CN110540835B - Preparation method and application of copper nanocluster CuNCs @ CAZ - Google Patents

Preparation method and application of copper nanocluster CuNCs @ CAZ Download PDF

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CN110540835B
CN110540835B CN201910792548.7A CN201910792548A CN110540835B CN 110540835 B CN110540835 B CN 110540835B CN 201910792548 A CN201910792548 A CN 201910792548A CN 110540835 B CN110540835 B CN 110540835B
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cuncs
dinitrophenol
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CN110540835A (en
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王治科
张柏爽
孙悦
刘嘉妍
韩全洲
叶存玲
范顺利
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Henan Normal University
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Abstract

The invention discloses a preparation method and application of a copper nanocluster CuNCs @ CAZ, and belongs to the technical field of analytical chemistry. The technical scheme of the invention is as follows: a preparation method of a copper nanocluster CuNCs @ CAZ comprises the following specific steps: 1.0mL of 10mM CuCl was taken2·2H2Adding 3.2mL, 5mM ceftazidime and 2.8mL of ultrapure water into a 50mL jacketed beaker under the condition of vigorous stirring, reacting in the dark for 1h under the condition of vigorous stirring at 80 ℃, adding 3mL and 50mM ascorbic acid, continuing to react for 3h, cooling the solution to room temperature, filtering by using a 0.45-micrometer hydrophilic PTFE needle filter, dialyzing for 24h by using a 1kDa dialysis bag, and storing the prepared copper nanoclusters CuNCs @ CAZ in the dark at 4 ℃ for later use. The preparation method of the copper nanocluster is simple and convenient, mild in conditions, excellent in fluorescence performance and capable of specifically responding to 2, 4-dinitrophenol in a surface water sample. The constructed determination method has high selectivity and high anti-interference performance, and can quickly realize the determination of the trace 2, 4-dinitrophenol in the surface water sample.

Description

Preparation method and application of copper nanocluster CuNCs @ CAZ
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a preparation method and application of a copper nanocluster CuNCs @ CAZ.
Background
Common metal nanoclusters mainly include gold nanoclusters, silver nanoclusters and copper nanoclusters. Copper is inexpensive compared to gold and silver, and has similar properties to gold and silver, and thus, research and development of new copper nanoclusters has drawn attention from a wide range of technologists.
Due to unique physicochemical properties, the copper nanocluster becomes a novel fluorescent probe with great development potential, and can be applied to detection of metal ions, small molecular substances, proteins, nucleic acids and the like and biomarker imaging.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of the copper nanocluster CuNCs @ CAZ, which is simple and convenient in synthesis method, mild in condition and excellent in fluorescence performance, and thus a new method for measuring 2, 4-dinitrophenol with high selectivity, high sensitivity and high anti-interference performance is constructed, and the method is used for rapidly measuring the content of trace 2, 4-dinitrophenol in a surface water sample.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the copper nanocluster CuNCs @ CAZ is characterized by comprising the following specific steps of: 1.0mL of 10mM CuCl was taken2·2H2O in a 50mL jacketed beaker, adding 3.2mL, 5mM ceftazidime and 2.8mL ultrapure water under the condition of vigorous stirring, reacting for 1h in the dark under the condition of vigorous stirring at 80 ℃, adding 3mL and 50mM ascorbic acid, continuing to react for 3h, cooling the solution to room temperature, filtering by using a 0.45 mu m hydrophilic PTFE needle filter, dialyzing for 24h by using a 1kDa dialysis bag, and storing the prepared copper nanoclusters CuNCs @ CAZ in the dark at 4 ℃ for later use.
The invention relates to an application of a copper nanocluster CuNCs @ CAZ in rapid and selective determination of the concentration of trace 2, 4-dinitrophenol in a surface water sample, which is characterized by comprising the following specific processes: taking 1mL of CuNCs @ CAZ diluted by 4 times and 0.2mL of BR buffer solution with the pH =9, adding 2, 4-dinitrophenol to be detected, fixing the volume to 4.00mL, reacting for 20min at 20 ℃, then exciting a slit at 382nm of excitation wavelength by 5nm and emitting a slit at 10nm, determining the fluorescence intensity of a mixed system, and then calculating according to the measured fluorescence intensity and combining with a linear equation to obtain the concentration of the 2, 4-dinitrophenol to be detected; the linear concentration range of the 2, 4-dinitrophenol is 0.4-20 mu g/mL,the linear equation is (F)0-F)/F=0.1848C2,4-DNP-0.1419，F0F is the fluorescence intensity of the system before and after the 2, 4-dinitrophenol is added, and the correlation coefficient R2=0.9931, limit of detection LOD 0.13 μ g/mL, 2, 4-dinitrophenol concentration 10 μ g/mL, 15 replicates, relative standard deviation RSD 2.99%.
The preparation method of the copper nanocluster is simple and convenient, mild in condition, excellent in fluorescence performance and capable of specifically responding to 2, 4-dinitrophenol in a surface water sample. The constructed determination method has high selectivity and high anti-interference performance, and can quickly realize the determination of the trace 2, 4-dinitrophenol in the surface water sample.
Drawings
FIG. 1 is a graph of the effect of pH on the fluorescence properties of CuNCs @ CAZ.
FIG. 2 is a graph showing the effect of storage time on the fluorescence properties of CuNCs @ CAZ.
FIG. 3 is a graph of the effect of exposure time on the fluorescence properties of CuNCs @ CAZ.
FIG. 4 is a graph of the effect of ionic strength on the fluorescence properties of CuNCs @ CAZ.
FIG. 5 is the excitation and emission spectra of CuNCs @ CAZ.
FIG. 6 is an infrared spectrum of CuNCs @ CAZ and Ceftazidime (CAZ).
FIG. 7 is the specific response of CuNCs @ CAZ to 2, 4-dinitrophenol.
FIG. 8 is a graph showing the interference of phenols and analogs in the determination of 2, 4-dinitrophenol.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be understood that the scope of the subject matter of the present invention is limited to the examples below, and any technique realized based on the above contents of the present invention falls within the scope of the present invention.
Examples
Preparation of CuNCs @ CAZ
1.0mL of 10mM CuCl was taken2·2H2O in a 50mL jacketed beaker, 3.2mL, 5mM Ceftazidime (CAZ) and 2.8mL of ultrapure water were added under vigorous stirring, the mixture was reacted for 1 hour under vigorous stirring at 80 ℃ in the dark, and 3 hours were addedAnd (3) continuously reacting for 3 hours by using 50mM Ascorbic Acid (AA) in the mL, cooling the solution to room temperature, filtering the solution by using a 0.45-micron hydrophilic PTFE needle filter, dialyzing the solution for 24 hours by using a 1kDa dialysis bag, and storing the prepared copper nanocluster CuNCs @ CAZ at the temperature of 4 ℃ in a dark place for later use.
Determination of 2, 4-dinitrophenol
1mL of 4-fold diluted CuNCs @ CAZ and 0.2mL of BR buffer (pH = 9) was taken, and a volume of 2,4-DNP solution was added to bring the volume to 4.00 mL. The above solutions were mixed and shaken up, reacted at 20 ℃ for 20min, and the fluorescence intensity of the mixed system was measured at an excitation wavelength of 382nm (excitation slit 5nm, emission slit 10 nm). The linear concentration range of 2,4-DNP is 0.4-20. mu.g/mL, and the linear equation is (F)0-F)/F=0.1848C2,4-DNP-0.1419（F0F is the fluorescence intensity of the system before and after the addition of 2,4-DNP, C 2，4-DNP2,4-DNP concentration in. mu.g/mL), correlation coefficient R2=0.9931, limit of detection (LOD) 0.13 μ g/mL, 2,4-DNP concentration 10 μ g/mL, 15 replicates, relative standard deviation (RSD%) 2.99%.
Fluorescence property and characterization of CuNCs @ CAZ
FIG. 1 is a graph of the effect of pH on the fluorescence properties of CuNCs @ CAZ. The stability of CuNCs @ CAZ is greatly affected by pH, and the fluorescence intensity is strongest when pH =3, indicating that the fluorescence intensity of CuNCs @ CAZ is higher under acidic conditions.
FIG. 2 is a graph showing the effect of storage time on the fluorescence properties of CuNCs @ CAZ. The CuNCs @ CAZ has little change of fluorescence intensity when being stored for one month in a dark condition at 4 ℃, which indicates that the CuNCs @ CAZ has good storage stability.
FIG. 3 is a graph of the effect of exposure time on the fluorescence properties of CuNCs @ CAZ. After the UV lamp is used for irradiating for 90min at the wavelength of 365nm, the fluorescence intensity of CuNCs @ CAZ is slightly reduced, and the fluorescence intensity is 92.9 percent of the initial value.
FIG. 4 is a graph of the effect of ionic strength on the fluorescence properties of CuNCs @ CAZ. The fluorescence intensity of CuNCs @ CAZ hardly changes as the concentration of NaCl added increases from 0mM to 300 mM.
FIG. 5 is the excitation and emission spectra of CuNCs @ CAZ. The optimal excitation wavelength of CuNCs @ CAZ is 382nm, and the optimal emission peak is 459 nm.
FIG. 6 is an infrared spectrum of CuNCs @ CAZ and Ceftazidime (CAZ). 1615.46cm-1For N-H bending vibration of primary amine in CAZ, 684.16cm-1Caused by N-H out-of-plane bending vibrations of secondary amides, 1534.69cm-1Is represented by-COO-Antisymmetric telescopic vibration of 1754.93cm-1And 1703.59cm-1Caused by C = O stretching vibration, 1155.40cm-1C-O telescopic vibration absorption is adopted. Hydrogenation of the S atom present on the thiazide ring to Cu2+Reduction to Cu+S present on the hydrogenated thiazide ring in CAZ is oxidized to sulfoxide (S = O), and the above-mentioned characteristic peak disappears in the infrared spectrum of CuNCs @ CAZ, indicating-S, -NH in CAZ2C = O, etc. may be involved in the synthesis of copper nanoclusters (CuNCs @ CAZ).
Selectivity and anti-interference performance of determination method
The influence of common phenols and similar substances such as 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), o-aminophenol (OAP), m-aminophenol (MAP), p-aminophenol (PAP), p-acetaminophenol (APAP), catechol (CC), Benzoic Acid (BA), bisphenol A (BPA) and the like on the fluorescence performance of the copper nanocluster CuNCs @ CAZ system is examined. As shown in fig. 7, the phenols and similar substances examined were not able to significantly reduce the fluorescence intensity of the system. The method is used for determining the concentration of the 2, 4-dinitrophenol in the sample by using the fluorescence detection method based on the copper nanocluster.
FIG. 8 is a graph of the interference of phenols and analogs with the determination of 2, 4-dinitrophenol. As can be seen from FIG. 8, the measurement of 2, 4-dinitrophenol is hardly interfered by common phenols and similar substances such as 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), o-aminophenol (OAP), m-aminophenol (MAP), p-aminophenol (PAP), p-acetaminophenol (APAP), catechol (CC), Benzoic Acid (BA), bisphenol A (BPA), and the like.
Determination of 2, 4-dinitrophenol in actual surface water sample
1mL of four-fold diluted CuNCs @ CAZ and 0.2mL of BR buffer (pH = 9) were added to a volume of aqueous sample to 4.00 mL. Mixing the above solutions, shaking, reacting at 20 deg.C for 20min, and scanning fluorescence spectrum of the mixed system at excitation wavelength 382nm (excitation slit 5nm, emission slit 10 nm). The concentration of the 2, 4-dinitrophenol is measured after the surface water sample is filtered, and the method is not detected. The results of the standard recovery experiments are shown in Table 1.
TABLE 1 measurement results of standard recovery experiment of 2,4-DNP in surface water sample
Figure DEST_PATH_IMAGE002
While there have been shown and described what are at present considered the fundamental principles of the invention, its essential features and advantages, the invention further resides in various changes and modifications which fall within the scope of the invention as claimed.

Claims (1)

1. The application of the copper nanocluster CuNCs @ CAZ in rapid and selective determination of the concentration of trace 2, 4-dinitrophenol in a surface water sample is characterized by comprising the following specific steps: taking 1mL of CuNCs @ CAZ diluted by 4 times and 0.2mL of BR buffer solution with the pH =9, adding 2, 4-dinitrophenol to be detected, fixing the volume to 4.00mL, reacting for 20min at 20 ℃, then exciting a slit at 382nm of excitation wavelength by 5nm and emitting a slit at 10nm, determining the fluorescence intensity of a mixed system, and then calculating according to the measured fluorescence intensity and combining with a linear equation to obtain the concentration of the 2, 4-dinitrophenol to be detected; the linear concentration range of the 2, 4-dinitrophenol is 0.4-20 mu g/mL, and the linear equation is (F)0-F)/F=0.1848C2,4-DNP-0.1419，F0F is the fluorescence intensity of the system before and after the 2, 4-dinitrophenol is added, and the correlation coefficient R is2=0.9931, detection limit LOD is 0.13 mug/mL, concentration of 2, 4-dinitrophenol is 10 mug/mL, parallel determination is carried out for 15 times, and relative standard deviation RSD is 2.99%;
the specific preparation process of the copper nanocluster CuNCs @ CAZ comprises the following steps: 1.0mL of 10mM CuCl was taken2·2H2O in a 50mL jacketed beaker, 3.2mL, 5mM ceftazidime and 2.8mL ultrapure water were added under vigorous stirring, and the mixture was reacted for 1 hour under vigorous stirring at 80 ℃ in the dark, then 3mL of,And (3) continuing the reaction for 3 hours by using 50mM ascorbic acid, cooling the solution to room temperature, filtering the solution by using a 0.45-micrometer hydrophilic PTFE needle filter, dialyzing the solution for 24 hours by using a 1kDa dialysis bag, and storing the prepared copper nanoclusters CuNCs @ CAZ at 4 ℃ in a dark place for later use.
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Publication number Priority date Publication date Assignee Title
CN104745194A (en) * 2015-03-24 2015-07-01 南昌大学 Preparation method of quantum dot@Cu nano-cluster ratiometric fluorescent sensor and application thereof in Cu<2+> detection
CN108776127A (en) * 2018-08-30 2018-11-09 河南师范大学 It a kind of AuAgNCs@APAP fluorescence probes and preparation method thereof and is applied in measuring amino acid
CN110102775A (en) * 2019-05-22 2019-08-09 西南大学 A kind of copper nano-cluster synthesized using Cu-MOFs as precursor and synthetic method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104745194A (en) * 2015-03-24 2015-07-01 南昌大学 Preparation method of quantum dot@Cu nano-cluster ratiometric fluorescent sensor and application thereof in Cu<2+> detection
CN108776127A (en) * 2018-08-30 2018-11-09 河南师范大学 It a kind of AuAgNCs@APAP fluorescence probes and preparation method thereof and is applied in measuring amino acid
CN110102775A (en) * 2019-05-22 2019-08-09 西南大学 A kind of copper nano-cluster synthesized using Cu-MOFs as precursor and synthetic method

Non-Patent Citations (2)

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Title
One-step，stabilizer-free and green synthesis of Cu nanoclusters as fluorescent probes for sensitive and selective detection of nitrite ions;Xiang-Juan Zheng et al.;《Sensors and Actuators B: Chemical》;20160218;第230卷;第315页2.3 *
tudy of the nucleation and growth of antibiotic labeled Au NPs and blue luminescent Au8 quantum clusters for Hg2+ ion sensing, cellular imaging and antibacterial applications;Puneet Khandelwal et al.;《Nanoscale》;20151022;第7卷;第19985页摘要 *

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