CN109975253B - Fluorescent indicator composition, fluorescent array sensor, preparation method and application thereof - Google Patents
Fluorescent indicator composition, fluorescent array sensor, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorescent indicator combination, a fluorescent array sensor, a preparation method and application thereof. The fluorescent indicator combination comprises a plurality of carbon quantum dot-metal ion complexes formed by panchromatic fluorescent carbon quantum dots and a plurality of metal ions under different pH values. The fluorescent array sensor comprises the fluorescent indicator, the sensor comprises a plurality of groups of response points, each group of response points comprises more than three independent response points corresponding to the excitation wavelengths of 360nm, 450nm and 540nm, and each response point comprises at least one carbon quantum dot-metal ion complex. The fluorescent array sensor can realize qualitative and semi-quantitative detection of four antibiotics such as tetracycline, quinolone, beta-lactam and aminosugamine; and the preparation process is simple, the storage time is long, the detection sensitivity is good, and the simultaneous distinguishing and detection of various antibiotics can be realized.
Description
Technical Field
The invention relates to an array sensor for detecting and distinguishing antibiotics, in particular to a fluorescent indicator combination for detecting and distinguishing multiple types of antibiotics, a multi-channel fluorescent array sensor and a preparation method thereof, and application thereof in simultaneous detection of multiple types of antibiotics, belonging to the technical field of food safety detection.
Background
Antibiotics, which are capable of killing or inhibiting the growth of bacteria, have been produced in large quantities worldwide and used to treat a variety of human and veterinary diseases over the past few decades. At present, overproof antibiotics are mostly found in milk, vegetables, grains, surface water and wastewater. The three antibiotics with higher detection frequency are quinolone antibiotics, tetracycline antibiotics and sulfonamide drugs respectively. Antibiotics are also used in large quantities in animal husbandry and fishery for the purpose of ensuring food quality and preventing infection from diseases. However, abuse of antibiotics can lead to increased bacterial resistance. Most of antibiotics ingested by people and livestock cannot be absorbed and utilized and are discharged out of the body in the form of a parent body or a metabolite, enter a sewage system or are directly discharged into the environment, and pose a threat to the ecological environment. This will eventually threaten human health and social security. At present, antibiotic drug residues and bacterial drug resistance are increasing and become a big problem in the global scope, and great challenges are brought to clinical treatment. Therefore, it would be of great interest to provide a simple and efficient method for the detection of antibiotics.
At present, common antibiotic detection methods comprise a high performance liquid chromatography, an enzyme-linked immunoassay method, a surface enhanced raman scattering method, a colorimetric method and the like. These methods have been successful in detecting trace amounts of antibiotics remaining in food products such as milk, honey, pork, etc. However, the methods have the biggest problems that the required detection instrument has extremely high cost, even needs professional operators to complete, has complex sample pretreatment process and the like, and is not suitable for on-site in-situ detection.
The detection methods of antibiotics are more common at present, wherein D.Vega (Analytical and biological Chemistry 2007,389, 951-958.) and other people adopt an electrochemical method to detect four tetracycline antibiotics by using electrodes modified by multi-wall carbon nanotubes, the detection limit is 0.44 mu M, and the detection and the differentiation of various antibiotics cannot be realized. Lu Haitao (Chromographics 2004,60, 259-264) and the like can realize the detection of various antibiotics by adopting a high performance liquid chromatography method, the detection range is between 0.21 and 104 mu M, the sensitivity is not enough, and meanwhile, the high performance liquid chromatography method needs expensive instruments and professional operators, the pretreatment of samples is more complex, and the cost performance is not high in the aspect of practical application.
The array sensor is an analog of the mammalian olfactory system. In the array sensor, the same sensing unit has different degrees of response to different substances, different sensing units also have different degrees of response to the same substance, and substance identification can be performed according to a fingerprint formed by the different degrees of response of the sensing units to the substances. Compared with a high-specificity single sensor based on a 'key and lock' mode, the array sensor reduces the requirement on a high-specificity receptor, greatly expands the range of detection objects, improves the detection efficiency and the detection flux, and has great application advantages in various detection fields, particularly the detection of complex samples. Among various array sensors such as optics, electrochemistry, chromatography and the like, the photochemical array sensor is concerned about because of the advantages of high response speed, high sensitivity, abundant output signals, no influence of electromagnetic interference on the signals, realization of visual detection and the like. In recent years, in order to improve the recognition capability and sensing sensitivity of the optical array sensor, many nanomaterials are widely used to increase the number of sensing materials and develop new sensing methods.
As a novel carbon nano material, the fluorescent carbon quantum dot has the characteristics of higher luminous performance, photobleaching resistance, good biocompatibility, low toxicity, easy functionalization modification and the like compared with semiconductor quantum dots, rare earth nano materials, organic fluorescent dyes and the like, and has good development prospect in the field of analysis and detection. Therefore, the fluorescent indicator composed of the carbon quantum dots and the metal ion compound realizes simultaneous detection and identification of multiple antibiotics by using a fluorescent array sensing technology, is applied to detection of actual samples, and has important significance for guaranteeing food safety.
Disclosure of Invention
The invention mainly aims to provide a fluorescent indicator combination, a fluorescent array sensor, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a fluorescence indicator composition, which comprises a plurality of carbon quantum dot-metal ion complexes (F-CDs-metal ion complexes for short) formed by panchromatic fluorescent carbon quantum dots (F-CDs for short) and a plurality of metal ions under different pH values.
In one embodiment, the fluorescence indicator combination specifically includes:
full-color fluorescent carbon quantum dot and Cu2+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with a pH value of 6.8-7.4,
full-color fluorescent carbon quantum dot and Cu2+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with a pH value of 7.4-8.2,
full-color fluorescent carbon quantum dot and Eu3+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with a pH value of 6.8-7.4,
full-color fluorescent carbon quantum dot and Eu3+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with a pH value of 7.4-8.2,
panchromatic fluorescent carbon quantum dot and Ce3+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with a pH value of 6.8-7.4,
panchromatic fluorescent carbon quantum dot and Ce3+The carbon quantum dot-metal ion composite is formed in HEPES buffer solution with the pH value of 7.4-8.2.
In one embodiment, the preparation method of the panchromatic fluorescent carbon quantum dot comprises the following steps: and reacting citric acid with formamide by using a microwave-assisted hydrothermal method to form the panchromatic fluorescent carbon quantum dot, wherein the reaction temperature is 140-180 ℃, the reaction time is 0.5-2 h, and the microwave power is 200-400W.
Further, the excitation wavelengths corresponding to the fluorescence indicator combinations were 360nm, 450nm, 540nm, respectively, while the corresponding emission wavelengths were 466nm, 555nm, 637nm, respectively.
The embodiment of the invention also provides application of the fluorescent indicator in detection of antibiotics.
Further, the antibiotic includes any one or a combination of two or more of tetracyclines, quinolones, β -lactams, and aminoglycosamines.
The embodiment of the invention also provides a fluorescence array sensor which comprises the fluorescence indicator combination.
Preferably, the sensor comprises a plurality of sets of response points, each set of response points comprising three or more independent response points corresponding to excitation wavelengths 360nm, 450nm and 540nm, respectively, each response point comprising at least one carbon quantum dot-metal ion complex, or the sensor comprises three or more sets of response points corresponding to excitation wavelengths 360nm, 450nm and 540nm, respectively, each set of response points comprising a plurality of independent response points, each response point comprising at least one carbon quantum dot-metal ion complex.
Further, any two response points in each set of response points contain different carbon quantum dot-metal ion complexes.
The embodiment of the invention also provides a preparation method of the fluorescent indicator composition, which comprises the following steps: the full-color fluorescent carbon quantum dots and various metal ions react under the condition of different pH values to form various carbon quantum dot-metal ion complexes.
The embodiment of the invention also provides an antibiotic detection method, which comprises the following steps:
providing a fluorescent indicator combination or fluorescent array sensor as described above;
and respectively mixing each carbon quantum dot-metal ion compound or a solution containing different carbon quantum dot-metal ion compounds with a solution to be detected containing antibiotics to form a plurality of response points, and detecting the fluorescence intensity change before and after the formation of each response point at least with the excitation wavelength of 360nm, 450nm and 540nm to realize the detection of the type and/or concentration of the antibiotics in the solution to be detected.
In one embodiment, the method comprises:
respectively mixing solutions containing different carbon quantum dot-metal ion complexes with a series of standard solutions containing antibiotics with different concentrations to form a plurality of response points, and detecting fluorescence intensity changes before and after the response points are formed at excitation wavelengths of 360nm, 450nm and 540nm, so as to establish a fluorescence intensity change-antibiotic concentration standard fitting curve;
mixing the solution containing different carbon quantum dot-metal ion compounds with the solution to be detected containing antibiotics to form a plurality of response points, detecting the fluorescence intensity change before and after the response points are formed at the excitation wavelengths of 360nm, 450nm and 540nm, and then comparing the obtained detection data with the standard fitting curve, thereby measuring the content of the antibiotics in the solution to be detected.
Further, the antibiotic includes any one or a combination of two or more of tetracyclines, quinolones, beta-lactams, and aminoglycosamines.
Compared with the prior art, the invention has the beneficial effects that:
1) the multi-channel fluorescent array sensor provided by the invention forms an F-CDs-metal ion compound by synthesizing full-color fluorescent carbon quantum dots really having excitation wavelength dependence and screening metal ions, so that a fluorescent indicator with high selectivity and high sensitivity is obtained; the array sensor is simple in manufacturing process, long in storage time and good in detection sensitivity, and can realize simultaneous distinguishing and detection of multiple antibiotics by recording multi-channel fluorescence intensity change by only using one fluorescent carbon dot;
2) the invention realizes the detection sensitivity to different antibiotics by changing the microenvironment of the fixed formula, can qualitatively and semi-quantitatively detect and distinguish four antibiotics such as tetracycline, quinolone, beta-lactam and aminosugamine and the like simultaneously only by the obtained standard fitting curve, and has strong anti-interference capability;
3) the antibiotic detection method constructed by the invention has the advantages of simple detection process, long storage time of the nano material, good detection sensitivity, no need of complex and expensive equipment, easy manufacture of a portable handheld fluorescence sensor and capability of realizing field detection of a sample.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the description of the embodiment or the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1a is a schematic diagram of the preparation of F-CDs in an exemplary embodiment of the present invention.
FIG. 1b is a transmission electron micrograph of F-CDs prepared in example 1 of the present invention.
FIG. 2 is a fluorescence emission spectrum of F-CDs prepared in example 1 of the present invention under visible light excitation at 360nm to 570 nm.
FIG. 3 is a schematic view showing the detection mechanism of the fluorescent array sensor prepared in example 1 of the present invention.
FIGS. 4a to 4F are graphs showing F-CDs prepared in example 1 of the present invention and three metal ions, Cu, respectively2+、Ce3+、Eu3+Fluorescence emission spectrograms before and after the action under the excitation of visible light of 360nm, 450nm and 540 nm.
FIG. 5 is a graph showing the principal component analysis of 20 antibiotics at the same concentration for the fluorescent array sensor prepared in example 4 of the present invention.
FIG. 6 is a graph of a cluster analysis of 20 antibiotics at the same concentration for the fluorescent array sensor prepared in example 4 of the present invention.
FIG. 7a is a graph showing the fluorescence response of the fluorescence array sensor prepared in example 4 of the present invention to different concentrations of the single antibiotic oxytetracycline.
FIG. 7b is a standard fit plot of oxytetracycline concentration versus fluorescence change in example 4 of the present invention.
Detailed Description
As described above, in view of the defects of the prior art, the present inventors have made extensive studies and extensive practices to provide a method for preparing an array sensor for simultaneously performing qualitative and semi-quantitative detection on four major antibiotics such as tetracyclines, quinolones, β -lactams, and aminosugamides, the method mainly comprising screening a fluorescent indicator composed of F-CDs-metal ion complexes, screening a fixed indicator formula, and constructing an array.
Further, the preparation method comprises the following steps: (1) selecting metal ions with high sensitivity and high selectivity to antibiotics to form an F-CDs-metal ion compound and construct a fluorescent indicator; (2) selecting a proper indicator fixing formula; (3) and recording the fluorescence intensity of the fluorescence indicator before and after the antibiotic is added by using a fluorescence spectrometer to construct the fluorescence array sensor.
The technical solution, its implementation and principles, etc. will be further explained as follows.
In one aspect, the present invention relates to a fluorescence indicator composition, which includes a plurality of carbon quantum dot-metal ion complexes (F-CDs-metal ion complexes) formed by panchromatic fluorescent carbon quantum dots (F-CDs) and a plurality of metal ions under different pH conditions.
In one embodiment, the fluorescence indicator combination specifically includes:
full-color fluorescent carbon quantum dot and Cu2+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with a pH value of 6.8-7.4,
full-color fluorescent carbon quantum dot and Cu2+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with a pH value of 7.4-8.2,
full-color fluorescent carbon quantum dot and Eu3+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with the pH value of 6.8-7.4,
full-color fluorescent carbon quantum dot and Eu3+A carbon quantum dot-metal ion complex formed in a HEPES buffer solution with a pH value of 7.4-8.2,
panchromatic fluorescent carbon quantum dot and Ce3+At a pH of 6.8 ℃ -7.4 of a carbon quantum dot-metal ion complex in HEPES buffer solution,
panchromatic fluorescent carbon quantum dot and Ce3+The carbon quantum dot-metal ion composite is formed in HEPES buffer solution with the pH value of 7.4-8.2.
In one embodiment, the method for preparing the panchromatic fluorescent carbon quantum dot is shown in fig. 1a, and comprises the following steps: and reacting citric acid with formamide by using a microwave-assisted hydrothermal method to form the panchromatic fluorescent carbon quantum dot, wherein the reaction temperature is 140-180 ℃, the reaction time is 0.5-2 h, and the microwave power is 200-400W.
Further, the excitation wavelengths corresponding to the fluorescence indicator combinations are 360nm, 450nm, 540nm, respectively, while the corresponding emission wavelengths are 466nm, 555nm, 637nm, respectively.
As another aspect of the technical scheme of the invention, the invention relates to the application of the combination of the fluorescent indicator and the antibiotic detection.
Further, the antibiotic includes any one or a combination of two or more of tetracyclines, quinolones, β -lactams, aminosugamides, and the like, but is not limited thereto.
In another aspect, the present invention relates to a fluorescence array sensor, which comprises the fluorescence indicator combination.
Preferably, the sensor comprises a plurality of sets of response points, each set of response points comprising three or more independent response points corresponding to excitation wavelengths 360nm, 450nm and 540nm, respectively, each response point comprising at least one carbon quantum dot-metal ion complex, or the sensor comprises three or more sets of response points corresponding to excitation wavelengths 360nm, 450nm and 540nm, respectively, each set of response points comprising a plurality of independent response points, each response point comprising at least one carbon quantum dot-metal ion complex.
Further, any two response points in each set of response points contain different carbon quantum dot-metal ion complexes.
In another aspect of the present invention, there is provided a method for preparing the above fluorescent indicator composition, comprising: the full-color fluorescent carbon quantum dots and various metal ions react under the conditions of different pH values to form various carbon quantum dot-metal ion complexes.
In one embodiment, the method of making comprises: and dissolving the full-color fluorescent carbon quantum dots in HEPES buffer solutions with different pH values to form full-color fluorescent carbon quantum dot aqueous solutions, respectively adding metal ions into the full-color fluorescent carbon quantum dot aqueous solutions with different pH values, and reacting for 5-10 min at room temperature to obtain the carbon quantum dot-metal ion composite.
Preferably, the pH value of the HEPES buffer solution is 6.8-8.2.
Further, the metal ions include Cu2+、Ce3+And Eu3+And the like, but is not limited thereto.
Further, the preparation method specifically comprises the following steps:
full color fluorescent carbon quantum dots and Cu2+Reacting in HEPES buffer solution with pH value of 6.8-7.4 to form carbon quantum dot-metal ion compound,
full color fluorescent carbon quantum dots and Cu2+Reacting in HEPES buffer solution with pH value of 7.4-8.2 to form carbon quantum dot-metal ion compound,
the full color fluorescent carbon quantum dots and Eu3+Reacting in HEPES buffer solution with pH value of 6.8-7.4 to form carbon quantum dot-metal ion compound,
the full color fluorescent carbon quantum dots and Eu3+Reacting in HEPES buffer solution with pH value of 7.4-8.2 to form carbon quantum dot-metal ion compound,
full color fluorescent carbon quantum dots and Ce3+Reacting in HEPES buffer solution with pH value of 6.8-7.4 to form carbon quantum dot-metal ion compound,
full color fluorescent carbon quantum dots and Ce3+And reacting in HEPES buffer solution with the pH value of 7.4-8.2 to form the carbon quantum dot-metal ion composite.
Further, the preparation method comprises the following steps: and reacting citric acid with formamide by using a microwave-assisted hydrothermal method to form the panchromatic fluorescent carbon quantum dot, wherein the reaction temperature is 140-180 ℃, the reaction time is 0.5-2 h, and the microwave power is 200-400W.
Further, the preparation method specifically comprises the following steps: in the process of enabling full-color fluorescent carbon quantum dots to be matched with Cu2+、Ce3+、Eu3+Before any one of the carbon quantum dots reacts in a HEPES buffer solution with the pH value of 6.8-8.2 to form a carbon quantum dot-metal ion composite, the concentration of the full-color fluorescent carbon quantum dots in the HEPES buffer solution is 1-10 mu g/mL, and the concentration of Cu is 1-10 mu g/mL2+、Ce3+Or Eu3+The concentration of (b) is 10-50 mu M.
In some embodiments, the method of preparing the fluorescent array sensor may specifically include:
(1) firstly, preparing panchromatic fluorescent carbon quantum dots (F-CDs for short) with real excitation wavelength dependence, dissolving the panchromatic fluorescent carbon quantum dots in HEPES buffer solutions with different pH values to finally obtain F-CDs aqueous solutions, and respectively adding metal ions Cu into the F-CDs solutions with different pH values2+、Ce3+、Eu3+Reacting for 5 minutes, and uniformly mixing to obtain different fluorescent indicators, namely F-CDs-metal ion compounds;
(2) and (2) respectively recording different fluorescence response indicators obtained in the step (1), namely F-CDs-metal ion compounds, and obtaining the carbon-point-based fluorescence array sensor for antibiotic detection and discrimination after the fluorescence response indicators are added into the object to be detected under the excitation wavelengths of 360nm, 450nm and 540nm (the corresponding emission wavelengths are 466nm, 555nm and 637 nm).
Further, in the step (2), the formula has an important influence on the fixation of the indicator, in order to realize the simultaneous discrimination of multiple antibiotics, the fluorescent indicator is firstly screened, the selected indicator has different degrees of response with different antibiotics, the indicator with an unobvious discrimination effect is excluded, then the selected indicator with a good discrimination effect is dispersed in different fixed formulas, different detection sensitivities are realized by changing the microenvironment of the formula, and the simultaneous qualitative and semi-quantitative detection of multiple antibiotics is realized.
Further, the fixing formula of the fluorescent indicator in the step (2) comprises the following six types:
①F-CDs-Cu2+the compound is as follows: 5. mu.g/mL of F-CDs and 10. mu.M of Cu2+Uniformly dispersing in buffer solution of HEPES 6.8-7.4, reacting for 5min at normal temperature, and respectively recording fluorescence under excitation wavelengths of 360nm, 450nm and 540nm to obtain a fluorescence indicator formula;
②F-CDs-Cu2+the compound is as follows: 5. mu.g/mL of F-CDs and 10. mu.M of Cu2+Uniformly dispersing in buffer solution of HEPES 7.4-8.2, reacting for 5min at normal temperature, and respectively recording fluorescence under excitation wavelengths of 360nm, 450nm and 540nm to obtain a fluorescence indicator formula;
③F-CDs-Ce3+the compound is as follows: 5. mu.g/mL of F-CDs and 50. mu.M of Ce3+Uniformly dispersing in a buffer solution of HEPES 6.8-7.4, reacting for 5min at normal temperature, and respectively recording the fluorescence under excitation wavelengths of 360nm, 450nm and 540nm to obtain a formula of the fluorescence indicator;
④F-CDs-Ce3+the compound is as follows: 5. mu.g/mL of F-CDs and 50. mu.M of Ce3+Uniformly dispersing in a buffer solution of HEPES 7.4-8.2, reacting for 5min at normal temperature, and respectively recording the fluorescence under excitation wavelengths of 360nm, 450nm and 540nm to obtain a formula of the fluorescence indicator;
⑤F-CDs-Eu3+the compound is as follows: 5 μ g/mL F-CDs and 50 μ M Eu3+Uniformly dispersing in buffer solution of HEPES 6.8-7.4, reacting for 5min at normal temperature, and respectively recording fluorescence under excitation wavelengths of 360nm, 450nm and 540nm to obtain a fluorescence indicator formula;
⑥F-CDs-Eu3+the compound is as follows: 5 μ g/mL F-CDs and 50 μ M Eu3+Uniformly dispersing in a buffer solution of HEPES 7.4-8.2, reacting for 5min at normal temperature, and respectively recording the fluorescence under excitation wavelengths of 360nm, 450nm and 540nm to obtain a formula of the fluorescence indicator;
the 6 kinds of fixed formulas and different antibiotics form a plurality of response points, and the response points which are independent from each other are arranged in parallel to construct the fluorescent array sensor. For the same indicator, different immobilization formulations are selected to produce different responses depending on the concentration of the antibiotic solution.
Wherein, when recording the fluorescence intensity, the selected excitation wavelength is at least one of 360nm, 450nm and 540nm, and the selected excitation wavelength is 540 nm.
Further, the preparation method comprises the following specific operations: and adding 10 mu g of the screened fluorescence indicator, namely F-CDs-metal ion compound into a 2mL fixed formula, carrying out ultrasonic dissolution, finally pouring into a cuvette, and respectively recording fluorescence intensities under different excitation wavelengths by using a fluorescence spectrophotometer to obtain array response points, thus obtaining the multi-channel fluorescence array sensor for antibiotic detection.
The invention utilizes the fluorescence indicator to construct a multi-channel fluorescence array sensor, three data can be acquired by one fluorescence indicator when the fluorescence intensity change is recorded by a fluorescence spectrometer, and the excitation wavelengths of 360nm, 450nm and 540nm are respectively selected.
In another aspect of the present invention, a method for detecting an antibiotic includes:
providing a fluorescent indicator combination or fluorescent array sensor as described above;
and respectively mixing each carbon quantum dot-metal ion compound or a solution containing different carbon quantum dot-metal ion compounds with a solution to be detected containing antibiotics to form a plurality of response points, and detecting the fluorescence intensity change before and after the formation of each response point at least with the excitation wavelength of 360nm, 450nm and 540nm to realize the detection of the type and/or concentration of the antibiotics in the solution to be detected.
In one embodiment, the method comprises:
respectively mixing solutions containing different carbon quantum dot-metal ion compounds with a series of standard solutions containing antibiotics with different concentrations to form a plurality of response points, and detecting fluorescence intensity changes before and after the response points are formed at excitation wavelengths of 360nm, 450nm and 540nm, so as to establish a fluorescence intensity change-antibiotic concentration standard fitting curve;
mixing the solution containing different carbon quantum dot-metal ion compounds with the solution to be detected containing antibiotics to form a plurality of response points, detecting the fluorescence intensity change before and after the response points are formed at the excitation wavelengths of 360nm, 450nm and 540nm, and then comparing the obtained detection data with the standard fitting curve, thereby measuring the content of the antibiotics in the solution to be detected.
In a more specific embodiment, the method specifically includes the following steps:
(1) mixing solutions containing different carbon quantum dot-metal ion complexes with a series of standard solutions containing antibiotics with different concentrations to form a plurality of response points, reading fluorescence intensity in each response point by a fluorescence scanner and recording the fluorescence intensity as F0And fluorescence intensity changes before and after the formation of each response point were detected at excitation wavelengths of 360nm, 450nm, and 540nm, and the fluorescence intensity after the formation of the response points was read by a fluorescence scanner and recorded as F1；
(2) Digitizing changes in fluorescence intensity before and after the formation of each response point read by the fluorescence scanner in step (1) by normalization processing, that is, (F)1-F0)/F0Further obtaining a fluorescence intensity change-antibiotic concentration standard fitting curve of antibiotics with different concentrations;
(3) mixing a solution containing different carbon quantum dot-metal ion complexes with a solution to be detected containing antibiotics to form a plurality of response points, detecting fluorescence intensity changes before and after the formation of each response point at excitation wavelengths of 360nm, 450nm and 540nm, reading the fluorescence intensity changes through a fluorescence scanner, carrying out digital processing, comparing with the standard fitting curve, and determining the type and/or concentration of the antibiotics in the solution to be detected according to the matching degree of the two.
Further, the method further specifically comprises:
(1) pouring the prepared fluorescent indicator solution into a cuvette, and placing the cuvette into a fluorescence spectrophotometer to record the fluorescence intensity at the moment and record the fluorescence intensity as F0(ii) a Adding antibiotic standard solutions with different known concentrations into the original cuvette, mixing uniformly for 5 minutes, and recording the fluorescence intensity at the moment as F1The fluorescent indicator on the array sensor respectively generates different fluorescent intensity changes after reacting with different antibiotics, and the fluorescent indicator on the array sensor generates different fluorescent intensity changes through fluorescenceScanning and measuring the change of fluorescence intensity by a spectrophotometer;
(2) the change in fluorescence intensity measured by the fluorescence spectrophotometer in step (1) is digitized by normalization, i.e. (F)1-F0)/F0,F0,F1Respectively indicating the fluorescence intensity before and after the antibiotics are added, utilizing origin software to carry out drawing, and making a linear fitting map of the fluorescence change and the concentration of the antibiotics with different concentrations to obtain a standard fitting linear equation;
(3) and (3) adding the liquid to be detected into the fluorescent indicator, reading fluorescent changes respectively generated after the response points on the array sensor react with the antibiotics through a fluorescent scanner, then carrying out digital processing on the fluorescent intensity change according to the processing method in the step (2), bringing the obtained result into a standard fitting linear equation, and determining the existence of the antibiotics in the solution to be detected and the existing antibiotic content range according to the matching degree of the two.
Further, the fluorescence scanner includes a fluorescence spectrophotometer, but is not limited thereto.
Further, the fluorescence intensity values read by the fluorescence scanner include fluorescence intensities at excitation wavelengths of 360nm, 450nm, and 540nm, respectively.
Further, the antibiotic includes any one or a combination of two or more of tetracyclines, quinolones, β -lactams, aminosugamides, and the like, but is not limited thereto.
In conclusion, according to the technical scheme, the F-CDs and the screened metal ions are used as fluorescent indicator materials for antibiotic response; the indicators are fixed in the formula, and the differentiation and different detection sensitivities of four antibiotics such as tetracycline, quinolone, beta-lactam and aminosugamine are realized by changing the microenvironment of the formula; in order to distinguish multiple antibiotics simultaneously, 3 metal ions and 6 fixed formulas are matched into 18 response points, the response points are placed on a fluorescence spectrometer to serve as a detection unit, fluorescence intensity information corresponding to each response point is extracted, all the fluorescence intensity change information is summarized, and an array system is constructed; based on different concentrations and different types of antibiotics with different degrees of reaction with the constructed response points, the fluorescence intensity information after the reaction of each response point is extracted, and all the fluorescence intensity information is summarized to construct an array system.
The multichannel fluorescence array sensor can realize qualitative and semi-quantitative detection of four major antibiotics such as tetracycline, quinolone, beta-lactam and aminosugamine; the method has the advantages of simple manufacturing process, long storage time and good detection sensitivity, and can realize the simultaneous distinguishing and detection of various antibiotics by only using one fluorescent carbon dot and recording the change of multi-channel fluorescence intensity.
The technical solutions in the embodiments of the present invention will be described in detail below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
EXAMPLE 1 construction of multichannel fluorescent array sensor
(1) Screening of fluorescent indicators:
in order to realize obvious differentiation of multiple classes of antibiotics, no cross interference exists among the antibiotics. When the fluorescent indicator is constructed, metal ions are screened based on the quenching degree of the metal ions to F-CDs, and the metal ions are Fe2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+、Hg2+、Pb2+、Ag+、Cr3+、Ce3+And Eu3+3 kinds of metal ions which have higher quenching degree on F-CDs and stronger binding capacity with antibiotics are screened, and the metal ions are respectively as follows: cu2+、Ce3+、Eu3+I.e. constituting F-CDs-Cu2+，F-CDs-Ce3+，F-CDs-Eu3+Three fluorescent indicators.
(2) Selection of a fixed formula:
1) F-CDs (5. mu.g/mL) and Cu2+(10μM) is dissolved in 2mL of HEPES buffer solution (10mM) with the pH value of 7.4 and reacts for 5min at normal temperature to obtain a formula 1;
2) F-CDs (5. mu.g/mL) and Cu2+Dissolving (10 μ M) in 2mL of HEPES buffer solution (10mM) with pH of 8.2, and reacting at room temperature for 5min to obtain formula 2;
3) F-CDs (5. mu.g/mL) and Ce3+Dissolving (50 μ M) in 2mL of HEPES buffer solution (10mM) with pH of 7.4, and reacting at room temperature for 5min to obtain formula 3;
4) F-CDs (5. mu.g/mL) and Ce3+Dissolving (50 μ M) in 2mL of HEPES buffer solution (10mM) with pH8.2, and reacting at room temperature for 5min to obtain formula 4;
5) F-CDs (5. mu.g/mL) and Eu2+Dissolving (50 μ M) in 2mL of HEPES buffer solution (10mM) with pH7.4, and reacting at room temperature for 5min to obtain formula 5;
6) F-CDs (5. mu.g/mL) and Eu2+Dissolving (50 μ M) in 2mL of HEPES buffer solution (10mM) with pH8.2, and reacting at room temperature for 5min to obtain formula 6;
preparing an array sensor: recording the fluorescence intensity changes of 3 indicators in (1) under three excitation wavelengths of 360nm, 450nm and 540nm respectively according to 6 fixed formulas in (2) to form 18 response points, wherein the 18 response points are independent from each other: formula 1-360nm, formula 1-450nm, formula 1-540nm, formula 2-360nm, formula 2-450nm, formula 2-540nm, formula 3-360nm, formula 3-450nm, formula 3-540nm, formula 4-360nm, formula 4-450nm, formula 4-540nm, formula 5-360nm, formula 5-450nm, formula 5-540nm, formula 6-360nm, formula 6-450nm, and formula 6-540 nm.
In order to simplify and save time of experiments, 18 response points are screened according to the distinguishing effect of different antibiotics, and 11 response points are selected to realize the distinguishing of various antibiotics, wherein the 11 response points are respectively 1-360nm of formula, 1-540nm of formula, 2-360nm of formula, 2-450nm of formula, 2-540nm of formula, 3-360nm of formula, 3-450nm of formula, 3-540nm of formula, 4-540nm of formula, 5-540nm of formula and 6-540nm of formula. The details are shown in Table 1 below:
adding the antibiotics to be detected into the 11 response points, reacting for 5min, respectively recording the fluorescence changes before and after adding the antibiotics, and performing PCA and HCA analysis on the obtained data through normalization processing to judge the distinguishing effect of different antibiotics.
FIG. 1a shows a schematic process diagram of F-CDs prepared in this example, and FIG. 1b shows a transmission electron micrograph of the obtained F-CDs. The fluorescence emission spectrum of F-CDs prepared in this example under excitation of visible light between 360nm and 570nm is shown in FIG. 2 (the excitation wavelength increases from left to right). Fig. 3 is a schematic diagram of a detection mechanism of the multi-channel fluorescence array sensor prepared in this embodiment. F-CDs prepared in this example and three metal ions Cu2+、Ce3+、Eu3+Fluorescence emission spectra before and after the action under excitation of visible light at 360nm, 450nm and 540nm are shown in FIGS. 4 a-4 f, respectively.
EXAMPLE 2 construction of multichannel fluorescent array Sensors
(1) Screening of sensing units
In order to realize the detection and the distinguishing of 4 types of antibiotics such as tetracycline, quinolone, beta-lactam, amino sugar amine and the like, 18 response points are screened according to the distinguishing effect of different antibiotics, 8 response points (sensing units) are selected to realize the distinguishing of various antibiotics, and the specific formula of the screened 8 response points is as follows:
(2) adding the antibiotics to be detected into the 8 response points, reacting for 5min, respectively recording the fluorescence changes before and after adding the antibiotics, and performing PCA and HCA analysis on the obtained data through normalization processing to judge the distinguishing effect of different antibiotics.
EXAMPLE 3 construction of multichannel fluorescent array sensor
(1) Screening of sensing units
In order to realize the detection and the distinguishing of 4 types of antibiotics such as tetracycline, quinolone, beta-lactam, amino sugar amine and the like, 18 response points are screened according to the distinguishing effect of different antibiotics, 6 response points (sensing units) are selected to realize the distinguishing of various antibiotics, and the specific formula of the 6 screened response points is as follows:
(2) adding the antibiotics to be detected into the 6 response points, reacting for 5min, respectively recording the fluorescence changes before and after adding the antibiotics, and performing PCA and HCA analysis on the obtained data through normalization processing to judge the distinguishing effect of different antibiotics.
EXAMPLE 4 construction of multichannel fluorescent array sensor
(1) Screening of sensing units
In order to realize the detection and the distinction of 4 major antibiotics such as tetracyclines, quinolones, beta-lactams, aminosugamides and the like, 18 response points are screened according to the distinguishing effect of different antibiotics, 5 response points (sensing units) are selected to realize the distinction of various antibiotics, and the specific formula of the screened 5 response points is as follows:
(2) the fluorescence change before and after the antibiotic is added is measured by adopting a fluorescence spectrometer, and the change relation between the antibiotic concentration and the fluorescence intensity is fitted into a standard curve by normalizing the fluorescence change before and after the antibiotic is added, so that a basis is provided for qualitative and semi-quantitative analysis.
(3) Differentiation results obtained by adding 50. mu.M of different antibiotic solutions according to the above method are shown in FIGS. 5 and 6. The plots were performed using MVSP v.3.1, Kovach Computing software, with a concentration of 50 μ M for all antibiotics, and five replicates for each antibiotic. Fig. 5 shows a principal component analysis graph of the multi-channel fluorescence array sensor prepared in the present example for the same concentration of 20 antibiotics. It is obvious from the figure that four types of antibiotics such as tetracycline, quinolone, beta-lactam and amino sugar amine can be well distinguished, even antibiotics with extremely similar structures in each type of antibiotics can be well distinguished, the repeatability is excellent, and the array sensor is proved to be capable of realizing qualitative and semi-quantitative distinguishing of the four types of antibiotics.
The same was plotted using MVSP v.3.1, Kovach Computing software, with a concentration of 50. mu.M for all antibiotics, and each antibiotic was tested in five replicates. Fig. 6 shows a cluster analysis graph of the multi-channel fluorescence array sensor prepared in this example for the same concentration of 20 antibiotics. Each type of antibiotics in the figure can be well classified into one type, and the distinguishing effect is excellent. It is obvious from the figure that four types of antibiotics such as tetracycline, quinolone, beta-lactam and aminosugamine can be well distinguished, even antibiotics with very similar structures in each type of antibiotics can be well distinguished, and further the array sensor can realize qualitative and semi-quantitative distinguishing of the four types of antibiotics.
From the results of the analyses of fig. 5 and 6, it can be seen that the addition of different antibiotic solutions at the same concentration will produce different responses from the array sensor, and that these four classes of antibiotics can be well distinguished without cross-interference between each other. Therefore, the prepared array sensor can well realize the differential detection of multiple antibiotics.
FIGS. 7a and 7b show the fluorescence response of the multichannel fluorescence array sensor prepared in this example to different concentrations of oxytetracycline, which is a single antibiotic, and the standard fit curve of oxytetracycline concentration to fluorescence change, respectively, wherein the oxytetracycline concentration is 0.1-300. mu.M, and each isThe concentration is repeatedly measured for three times, and the repeatability is excellent. The fluorescence intensity change of the constructed array sensor and the oxytetracycline concentration present a good linear relation in the range of 0.1-10 mu M, and the correlation coefficient R2The detection limit of the oxytetracycline can be calculated to be 0.06 mu M when the oxytetracycline is 0.997, and the sensitivity is extremely high, which indicates that the array sensor is sensitive enough to realize semi-quantitative detection of antibiotics.
Comparative example 1
The four tetracycline antibiotics are detected by an electrochemical method by utilizing the electrodes improved by the multi-walled carbon nano-tubes, the detection limit is 0.44 mu M, the detection and the distinguishing of the multiple antibiotics cannot be realized, and the sensitivity is not as sensitive as the multi-channel fluorescence array sensor designed by the invention.
Comparative example 2
The method adopts the high performance liquid chromatography to detect various antibiotics, the detection range is 0.21-104 mu M, the sensitivity is not enough, and simultaneously, the high performance liquid chromatography needs expensive instruments and professional operators, and the pretreatment of samples is complicated.
In conclusion, by the technical scheme, the multichannel fluorescence array sensor can realize qualitative and semi-quantitative detection of four antibiotics such as tetracyclines, quinolones, beta-lactams, aminosugamides and the like; the method has the advantages of simple manufacturing process, long storage time and good detection sensitivity, and can realize the simultaneous distinguishing and detection of various antibiotics by only using one fluorescent carbon dot and recording the change of multi-channel fluorescence intensity.
In addition, the inventor also refers to the modes of the examples 1-4, tests are carried out by using other raw materials, conditions and the like listed in the specification, and a multi-channel fluorescence array sensor capable of realizing qualitative and semi-quantitative detection of various antibiotics is also manufactured.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or apparatus that comprises the element.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (3)
1. A method for detecting an antibiotic, comprising:
providing a fluorescent array sensor, wherein the fluorescent array sensor comprises a plurality of groups of response points, each group of response points comprises three independent response points corresponding to excitation wavelengths of 360nm, 450nm and 540nm respectively, any two response points in each group of response points contain different carbon quantum dot-metal ion complexes, each response point contains at least one carbon quantum dot-metal ion complex, or, the sensor includes three groups of response points corresponding to excitation wavelengths 360nm, 450nm and 540nm respectively, each group of response points includes a plurality of independent response points, any two response points in each group of response points are different in carbon quantum dot-metal ion complex, each response point includes at least one carbon quantum dot-metal ion complex, and the preparation method of the carbon quantum dot-metal ion complex specifically includes:
reacting citric acid and formamide by a microwave-assisted hydrothermal method to form a full-color fluorescent carbon quantum dot, wherein the reaction temperature is 140-180 ℃, the reaction time is 0.5-2 h, and the microwave power is 200-400W;
full color fluorescent carbon quantum dots and Cu2+Reacting in HEPES buffer solution with pH value of 6.8-7.4 to form carbon quantum dot-metal ion compound,
full color fluorescent carbon quantum dots and Cu2+At a pH of 7.48.2, reacting in HEPES buffer solution to form a carbon quantum dot-metal ion compound,
the full color fluorescent carbon quantum dots and Eu3+Reacting in HEPES buffer solution with pH value of 6.8-7.4 to form carbon quantum dot-metal ion compound,
the full color fluorescent carbon quantum dots and Eu3+Reacting in HEPES buffer solution with pH value of 7.4-8.2 to form carbon quantum dot-metal ion compound,
full color fluorescent carbon quantum dots and Ce3+Reacting in HEPES buffer solution with pH value of 6.8-7.4 to form a carbon quantum dot-metal ion compound,
full color fluorescent carbon quantum dots and Ce3+Reacting in HEPES buffer solution with the pH value of 7.4-8.2 to form a carbon quantum dot-metal ion compound;
secondly, (1) mixing solutions containing different carbon quantum dot-metal ion complexes with a series of standard solutions containing antibiotics with different concentrations to form a plurality of response points, and reading fluorescence intensity in each response point by a fluorescence scanner to be recorded as F0And fluorescence intensity changes before and after the formation of each response point were detected at excitation wavelengths of 360nm, 450nm, and 540nm, and the fluorescence intensity after the formation of the response points was read by a fluorescence scanner and recorded as F1(ii) a The antibiotic is selected from one or the combination of more than two of tetracyclines, quinolones, beta-lactams and aminosamines;
(2) digitizing changes in fluorescence intensity before and after the formation of each response point read by the fluorescence scanner in step (1) by normalization processing, that is, (F)1-F0）/F0Further obtaining a fluorescence intensity change-antibiotic concentration standard fitting curve of antibiotics with different concentrations;
(3) mixing a solution containing different carbon quantum dot-metal ion complexes with a solution to be detected containing antibiotics to form a plurality of response points, detecting fluorescence intensity change before and after the response points are formed at excitation wavelengths of 360nm, 450nm and 540nm, reading the fluorescence intensity change through a fluorescence scanner, carrying out digital processing, comparing with the standard fitting curve, and determining the type and/or concentration of the antibiotics in the solution to be detected according to the matching degree of the two;
the fluorescence scanner is a fluorescence spectrophotometer.
2. The detection method according to claim 1, characterized in that: the full-color fluorescent carbon quantum dots and various metal ions react under the condition of different pH values to form various carbon quantum dot-metal ion complexes.
3. The detection method according to claim 1, characterized in that: in the process of enabling full-color fluorescent carbon quantum dots to be matched with Cu2+、Ce3+、Eu3+Before any one of the carbon quantum dots reacts in a HEPES buffer solution with the pH value of 6.8-8.2 to form a carbon quantum dot-metal ion composite, the concentration of the full-color fluorescent carbon quantum dots in the HEPES buffer solution is 1-10 mu g/mL, and the concentration of Cu is 1-10 mu g/mL2+、Ce3+Or Eu3+The concentration of (b) is 10 to 50 mu M.
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