技术领域technical field
本发明属于荧光分析技术领域，具体涉及一种基于金纳米簇AuNCs@APAP的荧光增强体系及其应用。The invention belongs to the technical field of fluorescence analysis, and in particular relates to a fluorescence enhancement system based on gold nano-cluster AuNCs@APAP and its application.
背景技术Background technique
在分析化学领域，荧光分析法得到了极大的关注，广泛应用于环境、生命科学和材料科学等许多领域。但是有些荧光分子的量子产率比较低，严重降低了分析方法的灵敏度。因此，进一步提高荧光强度是提高分析检测灵敏度的重要方法。In the field of analytical chemistry, fluorescence analysis has received great attention and is widely used in many fields such as the environment, life sciences, and materials science. However, the quantum yield of some fluorescent molecules is relatively low, which seriously reduces the sensitivity of the analytical method. Therefore, further increasing the fluorescence intensity is an important method to improve the analytical detection sensitivity.
金纳米簇由于具有较好的光稳定性、低毒性等诸多优点，在分析、催化、生物成像等领域都有广泛应用，但也存在着量子产率低的缺陷。因此，增强金纳米簇的荧光强度，提高检测灵敏度，是进一步拓展金纳米簇应用范围的必然环节。Gold nanoclusters are widely used in analysis, catalysis, bioimaging and other fields due to their good photostability, low toxicity and many other advantages, but they also have the drawback of low quantum yield. Therefore, enhancing the fluorescence intensity of gold nanoclusters and improving the detection sensitivity is an inevitable link to further expand the application scope of gold nanoclusters.
发明内容SUMMARY OF THE INVENTION
本发明解决的技术问题是提供了一种选择性强、灵敏度高且抗干扰能力强的基于金纳米簇AuNCs@APAP的荧光增强体系，该荧光增强体系针对本课题组曾经以对乙酰氨基酚（APAP）为还原剂和保护剂合成的金纳米簇（AuNCs@APAP），1,2-二甲基咪唑（1,2-MIm）、2-甲基咪唑（2-MIm）或4-甲基咪唑（4-MIm）能够显著增强上述金纳米簇AuNCs@APAP的荧光强度，荧光强度增加6.6-6.9倍，同时构建的荧光增强体系能够成功用于地表水样中2,4-二硝基酚（2,4-DNP）和4-硝基酚（4-NP）浓度的选择性测定。The technical problem solved by the present invention is to provide a fluorescence enhancement system based on gold nanoclusters AuNCs@APAP with strong selectivity, high sensitivity and strong anti-interference ability. Gold nanoclusters (AuNCs@APAP) synthesized by APAP) as reducing and protecting agents, 1,2-dimethylimidazole (1,2-MIm), 2-methylimidazole (2-MIm) or 4-methyl Imidazole (4-MIm) can significantly enhance the fluorescence intensity of the above-mentioned gold nanoclusters AuNCs@APAP, and the fluorescence intensity is increased by 6.6-6.9 times. At the same time, the constructed fluorescence enhancement system can be successfully used for 2,4-dinitrophenol in surface water samples. Selective determination of (2,4-DNP) and 4-nitrophenol (4-NP) concentrations.
本发明为解决上述技术问题采用如下技术方法，基于金纳米簇AuNCs@APAP的荧光增强体系，其特征在于：取0.2mL金纳米簇AuNCs@APAP，加入咪唑类化合物，定容至4.00mL，于25℃反应10min得到荧光强度明显增强的基于金纳米簇AuNCs@APAP的荧光增强体系，荧光强度增加6.6-6.9倍，其中咪唑类化合物为1,2-二甲基咪唑、2-甲基咪唑或4-甲基咪唑中的一种或多种。In order to solve the above technical problems, the present invention adopts the following technical method, based on the fluorescence enhancement system of gold nanoclusters AuNCs@APAP, characterized in that: take 0.2 mL of gold nanoclusters AuNCs@APAP, add imidazole compounds, set the volume to 4.00 mL, and put The fluorescence enhancement system based on gold nanoclusters AuNCs@APAP was obtained by reacting at 25 °C for 10 min, and the fluorescence intensity was increased by 6.6-6.9 times. The imidazole compounds were 1,2-dimethylimidazole, 2-methylimidazole or One or more of 4-methylimidazole.
优选的，所述1,2-二甲基咪唑、2-甲基咪唑、4-甲基咪唑的浓度均为0.5mM或2mM。Preferably, the concentrations of the 1,2-dimethylimidazole, 2-methylimidazole and 4-methylimidazole are all 0.5 mM or 2 mM.
本发明所述的基于金纳米簇AuNCs@APAP的荧光增强体系在选择性测定2,4-二硝基酚和4-硝基酚浓度中的应用，其特征在于具体过程为：The application of the fluorescence enhancement system based on gold nanoclusters AuNCs@APAP in the selective determination of the concentration of 2,4-dinitrophenol and 4-nitrophenol according to the present invention is characterized in that the specific process is as follows:
取0.2mL金纳米簇AuNCs@APAP和0.2mL、10mM 4-MIm，加入待测2,4-二硝基酚，定容至4.00mL，于25℃反应10min，在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度，根据测得的荧光强度并结合线性方程计算得到待测2,4-二硝基酚的浓度；2,4-二硝基酚线性浓度范围为0.375-12.5μg/mL，线性方程为（F0-F）/F =0.1454C2,4-DNP -0.0592，C2,4-DNP为2,4-DNP浓度，单位μg/mL，相关系数R2=0.9927，检出限LOD为0.301μg/mL，2,4-DNP浓度为5μg/mL，平行测定15次，相对标准偏差RSD%为2.37%；Take 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL, 10 mM 4-MIm, add the 2,4-dinitrophenol to be tested, make up the volume to 4.00 mL, react at 25 °C for 10 min, and excite the slit at the excitation wavelength of 322 nm. 5nm, the emission slit is 5nm, the fluorescence intensity of the mixed system is measured, and the concentration of 2,4-dinitrophenol to be tested is calculated according to the measured fluorescence intensity and combined with the linear equation; 2,4-dinitrophenol linear concentration range is 0.375-12.5 μg/mL, the linear equation is (F0 -F)/F = 0.1454C2,4-DNP -0.0592, C2,4-DNP is 2,4-DNP concentration, unit μg/mL, related The coefficient R2 =0.9927, the detection limit LOD was 0.301μg/mL, the concentration of 2,4-DNP was 5μg/mL, and the relative standard deviation (RSD%) was 2.37%.
取0.2mL金纳米簇AuNCs@APAP和0.2mL、10mM 4-MIm，加入待测4-硝基酚，定容至4.00mL，于25℃反应10min，在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度，根据测得的荧光强度并结合线性方程计算得到待测4-二硝基酚的浓度；4-硝基酚线性浓度范围为0.375-25μg/mL，线性方程为（F0-F）/F =0.1935C4-NP -0.1018，C4-NP为4-NP浓度，单位μg/mL，相关系数R2=0.9939，检出限LOD为0.246μg/mL，4-NP浓度为5μg/mL，平行测定15次，相对标准偏差RSD%为3.21%。Take 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL, 10 mM 4-MIm, add 4-nitrophenol to be tested, dilute to 4.00 mL, react at 25 °C for 10 min, at excitation wavelength 322 nm, excitation slit 5 nm, emission The slit is 5 nm, the fluorescence intensity of the mixed system is measured, and the concentration of 4-dinitrophenol to be tested is calculated according to the measured fluorescence intensity and combined with the linear equation; the linear concentration range of 4-nitrophenol is 0.375-25 μg/mL, linear The equation is (F0 -F)/F = 0.1935C4-NP -0.1018, C4-NP is the 4-NP concentration in μg/mL, the correlation coefficient R2 =0.9939, the detection limit LOD is 0.246 μg/mL , 4-NP concentration was 5μg/mL, 15 parallel determinations, the relative standard deviation RSD% was 3.21%.
本发明所述的基于金纳米簇AuNCs@APAP的荧光增强体系在选择性测定地表水样中2,4-二硝基酚和4-硝基酚浓度中的应用，其特征在于：取0.2mL金纳米簇AuNCs@APAP和0.2mL、10mM 4-MIm，加入过滤后的地表水样，定容至4.00mL，于25℃反应10min，在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度，所测定的地表水样中未检测出2,4-二硝基酚和4-硝基酚，2,4-二硝基酚和4-硝基酚加标回收的相对标准偏差为0.51%-2.82%之间和0.14%-3.20%之间以及加标回收率为96.28%-103.82%和97.91%-106.13%之间，表明构建的基于金纳米簇AuNCs@APAP的荧光增强体系能够用于选择性测定地表水样中的2,4-二硝基酚和4-硝基酚浓度。The application of the fluorescence enhancement system based on gold nanoclusters AuNCs@APAP in the selective determination of the concentration of 2,4-dinitrophenol and 4-nitrophenol in surface water samples is characterized in that: taking 0.2 mL Gold nanoclusters AuNCs@APAP and 0.2 mL, 10 mM 4-MIm were added to the filtered surface water sample, the volume was adjusted to 4.00 mL, and the reaction was carried out at 25 °C for 10 min. The fluorescence intensity of the mixed system was measured, and 2,4-dinitrophenol and 4-nitrophenol were not detected in the measured surface water samples, and 2,4-dinitrophenol and 4-nitrophenol were recovered by standard addition. The relative standard deviations were between 0.51%-2.82% and 0.14%-3.20% and the spiked recoveries were between 96.28%-103.82% and 97.91%-106.13%, indicating that the constructed gold nanoclusters AuNCs@APAP-based The fluorescence enhancement system can be used to selectively determine the concentration of 2,4-dinitrophenol and 4-nitrophenol in surface water samples.
本发明构建的基于金纳米簇AuNCs@APAP的荧光增强体系对2,4-二硝基酚和4-硝基酚均具有特异性响应能力，并由此构建了选择性强、灵敏度高且抗干扰能力强的测定2,4-二硝基酚和4-硝基酚浓度的方法，该荧光增强体系有望在地表水样2,4-二硝基酚和4-硝基酚浓度检测中得到推广应用。The fluorescence enhancement system based on the gold nanocluster AuNCs@APAP constructed in the present invention has specific response ability to both 2,4-dinitrophenol and 4-nitrophenol, and thus a highly selective, highly sensitive and anti- A method for the determination of 2,4-dinitrophenol and 4-nitrophenol concentration with strong interference ability, the fluorescence enhancement system is expected to be obtained in the detection of 2,4-dinitrophenol and 4-nitrophenol concentration in surface water samples Promote the application.
附图说明Description of drawings
图1是咪唑化合物种类对AuNCs@APAP荧光增强体系荧光增强的影响。Figure 1 shows the effect of imidazole compounds on the fluorescence enhancement of AuNCs@APAP fluorescence enhancement system.
图2是2,4-二硝基酚对不同咪唑类化合物AuNCs@APAP荧光增强体系的荧光猝灭效果比较。Figure 2 is a comparison of the fluorescence quenching effect of 2,4-dinitrophenol on different imidazole compounds AuNCs@APAP fluorescence enhancement system.
图3是 4-MIm-AuNCs@APAP荧光增强体系对酚类选择性和抗干扰性能。Figure 3 shows the phenolic selectivity and anti-interference performance of the 4-MIm-AuNCs@APAP fluorescence enhancement system.
图4是 4-MIm-AuNCs@APAP荧光增强体系对金属选择性和抗干扰性能。Figure 4 shows the metal selectivity and anti-interference performance of the 4-MIm-AuNCs@APAP fluorescence enhancement system.
图5是酚类对4-MIm-AuNCs@APAP荧光增强体系测定4-硝基酚的干扰。Figure 5 shows the interference of phenols on the determination of 4-nitrophenol by the 4-MIm-AuNCs@APAP fluorescence enhancement system.
图6是金属离子对4-MIm-AuNCs@APAP荧光增强体系测定4-硝基酚的干扰。Figure 6 shows the interference of metal ions on the determination of 4-nitrophenol by the 4-MIm-AuNCs@APAP fluorescence enhancement system.
具体实施方式Detailed ways
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。The above-mentioned content of the present invention is described in further detail below through the examples, but it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following examples, and all technologies realized based on the above-mentioned content of the present invention belong to the scope of the present invention.
实施例Example
AuNCs@APAP荧光增强体系AuNCs@APAP Fluorescence Enhancement System
取0.2mL金纳米簇AuNCs@APAP，分别加入一定量不同种类的咪唑类化合物，定容至4.00mL，于25℃反应10min。考察的咪唑类化合物的种类有：咪唑（Im），1-甲基咪唑（1-MIm），2-甲基咪唑（2-MIm），1,2-二甲基咪唑（1,2-MIm），1-乙烯基咪唑（1-VIm），咪唑的浓度分别为0.5mM和2mM。测定咪唑类化合物加入前后混合体系的荧光强度分别为I0和I，计算I/I0值。Take 0.2 mL of gold nanoclusters AuNCs@APAP, add a certain amount of different kinds of imidazole compounds, make up the volume to 4.00 mL, and react at 25 °C for 10 min. The types of imidazoles investigated are: imidazole (Im), 1-methylimidazole (1-MIm), 2-methylimidazole (2-MIm), 1,2-dimethylimidazole (1,2-MIm) ), 1-vinylimidazole (1-VIm), and the concentrations of imidazole were 0.5 mM and 2 mM, respectively. The fluorescence intensities of the mixed system before and after the addition of imidazole compounds were measured as I0 and I, respectively, and the I/I0 value was calculated.
图1是咪唑类化合物种类对AuNCs@APAP体系荧光增强的影响。由图1可知，1,2-二甲基咪唑（1,2-MIm），2-甲基咪唑（2-MIm）和4-甲基咪唑（4-MIm）能够显著增强金纳米簇AuNCs@APAP的荧光强度，荧光强度增加6.6-6.9倍。Figure 1 shows the effect of imidazole species on the fluorescence enhancement of AuNCs@APAP system. It can be seen from Figure 1 that 1,2-dimethylimidazole (1,2-MIm), 2-methylimidazole (2-MIm) and 4-methylimidazole (4-MIm) can significantly enhance the gold nanoclusters AuNCs@ The fluorescence intensity of APAP, the fluorescence intensity increased 6.6-6.9 times.
分别加入不同种类的咪唑类化合物，浓度均为0.5mM，0.2mL金纳米簇AuNCs@APAP和0.5mL、100μg/mL 2,4-二硝基酚，在25℃条件下反应10min。测定不同种类的咪唑类化合物-AuNCs@APAP荧光增强体系中加入2,4-二硝基酚前后的荧光强度，计算Fo/F值。图2为2,4-二硝基酚对不同咪唑类化合物-AuNCs@APAP荧光增强体系的荧光猝灭效果，由图2可知，2,4-二硝基酚更能有效猝灭4-甲基咪唑-AuNCs@APAP构建的荧光增强体系。Different kinds of imidazoles were added at a concentration of 0.5 mM, 0.2 mL of gold nanoclusters AuNCs@APAP and 0.5 mL, 100 μg/mL of 2,4-dinitrophenol, and reacted at 25 °C for 10 min. The fluorescence intensities of different kinds of imidazoles-AuNCs@APAP fluorescence enhancement system before and after adding 2,4-dinitrophenol were measured, and the Fo /F value was calculated. Figure 2 shows the fluorescence quenching effect of 2,4-dinitrophenol on different imidazoles-AuNCs@APAP fluorescence enhancement systems. It can be seen from Figure 2 that 2,4-dinitrophenol can quench 4-methyl methacrylate more effectively. Fluorescence-enhancing system constructed by imidazole-AuNCs@APAP.
测定2,4-二硝基酚和4-硝基酚Determination of 2,4-dinitrophenol and 4-nitrophenol
取0.2mL金纳米簇AuNCs@APAP和0.2mL、10mM 4-MIm，分别加入一定量的2,4-二硝基酚，定容至4.00mL，于25℃反应10min。在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度；2,4-二硝基酚线性浓度范围为0.375-12.5μg/mL，线性方程为（F0-F）/F =0.1454C2,4-DNP -0.0592，C2,4-DNP为2,4-DNP浓度，单位μg/mL，相关系数R2=0.9927，检出限LOD为0.301μg/mL。2,4-DNP浓度为5μg/mL，平行测定15次，相对标准偏差（RSD%）为2.37%。Take 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL, 10 mM 4-MIm, respectively, add a certain amount of 2,4-dinitrophenol, make up the volume to 4.00 mL, and react at 25 °C for 10 min. At the excitation wavelength of 322 nm, the excitation slit is 5 nm, and the emission slit is 5 nm, the fluorescence intensity of the mixed system is measured; the linear concentration range of 2,4-dinitrophenol is 0.375-12.5 μg/mL, and the linear equation is (F0 -F) /F =0.1454C2,4-DNP -0.0592, C2,4-DNP is the concentration of 2,4-DNP in μg/mL, the correlation coefficient R2 =0.9927, and the detection limit LOD is 0.301 μg/mL. The concentration of 2,4-DNP was 5μg/mL, and the relative standard deviation (RSD%) was 2.37%.
取0.2mL金纳米簇AuNCs@APAP和0.2mL 10mM 4-MIm，分别加入一定量的4-硝基酚，定容至4.00mL，于25℃反应10min。在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度；4-硝基酚线性浓度范围为0.375-25μg/mL，线性方程为（F0-F）/F =0.1935C4-NP -0.1018，C4-NP为4-NP浓度，单位μg/mL，相关系数R2=0.9939，检出限LOD为0.246μg/mL。4-NP浓度为5μg/mL，平行测定15次，相对标准偏差（RSD%）为3.21%。Take 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL of 10 mM 4-MIm, add a certain amount of 4-nitrophenol respectively, make up the volume to 4.00 mL, and react at 25 °C for 10 min. At the excitation wavelength of 322 nm, the excitation slit is 5 nm, and the emission slit is 5 nm, the fluorescence intensity of the mixed system is measured; the linear concentration range of 4-nitrophenol is 0.375-25 μg/mL, and the linear equation is (F0 -F)/F =0.1935 C4-NP -0.1018, C4-NP is the concentration of 4-NP in μg/mL, the correlation coefficient R2 =0.9939, and the detection limit LOD is 0.246 μg/mL. The concentration of 4-NP was 5 μg/mL, and the relative standard deviation (RSD%) was 3.21%.
测定方法的选择性和抗干扰性能Selectivity and anti-interference performance of assay methods
为了考察 4-MIm增强的AuNCs@APAP荧光增强体系（4-MIm-AuNCs@APAP）对有机物的选择性以及对测定2,4-DNP的干扰，取0.2mL金纳米簇AuNCs@APAP和0.2mL 10mM 4-MIm，分别加入一定量的2,4-DNP或者酚类及其类似物（2-硝基酚（2-NP）、3-硝基酚（3-NP）、4-硝基酚（4-NP）、邻氨基苯酚（OAP）、间氨基苯酚（MAP）、对氨基苯酚（PAP）、对乙酰氨基酚（APAP）、邻苯二酚（CC）、苯甲酸（BA）、双酚A（BPA）），浓度均为10μg/mL，定容至4.00mL，于25℃反应10min。在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度。同时考察了酚类及其类似物与2,4-DNP共存，且浓度均为10μg/mL时，对2,4-DNP测定的干扰。图3为4-MIm-AuNCs@APAP荧光增强体系对酚类选择性和抗干扰性能。由图3可知，2,4-二硝基酚（2,4-DNP）和4-硝基酚（4-NP）能有效猝灭4-MIm-AuNCs@APAP荧光增强体系荧光，考察的其它酚类及其类似物却不能有效猝灭4-MIm-AuNCs@APAP荧光增强体系荧光。这说明4-MIm-AuNCs@APAP荧光增强体系对2,4-二硝基酚（2,4-DNP）和4-硝基酚（4-NP）特异性响应，具有很强的选择性。而且除了4-硝基酚（4-NP）和苯甲酸（BA）干扰对2,4-二硝基酚（2,4-DNP）的测定外，考察的其它酚类及其类似物对2,4-二硝基酚（2,4-DNP）的测定几乎没有干扰。In order to investigate the selectivity of the 4-MIm-enhanced AuNCs@APAP fluorescence enhancement system (4-MIm-AuNCs@APAP) for organics and the interference on the determination of 2,4-DNP, 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL of gold nanoclusters were taken. 10mM 4-MIm, respectively add a certain amount of 2,4-DNP or phenols and their analogs (2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), Ortho-Aminophenol (OAP), Meta-Aminophenol (MAP), Para-Aminophenol (PAP), Paracetamol (APAP), Catechol (CC), Benzoic Acid (BA), Bis Phenol A (BPA)) at a concentration of 10 μg/mL, dilute to 4.00 mL, and react at 25 °C for 10 min. At an excitation wavelength of 322 nm, an excitation slit of 5 nm and an emission slit of 5 nm, the fluorescence intensity of the mixed system was measured. At the same time, the interference on the determination of 2,4-DNP was investigated when phenols and their analogs coexisted with 2,4-DNP at a concentration of 10 μg/mL. Figure 3 shows the phenolic selectivity and anti-interference performance of the 4-MIm-AuNCs@APAP fluorescence enhancement system. It can be seen from Figure 3 that 2,4-dinitrophenol (2,4-DNP) and 4-nitrophenol (4-NP) can effectively quench the fluorescence of 4-MIm-AuNCs@APAP fluorescence enhancement system. However, phenols and their analogs cannot effectively quench the fluorescence of the 4-MIm-AuNCs@APAP fluorescence enhancement system. This indicates that the 4-MIm-AuNCs@APAP fluorescence enhancement system has a strong selectivity to 2,4-dinitrophenol (2,4-DNP) and 4-nitrophenol (4-NP) in specific response. And in addition to 4-nitrophenol (4-NP) and benzoic acid (BA) interfering with the determination of 2,4-dinitrophenol (2,4-DNP), the other phenols and their analogs investigated were not effective for 2,4-dinitrophenol (2,4-DNP). ,4-Dinitrophenol (2,4-DNP) was determined with little interference.
为了考察 4-MIm增强的AuNCs@APAP荧光增强体系（4-MIm-AuNCs@APAP）对金属离子的选择性以及对测定2,4-DNP的干扰，取0.2mL金纳米簇AuNCs@APAP和0.2mL、10mM 4-MIm，分别加入一定量的2,4-DNP或者金属离子（Na+、Mg2+、K+、Zn2+、Fe3+、Ca2+、Ba2+、Pb2+、Cu2+、Co2+、Ni2+、Bi3+），2,4-DNP浓度为10μg/mL，金属离子浓度为125μM，定容至4.00mL，于25℃反应10min。在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度。同时考察了金属离子与2,4-DNP共存，2,4-DNP浓度为10μg/mL，金属离子浓度为125μM，对2,4-DNP测定的干扰。图4为4-MIm-AuNCs@APAP荧光增强体系对金属选择性和抗干扰性能。由图4可知，Fe3+、Pb2+、Cu2+能使4-MIm-AuNCs@APAP荧光增强体系荧光一定程度上猝灭，对2,4-DNP的测定有一定的干扰，通过加入焦磷酸根可以掩蔽 Fe3+的干扰。其它金属离子Na+、Mg2+、K+、Zn2+、Fe3+、Ca2+、Ba2+、Pb2+、Cu2+、Co2+、Ni2+、Bi3+几乎不能使4-MIm-AuNCs@APAP荧光增强体系荧光猝灭，对2,4-DNP的测定几乎没有干扰。In order to investigate the selectivity of 4-MIm-enhanced AuNCs@APAP fluorescence enhancement system (4-MIm-AuNCs@APAP) for metal ions and the interference on the determination of 2,4-DNP, 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL of gold nanoclusters were taken. mL, 10mM 4-MIm, respectively add a certain amount of 2,4-DNP or metal ions (Na+ , Mg2+ , K+ , Zn2+ , Fe3+ , Ca2+ , Ba2+ , Pb2+ ) , Cu2+ , Co2+ , Ni2+ , Bi3+ ), the concentration of 2,4-DNP was 10 μg/mL, the concentration of metal ions was 125 μM, the volume was adjusted to 4.00 mL, and the reaction was carried out at 25 °C for 10 min. At an excitation wavelength of 322 nm, an excitation slit of 5 nm and an emission slit of 5 nm were used to measure the fluorescence intensity of the mixed system. At the same time, the coexistence of metal ions and 2,4-DNP, the concentration of 2,4-DNP was 10μg/mL, and the concentration of metal ions was 125μM, which interfered with the determination of 2,4-DNP. Figure 4 shows the metal selectivity and anti-interference performance of the 4-MIm-AuNCs@APAP fluorescence enhancement system. It can be seen from Figure 4 that Fe3+ , Pb2+ , and Cu2+ can quench the fluorescence of the 4-MIm-AuNCs@APAP fluorescence enhancement system to a certain extent, which has a certain interference on the determination of 2,4-DNP. Pyrophosphate can mask the interference of Fe3+ . Other metal ions Na+ , Mg2+ , K+ , Zn2+ , Fe3+ , Ca2+ , Ba2+ , Pb2+ , Cu2+ , Co2+ , Ni2+ , Bi3+ can hardly The fluorescence quenching of the 4-MIm-AuNCs@APAP fluorescence enhancement system hardly interferes with the determination of 2,4-DNP.
为了考察 4-MIm增强的AuNCs@APAP荧光增强体系（4-MIm-AuNCs@APAP）测定4-硝基酚的抗干扰性能，分别考察干扰物如2-硝基酚（2-NP）、3-硝基酚（3-NP）、4-硝基酚（4-NP）、邻氨基苯酚（OAP）、间氨基苯酚（MAP）、对氨基苯酚（PAP）、对乙酰氨基酚（APAP）、邻苯二酚（CC）、苯甲酸（BA）、双酚A（BPA））与4-硝基酚（4-NP）对测定4-硝基酚（4-NP）的干扰。取0.2mL金纳米簇AuNCs@APAP和0.2mL、10mM 4-MIm，4-硝基酚（4-NP）和干扰物的浓度均为20μg/mL，定容至4.00mL，于25℃反应10min。在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度。图5为酚类对4-MIm-AuNCs@APAP荧光增强体系测定4-硝基酚的干扰。由图5可知，2,4-二硝基酚和苯甲酸对4-硝基酚的测定有一定干扰，其余酚类及其类似物几乎不干扰对4-硝基酚的测定。In order to investigate the anti-interference performance of the 4-MIm-enhanced AuNCs@APAP fluorescence enhancement system (4-MIm-AuNCs@APAP) for the determination of 4-nitrophenol, interfering substances such as 2-nitrophenol (2-NP), 3 - Nitrophenol (3-NP), 4-Nitrophenol (4-NP), Ortho-Aminophenol (OAP), Meta-Aminophenol (MAP), Para-Aminophenol (PAP), Paracetamol (APAP), Interference of catechol (CC), benzoic acid (BA), bisphenol A (BPA) and 4-nitrophenol (4-NP) on the determination of 4-nitrophenol (4-NP). Take 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL, 10 mM 4-MIm, 4-nitrophenol (4-NP) and interfering substances with a concentration of 20 μg/mL, dilute to 4.00 mL, and react at 25 °C for 10 min . At an excitation wavelength of 322 nm, an excitation slit of 5 nm and an emission slit of 5 nm were used to measure the fluorescence intensity of the mixed system. Figure 5 shows the interference of phenols on the determination of 4-nitrophenol by the 4-MIm-AuNCs@APAP fluorescence enhancement system. It can be seen from Figure 5 that 2,4-dinitrophenol and benzoic acid have some interference with the determination of 4-nitrophenol, and the other phenols and their analogs hardly interfere with the determination of p-4-nitrophenol.
分别考察金属离子（Na+、Mg2+、K+、Zn2+、Fe3+、Ca2+、Ba2+、Pb2+、Cu2+、Co2+、Ni2+、Bi3+）对测定4-硝基酚的干扰。取0.2mL金纳米簇AuNCs@APAP和0.2mL、10mM 4-MIm，4-硝基酚浓度为20μg/mL，金属离子浓度为125μM，定容至4.00mL，于25℃反应10min。在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度。图6为金属离子对4-MIm-AuNCs@APAP荧光增强体系测定4-硝基酚的干扰。由图6可知，Pb2+和Cu2+对测定4-硝基酚略有干扰，Fe3+干扰严重，其它金属离子Na+、Mg2+、K+、Zn2+、Ca2+、Ba2+、Co2+、Ni2+、Bi3+的存在几乎不干扰4-硝基酚的测定。Investigate metal ions (Na+ , Mg2+ , K+ , Zn2+ , Fe3+ , Ca2+ , Ba2+ , Pb2+ , Cu2+ , Co2+ , Ni2+ , Bi3+ , respectively ) interferes with the determination of 4-nitrophenol. Take 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL, 10 mM 4-MIm, 4-nitrophenol concentration of 20 μg/mL, metal ion concentration of 125 μM, dilute to 4.00 mL, and react at 25 °C for 10 min. At an excitation wavelength of 322 nm, an excitation slit of 5 nm and an emission slit of 5 nm were used to measure the fluorescence intensity of the mixed system. Figure 6 shows the interference of metal ions on the determination of 4-nitrophenol by the 4-MIm-AuNCs@APAP fluorescence enhancement system. It can be seen from Figure 6 that Pb2+ and Cu2+ interfere slightly with the determination of 4-nitrophenol, Fe3+ interferes seriously, and other metal ions Na+ , Mg2+ , K+ , Zn2+ , Ca2+ , The presence of Ba2+ , Co2+ , Ni2+ , Bi3+ hardly interferes with the determination of 4-nitrophenol.
实际样品的测定Determination of actual samples
地表水样过滤后可直接用于测定。取0.2mL金纳米簇AuNCs@APAP和0.2mL、10mM 4-MIm，加入一定体积过滤后的地表水样，定容至4.00mL，于25℃反应10min。在激发波长322nm，激发狭缝5nm，发射狭缝5nm，测定混合体系的荧光强度。所测定的四种水样中未检测出2,4-二硝基酚和4-硝基酚。加标回收实验结果见表1和表2。由表1和表2中的相对标准偏差以及加标回收率可知，本发明构建的测定地表水样中2,4-二硝基酚和4-硝基酚浓度的荧光增强体系是可行可靠的。Surface water samples can be directly used for determination after filtration. Take 0.2 mL of gold nanoclusters AuNCs@APAP and 0.2 mL, 10 mM 4-MIm, add a certain volume of filtered surface water sample, dilute the volume to 4.00 mL, and react at 25 °C for 10 min. At an excitation wavelength of 322 nm, an excitation slit of 5 nm and an emission slit of 5 nm were used to measure the fluorescence intensity of the mixed system. 2,4-Dinitrophenol and 4-nitrophenol were not detected in the four water samples tested. The results of the spike recovery experiments are shown in Tables 1 and 2. It can be seen from the relative standard deviation and the standard addition recovery rate in Table 1 and Table 2 that the fluorescence enhancement system constructed by the present invention for determining the concentration of 2,4-dinitrophenol and 4-nitrophenol in surface water samples is feasible and reliable. .
表1 地表水样中2,4-二硝基酚的加标回收实验Table 1 The recovery experiment of 2,4-dinitrophenol in surface water samples
表2 地表水样中4-硝基酚的加标回收实验Table 2 The recovery experiment of 4-nitrophenol in surface water samples
以上显示和描述了本发明的基本原理，主要特征和优点，在不脱离本发明精神和范围的前提下，本发明还有各种变化和改进，这些变化和改进都落入要求保护的本发明的范围。The basic principles, main features and advantages of the present invention have been shown and described above. Without departing from the spirit and scope of the present invention, the present invention has various changes and improvements, which all fall into the claimed invention. range.
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