CN110596082B - 用于检测痕量铀酰离子的探针及基于其的便携式ecl检测器 - Google Patents
用于检测痕量铀酰离子的探针及基于其的便携式ecl检测器 Download PDFInfo
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Abstract
本发明涉及一种用于痕量铀酰高灵敏度、高选择性、便携式的检测方法,具有11pM/2.6ppt的超低检测限,可用于对农副产品、食品、环境等方面的铀含量进行精确监控。同时,测试仪器可进行小型化、低成本化,实现野外的高精度便携式测量。本发明合成了一种新型聚集诱导发光(AIE)活性的共轭聚合物并制备成共轭聚合物点(Pdots),并修饰DNA或RNA作为铀酰的吸附配体,以此开发了新型的铀酰响应的电致化学发光(ECL)探针,该探针具有较好的生物相容性本发明将ECL技术运用到铀酰离子的检测中,该方法具有极高的灵敏度。本发明提供了一种具有AIE活性的铀酰离子探针,通过ECL技术用于痕量铀酰的便携式精确监控。
Description
技术领域
本发明涉及铀酰离子检测领域,尤其涉及一种用于对农副产品、食品、环境等方面痕量铀酰离子进行精确监控的探针及基于其的便携式ECL检测器。
背景技术
近些年来,随着核技术越来越广泛的应用,锕系元素铀(U)及其化合物已成为一类重要的工业材料,广泛地应用在民用核燃料、军事核工业等领域。铀化合物的毒性主要表现在放射性毒性及重金属毒性,其主要危害骨骼、循环系统及泌尿系统,并可诱发肺癌。因此核泄漏及铀矿尾矿引起的铀化合物的污染会引起严重的社会及环境问题,从而成为环境科学和能源科学领域的重要课题。由于铀元素在环境中主要以铀酰离子的形式存在(如UO2(NO3)2、UO2(OH)-及UO2(CO3)3 4-等),因此,开发具有高灵敏度,高选择性的铀酰探针,实现对农副产品、食品、环境等方面的痕量铀酰进行简便而精确的监控在近年来引起了广泛的关注。
目前广泛应用的铀酰离子检测方法主要有荧光探针法、吸收光谱法、比色法、电化学法、ICP-MS等。
荧光探针法是使用量子点(QDs)、有机小分子荧光探针、共轭有机聚合物等荧光分子对铀酰浓度进行检测。QDs虽然具有荧光量子产率高等优势,但是其含有Cd等重金属元素,具有明显的生物毒性,对环境有一定潜在威胁。目前已有的小分子有机荧光探针及共轭高分子荧光探针则大部分具有聚集诱导淬灭(ACQ)性质,在水溶液中存在荧光量子产率大幅降低的问题,对自然环境中的铀酰离子检测具有不利影响。吸收光谱法是使用某些配体在与铀酰离子配位前后吸收光谱的变化对铀酰离子进行检测。比色法是利用相应配体在与铀酰离子配位前后其颜色的变化对铀酰离子进行可视化的检测。比色法虽然直观,但是其难度较大,容易受到环境的干扰,选择性也存在问题。电化学法则利用循环伏安法(CV),通过配体与铀酰离子配位之后对氧化还原波形的改变进行铀酰离子检测。
现有的铀酰离子检测方法当中,其检测限仍旧偏高,灵敏度偏低,检测限接近或高于正常环境中的铀酰浓度,无法对环境中的铀酰进行实时的精确监控。而ICP-MS虽然具有很高的精确度,但是其仪器昂贵,设备笨重,成本较高,无法便携使用。因此提高检测灵敏度和仪器小型化也是目前亟待解决的问题。
发明内容
为解决目前铀酰离子检测当中存在的生物相容性低、受环境影响大、检测限偏高、探针在水溶液中的光量子产率较低等缺陷,本发明的目的是提供一种用于检测痕量铀酰离子的探针及基于其的ECL检测器。而相对于ICP-MS而言,ECL仪器成本低、体积小,甚至还可以作进一步的小型化设计,因此也解决了便携测量的问题。本发明提供了一种具有AIE活性的铀酰离子探针,通过ECL技术实现了对环境中痕量铀酰的高灵敏度、高选择性和便携式检测。
本发明的第一个目的是提供一种用于检测痕量铀酰离子的探针,其包括具有AIE活性的共轭聚合物量子点及修饰在共轭聚合物量子点表面的核苷酸序列,核苷酸序列为DNA和/或RNA序列,所述共轭聚合物量子点中的共轭聚合物的结构式如式(1)所示:
其中,R1为含有1-20个碳原子的烷基、烷氧基、取代烷基或取代烷氧基,所述取代烷基和取代烷氧基中的取代基独立地选自胺基、羧基、羟基、醚键、卤素、磷酸基、醛基、磺酸基、硫醚键、酯基、酰胺基、希夫碱、肟基、芳香基、砜基和亚砜基中的一种或几种;
n=2-300。
优选的,R1为含有1-20个碳原子的烷基;更优选地,R1为正辛基。
进一步地,共轭聚合物量子点的粒径为10nm-100nm。
进一步地,核苷酸序列的长度为5-100bp。
优选的,核苷酸序列为DNA序列。
本发明还提供了一种上述用于检测痕量铀酰离子的探针的制备方法,包括以下步骤:
(1)将式(2)所示的第一AIE活性单体与式(3)所示的第二AIE活性单体通过Suzuki偶联聚合反应聚合,得到式(1)所示的共轭聚合物;式(2)-(3)如下:
其中,R1为含有1-20个碳原子的烷基、烷氧基、取代烷基或取代烷氧基,所述取代烷基和取代烷氧基中的取代基独立地选自胺基、羧基、羟基、醚键、卤素、磷酸基、醛基、磺酸基、硫醚键、酯基、酰胺基、希夫碱、肟基、芳香基、砜基和亚砜基中的一种或几种;
R2为频哪醇硼酸酯基、三烷基锡基、硼酸基、卤素、乙炔基或乙烯基;
R3为卤素、频哪醇硼酸酯基、三烷基锡基、硼酸基、乙炔基或乙烯基;
(2)将所述共轭聚合物的醇溶液注入水中,去除纯溶剂后,得到共轭聚合物量子点的水溶液;
(3)将所述共轭聚合物量子点的水溶液与聚乙二醇和缓冲液混合,然后向其中加入5’端修饰有氨基的核苷酸序列和交联剂,核苷酸序列为DNA序列和/或RNA序列混合均匀后反应,得到所述用于检测痕量铀酰离子的探针。
优选地,在步骤(1)中,R1为正辛基,R2为频哪醇硼酸酯基,R3为卤素。
进一步地,在步骤(2)中,共轭聚合物的醇溶液的浓度为0.01-1.00mg/mL。
进一步地,在步骤(2)中,共轭聚合物量子点的水溶液的浓度为0.01-1.00mg/mL。
进一步地,在步骤(2)中,共轭聚合物量子点的粒径为10nm-100nm。
进一步地,在步骤(3)中,聚乙二醇的分子量为100-100000。
进一步地,在步骤(3)中,缓冲液为HEPES(4-羟乙基哌嗪乙磺酸)缓冲液。
进一步地,在步骤(3)中,交联剂为EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)。
进一步地,在步骤(3)中,核苷酸序列为DNA序列。优选地,自3’端至5’端,DNA的核苷酸序列为:taa ttc tgt gta tgt gtc tgt。
本发明的第三个目的是提供一种用于检测痕量铀酰离子的便携式ECL检测器,ECL检测器在胺类反应试剂的存在下检测痕量铀酰离子包括一工作电极,所述工作电极上修饰有本发明的上述用于检测痕量铀酰离子的探针。
进一步地,工作电极为GCE电极或金电极。
进一步地,ECL检测器包括电信号施加单元、发光池、光电倍增管、信号放大和处理单元;所述电信号施加单元的正极和负极分别连接所述工作电极和对电极,所述发光池用于容置待检测液和胺类反应试剂,所述工作电极和对电极置于所述发光池中,所述光电倍增管正对所述发光池设置,所述光电倍增管及信号放大和处理单元电连接。
进一步地,铀酰离子的检测限为11pM/2.6ppt。
进一步地,胺类反应试剂的浓度为25mM。优选地,胺类反应试剂为三级胺。更优选地,胺类反应试剂为三正丙胺(TPrA)。
进一步地,电信号施加单元为恒压直流电源。
进一步地,电信号施加单元所施加的电压为0.50V-2.00V。
本发明中的铀酰离子探针和基于其的便携式ECL检测器可用于对农副产品、食品、环境等方面痕量铀酰离子的精确监控。
本发明的第四个目的是提供一种检测痕量铀酰离子的方法,采用本发明的上述用于检测痕量铀酰离子的ECL检测器,包括以下步骤:
(1)利用所述ECL检测器测试铀酰离子标准溶液的ECL信号强度,根据检测结果,建立铀酰离子浓度与ECL信号强度之间的相互关系图;
(2)利用所述ECL检测器检测待测液的ECL信号强度Ax,所述待测液中的铀酰离子含量未知,根据ECL信号强度Ax在所述相互关系图的对应关系确定待测液中的铀酰离子浓度。
借由上述方案,本发明至少具有以下优点:
本发明的用于检测痕量铀酰离子的探针中包括共轭聚合物量子点(Pdots)及修饰于其上的核苷酸,其中,共轭聚合物量子点由一种新型聚集诱导发光(AIE)活性的共轭聚合制备得到,核苷酸中的磷酸基团作为铀酰的吸附配体,以此开发了新型的铀酰响应的电致化学发光(ECL)探针。本发明的探针利用Pdots的AIE特性,解决了传统铀酰发光探针在水溶液中发光淬灭的缺陷。该共轭聚合物不含有重金属离子,因此具有较好的生物相容性。本发明的ECL探针同时具有极高的铀酰离子选择性。
ECL技术具有无背景信号干扰、操作简便和重现性好等优点,大大提高了铀酰离子检测的灵敏度。因此,本发明实现了痕量铀酰离子的高灵敏检测,其检测限达11pM/2.6ppt,比已知的小分子及共轭聚合物有机发光探针降低了至少两个数量级,并实现了对海水及湖水中痕量铀酰离子的精确检测。基于本发明的探针所设计的便携化的ECL检测器实现了野外快捷精确的痕量铀酰离子检测。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1是本发明一种具有AIE活性的共轭聚合物的合成路线示意图;
图2为共轭聚合物THF溶液的紫外吸收光谱和荧光光谱测试结果;
图3为共轭聚合物的循环伏安图;
图4为Pdots的AFM和DLS测试结果;
图5为ECL仪器的结构示意图;
图6为Pdots的ECL信号测试结果及ECL光谱图;
图7为Pdots在修饰DNA单链之前及(B)之后的zeta电位;
图8为ECL检测器的结构示意图;
图9为不同浓度的铀酰(UO2 2+)存在下的Pdots ECL信号及ECL强度与铀酰浓度的对数值的校准曲线;
图10证明了铀酰到Pdots的RET过程;
图11图示了干扰离子及铀酰的ECL信号强度。
附图标记说明:
1:工作电极,2:对电极,3:恒压直流电源,4:导线,5:发光池,6:光电倍增管,7:电信号施加单元,8:信号放大和处理单元。
具体实施方式
下面结合附图和实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1
本实施例提供了一种具有AIE活性的共轭聚合物的制备方法,其合成路线图如图1所示,具体步骤如下:
化合物4的合成参照文献:ACS Appl.Mater.Interfaces2017,9,11546-11556.单体M-2的合成方法参照文献:Polym.Chem.2015,6,5070-5076。
单体M-1的合成:将化合物4(2.28g,3mmol)、化合物5(3.08g,12mmol)、醋酸钾(2.40g,12mmol)、Pd(dppf)2Cl2(0.3g,5%mmol)加入反应瓶,用60mL DMF溶解,在Ar气氛下加热至120℃反应24h。将反应液灌入200mL水中,以乙酸乙酯萃取,有机相水洗两次,硅胶柱层析纯化(流动相:乙酸乙酯:石油醚=1:30),得产物1.61g,产率64.0%。其NMR测试结果如下:
1H NMR(400MHz,CDCl3)δ7.52(d,J=8.1Hz,4H),7.00(d,J=8.1Hz,4H),6.90(d,J=8.7Hz,4H),6.60(d,J=8.8Hz,4H),3.86(t,J=6.6Hz,4H),1.81-1.66(m,4H),1.50-1.37(m,5H),1.37-1.24(m,40H),0.88(t,J=6.8Hz,6H).13C NMR(100MHz,CDCl3)δ157.80,147.35,141.33,138.76,135.96,134.10,132.61,130.84,113.55,83.66,67.78,31.82,29.40,29.33,29.24,26.09,24.90,22.67,14.11。
共轭聚合物的合成:将M-1(0.16g,0.19mmol)、M-2(0.10g,0.19mmol)、Pd(PPh3)4(0.04g,5%e.q.)、K2CO3(1.3g)溶于15mL甲苯、8mL乙醇和4mL水,回流3d,取有机相用Na2SO4干燥,旋干后用少量THF溶解,滴入100mL正己烷中,过滤得共轭聚合物0.10g,产率53.8%。其1H NMR测试结果如下:
1H NMR(400MHz,CDCl3)δ8.06-7.99(m,3H),7.73-7.63(m,5H),7.50-7.38(m,8H),7.12-7.11(m,2H),6.98-6.97(m,2H),6.77-6.76(m,3H),6.66-6.64(m,3H),6.53-6.51(m,3H),3.89-3.86(m,4H),2.88(s,6H),1.77-1.72(m,6H),1.42-1.41(m,3H),1.29-1.24(m,15H),0.87-0.86(m,6H).GPC data:Mw=19060,Mn=16720,PDI=1.14。
上述制备的共轭聚合物的光电性能测试结果如图2所示,其中图2A、B分别为共轭聚合物的紫外吸收光谱以及共轭聚合物在不同水含量THF-水混合溶剂中的荧光光谱。图2B中,激发光波长为370nm,各溶液中共轭聚合物浓度为1×10-5mol/L,图2B中百分比指的是水占整个溶剂的体积百分数。如图2A所示,共轭聚合物在363nm处表现出共轭骨架的吸收峰,421nm处的肩峰属于电子供体-受体(D-A)结构所引起的分子内电子转移(ICT)。如图2B,共轭聚合物在370nm的激发光下共轭聚合物在不同水含量的THF-水混合溶剂中具有明显的近红外区的AIE行为。图3为共轭聚合物在0.1M Bu4NBF4 CH2Cl2溶液中以GCE电极测定的循环伏安图(CVs),图中+0.487V和+0.815V两处氧化峰可以归属为TPE单元的氧化峰。其还原峰出现在-1.711V,可以计算出其LUMO、HOMO、带隙值分别为-2.849eV、-4.824eV和1.975eV。通过发射光谱计算的光学带隙为1.890eV(Eg=1239.8/λ(eV))。
实施例2
本实施例提供了一种用于检测痕量铀酰离子的探针的制备方法,具体步骤如下:
将实施例1制备的共轭聚合物溶于乙醇中,浓度为0.15mg/mL,然后将1mL共轭聚合物的溶液注入10mL水中,将乙醇通过减压蒸馏去除,得到10mL Pdots水溶液。
将含有PEG(5%w/v)水溶液、HEPES(1M)缓冲液加入到Pdots水溶液中(0.15mg/mL)中,然后向所得混合液中加入NH2-DNA(1μM)和EDC(5mg/mL)并震荡0.5h,得到DNA-Pdots。其中,DNA的序列如下:3’-taa ttc tgt gta tgt gtc tgt-5’-NH2。
本实施例中,所用的DNA序列中的碱基序列可随意选择,还可以替换为RNA序列。
图4(A)为Pdots的AFM图;图4(B)为AFM图中黑线的相对高度;图4(C)为Pdots的DLS测试结果,AFM图谱及DLS数据均显示Pdots的平均粒径在10nm左右。
将Pdots修饰于工作电极上,组装成简易ECL仪器,如图5所示,将经过修饰的工作电极插入发光池中,注入25mM三正丙胺(TPrA)缓冲液或0.1M pH=7.4的PBS缓冲液。同时,插入对电极和参比电极,然后以DNA-Pdots修饰的电极为工作电极进行试验,测试条件:扫速:100mV/s,PMT:600V,λex=370nm。当电位扫至+0.880V时开始出现光信号,电位扫至+1.264V时,光信号最强。
如图6A,Pdots在湮灭状态下不显示明显的ECL信号,仅当加入TPrA作为反应试剂时,它表现出明显的阳极ECL发射信号。ECL信号给出发射峰值为+1.264V,起始电位为+0.880V。
ECL机理如下:
TPrA–e–→TPrAH·+ (1)
TPrAH·+–H+→TPrA· (2)
Pdots–e–→Pdots·+ (3)
Pdots·++TPrA·→Pdots*+Pr2N+HC=CH2CH3 (4)
Pdots*→Pdots+hv (5)
如图6B,Pdots的ECL光谱与其荧光光谱基本重合,这说明其ECL发射机制遵从带隙发射模型。
向Pdots上修饰单链DNA,以DNA链上的磷酸基团作为结合铀酰的配体,并通过从铀酰离子到Pdots的共振能量转移(RET)过程增强Pdots的ECL信号,从而实现对铀酰的高灵敏度、高选择性检测。图7为Pdots在修饰DNA单链(A)之前及(B)之后的zeta电位,在DNA链修饰之前,Pdots的zeta电位为-22.1mV。DNA链修饰后,电位值增加至-37.5mV,表明DNA的成功修饰。
如图8所示,本实施例还提供了一种用于检测痕量铀酰离子的ECL检测器,ECL检测器由电信号施加单元、发光池、光电倍增管、信号放大和处理单元组成。电信号施加单元的正极和负极分别连接工作电极和对电极,工作电极上修饰有本发明的上述用于检测痕量铀酰离子的探针。发光池用于容置待检测液和胺类反应试剂,工作电极和对电极置于发光池中,光电倍增管正对发光池设置,光电倍增管及信号放大和处理单元电连接。
其中,工作电极的修饰方法如下:
使用Al2O3粉对GCE电极进行打磨抛光,将实施例2得到的DNA-Pdots与不同浓度的铀酰溶液、自然水样或者干扰离子溶液混合,将GCE电极浸泡于上述混合液中,使得DNA-Pdots修饰在GCE电极上。
图9(A)为不同浓度的UO2 2+存在下的Pdots ECL信号;图9(B)为ECL强度与铀酰浓度的对数值的校准曲线。扫描速率:100mV/s,PMT:600V。如图9A所示,随着铀酰浓度从0.05nM增加到100nM,Pdots的ECL信号也逐渐增强。ECL信号的强度I与铀酰浓度C的对数值在该区域中表现出明显的线性(图9B,I=8109.7+4108.3lgC,R2=0.996)。经计算得到检测限为11pM/2.6ppt,比目前所知的铀酰发光探针低至少两个数量级,特别是与已知的AIE活性探针相比。
为了证明从铀酰到Pdots的RET过程,图10A为含有25mM TPrA的0.1M pH 7.4PBS中铀酰离子的ECL信号测试结果,图10(B)为共轭聚合物THF溶液的紫外-可见光谱(a)以及含有25mM TPrA的0.1M pH 7.4PBS中铀酰的ECL光谱(b)。扫速:100mV/s,PMT:600V。如图10A,在25mM TPrA作为共反应剂的条件下,铀酰在阳极区域显示出明显的ECL信号,在+1.120V处产生发射峰,起始电位为+0.791V。UO2 2+离子的ECL光谱在大约500nm处出现发射峰,并且在400到560nm的区域内与共轭聚合物的UV-vis吸收光谱重叠,这证明了从铀酰到Pdots的RET过程(图10B)。
为了证明本发明的探针的选择性,选择几种干扰离子与UO2 2+离子进行比较。其中,K+、Ca2+、Na+,Mg2+和Sr2+是海水中含有的主要阳离子。Eu3+是一种具有ECL信号的离子,其与UO2 2+离子的吸附和检测具有密切关系。Cs+是经常与UO2 2+共存的离子,而Cu2+、Fe3+和Pb2+作为环境中重金属的代表。与浓度为0.5nM或5nM的UO2 2+离子相比,这些干扰离子即使在50nM溶液中也几乎没有明显的信号增强(图11),这种探针的选择性可归因于两点:i).DNA链上的磷酸基团对UO2 2+离子的特异性吸附以及ii).除Eu3+以外的干扰离子的不发光的性质。该实验结果证明了基于Pdots的UO2 2+ECL探针的优异选择性。
为了进一步证实这种探针的实用性,本实施例测量了一些实际水样中铀酰离子的浓度,包括渤海水(天津市)、骆马湖水(江苏省徐州市)、独墅湖水(江苏省苏州市)和千岛湖水(浙江省杭州市)(表1)。可以观察到ECL测量结果与ICP-MS结果非常接近,表明该探针对铀酰的检测具有高灵敏度和高选择性。此结果还可以证明这种新型ECL探针在环境应用中的实用性。
表1.铀酰浓度的ECL检测结果和ICP-MS检测结果对比
以上仅是本发明的优选实施方式,并不用于限制本发明,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。
Claims (10)
2.一种权利要求1所述的用于检测痕量铀酰离子的探针的制备方法,其特征在于,包括以下步骤:
(1)将式(2)所示的第一AIE活性单体与式(3)所示的第二AIE活性单体通过Suzuki偶联聚合反应聚合,得到式(1)所示的共轭聚合物;式(2)-(3)如下:
其中,R1为含有1-20个碳原子的烷基、烷氧基、取代烷基或取代烷氧基,所述取代烷基和取代烷氧基中的取代基独立地选自胺基、羧基、羟基、醚键、卤素、磷酸基、醛基、磺酸基、硫醚键、酯基、酰胺基、希夫碱、肟基、芳香基、砜基和亚砜基中的一种或几种;
R2为频哪醇硼酸酯基、三烷基锡基、硼酸基、卤素、乙炔基或乙烯基;
R3为卤素、频哪醇硼酸酯基、三烷基锡基、硼酸基、乙炔基或乙烯基;
(2)将所述共轭聚合物的醇溶液注入水中,去除醇溶剂后,得到共轭聚合物量子点的水溶液;
(3)将所述共轭聚合物量子点的水溶液与聚乙二醇和缓冲液混合,然后向其中加入5’端修饰有氨基的核苷酸序列和交联剂,混合均匀后反应,所述核苷酸序列为DNA和/或RNA序列,得到所述用于检测痕量铀酰离子的探针。
3.根据权利要求2所述的制备方法,其特征在于:在步骤(2)中,所述共轭聚合物量子点的粒径为10nm-200nm。
4.根据权利要求2所述的制备方法,其特征在于:在步骤(2)中,所述共轭聚合物量子点的水溶液的浓度为0.01-1.00mg/mL。
5.一种用于检测痕量铀酰离子的ECL检测器,其特征在于:所述ECL检测器在胺类反应试剂的存在下检测痕量铀酰离子,包括一工作电极,所述工作电极上修饰有权利要求1所述的用于检测痕量铀酰离子的探针。
6.根据权利要求5所述的ECL检测器,其特征在于:所述ECL检测器包括电信号施加单元、发光池、光电倍增管、信号放大和处理单元;所述电信号施加单元的正极和负极分别连接所述工作电极和对电极,所述发光池用于容置待检测液和所述胺类反应试剂,所述工作电极和对电极置于所述发光池中,所述光电倍增管正对所述发光池设置,所述光电倍增管及信号放大和处理单元电连接。
7.根据权利要求5所述的ECL检测器,其特征在于:所述铀酰离子的检测限为11pM。
8.根据权利要求5所述的ECL检测器,其特征在于:所述胺类反应试剂的浓度为5-100mM。
9.根据权利要求6所述的ECL检测器,其特征在于:所述电信号施加单元所施加的电压为0.50V-2.00V。
10.一种检测痕量铀酰离子的方法,其特征在于:采用权利要求5-9中任一项所述的用于检测痕量铀酰离子的ECL检测器,包括以下步骤:
(1)利用所述ECL检测器测试铀酰离子标准溶液的ECL信号强度,根据检测结果,建立铀酰离子浓度与ECL信号强度之间的相互关系图;
(2)利用所述ECL检测器检测待测液的ECL信号强度Ax,所述待测液中的铀酰离子含量未知,根据ECL信号强度Ax在所述相互关系图的对应关系确定待测液中的铀酰离子浓度。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107589098A (zh) * | 2017-08-30 | 2018-01-16 | 苏州大学 | 一种对痕量铀酰离子荧光检测的方法 |
CN108821998A (zh) * | 2018-06-21 | 2018-11-16 | 中国工程物理研究院材料研究所 | 基于聚集诱导发光的铀酰离子检测的有机荧光分子 |
CN109946279A (zh) * | 2019-03-29 | 2019-06-28 | 重庆工商大学 | 一种铀酰离子的检测方法 |
CN110106226A (zh) * | 2019-06-04 | 2019-08-09 | 中国工程物理研究院化工材料研究所 | 可循环检测痕量铀酰离子的生物传感芯片及其制备方法、应用方法 |
CN110146566A (zh) * | 2019-06-14 | 2019-08-20 | 西南大学 | 修饰电极、组合产品及其电致化学发光生物传感器与应用 |
CN110294837A (zh) * | 2019-07-05 | 2019-10-01 | 南华大学 | 一种偕胺肟化聚合物、其制备方法与应用 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10627383B2 (en) * | 2016-04-21 | 2020-04-21 | Virginia Commonwealth University | Method and apparatus for measuring trace levels of fluorescent minerals in water |
KR102055660B1 (ko) * | 2018-03-07 | 2019-12-13 | 경상대학교산학협력단 | 나프타미도-페닐아잔디일 유도체, 이를 포함하는 우라닐 이온 검출용 조성물 및 이를 이용한 우라닐 이온 검출 방법 |
-
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107589098A (zh) * | 2017-08-30 | 2018-01-16 | 苏州大学 | 一种对痕量铀酰离子荧光检测的方法 |
CN108821998A (zh) * | 2018-06-21 | 2018-11-16 | 中国工程物理研究院材料研究所 | 基于聚集诱导发光的铀酰离子检测的有机荧光分子 |
CN109946279A (zh) * | 2019-03-29 | 2019-06-28 | 重庆工商大学 | 一种铀酰离子的检测方法 |
CN110106226A (zh) * | 2019-06-04 | 2019-08-09 | 中国工程物理研究院化工材料研究所 | 可循环检测痕量铀酰离子的生物传感芯片及其制备方法、应用方法 |
CN110146566A (zh) * | 2019-06-14 | 2019-08-20 | 西南大学 | 修饰电极、组合产品及其电致化学发光生物传感器与应用 |
CN110294837A (zh) * | 2019-07-05 | 2019-10-01 | 南华大学 | 一种偕胺肟化聚合物、其制备方法与应用 |
Non-Patent Citations (7)
Title |
---|
Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection;Jun Wen等;《Journal of Hazardous Materials》;20160705;第318卷;全文 * |
Near-infrared aggregation-induced enhanced electrochemiluminescence from tetraphenylethylene nanocrystals: a new generation of ECL emitters;Jia-Li Liu等;《 Chem. Sci.》;20190315;第10卷;全文 * |
Trace analysis of uranyl ion(UO2 2+) in aqueous solution by fluorescence turn on detection via aggragation induced emission enhancement effect;Xiaotong Chen等;《Analytica chimica acta》;20140804;第847卷;全文 * |
基于AIE活性多组分功能高分子的设计、合成及应用性质研究;王子昱;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20190415(第4期);全文 * |
新型共轭聚合物荧光纳米材料的合成;戴春辉;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20170815(第8期);全文 * |
有机荧光探针在铀酰离子检测方面的研究进展;胡家宁等;《核化学与放射化学》;20181231;第40卷(第6期);全文 * |
荧光聚合物和碲化镉量子点对痕量铀酰离子的检测;马嘉琦;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180515(第5期);全文 * |
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