CN112760090B - 一种钯离子探针及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种钯离子探针及其制备方法和应用，具体是将Cy7‑Cl、二(2‑甲基吡啶)胺和三乙胺在有机溶剂中充分反应，反应期间溶液颜色从绿色变为蓝色；反应完毕后产物用二氯甲烷和水萃取，将二氯甲烷层干燥后旋蒸后得到蓝色产物即为钯离子探针。本发明制备的钯离子探针属于比率型钯离子探针，其具备抗干扰性，检测精度高。能够用于对环境、生物体内微量甚至痕量钯离子的检测。
Description
技术领域
本发明属于分子探针技术领域，涉及一种钯离子探针及其制备和应用，更具体是涉及一种比率型钯离子荧光探针及其制备方法和应用。
背景技术
重金属在物理、化学和环境等科学中发挥着重要的作用,其中,钯金属由于其特殊的物理化学性质已被广泛应用在各个行业。然而,钯的大量使用不可避免会造成其在环境中的残留,引起环境重金属污染问题和人们的健康问题。因此,钯离子的检测尤为重要。研究人员发现健康人群每天机体的最大摄取量应该小于15μg。在制药行业中,药品中钯的残留量规定值为5～10mg/kg。大量负载钯及其化合物的排放会迅速提高土壤、植被、河流和海洋等不同环境中钯的含量,机体通过食物链富集效应对钯的过量摄入,吸收后的钯很快被运至肝脏、肾脏和脾等器官,会对身体造成非常严重的危害。经研究证实,在体内钯离子与氨基酸、蛋白质、DNA和维生素B6等生物大分子结合后发生作用,扰乱细胞正常的信号传导与生理活动等过程。宏观症状表现患哮喘、脱发、流产、恶心和其它严重的身体疾病的机率随着增大。除此之外,对于易受感染的人群,即使在受到很低的钯离子入侵下也会引起严重的过敏反应。
钯离子在水、土壤和沉积物等环境的样品中含量非常低,所以很难对它精确地检测。尽管传统的检测方法(电感耦合等离子体、原子吸收光谱、原子发射光谱和高效液相色谱法等)能得到较高的测量精度,但是需要昂贵的仪器与运行成本以及专业的操作技术人员。另外,在传统的检测方法中,为了避免污染或者损坏仪器,仍需要对样品进行繁杂的前处理。综上所述,这些因素将大大限制传统仪器在日常检测中的广泛应用。因此构建高效、高选择性、高灵敏性和短时间响应定量检测钯的方法是人们目前亟待解决的问题。
相比较而言,钯离子的荧光探针法不仅能够克服传统方法的不足,而且还能快速、准确对客体响应。因此,该检测方法近年来备受研究人员的关注。然而，荧光探针法仍然有穿透力差，分辨率低等缺点，使其在生物体内的应用受限。光声成像(Photoacousticimaging,PA)是近年来发展起来的一种新型光学成像技术，它融合了光学成像和超声成像的优势，表现出对深部组织的高分辨率、高对比度的成像能力，展现出了广阔的临床应用前景。目前所报道的钯离子探针大部分都是“turn-on”型荧光探针。“turn-on”型荧光探针检测钯离子时依赖于单一发射峰的变化，易受仪器效率、光散射、以及微环境的影响。相较而言，比率型荧光探针通过测定两个发射峰比值的变化对待测物进行检测，在一定程度上可避免上述干扰，从而可对生物样品中的钯离子进行更准确的追踪和定量。为了解决目前所遇到的问题和基于以上的分析，本提案设计和开发了高灵敏和高选择性光声比率型钯离子探针。
发明内容
针对目前钯离子检测方法存在的操作复杂、准确率低等问题，本发明设计和开发了高灵敏和高选择性光声比率型钯离子探针。以实现对钯离子定性和定量的准确、便捷的测量。
本发明公开了一种钯离子探针，具有如下式1所示的结构式：
进一步地，所述的钯离子探针为比率型荧光探针。
本发明还涉及一种钯离子探针化合物1的制备方法，具体采用以下路线制备：
进一步地，具体为：将Cy7-Cl、二(2-甲基吡啶)胺和三乙胺在有机溶剂中充分反应，反应期间溶液颜色从绿色变为蓝色；反应完毕后待反应体系冷却后，用二氯甲烷和水萃取，将二氯甲烷层干燥后旋蒸除去溶剂，过柱子后得到蓝色产物即为化合物1。其中，加入三乙胺是作为促进反应的一种碱，作用是让DPA去质子化，同时中和反应过程中产生的HCl，促进反应正向进行。
进一步地，所述的有机溶剂选自N,N-二甲基甲酰胺(DMF)。
进一步地，所述的反应温度为35-50℃，优选40℃，反应时间3-8个小时，优选5-6小时。
进一步地，所述的Cy7-Cl、二(2-甲基吡啶)胺和三乙胺的摩尔比为(1-2)：(1-2)：1，优选1：1：1。
进一步地，所述的有机溶剂的用量为10ml/1mmol Cy7-Cl。
进一步地，所述的萃取时二氯甲烷和水的体积比为(1-2)：10，优选1:10。
进一步地，所述的萃取后二氯甲烷层采用无水硫酸镁干燥。
另外，本发明还涉及一种钯离子探针的的应用，具体是将所述钯离子探针用于环境或生物体内钯离子的定性或定量检测。
进一步地，所述的将钯离子探针用于检测金属钯离子的方法包括将含Pd2+的待测样品加入到钯离子探针溶液中，然后目测该体系颜色的变化和/或测试该体系的紫外吸收变化。
进一步地，所述的钯离子探针溶液采用水和有机溶剂的混合溶剂。
进一步地，所述的有机溶剂选自二甲基亚砜(DMSO)。
进一步地，所述的水和有机溶剂的体积比为997:3至980:20，优选为995:5至990:10。
本发明的有益效果是：
1、本发明的钯离子探针，是以花菁为荧光基团，二(2-甲基吡啶)胺(DPA)为识别基团的化合物1。化合物1可以选择性地识别钯离子，不受其他金属离子的干扰。
2、随着钯离子的加入，化合物1溶液由蓝色变为绿色，溶液在770nm处的荧光逐渐减弱，在800nm处的荧光逐渐增强，在710nm处的吸收不断减小，在770nm处的吸收不断增大。同时在770nm处的光声信号也逐渐减弱，在860nm处的光声信号逐渐增强。化合物1和钯离子的配位比为1:1。
3、本发明的钯离子探针对钯离子表现出优越的高选择性，可以选择性识别钯离子，并与之结合改变溶液荧光吸收波长的变化。
4、本发明的钯离子探针对钯离子表现出优越的高灵敏性，通过化合物1对Pd2+的紫外-可见滴定实验能够发现化合物1的溶液，在λ＝710nm处和λ＝770nm处的紫外-可见吸收强度都与Pd2+的浓度在0-0.28当量的范围内有良好的线性关系。通过拟合的线性方程，根据国际纯粹与应用化学协会(IUPAC)的规定，检测限的计算公式DL＝3s/k,计算出探针对Pd2+的检测限为39.29nM。说明探针化合物1的灵敏度很高，可以用于Pd2+的痕量检测。
附图说明：
下面结合附图和具体实施方式来详细说明本发明；
图1为25μM探针化合物1溶液分别加入1.0当量的不同金属离子后溶液的紫外吸收图。
图2为为25μM探针化合物1溶液分别加入1.0当量的不同金属离子后溶液在770nm处的荧光比值F/F0(F是化合物1的荧光值，F0是加入不同金属离子后的荧光值)。
图3为不同浓度的Pd2+对25μM探针化合物1溶液的紫外-可见吸收强度曲线。
图4包括图4(a)、图4(b)和图4(c)，分别是为Pd2+对25μM探针化合物1溶液在700nm、770nm和860nm波长下的紫外-可见滴定曲线。
图5不同浓度的d2+对25μM探针化合物1溶液在770nm处的荧光强度曲线。
图6不同浓度的d2+对25μM探针化合物1溶液在800nm处的荧光强度曲线。
图7在老鼠体内加入化合物1溶液和Pd2+的光声信号变化图。
图8Pd2+对25μM探针化合物1溶液在860nm处的光声信号滴定曲线。
具体实施方式
以下结合实施例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。下面举例对本发明的内容进行详细的说明。
本发明实施方式涉及的钯离子探针为具有如下式1所示的结构式：
实施例1：化合物1的制备
本实施例也是采用一步法制备，按照如下路线进行制备：
具体工艺为：将Cy7-Cl、二(2-甲基吡啶)胺和三乙胺按照摩尔比1：1:1各取1mmol加入到10ml在有机溶剂DMF中充分反应4h，反应温度40℃，反应期间溶液颜色从绿色变为蓝色，反应完毕后待反应体系冷却至室温后，用二氯甲烷和水的体积比1:10进行萃取，使用二氯甲烷20ml和水200ml进行萃取，萃取分层后，将二氯甲烷层用1g无水硫酸镁干燥，干燥后旋蒸除去溶剂，得到约0.4g蓝色产物即为化合物1。
实施例2：化合物1的鉴定
对实施例1制备得到的蓝色化合物1进行核磁分析，核磁型号为Bruker AVANCE400，测试条件为室温，核磁共振数据为：
1H NMR(400MHz,CDCl3)δ8.72(d,J＝4.5Hz,2H),7.85(t,J＝6.5Hz,2H),7.67(d,J＝13.5Hz,2H),7.40(dd,J＝7.1,5.2Hz,2H),7.32(m,J＝7.5Hz,6H),7.15(t,J＝7.4Hz,2H),7.00(d,J＝7.9Hz,2H),5.90(d,J＝13.6Hz,2H),4.74(s,4H),4.01(q,J＝7.1Hz,4H),2.60(t,J＝6.4Hz,4H),1.94(dd,J＝12.7,6.5Hz,2H),1.45(s,12H),1.38(t,J＝7.2Hz,6H).13C NMR(101MHz,CDCl3)δ173.41,169.06,156.29,149.72,143.67,142.14,140.47,138.19,128.56,124.66,124.28,123.66,123.43,122.19,109.39,96.90,59.97,48.26,38.78,29.69,28.62,25.07,21.95,11.90.
对实施例1制备得到的蓝色化合物1进行质朴分析，质谱分析仪的设备型号为Orbitrap Fusion Tribrid mass spectrometer、测试条件为室温，蓝色化合物1的高分辨质谱分析结果为：HRMS m/z calculated for C46H52N5+:[(M+H)+]674.4217,found674.4223。
实施例3：化合物1对Pd2+的选择性。
在0.5％的二甲基亚砜(DMSO)纯水中，向化合物1的25μM溶液中分别加入1.0当量不同的金属阳离子(Pd2+，Ca2+,Cd2+,Co2+,Cr2+,Cs+,Cu2+,Fe2+,Fe3+,Ir3+,Mg2+,Mn2+,Ni2+,Pb2+,Pt2+,Re+,Rh3+,Zn2+)。由图1可以看出，当向化合物1溶液中加入1.0当量的Pd2+后，化合物1在710nm处的吸收完全消失，同时在770nm处出现一个新的吸收峰，而其他的金属离子对化合物1的吸收几乎没有影响。
同时，溶液颜色视觉上的变化为：当加入Pd2+后，溶液由蓝色变为绿色，当加入其他金属离子，溶液颜色几乎不变。
其次，试验了金属离子对溶液荧光的影响。向化合物1溶液(25μM)中加入1.0当量的Pd2+，溶液在770nm处的荧光减弱，同时在800nm处的荧光增强。当加入其他金属离子后，溶液的荧光基本上没有变化。从770nm处的F/F0(图2)，其中F是化合物1的荧光值，F0是加入不同金属离子后的荧光值，可以看出化合物1可以选择性识别Pd2+。
实施例4：化合物1对Pd2+的紫外-可见滴定实验
在0.5％的二甲基亚砜(DMSO)纯水中，向化合物1的25μM溶液中加入不同浓度的Pd2+，如图3所示，随着Pd2+浓度的增加(0-8μM)，溶液在λ＝710nm处的紫外-可见吸收逐渐减小，吸收峰逐渐红移，在λ＝770nm处的紫外-可见吸收逐渐增强。并且λ＝710nm处和λ＝770nm处的紫外-可见吸收强度都与Pd2+的浓度在0-0.28当量的范围内有良好的线性关系(图4)。通过拟合的线性方程，根据国际纯粹与应用化学协会(IUPAC)的规定，检测限DL(Detection Limit)的计算公式DL＝3s/k(s为空白样品的标准偏差，k为斜率),计算出探针对Pd2+的检测限为39.29nM。说明探针化合物1的灵敏度很高，可以用于Pd2+的痕量检测。
实施例5：化合物1对Pd2+的荧光滴定实验
在0.5％的DMSO纯水中，向化合物1的25μM溶液中加入不同浓度的Pd2+，如图5和图6所示，随着Pd2+浓度的增加(0-60μM)，溶液在λ＝770nm处的荧光强度逐渐降低，在λ＝800nm处的荧光强度逐渐增加。说明化合物1可以识别钯离子，并与之结合改变溶液荧光吸收波长的变化。
实施例6：在老鼠体内化合物1对Pd2+的光声成像实验
向老鼠体内注射化合物1溶液前后，对其进行紫外声光成像比较试验，发现注射化合物1之后，在770nm处观察到很强的光声信号，在860nm处几乎无光声信号。当加入Pd2+后，770nm处的光声信号消失，在860nm处出现很强的光声信号(图6)。同时860nm处的光声信号与Pd2+的浓度有良好的线性关系(图7)。说明化合物1溶液对Pd2+的选择性和紫外光相应的变化特性能够用在生物体内Pd2+的定性和定量检测中。
通过上述实施例，能够具体的说明本发明所制备得到的化合物1的具体结构，并且该化合物1能够对Pd2+具有高的选择性和灵敏性，可以选择性地识别钯离子，不受其他金属离子的干扰。随着钯离子的加入，化合物1溶液由蓝色变为绿色，溶液在770nm处的荧光逐渐减弱，在800nm处的荧光逐渐增强，在710nm处的吸收不断减小，在770nm处的吸收不断增大。同时在770nm处的光声信号也逐渐减弱，在860nm处的光声信号逐渐增强。因此，化合物1能够用作一种新的光声比率型钯离子探针，用于定性和定量测定溶液样品或生物体内Pd2+的含量情况。
本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (5)
1.一种钯离子探针的应用，其特征在于：将所述钯离子探针用于环境钯离子的定性或定量检测；所述钯离子探针具有如下式1所示的结构式：
2.根据权利要求1所述的应用，其特征在于：将钯离子探针用于检测金属钯离子的方法包括将含Pd2+的待测样品加入到钯离子探针溶液中，然后目测该体系颜色的变化和/或测试该体系的紫外吸收变化。
3.根据权利要求2所述的应用，其特征在于：所述钯离子探针溶液采用水和有机溶剂的混合溶剂。
4.根据权利要求3所述的应用，其特征在于：所述有机溶剂选自二甲基亚砜。
5.根据权利要求3或4所述的应用，其特征在于：所述水和有机溶剂的体积比为995:5至990:10。
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