Fluorescence enhancement system and its application based on gold nanoclusters AuNCs@APAP
阅读说明：本技术 基于金纳米簇AuNCs@APAP的荧光增强体系及其应用 (Fluorescence enhancement system and its application based on gold nanoclusters AuNCs@APAP ) 是由 王治科 张柏爽 韩全洲 王全坤 叶存玲 范顺利 于 2019-08-26 设计创作，主要内容包括：本发明公开了一种基于金纳米簇AuNCs@APAP的荧光增强体系及其应用,属于荧光分析技术领域。本发明的技术方案要点为：1,2-二甲基咪唑、2-甲基咪唑或4-甲基咪唑能够显著增强金纳米簇AuNCs@APAP的荧光强度进而构建基于金纳米簇AuNCs@APAP的荧光增强体系,荧光强度增加6.6-6.9倍,构建的荧光增强体系能够成功用于地表水样中2,4-二硝基酚和4-硝基酚浓度的选择性测定。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水样检测中得到推广应用。(The invention discloses a kind of fluorescence enhancement systems and its application based on gold nanoclusters AuNCs@APAP, belong to fluorescence analysis field.Technical solution of the present invention main points are as follows: 1,2- methylimidazole, 2-methylimidazole or 4-methylimidazole can significantly increase the fluorescence intensity of gold nanoclusters AuNCs@APAP and then construct the fluorescence enhancement system based on gold nanoclusters AuNCs@APAP, fluorescence intensity increases 6.6-6.9 times, the fluorescence enhancement system of building can be used successfully to the selective determination of 2,4- dinitrophenol dinitrophenolate and 4- nitrophenols concentration in earth's surface water sample.The fluorescence enhancement system based on gold nanoclusters AuNCs@APAP that the present invention constructs is to 2,4- dinitrophenol dinitrophenolate and 4- nitrophenols all have specificly-response ability, and thus construct selective strong, high sensitivity and strong antijamming capability measurement 2, the method of 4- dinitrophenol dinitrophenolate and 4- nitrophenols concentration, the fluorescence enhancement system are expected to be widely applied in water sample detection.)
1. the fluorescence enhancement system based on gold nanoclusters [email protected], it is characterised in that: take 0.2mL gold nanoclusters [email protected] APAP is added glyoxaline compound, is settled to 4.00mL, react that 10min obtain that fluorescence intensity is remarkably reinforced in 25 DEG C based on The fluorescence enhancement system of gold nanoclusters [email protected], fluorescence intensity increase 6.6-6.9 times, and wherein glyoxaline compound is 1,2- One of methylimidazole, 2-methylimidazole or 4-methylimidazole are a variety of.
2. the fluorescence enhancement system according to claim 1 based on gold nanoclusters [email protected], it is characterised in that: described DMIZ 1,2 dimethylimidazole, 2-methylimidazole, 4-methylimidazole concentration be 0.5mM or 2mM.
3. the fluorescence enhancement system of any of claims 1 or 2 based on gold nanoclusters [email protected] is selectively measuring 2,4- Application in dinitrophenol dinitrophenolate and 4- nitrophenols concentration, it is characterised in that detailed process are as follows:
0.2mL gold nanoclusters [email protected] and 0.2mL 10mM 4-MIm is taken, 2,4- dinitrophenol dinitrophenolate to be measured is added, is settled to 4.00mL measures mixed system in excitation wavelength 322nm, exciting slit 5nm, transmite slit 5nm in 25 DEG C of reaction 10min Fluorescence intensity obtains the concentration of 2,4- dinitrophenol dinitrophenolate to be measured according to the fluorescence intensity measured and in conjunction with linear equation calculation；2,4- Dinitrophenol dinitrophenolate linear concentration range is 0.375-12.5 μ g/mL, and linear equation is (F0- F)/F=0.1454C2,4-DNP - 0.0592, C2,4-DNPFor 2,4-DNP concentration, unit μ g/mL, coefficient R2=0.9927, detection limit LOD are 0.301 μ g/mL, 2,4-DNP concentration are 5 μ g/mL, are measured in parallel 15 times, and relative standard deviation RSD% is 2.37%；
0.2 mL gold nanoclusters [email protected] and 0.2mL, 10mM 4-MIm are taken, 4- nitrophenols to be measured is added, is settled to 4.00mL measures mixed system in excitation wavelength 322nm, exciting slit 5nm, transmite slit 5nm in 25 DEG C of reaction 10min Fluorescence intensity obtains the concentration of 4- dinitrophenol dinitrophenolate to be measured according to the fluorescence intensity measured and in conjunction with linear equation calculation；4- nitro Phenol linear concentration range is 0.375-25 μ g/mL, and linear equation is (F0- F)/F=0.1935C4-NP- 0.1018, C4-NPFor 4- NP concentration, unit μ g/mL, coefficient R2=0.9939, detection limit LOD are that 0.246 μ g/mL, 4-NP concentration is 5 μ g/mL, are put down Row measurement 15 times, relative standard deviation RSD% are 3.21%.
4. the fluorescence enhancement system of any of claims 1 or 2 based on gold nanoclusters [email protected] is selectively measuring earth's surface Application in water sample in 2,4- dinitrophenol dinitrophenolate and 4- nitrophenols concentration, it is characterised in that detailed process are as follows: take 0.2mL gold nanoclusters AuNCs APAP and 0.2mL, 10mM 4-MIm are added filtered earth's surface water sample, are settled to 4.00mL, react in 25 DEG C 10min measures the fluorescence intensity of mixed system, is measured in excitation wavelength 322nm, exciting slit 5nm, transmite slit 5nm Do not detect 2,4- dinitrophenol dinitrophenolate and 4- nitrophenols in earth's surface water sample, 2,4- dinitrophenol dinitrophenolates and 4- nitrophenols mark-on reclaims it is opposite Standard deviation be between 0.51%-2.82% between 0.14%-3.20% and recovery of standard addition be 96.28%-103.82% and Between 97.91%-106.13%, show that the fluorescence enhancement system based on gold nanoclusters [email protected] of building can be used in selecting Property measurement earth's surface water sample in 2,4- dinitrophenol dinitrophenolate and 4- nitrophenols concentration.
Technical field
The invention belongs to fluorescence analysis fields, and in particular to a kind of fluorescence increasing based on gold nanoclusters [email protected] Strong system and its application.
Background technique
In analytical chemistry field, fluorescence analysis has obtained great concern, is widely used in environment, life science and material Many fields such as material science.But the quantum yield of some fluorescent molecules is relatively low, seriously reduces the sensitivity of analysis method. Therefore, further increasing fluorescence intensity is to improve the important method of analysis detection sensitivity.
Gold nanoclusters are due to having many advantages, such as preferable photostability, hypotoxicity, in analysis, catalysis, bio-imaging Equal fields are all widely used, but the defect low there is also quantum yield.Therefore, the fluorescence intensity for enhancing gold nanoclusters, mentions High detection sensitivity is the further inevitable link for expanding gold nanoclusters application range.
Summary of the invention
Strong, high sensitivity that the technical problem to be solved by the present invention is to provide a kind of selectivity and strong antijamming capability based on The fluorescence enhancement system of gold nanoclusters [email protected], the fluorescence enhancement system is for this seminar once with paracetamol (APAP) gold nanoclusters ([email protected]) synthesized for reducing agent and protective agent, 1,2- methylimidazole (1,2-MIm), 2- first Base imidazoles (2-MIm) or 4-methylimidazole (4-MIm) can significantly increase the fluorescence intensity of above-mentioned gold nanoclusters [email protected], Fluorescence intensity increases 6.6-6.9 times, while the fluorescence enhancement system constructed can be used successfully to 2,4- dinitro in earth's surface water sample The selective determination of phenol (2,4-DNP) and 4- nitrophenols (4-NP) concentration.
The present invention uses following technical method to solve above-mentioned technical problem, the fluorescence based on gold nanoclusters [email protected] Enhancing system, it is characterised in that: 0.2mL gold nanoclusters AuNCs APAP is taken, glyoxaline compound is added, is settled to 4.00mL, 10min is reacted in 25 DEG C obtains the fluorescence enhancement system based on gold nanoclusters [email protected] that fluorescence intensity is remarkably reinforced, it is glimmering Luminous intensity increases 6.6-6.9 times, and wherein glyoxaline compound is in 1,2- methylimidazole, 2-methylimidazole or 4-methylimidazole It is one or more.
Preferably, 1, the 2- methylimidazole, 2-methylimidazole, 4-methylimidazole concentration be 0.5mM or 2mM.
Fluorescence enhancement system of the present invention based on gold nanoclusters [email protected] is selectively measuring 2,4- dinitro Application in base phenol and 4- nitrophenols concentration, it is characterised in that detailed process are as follows:
0.2mL gold nanoclusters [email protected] and 0.2mL, 10mM 4-MIm are taken, 2,4- dinitrophenol dinitrophenolate to be measured is added, is settled to 4.00mL measures mixed system in excitation wavelength 322nm, exciting slit 5nm, transmite slit 5nm in 25 DEG C of reaction 10min Fluorescence intensity obtains the concentration of 2,4- dinitrophenol dinitrophenolate to be measured according to the fluorescence intensity measured and in conjunction with linear equation calculation；2,4- Dinitrophenol dinitrophenolate linear concentration range is 0.375-12.5 μ g/mL, and linear equation is (F0- F)/F=0.1454C2,4-DNP - 0.0592, C2,4-DNPFor 2,4-DNP concentration, unit μ g/mL, coefficient R2=0.9927, detection limit LOD are 0.301 μ g/mL, 2,4-DNP concentration are 5 μ g/mL, are measured in parallel 15 times, and relative standard deviation RSD% is 2.37%；
0.2mL gold nanoclusters [email protected] and 0.2mL, 10mM 4-MIm are taken, 4- nitrophenols to be measured is added, is settled to 4.00mL measures mixed system in excitation wavelength 322nm, exciting slit 5nm, transmite slit 5nm in 25 DEG C of reaction 10min Fluorescence intensity obtains the concentration of 4- dinitrophenol dinitrophenolate to be measured according to the fluorescence intensity measured and in conjunction with linear equation calculation；4- nitro Phenol linear concentration range is 0.375-25 μ g/mL, and linear equation is (F0- F)/F=0.1935C4-NP- 0.1018, C4-NPFor 4- NP concentration, unit μ g/mL, coefficient R2=0.9939, detection limit LOD are that 0.246 μ g/mL, 4-NP concentration is 5 μ g/mL, are put down Row measurement 15 times, relative standard deviation RSD% are 3.21%.
Fluorescence enhancement system of the present invention based on gold nanoclusters AuNCs APAP is selectively measuring earth's surface water sample In application in 2,4- dinitrophenol dinitrophenolate and 4- nitrophenols concentration, it is characterised in that: take 0.2mL gold nanoclusters [email protected] and 0.2mL, 10mM 4-MIm are added filtered earth's surface water sample, are settled to 4.00mL, in 25 DEG C of reaction 10min, in excitation wavelength 322nm, exciting slit 5nm, transmite slit 5nm measure the fluorescence intensity of mixed system, do not detect in the earth's surface water sample measured The relative standard deviation of 2,4- dinitrophenol dinitrophenolate and 4- nitrophenols out, 2,4- dinitrophenol dinitrophenolates and 4- nitrophenols mark-on reclaims is 0.51%- Between 2.82% between 0.14%-3.20% and recovery of standard addition is between 96.28%-103.82% and 97.91%-106.13%, Show that the fluorescence enhancement system based on gold nanoclusters AuNCs APAP of building can be used in selectively measuring in earth's surface water sample 2,4- dinitrophenol dinitrophenolate and 4- nitrophenols concentration.
The fluorescence enhancement system based on gold nanoclusters [email protected] that the present invention constructs is to 2,4- dinitrophenol dinitrophenolate and 4- nitre Base phenol all has specificly-response ability, and thus constructs selective strong, high sensitivity and strong antijamming capability measurement 2, The method of 4- dinitrophenol dinitrophenolate and 4- nitrophenols concentration, the fluorescence enhancement system are expected in earth's surface water sample 2,4- dinitrophenol dinitrophenolate and 4- nitre It is widely applied in base phenol Concentration Testing.
Detailed description of the invention
Fig. 1 is influence of the imidazolium compounds type to [email protected] fluorescence enhancement system fluorescence enhancement.
Fig. 2 is that 2,4- dinitrophenol dinitrophenolate imitates the fluorescent quenching of different glyoxaline compound [email protected] fluorescence enhancement systems Fruit is compared.
Fig. 3 is [email protected] fluorescence enhancement system to phenols selectivity and interference free performance.
Fig. 4 is [email protected] fluorescence enhancement system to metal selective and interference free performance.
Fig. 5 is interference of the phenols to [email protected] fluorescence enhancement system of determination 4- nitrophenols.
Fig. 6 is interference of the metal ion to [email protected] fluorescence enhancement system of determination 4- nitrophenols.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.