CN106117219B - 一种十四元瓜环tQ[14]的应用 - Google Patents
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Abstract
本发明公开了一种十四元瓜环tQ[14]的应用,是用于识别赖氨酸或精氨酸;由于十四元瓜环tQ[14]具有两个空腔结构的特点,以及特殊的溶解性。氨基酸这种小分子与十四元瓜环tQ[14]有着不同的作用位点,同样形成超分子配合物的结构就不同,不同的氨基酸作用模式不同,表现出的性质就不同,以及作用强弱不同,在识别氨基酸方面有着潜在的应用价值。
Description
技术领域
本发明涉及一种十四元瓜环tQ[14],特别是一种十四元瓜环tQ[14]的应用。
背景技术
瓜环作为一类大环化合物,是由苷脲单元通过亚甲基桥联起来的大环笼状化合物,其结构特征为具有两端开口的空腔,其两端口大小相同,端口直径小于空腔直径。瓜环两端口分别分布着与其结构单元数相同的羰基氧原子,形成了阳离子键结合位点,所以能与亲水性的物质、金属离子等相互作用;而其空腔是疏水性的,不仅可以包结有机分子,还可以包结无机小分子,无机阴离子。与冠醚、环糊精、杯芳烃等大环分子相比,瓜环具有更强的结构刚性,不容易改变自身形状以适合客体分子,所以能根据自身空腔的大小,选择性的容纳尺寸、形状相匹配的客体分子。
2013年首次报道瓜环家族中大聚合度的成员——铰接十四元瓜环tQ[14](tQ[14])后,通过两年多的探索初步发现:tQ[14]是由十四个苷脲单元通过26个亚甲基桥联后形成的长带一端旋转180°后,再由2个亚甲基桥联关环而成,其结构类似阿拉伯数字“8”的形状(如附图9所示)。
通常,具有奇数聚合度的普通瓜环的水溶性较好,如常温下,五元瓜环(Q[5])及七元瓜环(Q[7])的溶解度为20-30mM,和β-环糊精(β-CD)的溶解度相当(16mM);而具有偶数聚合度的普通瓜环的水溶性较差,如六元瓜环(Q[6]),八元瓜环(Q[8])及十元瓜环(Q[10])的水溶性较差(<0.01mM),并且普通瓜环不溶于有机溶剂,仅能溶于甲酸、乙酸、盐酸等浓酸。相比较于普通瓜环十四元瓜环tQ[14]tQ[14]的溶解性能独特,它既能溶于水(~50mM),又能溶于二甲基亚砜(~20mM)。这一特性使得tQ[14]有着更广泛的用途。
氨基酸是生物体中非常重要的有机小分子,它的分子结构(例如手性和侧链结构)是生命中最基本的分子信息。手性氨基酸分子与功能有机分子的共组装能有效的将生物分子的结构信息转换为物理化学信号。对以氨基酸为底物的分子识别作用研究有助于更详细地了解t-RNA识别、转移某一特定氨基酸用于合成蛋白质的表达过程,及化学领域中其它多种分子识别作用机理。氨基酸是指含有氨基的羧酸。生物体内的各种蛋白质是由20种基本氨基酸构成的。除甘氨酸外均为α-氨基酸其中(脯氨酸是一种α-亚氨基酸)。除甘氨酸外,其它蛋白质氨基酸的α-碳原子均为不对称碳原子(即与α-碳原子键合的四个取代基各不相同),因此氨基酸可以有立体异构体,即可以有不同的构型(D-型与型两种构型)。
氨基酸中与羧基直接相连的碳原子上有个氨基,这个碳原子上连的基团或原子都不一样,称手性碳原子,当一束偏振光通过它们时,光的偏振方向将被旋转,根据旋光性的不同,分为左旋和右旋,即L系和D系,如D-丙氨酸是右旋的和丙氨酸是左旋的,恰似左、右手,互为镜像。而构成天然蛋白质的氨基酸都是L系。注意,一般称D型、L型。生物界各种蛋白质(除一些细菌的细胞壁中的短肽和个别抗生素外)几乎都是由氨基酸所构成的,含D-氨基酸的极少。
分子识别这一概念最初是被有机化学家、生物化学家用来在分子研究生物体系中的化学问题而提出的,分子识别通过变换和易位过程产生催化作用,在生物体系中,是理解酶反应、信息传递和不同介质间物种能量转移现象的信息来源,在分析化学领域则是构成分离、检测和定量测定的基础超分子包结物的形成则是建立在分子识别的基础之上。
基于氨基酸在生物界的重要作用,tQ[14]这一新型大环化合物的特性,以及杯芳烃,柱芳烃,冠醚等与氨基酸的超分子自组装,我们探索了tQ[14]与氨基酸之间的超分子自组装,及其分子识别性能的研究。
发明内容
本发明的目的在于,以一种新型大瓜环十四元瓜环tQ[14]为主体,选取20种氨基酸作为客体分子。由于十四元瓜环tQ[14]具有两个空腔结构的特点,以及特殊的溶解性。氨基酸这种小分子与十四元瓜环tQ[14]有着不同的作用位点,同样形成超分子配合物的结构就不同,不同的氨基酸作用模式不同,表现出的性质就不同,以及作用强弱不同,在识别氨基酸方面有着潜在的应用价值。
本发明的技术方案:一种十四元瓜环tQ[14]的应用,是用于识别氨基酸;所述氨基酸为赖氨酸或精氨酸。
前述的十四元瓜环tQ[14]的应用,其特征在于:所述应用的应用方法如下:
1)称取十四元瓜环tQ[14]3mg放入核磁管中,加入氘代的DMSO 0.5mL使其溶解,得十四元瓜环tQ[14]溶液;
2)称取5mg氨基酸放于冻存管中,加入氘代的DMSO 1mL使其溶解,得氨基酸溶液;
3)将步骤2)制备得到的氨基酸溶液用移液枪逐次加入核磁管中,每滴加一次就会出现一张相对应的核磁谱图,然后对核磁谱图进行观察;当核磁管中的十四元瓜环tQ[14]溶液:氨基酸溶液≦1:1时,图谱中出现一组信号峰A’、B’、β’、γ’、δ’,当核磁管中的十四元瓜环tQ[14]:氨基酸≧1:1时,若出现第二组质子峰A”、B”、β”、γ”、δ”,且该质子峰高度随氨基酸溶液量的增加而升高,则该氨基酸溶液中含赖氨酸;当核磁管中的十四元瓜环tQ[14]溶液:氨基酸溶液≦1:1时,图谱中氨基质子只有一组信号峰A′,B′,当核磁管中的十四元瓜环tQ[14]:氨基酸摩尔比≧1:1时,若氨基质子会出现另外一组峰A″,B″,C″,则该氨基酸溶液中含精氨酸;当核磁管中的十四元瓜环tQ[14]溶液:氨基酸溶液≦1:1时,图谱中出现一组信号峰,并且随着氨基酸溶液浓度的增加,只有峰的高度的增加,不会出现第二组质子峰,则该氨基酸溶液即不含赖氨酸,也不含精氨酸。
一种前述的十四元瓜环tQ[14]的应用,所述十四元瓜环tQ[14]的分子式为C84H84O28N56,结构式如附图1所示。
一种制备前述的十四元瓜环tQ[14]的方法,包括如下步骤:
(1)将苷脲和多聚甲醛按重量比2.5:1混合加入冰镇的浓盐酸介质中,在100-120℃加热回流3-5小时,冷却,得混合液;
(2)向混合液中边加蒸馏水边搅拌,然后静置沉淀,得淡黄色沉淀,然后抽滤,滤渣为多种瓜环的混合物,然后再向滤液中加入蒸馏水,重复上述步骤,直至滤液为淡黄色透明液体;
(3)将淡黄色透明液体浓缩并不断过滤除去白色沉淀,最终得到浓缩液;
(4)将浓缩液装填上硅胶G或Dowex阳离子型交换树脂柱,用水:乙酸为1:1的淋洗液淋洗,并不断向淋洗液中加入盐酸调节淋洗液的酸度,使淋洗液的酸度在0.1M-4M之间,最后分离得到十四元瓜环tQ[14]纯品。
本发明的有益效果:通过本发明提供的识别材料以及所述的方法,我们可以在20种氨基酸中识别出精氨酸和赖氨酸。
为进一步验证本发明具有该识别功能,发明人做了如下实验:
一、赖氨酸及精氨酸的识别验证:
方法如下:
1.称取十四元瓜环tQ[14]3mg放入核磁管中,加入氘代的DMSO 0.5mL使其溶解,得十四元瓜环tQ[14]溶液;
2.称取5mg氨基酸放于冻存管中,加入氘代的DMSO 1mL使其溶解,得氨基酸溶液;
3.将步骤(2)制备得到的氨基酸溶液用移液枪逐次加入核磁管中,每滴加一次就会出现一张相对应的核磁谱图,然后对核磁谱图进行观察:
3.1当核磁管中的十四元瓜环tQ[14]溶液:氨基酸溶液≦1:1时,图谱中出现一组信号峰A’、B’、β’、γ’、δ’,当核磁管中的十四元瓜环tQ[14]:氨基酸≧1:1时,若出现第二组质子峰A”、B”、β”、γ”、δ”(如附图3所示),且该质子峰高度随氨基酸溶液量的增加而升高,则该氨基酸溶液中含赖氨酸;
3.2当核磁管中的十四元瓜环tQ[14]溶液:氨基酸溶液≦1:1时,图谱中氨基质子只有一种A′,B′,当核磁管中的十四元瓜环tQ[14]:氨基酸摩尔比≧1:1时,氨基质子会出现另外一组峰A″,B″,C″。则该氨基酸溶液中含精氨酸(如附图4所示)。
3.3当核磁管中的十四元瓜环tQ[14]溶液:氨基酸溶液≦1:1时,图谱中出现一组信号峰,并且随着氨基酸溶液浓度的增加,只有峰的高度的增加,不会出现第二组质子峰,则该氨基酸溶液即不含赖氨酸,也不含精氨酸。
4.十四元瓜环tQ[14]与赖氨酸的等温量热滴定:
将十四元瓜环tQ[14]加入样品池中,向十四元瓜环tQ[14]中滴入赖氨酸,进行等温量热测定实验,实验结束后导出图谱如附图5所示。附图5的ITC数据图形为阶梯形,说明赖氨酸与十四元瓜环tQ[14]有两种作用模式,当赖氨酸少量时,是如附图7所示的模拟图;当赖氨酸逐渐增多,赖氨酸可以同时存在在十四元瓜环tQ[14]的两个空腔里面,即附图8所示的作用模式图。
5.十四元瓜环tQ[14]与精氨酸的等温量热滴定:
将十四元瓜环tQ[14]加入样品池中,向十四元瓜环tQ[14]中滴入精氨酸,进行等温量热测定实验,实验结束后导出图谱如附图6所示。附图6的ITC数据图形也为阶梯形,与附图5类似,说明精氨酸与十四元瓜环tQ[14]也有两种作用模式。
附图说明
附图1为主体分子十四元瓜环tQ[14]的结构图;
附图2为主体分子十四元瓜环tQ[14]的1H NMR图(500MHz,DMSO);
附图3为十四元瓜环tQ[14]与氨基酸的1H NMR滴定图(500MHz,DMSO);
附图4为十四元瓜环tQ[14]与精氨酸的1H NMR滴定图(500MHz,DMSO);
附图5为十四元瓜环tQ[14]与赖氨酸的等温量热滴定(ITC,溶剂为超纯水)图;
附图6为十四元瓜环tQ[14]与精氨酸的等温量热滴定(ITC,溶剂为超纯水)图;
附图7为十四元瓜环tQ[14]与赖氨酸的一种可能作用模拟图;
附图8为十四元瓜环tQ[14]与赖氨酸的另一种可能作用模拟图;
附图9为十四元瓜环tQ[14]的结构形状示意图。
具体实施方式
本发明的实施例:
实施例1:一种十四元瓜环tQ[14]的应用,是用于识别精氨酸,识别方法如下:
(1)称取十四元瓜环tQ[14]3mg放入核磁管中,加入氘代的DMSO0.5mL使其溶解,得十四元瓜环tQ[14]溶液;
(2)称取5mg氨基酸放于冻存管中,加入氘代的DMSO1mL使其溶解,得氨基酸溶液;
(3)将步骤(2)制备得到的氨基酸溶液用移液枪逐次加入核磁管中,每滴加一次就会出现一张相对应的核磁谱图,当核磁管中的十四元瓜环tQ[14]溶液:氨基酸溶液≦1:1时,图谱中出现一组信号峰A’、B’,当核磁管中的十四元瓜环tQ[14]:氨基酸≧1:1时,若出现第二组质子峰A”、B”、C”(如附图4所示),则说明该氨基酸为精氨酸,若为其他情况,则说明该氨基酸不是精氨酸。
实施例2:一种十四元瓜环tQ[14]的应用,是用于识别赖氨酸,识别方法如下:
(1)称取十四元瓜环tQ[14]3mg放入核磁管中,加入氘代的DMSO 0.5mL使其溶解,得十四元瓜环tQ[14]溶液;
(2)称取5mg氨基酸放于冻存管中,加入氘代的DMSO 1mL使其溶解,得氨基酸溶液;
(3)将步骤(2)制备得到的氨基酸溶液用移液枪逐次加入核磁管中,每滴加一次就会出现一张相对应的核磁谱图,当核磁管中的十四元瓜环tQ[14]溶液:氨基酸溶液≦1:1时,图谱中出现一组信号峰A’、B’、β’、γ’、δ’,当核磁管中的十四元瓜环tQ[14]:氨基酸≧1:1时,若出现第二组质子峰A”、B”、β”、γ”、δ”(如附图3所示),且该质子峰高度随氨基酸溶液量的增加而升高,则说明该氨基酸为赖氨酸。
实施例3:一种十四元瓜环tQ[14],其制备方法如下:
(1)将苷脲和多聚甲醛按重量比2.5:1混合加入冰镇的浓盐酸介质中,在100℃加热回流5小时,冷却,得混合液;
(2)向混合液中边加蒸馏水边搅拌,然后静置沉淀,得淡黄色沉淀,然后抽滤,滤渣为多种瓜环的混合物,然后再向滤液中加入蒸馏水,重复上述步骤,直至滤液为淡黄色透明液体;
(3)将淡黄色透明液体浓缩并不断过滤除去白色沉淀,最终得到浓缩液;
(4)将浓缩液装填上硅胶G阳离子型交换树脂柱,用水:乙酸为1:1的淋洗液淋洗,并不断向淋洗液中加入盐酸调节淋洗液的酸度,使淋洗液的酸度在0.1M-4M之间,最后分离得到十四元瓜环tQ[14]纯品。
实施例4:一种十四元瓜环tQ[14],其制备方法如下:
(1)将苷脲和多聚甲醛按重量比2.5:1混合加入冰镇的浓盐酸介质中,在120℃加热回流3小时,冷却,得混合液;
(2)向混合液中边加蒸馏水边搅拌,然后静置沉淀,得淡黄色沉淀,然后抽滤,滤渣为多种瓜环的混合物,然后再向滤液中加入蒸馏水,重复上述步骤,直至滤液为淡黄色透明液体;
(3)将淡黄色透明液体浓缩并不断过滤除去白色沉淀,最终得到浓缩液;
(4)将浓缩液装填上Dowex阳离子型交换树脂柱,用水:乙酸为1:1的淋洗液淋洗,并不断向淋洗液中加入盐酸调节淋洗液的酸度,使淋洗液的酸度在0.1M-4M之间,最后分离得到十四元瓜环tQ[14]纯品。
Claims (1)
1.一种十四元瓜环tQ[14]的应用,其特征在于:是用于识别氨基酸;所述氨基酸为赖氨酸或精氨酸。
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