锌中的金属离子与含有羧酸基团的柔性对称有机配体摩尔比为1~3:1。
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New Metal-Organic Framework with Uninodal 4-Connected Topology Displaying Interpenetration, Self-Catenation, and Second-Order Nonlinear Optical Response;Tian-Fu Liu et al.,;《Crystal Growth & Design》;20100301;第10卷(第4期);第1489-1491页 * |
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