阅读说明：本技术 基于金纳米簇AuNCs@CFP构建的用于特异性响应对硝基苯酚的荧光分析体系 (The use in fluorescence assay systems for specificly-response p-nitrophenol based on gold nanoclusters AuNCs@CFP building ) 是由 王治科 张楠 赵书南 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@CFP构建的用于特异性响应对硝基苯酚的荧光分析体系,取200μL金纳米簇AuNCs@CFP、500μL、pH=10的PB缓冲溶液和待测对硝基苯酚定容至4mL,在45℃条件下反应50min,在激发波长334nm处测定其荧光强度,根据测定荧光强度结合回归方程计算得到待测对硝基苯酚浓度；对硝基苯酚线性浓度范围在1.25-40μΜ,回归方程为F<Sub>0</Sub>/F<Sub>i(The invention discloses a kind of use in fluorescence assay systems for specificly-response p-nitrophenol based on gold nanoclusters AuNCs@CFP building, 200 μ L gold nanoclusters AuNCs@CFP, 500 μ L, the PB buffer solution of pH=10 and p-nitrophenol to be measured is taken to be settled to 4mL, 50min is reacted under the conditions of 45 DEG C, its fluorescence intensity is measured at excitation wavelength 334nm, and p-nitrophenol concentration to be measured is obtained according to measurement fluorescence intensity combination regression equation calculation；P-nitrophenol linear concentration range is in 1.25-40 μ Μ, regression equation F 0 /F i =0.0258C+1.0003, F 0 And F i The fluorescence intensity of p-nitrophenol front and back mixed system, coefficient R is respectively added 2 =0.9922, detection limit LOD are 1.92 μ Μ, and p-nitrophenol concentration is 25 μM, are repeated 11 times measurement, and relative standard deviation RSD is 1.13%.The preparation method of gold nanoclusters AuNCs@CFP is simple in the present invention, is readily synthesized, and the fluorescence property of gold nanoclusters AuNCs@CFP is excellent.)

1. special based on the use in fluorescence assay systems for specificly-response p-nitrophenol of gold nanoclusters [email protected] building Sign is: 200 μ L gold nanoclusters [email protected], 500 μ L, the PB buffer solution of pH=10 and p-nitrophenol to be measured being taken to be settled to 4mL reacts 50min under the conditions of 45 DEG C, its fluorescence intensity is measured at excitation wavelength 334nm, according to measurement fluorescence intensity knot It closes regression equation calculation and obtains p-nitrophenol concentration to be measured；P-nitrophenol linear concentration range is returned in 1.25-40 μ Μ Equation is F₀/F_i=0.0258C+1.0003, F₀And F_iThe fluorescence intensity of p-nitrophenol front and back mixed system, phase is respectively added Close coefficients R²=0.9922, detection limit LOD are 1.92 μ Μ, and p-nitrophenol concentration is 25 μM, are repeated 11 times measurement, relative standard Deviation RSD is 1.13%；

The specific preparation process of the gold nanoclusters [email protected] are as follows: take the HAuCl of 0.5mL, 24.28mM₄Solution is in 50mL circle In the flask of bottom, 8.28mL pure water is added, is heated while stirring, the cefoperazone of 1.22mL, 5mM are added after solution boils Sodium is cooled to room temperature after the reaction was continued 11h, is filtered using 0.45 μm of hydrophilic PTFE, finally by the gold nanoclusters [email protected] synthesis It is spare that CFP is stored in 4 DEG C of refrigerators.

2. according to claim 1 be used for specificly-response p-nitrophenol based on gold nanoclusters [email protected] building Use in fluorescence assay systems, it is characterised in that: common phenolic compound does not respond to the use in fluorescence assay systems of building substantially, and Common phenolic compound does not interfere the measurement of p-nitrophenol substantially, shows to be used for based on what gold nanoclusters [email protected] was constructed The selectivity of the use in fluorescence assay systems of specificly-response p-nitrophenol is strong and strong antijamming capability, wherein common phenolic compound For 2- nitrophenol, o-aminophenol, para-aminophenol, m-aminophenol, 3- nitrophenol, bisphenol-A, acamol Or one of benzoic acid or a variety of.

3. according to claim 1 be used for specificly-response p-nitrophenol based on gold nanoclusters [email protected] building Use in fluorescence assay systems, it is characterised in that: the use in fluorescence assay systems is for analyzing filtered earth's surface water sample, the ground P-nitrophenol is not detected in table water sample, the recovery of standard addition of p-nitrophenol is between 99.10%-102.87%, relatively For standard deviation RSD between 0.42%-3.21%, it is right in earth's surface water sample that this shows that the use in fluorescence assay systems of building can be used successfully to The selective determination of nitrophenol.

Technical field

The invention belongs to the constructing technology fields of the use in fluorescence assay systems for specificly-response p-nitrophenol, specifically relate to And a kind of use in fluorescence assay systems for specificly-response p-nitrophenol based on gold nanoclusters [email protected] building.

Background technique

P-nitrophenol (4-NP) is widely used in pesticide synthesis, dyestuff processing, colored leather, wood preservation, pharmaceutical synthesis With explosive etc..Although it is widely used, since its is carcinogenic, causes gene mutation and cause skin disease, therefore the compound is claimed For the phenols of highly dangerous in organic matter.Therefore, it is necessary to develop the effective and easy analysis side of highly sensitive detection p-nitrophenol Method.The detection method of report, including high performance liquid chromatography, UV-VIS spectrophotometry, capillary electrophoresis and fluorescence side Method etc., for the p-nitrophenol in determination of the environment water sample.These methods are most of relatively expensive, time-consuming, and complicated and needs are big Measure organic solvent.Fluorescence analysis based on nano-cluster provides a kind of new selection for detection p-nitrophenol.

Summary of the invention

The technical problem to be solved by the present invention is to provide a kind of responses fastly, high sensitivity and selectivity are good based on gold nano The use in fluorescence assay systems for specificly-response p-nitrophenol of cluster [email protected] building, Jenner in the use in fluorescence assay systems The preparation method of rice cluster is simple, is readily synthesized and has excellent fluorescence property.

1. the present invention adopts the following technical scheme that solve above-mentioned technical problem, constructed based on gold nanoclusters [email protected] The use in fluorescence assay systems for specificly-response p-nitrophenol, it is characterised in that: take 200 μ L gold nanoclusters [email protected], 500 μ L, the PB buffer solution of pH=10 and p-nitrophenol to be measured are settled to 4mL, react 50min under the conditions of 45 DEG C, are exciting Its fluorescence intensity is measured at wavelength 334nm, and p-nitrophenol to be measured is obtained according to measurement fluorescence intensity combination regression equation calculation Concentration；P-nitrophenol linear concentration range is in 1.25-40 μ Μ, regression equation F₀/F_i=0.0258C+1.0003, F₀And F_i The fluorescence intensity of p-nitrophenol front and back mixed system, coefficient R is respectively added²=0.9922, detection limit LOD are 1.92 μ Μ, p-nitrophenol concentration are 25 μM, are repeated 11 times measurement, and relative standard deviation RSD is 1.13%；

The specific preparation process of the gold nanoclusters [email protected] are as follows: take the HAuCl of 0.5mL, 24.28mM₄Solution is in 50mL circle In the flask of bottom, 8.28mL pure water is added, is heated while stirring, the cefoperazone of 1.22mL, 5mM are added after solution boils Sodium is cooled to room temperature after the reaction was continued 11h, is filtered using 0.45 μm of hydrophilic PTFE, finally by the gold nanoclusters [email protected] synthesis It is spare that CFP is stored in 4 DEG C of refrigerators.

Preferably, common phenolic compound does not respond to the use in fluorescence assay systems of building substantially, and common phenol generalization The measurement that object does not interfere p-nitrophenol substantially is closed, shows that is constructed based on gold nanoclusters [email protected] is used for specificly-response The selectivity of the use in fluorescence assay systems of p-nitrophenol is strong and strong antijamming capability, wherein common phenolic compound is 2- nitrobenzene In phenol, o-aminophenol, para-aminophenol, m-aminophenol, 3- nitrophenol, bisphenol-A, acamol or benzoic acid It is one or more.

Preferably, the use in fluorescence assay systems does not have in the earth's surface water sample for analyzing filtered earth's surface water sample Detect p-nitrophenol, the recovery of standard addition of p-nitrophenol is between 99.10%-102.87%, relative standard deviation RSD Between 0.42%-3.21%, this shows that the use in fluorescence assay systems of building can be used successfully to p-nitrophenol in earth's surface water sample It selectively measures.

The preparation method of gold nanoclusters [email protected] is simple in the present invention, is readily synthesized, and gold nanoclusters [email protected] The fluorescence property of CFP is excellent, and the linear concentration range of p-nitrophenol is in 1.25-40 μ Μ, coefficient R²=0.9922, relatively Standard deviation is 1.13%, and detection is limited to 1.92 μ Μ, can be successfully applied to the specificity inspection of p-nitrophenol in earth's surface water sample It surveys.

Detailed description of the invention

Fig. 1 is influence of the resting period to gold nanoclusters [email protected] fluorescence property.It is saved 50 days at 4 DEG C in refrigerator, The fluorescence intensity level of gold nanoclusters [email protected] hardly happens variation.

Fig. 2 is influence of the pH to gold nanoclusters [email protected] fluorescence property.PH is within the scope of 4-7, gold nanoclusters [email protected] The fluorescence intensity of CFP hardly happens variation.PH value is continued growing, fluorescence intensity slightly reduces.

Fig. 3 is influence of the sodium chloride concentration to gold nanoclusters [email protected] fluorescence property.Sodium chloride concentration is in 50-300mM In range, the fluorescence intensity of use in fluorescence assay systems does not have significant change.

Fig. 4 is influence of the time for exposure to gold nanoclusters [email protected] fluorescence property.After ultraviolet light irradiation 60min, Jenner Rice cluster [email protected] fluorescence intensity does not change substantially.

Fig. 5 is the excitation and emission spectra of gold nanoclusters [email protected] maximum excitation of gold nanoclusters [email protected] and The position of emission peak is respectively at 334nm and 382nm.

Fig. 6 is emission spectrum of the gold nanoclusters [email protected] under different excitation wavelengths.Excitation wavelength is increased by 319nm Movement is hardly happened to the position of 349nm, gold nanoclusters [email protected] emission peak, this shows gold nanoclusters [email protected] Partial size it is small and uniform.

Fig. 7 is the infrared spectrum of cefoperazone sodium CFP and gold nanoclusters [email protected] sodium and gold nanoclusters There are nuance, such as 1658cm between the infrared spectrum of [email protected]^-1Place absorption peak be by-the C in cefoperazone sodium=O not Caused by symmetrical stretching vibration, due to the interaction of CFP and Au, had occurred in gold nanoclusters [email protected] infrared spectrum Blue shift.

Fig. 8 is the selectivity and interference free performance of use in fluorescence assay systems measuring method.

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.