CN115340478B - 一种席夫碱配体及其多核稀土配合物的制备方法和应用 - Google Patents
一种席夫碱配体及其多核稀土配合物的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种席夫碱配体及其多核稀土配合物的制备方法和应用,该配体由3,5‑二氯‑2‑羟基苯甲醛和3,3'‑二氨基‑4,4'‑二羟基二苯砜反应获得;还包括由该席夫碱配体制备获得的多核稀土配合物和其应用,所制备获得的配合物随着RNA的加入,荧光强度逐渐增强,荧光强度的增强和RNA的浓度呈线性关系,因此可以用于检测RNA的浓度,方法简单快速且稳定性较好。
Description
技术领域
本发明涉及RNA检测领域,特别涉及含稀土金属铽的多核配合物,特别涉及一种席夫碱配体及其多核稀土配合物的制备方法和应用。
背景技术
检测生物物种的分析技术的发展在临床和药剂学中具有重要意义。RNA是一种核苷酸单体的核酸聚合物,在编码蛋白质序列、调节基因表达和基因组组织中起着关键作用。许多传统分析技术,例如,液相色谱-质谱、阴离子交换液相色谱和电化学方法已用于检测RNA,但这些传统方法会受到使用试剂、缓冲液选择性差、灵敏度差、不兼容等问题的制约。因此目前,一些荧光传感器,如有机化学传感器、金纳米颗粒、碳纳米管已被用于检测RNA。
但使用荧光传感器时,一般会由于生物***中的自体荧光,导致传统的荧光分析方法在检测生物时很可能会因其被干扰,表现出灵敏度较差和实用性有限,因此有待改进。
发明内容
本发明旨在提供一种席夫碱配体及其多核稀土配合物的制备方法和应用,提出一种针对RNA的荧光检测的高灵敏度和实用性的解决方案。
为了实现本发明的目的,提供了如下技术方案:
一种席夫碱配体,所述的席夫碱配体的结构式为
一种席夫碱配体的制备方法,包括以下步骤:
(1)合成:使用无水乙醇作为反应溶剂,将3,5-二氯-2-羟基苯甲醛和3,3'-二氨基-4,4'-二羟基二苯砜进行反应,加热搅拌回流8小时后反应结束,冷却,过滤后的固体即为产物A;
(2)洗涤并干燥:用乙醇洗涤产物A,然后在真空下干燥,得到红色产物,即为席夫碱配体。
本发明进一步设置为,所述3,5-二氯-2-羟基苯甲醛和3,3'-二氨基-4,4'-二羟基二苯砜的摩尔比为2:1。
一种多核稀土配合物的制备方法,包括如下步骤:
S1、席夫碱配体的合成:使用无水乙醇作为反应溶剂,将3,5-二氯-2-羟基苯甲醛和3,3'-二氨基-4,4'-二羟基二苯砜以摩尔比为2:1进行反应,加热搅拌回流8小时后反应结束,冷却,过滤,过滤后的固体用乙醇洗涤,然后在真空下干燥,即为席夫碱配体;
S2、多核稀土配合物的合成和分离:将S1步骤制备的席夫碱配体与六水硝酸锌、五水合硝酸铽以摩尔比1:1:1进行反应,以无水乙醇,氯仿和DMF做反应溶剂,80℃加热搅拌回流30min,反应结束后静置,冷却后过滤得到滤液;
S3、单晶培养:将将步骤S2中的滤液转移至20mL试管内,将试管置于***的密封瓶中,等待***慢慢扩散于试管内(试管的上端要高于***的液面高度,然后***在密封瓶内挥发,慢慢扩散至试管内),7天后得到橙黄色晶体即为该多核稀土配合物。
本发明进一步设置为,所述多核稀土配合物的化学经验式为:
[Zn6Tb5L5(HL)(NO3)4(DMF)6(EtOH)2(H2O)6]。
本发明进一步设置为,所述多核稀土配合物在293K温度下,在X-射线单晶衍射仪上,用经石墨单色器单色化的Mo Kα射线以ω-θ扫描方式收集衍射数据,其晶体属于单斜晶系,空间群为C2/c;
其晶胞参数为:
α=90.00°;
β=101.438(3)°;
γ=90.00°。
本发明进一步设置为,所述步骤S2中的反应溶剂,无水乙醇、氯仿和DMF的体积比为2:2:3。
本发明进一步设置为,所述多核稀土配合物的晶体体积为
本发明进一步设置为,所述多核稀土配合物用于检测RNA,RNA的浓度与配合物的荧光强度呈现线性关系,且显示出金属铽在545nm处的特征发射峰。
综上所述,上述技术方案中具有以下有益效果:
(1)本发明设计的席夫碱配体是为了增强稀土铽对RNA特异性的荧光性能,多核稀土配合物的荧光强度随着RNA的加入逐渐增加,呈现线性关系,可以用于检测RNA的浓度。
(2)本申请创造性的实现了异质金属d-4f配合物对RNA TGL检测。异质金属d-4f配合物可能显示出优异的发光性能,因为其具有d-嵌段金属离子(例如Cd2+、Zn2+、Ru2+、Pt2+和Cr2+)的光吸收单元可以有效地敏化镧系元素发射。稀土相关时间门控发光(TGL)可以排除短寿命背景信号,并通过延迟信号记录提高信噪比。从而克服传统的荧光分析方法在检测生物物种时可能具有较差的灵敏度和有限的实用性的问题。
(3)本发明提供席夫碱配体的结构式,通过实验发现,该配体制备的含稀土金属铽的多核稀土配合物,显示不出金属铽(Tb)的特征发射峰。但在加入RNA之后,荧光强度增强,且随着加入的浓度增加,荧光逐渐增强且显示出Tb在545nm处的特征发射峰。经过实验,RNA的浓度与配合物的荧光强度呈现较好的线性关系,可以用于检测RNA的浓度,也可以测出未知的RNA浓度大小,方法简单快速且稳定性较好。
附图说明
图1为一种席夫碱配体的核磁共振1H NMR谱,条件为DMSO-d6,500MHz。
图2为一种席夫碱配体的核磁共振13C NMR谱,条件为DMSO-d6,125MHz。
图3为多核稀土配合物的单晶衍射图。
图4为多核稀土配合物逐渐加入RNA后的荧光滴定光谱图和线性拟合图;
图5是多核稀土配合物特异性感应RNA的筛选试验图。
具体实施方式
下面结合附图和实施例,对本发明进一步详细说明。
本发明为了实现背景技术的目的,提供了一种席夫碱配体,该席夫碱配体的结构式为:
本发明还提供了上述席夫碱配体制备方式,其具体实施方式为:
(1)合成:称取3,3'-二氨基-4,4'-二羟基二苯砜2.8030g放入250mL圆底烧瓶中,加入30mL无水乙醇并搅拌使其溶解;将3.8202g 3,5-二氯-2-羟基苯甲醛加入上述溶液,加热搅拌回流8h后,待冷却后进行过滤获得固体产物A;
(2)洗涤并干燥:用乙醇洗涤产物A三次,然后在真空下干燥,得到红色产物,该红色产物即为席夫碱配体。产率为93%。
其中反应的化学方程式为:
将获得席夫碱配体的进行核磁共振数据为:
1H NMR(DMSO-d6,500MHz):14.75(s,2H),11.23(s,2H),9.17(s,2H),8.08(d,J=2.2Hz,2H),7.80–7.73(m,4H),7.71(d,J=2.6Hz,2H),7.16(d,J=8.5Hz,2H)。
13C NMR(125MHz,DMSO-d6):162.06,157.04,155.39,135.55,132.62,132.43,130.63,128.05,122.14,121.44,120.25,118.95,117.16。
本发明还提供了一种多核稀土配合物制备方式为,其具体实施方式为:
(1)S1、席夫碱配体的合成,和前文席夫碱配体制备方式相同不再赘述;
(2)S2、多核稀土配合物的合成和分离:取席夫碱配体0.1248g放入50mL圆底烧瓶,加入4mL无水乙醇,4mL氯仿和6mL DMF做反应溶剂,加热搅拌并使其溶解,往上述溶液加入0.0595g六水合硝酸锌和0.0870g五水合硝酸铽,80℃加热搅拌回流30min,反应结束后静置,冷却后过滤,冷却后过滤得到滤液;
(3)S3、单晶培养:将将步骤S2中的滤液转移至20mL试管内,将试管置于***的密封瓶中,等待***慢慢扩散于试管内(试管的上端要高于***的液面高度,然后***挥发,慢慢扩散至试管内),7天后得到橙黄色晶体即得到多核稀土配合物。
进一步的,步骤S2中的反应溶剂,无水乙醇、氯仿和DMF的体积比为2:2:3。
获得的晶体单晶衍射图如图3所示,其晶体数据如下:
晶体典型键长数据如表一所示:
表一:晶体典型键长
晶体典型键角(°)数据如表二所示:
表二:晶体典型键角(°)
本发明还提供了该种多核稀土配合物检测RNA中的具体应用,包括:
将多核稀土配合物用DMF溶剂配制成浓度为10μM的溶液,取100μL的配合物溶液加入黑底96孔板中作为空白样品,用酶标仪扫描出初始荧光谱图,将RNA配制成60ng/μL的溶液,取2μL RNA溶液加入空白样品中,几秒后扫描出荧光谱图,继续重复此次操作,直至荧光强度不再上升后停止。
平行测试三组数据,将荧光谱图叠加后得到荧光滴定光谱图,即图4,可以看出随着RNA的浓度逐渐增加,545nm处的荧光强度逐渐上升,即为金属铽在545nm处的特征发射峰。
同时将数据处理为(I/I0-1)时,发现与RNA浓度存在良好的线性关系,如图4所示,拟合系数R2为0.9909大于0.99,线性较好,斜率为6.0557。由此可以得出,RNA的浓度与配合物的荧光强度呈现线性关系,因此在实际应用中,该多核稀土配合物可以测出未知的RNA浓度大小。
图5为在相同的条件下,选用CMP、TMP、U(URACIL尿嘧啶)、A(ADENINE腺嘌呤)、C(CYTOSINE胞嘧啶)、T(THYMINE胸腺嘧啶)、G(GUANINE鸟嘌呤)、Phe、Asp、Gly、K+、Na+、NH4 -、Mg2+、I-、Cl-、Cl04 -、OAc-作为对比例,在不同浓度下多核稀土配合物的特异性识别筛选试验。结果显示:多核稀土配合物对RNA具备特异性感应。
以上所述仅是本发明的优选实施方式,本发明的保护范围并不仅局限于上述实施例,凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理前提下的若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种席夫碱配体,其特征在于,所述的席夫碱配体的结构式为
2.一种席夫碱配体的制备方法,其特征在于,包括以下步骤:
(1)合成:使用无水乙醇作为反应溶剂,将3,5-二氯-2-羟基苯甲醛和3,3'-二氨基-4,4'-二羟基二苯砜进行反应,加热搅拌回流8小时后反应结束,冷却,过滤后的固体即为产物A;
(2)洗涤并干燥:用乙醇洗涤产物A,然后在真空下干燥,得到红色产物,即为席夫碱配体。
3.根据权利要求2所述的一种席夫碱配体的制备方法,其特征在于,所述3,5-二氯-2-羟基苯甲醛和3,3'-二氨基-4,4'-二羟基二苯砜的摩尔比为2:1。
4.一种多核稀土配合物的制备方法,其特征在于,包括如下步骤:
S1、席夫碱配体的合成:使用无水乙醇作为反应溶剂,将3,5-二氯-2-羟基苯甲醛和3,3'-二氨基-4,4'-二羟基二苯砜以摩尔比为2:1进行反应,加热搅拌回流8小时后反应结束,冷却,过滤,过滤后的固体用乙醇洗涤,然后在真空下干燥,得到红色产物,即为席夫碱配体;
S2、多核稀土配合物的合成和分离:将步骤S1制备的席夫碱配体与六水硝酸锌、五水合硝酸铽以摩尔比1:1:1进行反应,以无水乙醇,氯仿和DMF做反应溶剂,80℃加热搅拌回流30min,反应结束后静置,冷却后过滤得到滤液;
S3、单晶培养:将步骤S2中的滤液转移至试管内,将试管置于***的密封瓶中,等待***慢慢扩散于试管内,7天后得到橙黄色晶体即为该多核稀土配合物。
5.根据权利要求4所述的一种多核稀土配合物的制备方法,其特征在于,所述多核稀土配合物的化学经验式为:
[Zn6Tb5L5(HL)(NO3)4(DMF)6(EtOH)2(H2O)6]。
6.根据权利要求4所述的一种多核稀土配合物的制备方法,其特征在于,所述多核稀土配合物在293K温度下,在X-射线单晶衍射仪上,用经石墨单色器单色化的MoK α射线以ω-θ扫描方式收集衍射数据,其晶体属于单斜晶系,空间群为C2/c;
其晶胞参数为:
α=90.00°;
β=101.438(3)°;
γ=90.00°。
7.根据权利要求4所述的一种多核稀土配合物的制备方法,其特征在于,所述步骤S2中的反应溶剂,无水乙醇、氯仿和DMF的体积比为2:2:3。
8.根据权利要求4所述的一种多核稀土配合物的制备方法,其特征在于,所述多核稀土配合物的晶体体积为
9.根据权利要求4-8任一所述的一种多核稀土配合物的应用,其特征在于:
所述多核稀土配合物用于检测RNA,RNA的浓度与配合物的荧光强度呈现线性关系,且显示出金属铽在545nm处的特征发射峰。
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