CN113686828B - 基于CdTe量子点的比率荧光探针及其在检测水合肼中的应用 - Google Patents
基于CdTe量子点的比率荧光探针及其在检测水合肼中的应用 Download PDFInfo
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Abstract
本发明的探针能很好的识别水合肼,产生紫外光谱和荧光光谱的变化;该探针对水合肼具有很好的比率型荧光响应,该探针的有机探针部分与水合肼发应会导致自身的绿色荧光减弱,而量子点的红色荧光则不受影响,因此本探针整体的荧光会由绿色到橘红色的荧光变化;本发明提供的探针能应用于纯水体系,减少了有机溶剂的使用;本发明提供的探针合成简单,不需要复杂的合成过程。本发明公开了一种用于检测水合肼的比率型荧光探针,该探针具有较低的检测限,响应时间较快,合成简便的优点。当与水合肼反应时,溶液颜色由绿色变为橘红色,颜色明显,相应较快。该反应型探针具有特异性选择水合肼的优点,对复杂环境中的水合肼具有现场可视化检测的潜力。
Description
技术领域
本发明属于荧光探针的制备与研发领域,具体设计了一种基于CdTe量子点表面修饰邻羟基酸酐的比率荧光探针,用于水溶液中检测水合肼。
背景技术
水合肼具有刺鼻性气味,无色油状液体,具有强氧化性极易溶于水。水合肼作为化工工业中一种重要的的试剂,在农药,化工工业等领域中有着广泛的应用作为添加剂常作为药物中间体,杀虫剂等,以及用于航空导弹推进剂。水合肼在化工行业与农药领域的广泛应用,导致其在环境中残留,具有较强的毒性和致癌作用。在化工制造中,水合肼可通过皮肤或者呼吸作用进入人体。美国环境保护局已经将其列为有毒物质,其安全范围限定在小于10mg/L.在水合肼的检测过程中,色谱法,电化学法,HPLC等是常规检测方法。但是,这些方法常具有一些缺点,例如,复杂的样品预处理,昂贵的仪器设备和人员培训,以及耗时时间长等。荧光检测方法具有高灵敏度,成本低,选择性好的优点。比率型荧光探针相较于一般的打开或者猝灭型探针,具有环境干扰性小,灵敏度高的优点,是一种可应用于实时现场检测的检测手段。很多研究工作设计的荧光检测水合肼的探针都是基于水合肼与脂反应,切断脂基团,反应时间较长,如Hao Y.,Zhang Y.,Ruan K.,et al.A naphthalimide-basedchemodosimetric probe for ratiometric detection of hydrazine[J].Sensors andActuators B:Chemistry 2017,244(6):417-424中反应时间40-60min,灵敏度受反应速率影响较大。因此,开发一种适用于现场快速检测水合肼的新方法具有十分重要的意义。
发明内容
本发明的目的在于设计一种适用于水环境中水合肼检测的有机小分子探针和CdTe量子点结合的比率型荧光探针。将量子点表面用有机荧光探针修饰后,其与水合肼发生反应快速,识别性专一,灵敏度高,且响应时间较短,具备现场快速检测的优势。
本发明的比率荧光探针,主要由探针有机片段与无机量子点结合形成,结构式如下:
其中,探针有机片段结构如下:
所述QDS为CdTe量子点,CdTe量子点外表面包覆有硅,硅经过氨基化修饰。
本发明还提供了该比率荧光探针的制备方法,其是将探针有机片段的羧基部分作为反应位点与氨基化修饰(APTES修饰)的无机量子点表面的氨基通过酰胺化反应连接在一起。
所述比率荧光探针的制备方法,可包括步骤:有机探针的合成、CdTe量子点的合成、在CdTe量子点表面包硅壳、氨基化修饰、比率型荧光探针的构建。其中,所述探针有机片段的合成是将3-羟基邻苯二甲酸酐与γ-氨基丁酸在乙酸中回流反应;所述CdTe量子点可购买或采用常用方法自制;所述CdTe量子点表面包硅壳、氨基化修饰是将CdTe量子点分散在乙醇(实验常用95%)中,搅拌均匀,逐滴向溶液中加入硅酸四乙酯(TEOS)接着向溶液中加入氨水(实验常用28%),然后搅拌后加入3-氨丙基三乙氧基硅烷(APTES),搅拌,将产物离心,得到的沉淀物分别用乙醇和超纯水洗涤。最后,将产物分散在超纯水中;所述比率型荧光探针的构建是将有机探针氨基化修饰的无机量子点在EDC/NHS溶液中反应。
CdTe量子点具有发光光学性质,在监测环境中为了保持稳定-作为稳定的内参,包裹一层二氧化硅壳层,保护量子点,使其具有更高的稳定性,防止量子点与外界的物质反应而引起荧光的变化。
本发明的比率荧光探针可以在水合肼和/或含水合肼的溶液检测中应用,尤其可用于可视化检测水合肼和/或含水合肼的溶液的应用。该应用过程可以是:将探针溶液置于手提式365nm紫外灯下,溶液颜色为绿色,再加入水合肼溶液,10-30min后,该溶液的颜色由绿色转变为橘红色。
本发明的比率探针能很好的识别水合肼,产生紫外光谱和荧光光谱的变化;该探针对水合肼具有很好的比率型荧光响应,该探针的有机探针部分与水合肼反应会导致自身的绿色荧光减弱(肉眼难以区别),而量子点的红色荧光则不受影响,因此本探针整体的荧光会由绿色到橘红色的荧光变化(肉眼易识别);本发明提供的探针能应用于纯水体系,减少了有机溶剂的使用;本发明提供的探针合成简单,不需要复杂的合成过程。
本发明公开了一种用于检测水合肼的比率型荧光探针,该探针具有较低的检测限,响应时间较快,合成简便的优点。当与水合肼反应时,发生吉尔布斯反应,溶液颜色由绿色变为橘红色,颜色转变明显易识别,响应较快。该反应型探针具有特异性选择水合肼的优点,对复杂环境中的水合肼具有现场可视化检测的潜力。
附图说明
图1是探针有机片段的核磁共振氢谱。
图2是有机探针片段的核磁共振碳谱。
图3是包硅量子点的透射电镜图。
图4是探针有机片段加入水合肼前后的紫外吸收光谱。
图5是探针有机片段随水合肼浓度变化的荧光光谱。
图6是探针加入水合肼前后的荧光光谱。
图7是探针对几种干扰物的荧光响应。
图8是水合肼浓度与探针荧光响应之间的线性关系图。
图9是探针加入水合肼后365nm紫外灯照射下荧光的变化。
具体实施方式
下述实施例是对于本发明内容的进一步说明以作为对本发明技术内容的阐释,但本发明的实质内容并不仅限于下述实施例所述,本领域的普通技术人员可以且应当知晓任何基于本发明实质精神的简单变化或替换均应属于本发明所要求的保护范围。
实施例1
探针有机片段(probe)的合成与结构表征
由3-羟基邻苯二甲酸酐为起始原料,与γ-氨基丁酸反应得到最终产物。
探针有机片段的合成路线如下:
将3-羟基邻苯二甲酸酐(4mmol,656mg)和γ-氨基丁酸(8mmol,823mg)溶与15mL乙酸中,反应体系在120℃下回流加热搅拌6h。在自然冷却至室温过程中,析出白色固体。将析出的固体减压过滤并干燥,得到白色固体产物560mg,产率56%。
通过核磁共振氢谱(图1)核磁共振碳谱(图2)确认了该探针有机片段的结构。
1H NMR(400MHz,DMSO-d6)δ12.29–11.79(s,1H),11.31–10.70(s,1H),7.82–7.39(m,1H),7.39–6.99(dd,J=27.6,7.7Hz,2H),3.61–3.47(t,J=6.8Hz,2H),2.31–2.13(t,J=7.2Hz,2H),1.87–1.66(p,J=7.0Hz,2H).
13C NMR(101MHz,DMSO-d6)δ174.32–174.26,168.27–168.22,167.20–167.16,136.36–136.19,134.06–134.03,123.68–123.45,115.20–115.13,114.47–114.26,37.07–36.86,31.48–31.31,23.93–23.74.
实施例2
CdTe量子点的合成
称取碲粉0.0638g(0.2mmol)和0.1gNaBH4至三口瓶1中,通入氮气保30min,液封。加入0.5M的硫酸,氮气保护。从胶管处注入3ml超纯水,冰浴反应4h,氮气持续通入。当黑色消失而剩下白色混合物时停止反应,得到NaTeH溶液。
称取0.2284g的CdCl2﹒2H2O和210μL的3-巯基丙酸(MPA)溶解在125ml的超纯水中于三口瓶2中。用NaOH调节混合体系的pH至约11,氮气保护30min。用针头向之前制得的NaTeH溶液中加入0.5M的硫酸,再将H2Te通过胶管转移到三口瓶2中,溶液由无色迅速变为橙红色,这一过程无需氮气保护。170℃下回流加热12h,120℃下回流加热11h,得到橙红色量子点。
实施例3
包硅量子点的合成与表征
通过在发红光的CdTe量子点外面包上一层硅壳,并对其进行表面修饰得到能与有机片段连接在一起的包硅量子点。
将200μL的CdTe量子点分散在20mL乙醇中,然后在1000r/min下搅拌10min.用铝箔将烧瓶包裹起来,向溶液中加入20μL硅酸四乙酯(TEOS)接着向溶液中加入200μL的氨水(25wt%),然后搅拌6h得到嵌入二氧化硅纳米球的发红光量子点。接着向上述混合物中加入6μL的3-氨丙基三乙氧基硅烷(APTES),搅拌12h。将产物离心,得到的沉淀物分别用乙醇和超纯水洗涤3次。最后,将产物分散在5mL的超纯水中。通过图3透射电镜图可以清楚的看到在中心黑色的量子点外面有一层硅壳。
实施例4
比率型荧光探针(probe+QDs)的构建
在典型方法中,取10μL的有机探针(2mM)溶解在1mLDMF中,与1mL水混合,在10mL烧瓶中形成均匀溶液。然后将3mL的EDC/NHS溶液(2mg/mL)注入上述溶液并搅拌15min。在上述溶液中添加50μLAPTES修饰的硅量子点,并在室温下搅拌6小时。所得到的溶液通过离心沉淀,用超纯水洗涤三次纯化,以去除未反应的试剂。所得产物分散在超纯水中,供将来使用。
最后确认探针的结构如下:
实施例5
探针对水合肼紫外吸收与荧光的影响
1.如图4所示在纯水中,探针有机片段(50μM)本身的紫外吸收在330nm处,加入30当量(eq)的水合肼后,位于330nm处的吸收峰明显降低,在399nm处出现一个新的吸收峰。
2.如图5所示,向探针有机片段(10μM)中加入水合肼后,515nm处的荧光逐渐下降,当加入50eq水合肼后,探针与水合肼完全反应,荧光强度基本不再变化。
3.如图6所示,探针有机片段(60μM)在结合CdTe量子点后,自身515nm处的荧光基本没有变化,而且在630nm处有一个发红光的量子点的荧光发射峰。当加入水合肼后,515nm处的荧光降低,而630nm处的荧光不变。
4.如图7所示,有机探针对水合肼显示出很好的选择性的荧光响应。其他的干扰物如Zn2+、Mg2+、Br-、HCO3 -、Ca2+、Cl-、半胱氨酸均不会对该比率探针的荧光信号产生影响。
荧光线性与检测限的测定,如图8所示在50-350μM浓度范围内,水合肼具有线性的荧光响应,使用公式计算出检测限:其中σ为扫描10次空白样品求出的标准差,数值为0.4158,K为线性曲线斜率,数值为5.94,将其带入检测限公式测得检测限为0.21μM。
实施例6
探针的可视化应用
将探针溶液置于手提式365nm紫外灯下,加入之前溶液颜色为绿色,再加入水合肼溶液,20min后,如图9所示,该溶液的颜色由绿色转变为橘红色。由此可见,该探针可应用于可视化检测水合肼的潜力。
应当说明的是,本发明的上述所述之技术内容仅为使本领域技术人员能够获知本发明技术实质而进行的解释与阐明,故所述之技术内容并非用以限制本发明的实质保护范围。本发明的实质保护范围应以权利要求书所述之为准。本领域技术人员应当知晓,凡基于本发明的实质精神所作出的任何修改、等同替换和改进等,均应在本发明的实质保护范围之内。
Claims (9)
1.基于CdTe量子点的用于水合肼检测的比率荧光探针,由探针有机片段与无机量子点结合形成,结构式如下:
探针有机片段结构如下:
所述无机量子点即QDs为CdTe量子点,CdTe量子点外表面包覆一层二氧化硅硅壳,硅壳经过氨基化修饰。
2.权利要求1所述比率荧光探针的制备方法,其是将探针有机片段的羧基作为反应位点与氨基化修饰的无机量子点表面的氨基通过酰胺化反应连接在一起。
3.如权利要求2所述比率荧光探针的制备方法,其特征在于,包括步骤:探针有机片段的合成、在CdTe量子点表面包硅壳、氨基化修饰、比率型荧光探针的构建。
4.如权利要求3所述比率荧光探针的制备方法,其特征在于,所述探针有机片段的合成是将3-羟基邻苯二甲酸酐与γ-氨基丁酸在乙酸中回流反应。
5.如权利要求3所述比率荧光探针的制备方法,其特征在于,所述CdTe量子点表面包硅壳、氨基化修饰是将CdTe量子点分散在乙醇中,搅拌均匀,逐滴向溶液中加入硅酸四乙酯接着向溶液中加入氨水,然后搅拌后加入3-氨丙基三乙氧基硅烷,搅拌,将产物离心,得到的沉淀物分别用乙醇和超纯水洗涤;最后,将产物分散在超纯水中。
6.如权利要求3所述比率荧光探针的制备方法,其特征在于,所述比率型荧光探针的构建是将有机探针氨基化修饰的无机量子点在EDC/NHS溶液中反应。
7.权利要求1所述的比率荧光探针或者由权利要求2-6任一项所述制备方法得到的比率荧光探针在水合肼和/或含水合肼的溶液检测中的应用。
8.如权利要求7所述的应用,其特征在于,所述比率荧光探针在可视化检测水合肼和/或含水合肼的溶液的应用。
9.如权利要求8所述的应用,其特征在于,将探针溶液置于手提式365nm紫外灯下,溶液颜色为绿色,再加入水合肼溶液,10-30min后,该溶液的颜色由绿色转变为橘红色。
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