CN109975253A - Fluorescence indicator combination, fluorescence sensor array, preparation method and application - Google Patents
Fluorescence indicator combination, fluorescence sensor array, preparation method and application Download PDFInfo
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- CN109975253A CN109975253A CN201711445375.9A CN201711445375A CN109975253A CN 109975253 A CN109975253 A CN 109975253A CN 201711445375 A CN201711445375 A CN 201711445375A CN 109975253 A CN109975253 A CN 109975253A
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Abstract
The invention discloses a kind of combination of fluorescence indicator, fluorescence sensor array, preparation method and applications.The fluorescence indicator combination includes a variety of carbon quantum dot-metal ion complex that panchromatic fluorescent carbon quantum dot and various metals ion are formed under different ph values.The fluorescence sensor array includes the fluorescence indicator, the sensor includes plural groups response point, each group of response point includes corresponding respectively to three of excitation wavelength 360nm, 450nm, 540nm or more separate responses points, and each response point includes at least one carbon quantum dot-metal ion complex.Fluorescence sensor array of the invention can be realized while be detected to the quantitative and semi-quantitative of the four major class antibiotic such as Tetracyclines, quinolones, beta-lactam and aminoglycosides；And its manufacturing process is simple, and the holding time is long and detection sensitivity is preferable, distinguishes and detects while being able to achieve multiclass antibiotic.
Description
Technical field
The present invention relates to a kind of sensor arrays of detection and differentiation for antibiotic more particularly to a kind of detection to distinguish
The fluorescence indicator combination of multiclass antibiotic, multichannel fluorescence sensor array and preparation method thereof and its realizing multiclass
Application while antibiotic in detection, belongs to technical field of food safety detection.
Background technique
Antibiotic can kill or inhibit the growth ability of bacterium, be mass produced in the past few decades antibiotic in the whole world
And it is used to treat the various mankind and veterinary disease.Currently, mostly being found in milk, vegetables, cereal, surface water and waste water exceeded
Antibiotic.Wherein the three classes detection higher antibiotic of frequency is quinolones, tetracycline antibiotics and sulfonamides respectively
Object.In order to guarantee the quality of food and prevent the infection of disease, antibiotic is also widely used in animal husbandry and fishery.So
And the abuse of antibiotic will lead to bacterial drug resistance increase.People, animal intake antibiotic majority cannot be absorbed and used and with mother
The form of body or metabolite excretes, and into sewerage or is directly discharged in environment, threatens to ecological environment.
This will eventually threaten the health and social safety of the mankind.Currently, antibiotics residues and bacterial drug resistance are continuously increased
The a great problem in global range is had become, brings huge challenge to clinical treatment.Therefore it provides a kind of simple and effective
Method come to detect antibiotic be great meaning.
Currently, common antibiotic detection method includes high performance liquid chromatography, enzyme-linked immunosorbent assay, surface enhanced drawing
Graceful scattering method, colorimetric method etc..These methods can successfully detect remaining micro antibiosis in the food such as milk, honey, pork
Element.But greatest problem existing for these methods is exactly that required detecting instrument cost is high, or even needs professional operator
It could complete, sample pretreatment process complexity etc., discomfort detects at once on site.
Antibiotic detection method common at present is more, wherein D.Vega (Analytical and Bioanalytical
Chemistry 2007,389,951-958.) et al. using electrochemical process utilize the improved electrode detection four of multi-walled carbon nanotube
Kind tetracycline antibiotics, detection are limited to 0.44 μM, can not achieve detection and differentiation to Multiple Classes of Antibiotics.Lu Haitao
(Chromatographia 2004,60,259-264.) et al. may be implemented using the method for high performance liquid chromatography to a variety of anti-
The detection of raw element, detection range is between 0.21-104 μM, and sensitivity is inadequate, while using high performance liquid chromatography, is needed
Instrument, the professional operator of valuableness are wanted, sample pre-treatments are also more complicated, not high for cost performance in terms of practical application.
Sensor array is a kind of simulation to mammalian sense of smell system.In sensor array, the same sensing is single
Member has different degrees of response to different material, and different sensing units also have different degrees of response to substance of the same race, according to
The finger-print of multiple sensing units response composition different degrees of to substance can carry out material identification.With based on " key and
The high specific single-sensor of lock " mode is compared, and sensor array reduces the demand to high specific receptor, expands significantly
The range of test object improves detection efficiency and detection flux, in the detection of a variety of detection fields especially complex sample
Aspect has huge application advantage.In the multiclass sensor array such as optics, electrochemistry, chromatography, photochemistry sensor array
Because having, fast response time, high sensitivity, output signal are enriched, signal is not influenced and can be realized visualization by electromagnetic interference
The advantages that detection and be concerned.In recent years, many in order to improve the recognition capability and sensing sensitivity of optical array sensor
Nano material is widely used in increasing sensing material quantity and develops new method for sensing.
Fluorescent carbon quantum dot is as a kind of novel carbon nanomaterial, with semiconductor-quantum-point, rare earth nano material, organic
Fluorescent dye etc. in comparison, with more efficient luminescent properties, anti-light bleaching power, good biocompatibility, hypotoxicity,
The features such as being easy to functionalized modification has good development prospect in analysis detection field.Therefore, carbon quantum dot and metal are based on
Ion complex constitute fluorescence indicator, while realization using fluorescence array sensing technology to multiclass antibiotic detection with
Identification, and it is applied to the detection of actual sample, have great importance for ensuring food safety.
Summary of the invention
The main purpose of the present invention is to provide a kind of combinations of fluorescence indicator, fluorescence sensor array and preparation method thereof
With application, with overcome the deficiencies in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of combinations of fluorescence indicator comprising panchromatic fluorescent carbon quantum dot (abbreviation F-
CDs) a variety of carbon quantum dot-metal ion complex (the abbreviation F- formed under different ph values with various metals ion
CDs- metal ion complex).
Among an embodiment, the fluorescence indicator combination is specifically included:
Panchromatic fluorescent carbon quantum dot and Cu2+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Cu2+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Eu3+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Eu3+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Ce3+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Ce3+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex.
Among an embodiment, the preparation method of the panchromatic fluorescent carbon quantum dot includes: with microwave-assisted hydro-thermal method
Make citric acid and formamide forms the panchromatic fluorescent carbon quantum dot, wherein reaction temperature is 140~180 DEG C, and the time is
0.5~2h, microwave power are 200~400W.
Further, the excitation wavelength corresponding to fluorescence indicator combination is respectively 360nm, 450nm, 540nm, and
Corresponding launch wavelength is respectively 466nm, 555nm, 637nm.
The embodiment of the invention also provides fluorescence indicators above-mentioned to be combined in the application in detection antibiotic.
Further, the antibiotic includes appointing in Tetracyclines, quinolones, beta-lactam and aminoglycosides
Meaning a combination of one or more.
The embodiment of the invention also provides a kind of fluorescence sensor arrays, and it includes fluorescence indicator above-mentioned combinations.
Preferably, the sensor includes plural groups response point, and each group of response point includes corresponding respectively to excitation wavelength
Three or more the separate responses points of 360nm, 450nm, 540nm, each response point include at least one carbon quantum dot-metal ion
Compound, alternatively, the sensor includes corresponding respectively to three groups of excitation wavelength 360nm, 450nm, 540nm or more to respond
Point, each group of response point include multiple separate responses points, and each response point includes that at least one carbon quantum dot-metal ion is compound
Object.
Further, carbon quantum dot-metal ion complex contained by any two response point is not in each group of response point
Together.
The embodiment of the invention also provides the preparation methods of fluorescence indicator above-mentioned combination comprising: make panchromatic fluorescence
Carbon quantum dot reacts to form a variety of carbon quantum dot-metal ion complex with various metals ion under different ph values.
The embodiment of the invention also provides a kind of antibiotic detection methods comprising:
Fluorescence indicator combination above-mentioned or fluorescence sensor array are provided；
By each carbon quantum dot-metal ion complex or contain the molten of different carbon quantum dot-metal ion complex respectively
Liquid and the solution to be measured containing antibiotic are mixed to form multiple response points, and at least with the excitation wave of 360nm, 450nm, 540nm
The long fluorescence intensity change for detecting each response point and forming front and back is realized to the type of antibiotic in solution to be measured and/or concentration
Detection.
Among an embodiment, which comprises
The solution containing different carbon quantum dot-metal ion complex is contained into various concentration antibiotic with a series of respectively
Standard solution be mixed to form multiple response points, and each response point is detected with the excitation wavelength of 360nm, 450nm, 540nm and is formed
Thus the fluorescence intensity change of front and back establishes fluorescence intensity change-antibiotic concentration standard fit curve；
Solution containing different carbon quantum dot-metal ion complex is mixed to form with the solution to be measured containing antibiotic
Multiple response points, and the fluorescence intensity change that each response point forms front and back is detected with the excitation wavelength of 360nm, 450nm, 540nm,
Detection data and the standard fit curve control will be obtained later, to measure the content of antibiotic in solution to be measured.
Further, the antibiotic includes appointing in Tetracyclines, quinolones, beta-lactam and aminoglycosides
Meaning a combination of one or more.
Compared with prior art, the beneficial effect comprise that
1) multichannel fluorescence sensor array provided by the invention is really complete with excitation wavelength dependence by synthesis
Color fluorescent carbon quantum dot and screening metal ion, constitute F-CDs- metal ion complex, to obtain having highly selective
With highly sensitive fluorescence indicator；And the sensor array manufacturing process is simple, the holding time is long and detection sensitivity compared with
It is good, it realizes merely with a kind of fluorescent carbon point, by recording multichannel fluorescence intensity change, can be achieved with the same of multiclass antibiotic
When distinguish and detection；
2) present invention realizes the detection sensitivity to different antibiotic, finally by changing the fixed microenvironment being formulated
It only can quantitative and semi-quantitative while detection and differentiation Tetracyclines, quinolones, the interior acyl of β-by obtained standard fit curve
The four class antibiotic such as amine and aminoglycosides, and strong antijamming capability；
3) the antibiotic detection method constructed by the present invention, detection process is simple, and the nano material holding time is long and detects
Sensitivity is preferable, the equipment for not needing complex and expensive, can be easily made portable portable fluorescent optical sensor, to realize showing for sample
Field detecting provides possibility.
Detailed description of the invention
It, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical solution of the present invention
The attached drawing used is simply introduced, it should be apparent that, drawings discussed below is as just some implementations invented herein
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other accompanying drawings.
Fig. 1 a is the preparation method schematic diagram of F-CDs in an exemplary embodiments of the invention.
Fig. 1 b is the transmission electron microscope picture of F-CDs prepared in the embodiment of the present invention 1.
Fig. 2 is glimmering under excited by visible light of the F-CDs prepared in the embodiment of the present invention 1 between 360nm to 570nm
Optical emission spectroscopy figure.
Fig. 3 is the detection mechanism schematic diagram of fluorescence sensor array prepared in the embodiment of the present invention 1.
Fig. 4 a- Fig. 4 f is F-CDs and three metal ion species Cu prepared in the embodiment of the present invention 1 respectively2+、Ce3+、Eu3+
Fluorescence emission spectrogram of compound of the effect front and back under 360nm, 450nm, 540nm excited by visible light.
Fig. 5 is master of the fluorescence sensor array prepared in the embodiment of the present invention 4 to 20 kinds of antibiotic of same concentrations
Constituent analysis figure.
Fig. 6 is fluorescence sensor array prepared in the embodiment of the present invention 4 to the poly- of 20 kinds of antibiotic of same concentrations
Alanysis figure.
Fig. 7 a is that fluorescence sensor array prepared in the embodiment of the present invention 4 is mould to the single antibiotic soil of various concentration
The fluorescence response situation schematic diagram of element.
Fig. 7 b is the standard fit curve graph of terramycin concentration and change in fluorescence in the embodiment of the present invention 4.
Specific embodiment
As previously mentioned, inventor is studied for a long period of time and largely practiced in view of the defect of the prior art, it is able to propose this
The technical solution of invention is mainly to provide a kind of for Tetracyclines, quinolones, beta-lactam and aminoglycosides
Deng the preparation method of the four major class antibiotic sensor array with half-quantitative detection qualitative simultaneously, the preparation method mainly include by
The screening for the fluorescence indicator that F-CDs- metal ion complex is constituted, the screening of immobilizing indicator formula and the structure of array
It makes.
Further, preparation method of the invention has highly sensitive and height to antibiotic the following steps are included: (1) is chosen
The metal ion of selectivity forms F-CDs- metal ion complex, constructs fluorescence indicator；(2) suitable indicator is chosen
Fixed formula；(3) fluorescence intensity that the fluorescence indicator before and after antibiotic is added is recorded with Fluorescence Spectrometer constructs fluorescence array
Sensor.
The technical solution, its implementation process and principle etc. will be further explained as follows.
As the one aspect of technical solution of the present invention, involved in be a kind of fluorescence indicator combination comprising it is complete
A variety of carbon quantum dot-gold that color fluorescent carbon quantum dot (abbreviation F-CDs) and various metals ion are formed under different ph values
Belong to ion complex (abbreviation F-CDs- metal ion complex).
Among an embodiment, the fluorescence indicator combination is specifically included:
Panchromatic fluorescent carbon quantum dot and Cu2+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Cu2+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Eu3+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Eu3+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Ce3+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Panchromatic fluorescent carbon quantum dot and Ce3+Carbon quantum dot-the gold formed in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex.
Among an embodiment, the preparation method of the panchromatic fluorescent carbon quantum dot is as shown in Figure 1a comprising: with micro-
Wave assisting alcohol-hydrothermal method makes citric acid and formamide forms the panchromatic fluorescent carbon quantum dot, wherein reaction temperature be 140~
180 DEG C, the time is 0.5~2h, and microwave power is 200~400W.
Further, the excitation wavelength corresponding to fluorescence indicator combination is respectively 360nm, 450nm, 540nm, and
Corresponding launch wavelength is respectively 466nm, 555nm, 637nm.
As the other side of technical solution of the present invention, involved in be that fluorescence indicator above-mentioned is combined in detection
Application in antibiotic.
Further, the antibiotic includes in Tetracyclines, quinolones, beta-lactam and aminoglycosides etc.
Any one or two or more combinations, but not limited to this.
As the other side of technical solution of the present invention, involved in be a kind of fluorescence sensor array, it includes
Fluorescence indicator combination above-mentioned.
Preferably, the sensor includes plural groups response point, and each group of response point includes corresponding respectively to excitation wavelength
Three or more the separate responses points of 360nm, 450nm, 540nm, each response point include at least one carbon quantum dot-metal from
Sub- compound, alternatively, the sensor includes corresponding respectively to three groups of excitation wavelength 360nm, 450nm, 540nm or more to respond
Point, each group of response point include multiple separate responses points, and each response point includes that at least one carbon quantum dot-metal ion is compound
Object.
Further, carbon quantum dot-metal ion complex contained by any two response point is not in each group of response point
Together.
As the other side of technical solution of the present invention, involved in be fluorescence indicator combination above-mentioned preparation
Method comprising: make panchromatic fluorescent carbon quantum dot react to form a variety of carbon amounts under different ph values with various metals ion
Sub- point-metal ion complex.
Among an embodiment, the preparation method includes: that panchromatic fluorescent carbon quantum dot is dissolved in different pH
In HEPES buffer, panchromatic fluorescent carbon quantum dot aqueous solution is formed, in the panchromatic fluorescent carbon quantum dot aqueous solution of different pH
It is separately added into metal ion, in reacting 5~10min under room temperature, obtains the carbon quantum dot-metal ion complex.
Preferably, the pH of the HEPES buffer solution is 6.8~8.2.
Further, the metal ion includes Cu2+、Ce3+And Eu3+Any one in or two or more combinations,
But not limited to this.
Further, the preparation method specifically includes:
Make panchromatic fluorescent carbon quantum dot and Cu2+Reaction forms carbon quantum in the HEPES buffer solution that pH value is 6.8~7.4
Point-metal ion complex,
Make panchromatic fluorescent carbon quantum dot and Cu2+Reaction forms carbon quantum in the HEPES buffer solution that pH value is 7.4~8.2
Point-metal ion complex,
Make panchromatic fluorescent carbon quantum dot and Eu3+Reaction forms carbon quantum in the HEPES buffer solution that pH value is 6.8~7.4
Point-metal ion complex,
Make panchromatic fluorescent carbon quantum dot and Eu3+Reaction forms carbon quantum in the HEPES buffer solution that pH value is 7.4~8.2
Point-metal ion complex,
Make panchromatic fluorescent carbon quantum dot and Ce3+Reaction forms carbon quantum in the HEPES buffer solution that pH value is 6.8~7.4
Point-metal ion complex,
Make panchromatic fluorescent carbon quantum dot and Ce3+Reaction forms carbon quantum in the HEPES buffer solution that pH value is 7.4~8.2
Point-metal ion complex.
Further, the preparation method includes: so that citric acid and formamide is formed institute with microwave-assisted hydro-thermal method
State panchromatic fluorescent carbon quantum dot, wherein reaction temperature be 140~180 DEG C, the time be 0.5~2h, microwave power be 200~
400W。
Further, the preparation method specifically includes: making panchromatic fluorescent carbon quantum dot and Cu2+、Ce3+、Eu3+In
Any one pH value be 6.8~8.2 HEPES buffer solution in reaction form carbon quantum dot-metal ion complex before, entirely
Concentration of the color fluorescent carbon quantum dot in the HEPES buffer solution is 1~10 μ g/mL, Cu2+、Ce3+Or Eu3+Concentration 10
~50 μM.
In some embodiments, the preparation method of the fluorescence sensor array may particularly include:
(1) the panchromatic fluorescent carbon quantum dot (abbreviation F-CDs) with real excitation wavelength dependence is prepared first, by it
It is dissolved in the HEPES buffer solution of different pH, finally obtains F-CDs aqueous solution, be separately added into the F-CDs solution of different pH
Metal ion Cu2+、Ce3+、Eu3+, react 5 minutes, be uniformly mixed and obtain different fluorescence indicators, i.e. F-CDs- metal ion
Compound；
(2) the different fluorescence response indicator that recording step (1) obtains respectively, i.e. F-CDs- metal ion complex,
Determinand is added in (corresponding launch wavelength is 466nm, 555nm, 637nm) under the excitation wavelength of 360nm, 450nm, 540nm
The fluorescence array sensing distinguished for antibiotic detection based on carbon dots can be obtained in the fluorescence intensity change of front and back
Device.
Further, in step (2), the formula is fixed with important influence to indicator, same in order to realize
When distinguish Multiple Classes of Antibiotics, fluorescence indicator is screened first, selected indicator must have not from different antibiotic
It with the response of degree, excludes and distinguishes the unconspicuous indicator of effect, then the indicator point that selected differentiation effect is good
It dissipates in different fixed formulas, the microenvironment by changing formula realizes different detection sensitivities, realizes to a variety of
Quantitative and semi-quantitative detects while antibiotic.
Further, the fixed formula of the fluorescence indicator in step (2) includes following six kinds:
①F-CDs-Cu2+Compound: F-CDs and 10 μM of the Cu of 5 μ g/mL2+It is evenly dispersed in HEPES 6.8~7.4
Buffer in, react 5min under room temperature, the fluorescence being separately recorded under 360nm, 450nm, 540nm excitation wavelength obtains fluorescence
Indicate agent prescription；
②F-CDs-Cu2+Compound: F-CDs and 10 μM of the Cu of 5 μ g/mL2+It is evenly dispersed in HEPES 7.4~8.2
Buffer in, react 5min under room temperature, the fluorescence being separately recorded under 360nm, 450nm, 540nm excitation wavelength obtains fluorescence
Indicate agent prescription；
③F-CDs-Ce3+Compound: F-CDs and 50 μM of the Ce of 5 μ g/mL3+It is evenly dispersed in HEPES 6.8~7.4
Buffer in, react 5min under room temperature, the fluorescence being separately recorded under 360nm, 450nm, 540nm excitation wavelength obtains fluorescence
Indicate agent prescription；
④F-CDs-Ce3+Compound: F-CDs and 50 μM of the Ce of 5 μ g/mL3+It is evenly dispersed in HEPES 7.4~8.2
Buffer in, react 5min under room temperature, the fluorescence being separately recorded under 360nm, 450nm, 540nm excitation wavelength obtains fluorescence
Indicate agent prescription；
⑤F-CDs-Eu3+Compound: F-CDs and 50 μM of the Eu of 5 μ g/mL3+It is evenly dispersed in HEPES 6.8~7.4
Buffer in, react 5min under room temperature, the fluorescence being separately recorded under 360nm, 450nm, 540nm excitation wavelength obtains fluorescence
Indicate agent prescription；
⑥F-CDs-Eu3+Compound: F-CDs and 50 μM of the Eu of 5 μ g/mL3+It is evenly dispersed in HEPES 7.4~8.2
Buffer in, react 5min under room temperature, the fluorescence being separately recorded under 360nm, 450nm, 540nm excitation wavelength obtains fluorescence
Indicate agent prescription；
Above-mentioned 6 kinds fixed formulas are formed into multiple response points from different antibiotic, each response point independent of each other is arranged side by side
Arrangement constructs fluorescence sensor array.For same indicator, after selecting different immobilizations to be formulated, to according to anti-
The difference of raw element solution concentration, and generate different responses.
Wherein 1. 2. 3. 4. when recording fluorescence intensity, the excitation wavelength of selection be in 360nm, 450nm, 540nm extremely
Few one kind, the excitation wavelength 5. 6. selected are 540nm.
Further, the concrete operations of the preparation method are as follows: by the fluorescence indicator filtered out i.e. F-CDs- metal ion
10 μ g of compound is added in the fixed formula of 2mL, and ultrasonic dissolution finally pours into cuvette, utilizes sepectrophotofluorometer
The fluorescence intensity under different excitation wavelengths is recorded respectively, obtains array response point to get the multichannel arrived for antibiotic detection
Fluorescence sensor array.
The present invention constructs multichannel fluorescence sensor array using the fluorescence indicator, and acquisition data are needed by glimmering
Photothermal spectroscopic analyzer, when recording fluorescence intensity change, one fluorescence indicator can acquire three data, respectively selective exitation wave
Long 360nm, 450nm, 540nm.
As the other side of technical solution of the present invention, involved in be a kind of antibiotic detection method comprising:
Fluorescence indicator combination above-mentioned or fluorescence sensor array are provided；
By each carbon quantum dot-metal ion complex or contain the molten of different carbon quantum dot-metal ion complex respectively
Liquid and the solution to be measured containing antibiotic are mixed to form multiple response points, and at least with the excitation wave of 360nm, 450nm, 540nm
The long fluorescence intensity change for detecting each response point and forming front and back is realized to the type of antibiotic in solution to be measured and/or concentration
Detection.
Among an embodiment, which comprises
The solution containing different carbon quantum dot-metal ion complex is contained into various concentration antibiotic with a series of respectively
Standard solution be mixed to form multiple response points, and each response point is detected with the excitation wavelength of 360nm, 450nm, 540nm and is formed
Thus the fluorescence intensity change of front and back establishes fluorescence intensity change-antibiotic concentration standard fit curve；
Solution containing different carbon quantum dot-metal ion complex is mixed to form with the solution to be measured containing antibiotic
Multiple response points, and the fluorescence intensity change that each response point forms front and back is detected with the excitation wavelength of 360nm, 450nm, 540nm,
Detection data and the standard fit curve control will be obtained later, to measure the content of antibiotic in solution to be measured.
Wherein, among one more specifically case study on implementation, the method specifically comprises the following steps:
(1) solution containing different carbon quantum dot-metal ion complex is contained into various concentration antibiotic with a series of
Standard solution be mixed to form multiple response points, the fluorescence intensity in each response point is read by Fluorescence Scanner and is denoted as F0, and
The fluorescence intensity change that each response point forms front and back is detected with the excitation wavelength of 360nm, 450nm, 540nm, passes through fluorescent scanning
Instrument reads the fluorescence intensity after response point is formed and is denoted as F1；
(2) fluorescence of front and back is formed to each response point that the Fluorescence Scanner in step (1) is read by normalized
Strength Changes carry out digitized processing, i.e. (F1-F0)/F0, and then the fluorescence intensity change-for obtaining the antibiotic of various concentration is anti-
Raw element concentration standard matched curve；
(3) solution containing different carbon quantum dot-metal ion complex is mixed with the solution to be measured containing antibiotic
Multiple response points are formed, and the fluorescence intensity that each response point forms front and back is detected with the excitation wavelength of 360nm, 450nm, 540nm
Variation, by Fluorescence Scanner read the fluorescence intensity change go forward side by side digitized processing, later with the standard fit curve
Control, the type and/or concentration of antibiotic in solution to be measured are determined according to the degree of agreement of the two.
Further, the method also specifically includes:
(1) the fluorescence indicator solution prepared in advance is poured into cuvette, is put into sepectrophotofluorometer
The fluorescence intensity of record at this time is denoted as F0；Then the antibiotic standard solution of different known concentrations is added in former cuvette,
It is uniformly mixed reaction 5 minutes, the fluorescence intensity re-recorded at this time is denoted as F1, fluorescence indicator on the sensor array with not
With different fluorescence intensity changes is generated respectively after antibiotic reaction, become by sepectrophotofluorometer sweep measuring fluorescence intensity
Change；
(2) it is counted by fluorescence intensity change of the normalized to the fluorescent spectrophotometer assay in step (1)
Wordization processing, i.e. (F1-F0)/F0,F0,F1The fluorescence intensity before and after generation addition antibiotic is respectively referred to, is mapped using origin software,
The change in fluorescence of the antibiotic of various concentration and the linear fit map of concentration are made, standard fit linear equation is obtained；
(3) prepare liquid is added in the fluorescence indicator, is read on the sensor array by Fluorescence Scanner
Response point reacted with antibiotic after the change in fluorescence that generates respectively, then according to the processing method of step (2) to fluorescence intensity
Variation carries out digitized processing, and obtained result is brought into standard fit linear equation, determined according to the degree of agreement of the two
There are antibiotic-free and already present antibiotic content range in solution to be measured.
Further, the Fluorescence Scanner includes sepectrophotofluorometer, but not limited to this.
It further, include respectively in 360nm, 450nm, 540nm by the fluorescence intensity level that Fluorescence Scanner is read
Fluorescence intensity under excitation wavelength.
Further, the antibiotic includes in Tetracyclines, quinolones, beta-lactam and aminoglycosides etc.
Any one or two or more combinations, but not limited to this.
In conclusion the present invention is rung using F-CDs and the metal ion filtered out as antibiotic by above-mentioned technical proposal
The fluorescence indicator material answered；These indicator are fixed in formula, the microenvironment by changing formula is realized to Fourth Ring
The differentiation and different detection sensitivities of the four class antibiotic such as plain class, quinolones, beta-lactam and aminoglycosides；
To distinguish multiclass antibiotic simultaneously, 3 metal ion species and 6 kinds of fixed formulas are mixed into 18 response points, are put into fluorescence spectrum
It is used as detection unit on instrument, the corresponding fluorescence intensity information of each response point is extracted, by all these fluorescence intensity change information
It sums up, constructs array system；It is differed, is mentioned based on various concentration and inhomogeneity antibiotic and the constructed response point extent of reaction
Fluorescence intensity information after taking each response point to react, all these fluorescence intensity information are summed up, and construct array system.
Multichannel fluorescence sensor array of the invention can be realized while to Tetracyclines, quinolones, beta-lactam
And the quantitative and semi-quantitative detection of the four major class antibiotic such as aminoglycosides；And its manufacturing process is simple, and the holding time is long
And detection sensitivity is preferable, realizes merely with a kind of fluorescent carbon point, by recording multichannel fluorescence intensity change, can be achieved with
It distinguishes and detects while multiclass antibiotic.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out detailed retouch
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, those of ordinary skill in the art's every other implementation obtained without making creative work
Example, shall fall within the protection scope of the present invention.
The building of 1 multichannel fluorescence sensor array of embodiment
(1) screening of fluorescence indicator:
In order to realize the obvious differentiation of multiclass antibiotic, each other without cross jamming.When constructing fluorescence indicator, based on gold
The quenching degree for belonging to ion pair F-CDs, screens metal ion, in metal cations Fe2+、Fe3+、Co2+、Ni2+、Cu2+、
Zn2+、Cd2+、Hg2+、Pb2+、Ag+、Cr3+、Ce3+And Eu3+In screened 3 kinds degree be larger while and antibiotic to F-CDs quenching
Binding ability also stronger metal ion, is respectively as follows: Cu2+、Ce3+、Eu3+, i.e. composition F-CDs-Cu2+, F-CDs-Ce3+, F-
CDs-Eu3+Three kinds of fluorescence indicators.
(2) selection of fixed formula:
1) F-CDs (5 μ g/mL) and Cu2+(10 μM) are dissolved in the HEPES buffer solution (10mM) of the pH7.4 of 2mL, often
Temperature is lower to react 5min, obtains formula 1；
2) F-CDs (5 μ g/mL) and Cu2+(10 μM) are dissolved in the HEPES buffer solution (10mM) of the pH8.2 of 2mL, often
Temperature is lower to react 5min, obtains formula 2；
3) F-CDs (5 μ g/mL) and Ce3+(50 μM) are dissolved in the HEPES buffer solution (10mM) of the pH7.4 of 2mL, often
Temperature is lower to react 5min, obtains formula 3；
4) F-CDs (5 μ g/mL) and Ce3+(50 μM) are dissolved in the HEPES buffer solution (10mM) of the pH8.2 of 2mL, often
Temperature is lower to react 5min, obtains formula 4；
5) F-CDs (5 μ g/mL) and Eu2+(50 μM) are dissolved in the HEPES buffer solution (10mM) of the pH7.4 of 2mL, often
Temperature is lower to react 5min, obtains formula 5；
6) F-CDs (5 μ g/mL) and Eu2+(50 μM) are dissolved in the HEPES buffer solution (10mM) of the pH8.2 of 2mL, often
Temperature is lower to react 5min, obtains formula 6；
The preparation of sensor array: 3 kinds of indicator of (1) are separately recorded in three by 6 kinds of fixed formula collocation in (2)
For fluorescence intensity change under kind excitation wavelength 360nm, 450nm, 540nm to form 18 response points, 18 independent of each other
Response point is respectively as follows: formula 1-360nm, is formulated 1-450nm, is formulated 1-540nm, is formulated 2-360nm, is formulated 2-450nm, formula
2-540nm is formulated 3-360nm, is formulated 3-450nm, is formulated 3-540nm, is formulated 4-360nm, is formulated 4-450nm, is formulated 4-
540nm is formulated 5-360nm, is formulated 5-450nm, is formulated 5-540nm, is formulated 6-360nm, is formulated 6-450nm, is formulated 6-
540nm。
It is simple time saving for experiment, according to the differentiation effect of different antibiotic, 18 response points are screened, are selected
The differentiation of Multiple Classes of Antibiotics can be realized in 11 response points, and 11 response points are respectively to be formulated 1-360nm, is formulated 1-540nm,
It is formulated 2-360nm, is formulated 2-450nm, is formulated 2-540nm, is formulated 3-360nm, is formulated 3-450nm, is formulated 3-540nm, formula
4-540nm is formulated 5-540nm, is formulated 6-540nm.Particular content table 1 is expressed as follows:
Antibiotic to be measured is added in above 11 response points, after reacting 5min, before antibiotic is added in record respectively
Change in fluorescence afterwards, by normalized, obtained data, which are carried out PCA and HCA analysis, can determine whether inhomogeneity antibiotic
Differentiation effect.
The process schematic of F-CDs manufactured in the present embodiment is as shown in Figure 1a, and the transmission electron microscope picture of obtained F-CDs is as schemed
Shown in 1b.Fluorescence emission spectrogram of compound under excited by visible light of the F-CDs prepared by the present embodiment between 360nm to 570nm
(excitation wavelength is sequentially increased from left to right) as shown in Figure 2.The inspection of multichannel fluorescence sensor array prepared by the present embodiment
It is shown in Figure 3 to survey mechanism schematic diagram.F-CDs prepared by the present embodiment and three metal ion species Cu2+、Ce3+、Eu3+Effect
Front and back is in the fluorescence emission spectrogram of compound under 360nm, 450nm, 540nm excited by visible light respectively as shown in Fig. 4 a- Fig. 4 f.
The building of 2 multichannel fluorescence sensor array of embodiment
(1) screening of sensing unit
In order to realize the detection of the 4 major class antibiotic such as Tetracyclines, quinolones, beta-lactam and aminoglycosides
It distinguishes, according to the differentiation effect of different antibiotic, 18 response points is screened, select 8 response points (sensing unit) i.e.
The differentiation of Multiple Classes of Antibiotics can be achieved, 8 response point specific formulas of screening are as follows:
(2) antibiotic to be measured is added in above 8 response points, after reacting 5min, antibiotic is added in record respectively
The change in fluorescence of front and back, by normalized, obtained data, which are carried out PCA and HCA analysis, can determine whether inhomogeneity antibiosis
The differentiation effect of element.
The building of 3 multichannel fluorescence sensor array of embodiment
(1) screening of sensing unit
In order to realize the detection of the 4 major class antibiotic such as Tetracyclines, quinolones, beta-lactam and aminoglycosides
It distinguishes, according to the differentiation effect of different antibiotic, 18 response points is screened, select 6 response points (sensing unit) i.e.
The differentiation of Multiple Classes of Antibiotics can be achieved, 6 response point specific formulas of screening are as follows:
(2) antibiotic to be measured is added in above 6 response points, after reacting 5min, antibiotic is added in record respectively
The change in fluorescence of front and back, by normalized, obtained data, which are carried out PCA and HCA analysis, can determine whether inhomogeneity antibiosis
The differentiation effect of element.
The building of 4 multichannel fluorescence sensor array of embodiment
(1) screening of sensing unit
In order to realize the detection of the 4 major class antibiotic such as Tetracyclines, quinolones, beta-lactam and aminoglycosides
It distinguishes, according to the differentiation effect of different antibiotic, 18 response points is screened, select 5 response points (sensing unit) i.e.
The differentiation of Multiple Classes of Antibiotics can be achieved, 5 response point specific formulas of screening are as follows:
| S1 | F-CDs(5μg/mL)in 10mM HEPES(pH 8.2)+Cu2+(10μM)—atλex=540nm |
| S2 | F-CDs(5μg/mL)in 10mM HEPES(pH 8.2)+Eu3+(50μM)—atλex=540nm |
| S3 | F-CDs(5μg/mL)in 10mM HEPES(pH 7.4)+Ce3+(50μM)—atλex=450nm |
| S4 | F-CDs(5μg/mL)in 10mM HEPES(pH 7.4)+Ce3+(50μM)—atλex=540nm |
| S5 | F-CDs(5μg/mL)in 10mM HEPES(pH 7.4)+Eu3+(50μM)—atλex=540nm |
(2) change in fluorescence before and after antibiotic is added using Fluorescence Spectrometer measurement, produced by before and after addition antibiotic
Change in fluorescence by normalized, the variation relation of antibiotic concentration and fluorescence intensity is fitted to standard curve, is fixed
Property and semi-quantitative analysis provide foundation.
(3) according to the method described above, 50 μM of different antibiotic solutions are added, obtained differentiation result is as illustrated in Figures 5 and 6.
V.3.1 using MVSP, Kovach Computing software is mapped, and the concentration of all antibiotic is 50 μM, and every kind of antibiotic repeats
It surveys five times.Fig. 5 shows multichannel fluorescence sensor array prepared in the present embodiment to 20 kinds of antibiotic of same concentrations
Principal component analysis figure.This it appears that Tetracyclines, quinolones, beta-lactam and aminoglycosides etc. from figure
Four class antibiotic can distinguish well or even the very much like antibiotic of structure in every class antibiotic or well
It distinguishes, repeatability is fabulous, it was demonstrated that the sensor array is able to achieve the quantitative and semi-quantitative differentiation to these four types of antibiotic.
Equally v.3.1 using MVSP, Kovach Computing software mapping, the concentration of all antibiotic are 50 μM, often
Kind antibiotic repeats to survey five times.Fig. 6 shows multichannel fluorescence sensor array prepared in the present embodiment to same concentrations
20 kinds of antibiotic clustering figure.Every class antibiotic can return well in one kind in figure, and it is fabulous to distinguish effect.From figure
This it appears that the four class antibiotic such as Tetracyclines, quinolones, beta-lactam and aminoglycosides can be well
Distinguish in addition every class antibiotic in the very much like antibiotic of structure can also distinguish well, further demonstrate
The sensor array is able to achieve the quantitative and semi-quantitative differentiation to these four types of antibiotic.
Sensor array can be made to generate it is found that the different antibiotic solutions of same concentrations are added by the result of Figures 5 and 6 analysis
Different responses can distinguish these four types of antibiotic well, each other will not cross jamming.Therefore, array of preparation
The differentiation detection of Multiple Classes of Antibiotics can be well realized in sensor.
Fig. 7 a, Fig. 7 b respectively illustrate multichannel fluorescence sensor array prepared in the present embodiment to various concentration
The fluorescence response situation and terramycin concentration of single antibiotic terramycin and the standard fit curve of change in fluorescence, wherein soil
The concentration of mycin is at 0.1-300 μM, and each concentration repeats to survey three times, and repeatability is fabulous.The fluorescence of constructed sensor array
Linear relationship well, coefficient R is presented in Strength Changes and terramycin concentration within the scope of 0.1-10 μM2=0.997, thus
The detection that terramycin can be calculated is limited to 0.06 μM, and sensitivity is high, shows that the sensor array is sensitive enough, may be implemented
The half-quantitative detection of antibiotic.
Comparative example 1
Four kinds of tetracycline antibiotics of the improved electrode detection of multi-walled carbon nanotube, detection limit are utilized using electrochemical process
It is 0.44 μM, can not achieve the detection and differentiation to Multiple Classes of Antibiotics, while sensitivity is also not so good as multi-pass designed by the present invention
Road fluorescence sensor array is sensitive.
Comparative example 2
Multiple Classes of Antibiotics is detected using the method for high performance liquid chromatography, detection range be 0.21-104 μM it
Between, sensitivity is inadequate, while using high performance liquid chromatography, needs expensive instrument, professional operator, sample pre-treatments
Also more complicated.
In conclusion multichannel fluorescence sensor array of the invention can be realized by above-mentioned technical proposal of the invention
Simultaneously to the quantitative and semi-quantitative of the four major class antibiotic such as Tetracyclines, quinolones, beta-lactam and aminoglycosides
Detection；And its manufacturing process is simple, and the holding time is long and detection sensitivity is preferable, realizes merely with a kind of fluorescent carbon point,
By recording multichannel fluorescence intensity change, can be achieved with distinguishing and detecting while multiclass antibiotic.
In addition, inventor also refers to the mode of Examples 1 to 4, with the other raw materials and item listed in this specification
Part etc. is tested, and the multichannel fluorescence battle array that the quantitative and semi-quantitative detection to Multiple Classes of Antibiotics can be achieved equally has been made
Sensor.
It should be noted that, in this document, the terms "include", "comprise" or its any other variant are intended to non-row
His property includes, so that the process, method, article or equipment for including a series of elements not only includes those elements, and
And further include other elements that are not explicitly listed, or further include for this process, method, article or equipment institute it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including institute
State in the process, method, article or equipment of element that there is also other identical elements.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (10)
1. fluorescence indicator combines, it is characterised in that including panchromatic fluorescent carbon quantum dot from various metals ion in different pH value items
A variety of carbon quantum dot-the metal ion complex formed under part.
2. fluorescence indicator combination according to claim 1, which is characterized in that the specific packet of fluorescence indicator combination
It includes: panchromatic fluorescent carbon quantum dot and Cu2+In the HEPES buffer solution that pH value is 6.8~7.4 carbon quantum dot-metal for being formed from
Sub- compound,
Panchromatic fluorescent carbon quantum dot and Cu2+In the HEPES buffer solution that pH value is 7.4~8.2 carbon quantum dot-metal for being formed from
Sub- compound,
Panchromatic fluorescent carbon quantum dot and Eu3+In the HEPES buffer solution that pH value is 6.8~7.4 carbon quantum dot-metal for being formed from
Sub- compound,
Panchromatic fluorescent carbon quantum dot and Eu3+In the HEPES buffer solution that pH value is 7.4~8.2 carbon quantum dot-metal for being formed from
Sub- compound,
Panchromatic fluorescent carbon quantum dot and Ce3+In the HEPES buffer solution that pH value is 6.8~7.4 carbon quantum dot-metal for being formed from
Sub- compound,
Panchromatic fluorescent carbon quantum dot and Ce3+In the HEPES buffer solution that pH value is 7.4~8.2 carbon quantum dot-metal for being formed from
Sub- compound；
And/or the preparation method of the panchromatic fluorescent carbon quantum dot includes: to make citric acid and formamide with microwave-assisted hydro-thermal method
Reaction forms the panchromatic fluorescent carbon quantum dot, and wherein reaction temperature is 140~180 DEG C, and the time is 0.5~2h, microwave power
For 200~400W；
And/or the excitation wavelength corresponding to fluorescence indicator combination is respectively 360nm, 450nm, 540nm, and accordingly send out
Long ejected wave is respectively 466nm, 555nm, 637nm.
3. fluorescence indicator of any of claims 1-2 is combined in the application in detection antibiotic；Preferably, described
Antibiotic includes any one or two or more groups in Tetracyclines, quinolones, beta-lactam and aminoglycosides
It closes.
4. a kind of fluorescence sensor array, it is characterised in that include fluorescence indicator group of any of claims 1-2
It closes；Preferably, the sensor includes plural groups response point, each group of response point include correspond respectively to excitation wavelength 360nm,
Three or more the separate responses points of 450nm, 540nm, each response point include that at least one carbon quantum dot-metal ion is compound
Object, alternatively, the sensor includes corresponding respectively to three groups of excitation wavelength 360nm, 450nm, 540nm or more response points, often
One group of response point includes multiple separate responses points, and each response point includes at least one carbon quantum dot-metal ion complex；More
Preferably, carbon quantum dot contained by any two response point-metal ion complex is different in each group of response point.
5. the preparation method of fluorescence indicator combination of any of claims 1-2, characterized by comprising: make panchromatic
Fluorescent carbon quantum dot reacts that form a variety of carbon quantum dot-metal ions compound with various metals ion under different ph values
Object.
6. preparation method according to claim 5, which is characterized in that the preparation method specifically includes:
Make panchromatic fluorescent carbon quantum dot and Cu2+Reaction forms carbon quantum dot-gold in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Make panchromatic fluorescent carbon quantum dot and Cu2+Reaction forms carbon quantum dot-gold in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex,
Make panchromatic fluorescent carbon quantum dot and Eu3+Reaction forms carbon quantum dot-gold in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Make panchromatic fluorescent carbon quantum dot and Eu3+Reaction forms carbon quantum dot-gold in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex,
Make panchromatic fluorescent carbon quantum dot and Ce3+Reaction forms carbon quantum dot-gold in the HEPES buffer solution that pH value is 6.8~7.4
Belong to ion complex,
Make panchromatic fluorescent carbon quantum dot and Ce3+Reaction forms carbon quantum dot-gold in the HEPES buffer solution that pH value is 7.4~8.2
Belong to ion complex；
And/or the preparation method includes: that form citric acid with formamide with microwave-assisted hydro-thermal method described panchromatic glimmering
Light carbon quantum dot, wherein reaction temperature is 140~180 DEG C, and the time is 0.5~2h, and microwave power is 200~400W.
7. preparation method according to claim 6, it is characterised in that specifically include: making panchromatic fluorescent carbon quantum dot and Cu2 +、Ce3+、Eu3+Any one of to form carbon quantum dot-metal ion multiple for reaction in the HEPES buffer solution that pH value is 6.8~8.2
Before closing object, concentration of the panchromatic fluorescent carbon quantum dot in the HEPES buffer solution is 1~10 μ g/mL, Cu2+、Ce3+Or Eu3+
Concentration at 10~50 μM.
8. a kind of detection method of antibiotic, characterized by comprising:
Fluorescence indicator combination of any of claims 1-2 or fluorescence array sensing as claimed in claim 4 are provided
Device；
Respectively by each carbon quantum dot-metal ion complex or solution containing different carbon quantum dot-metal ion complex with
Solution to be measured containing antibiotic is mixed to form multiple response points, and is at least examined with the excitation wavelength of 360nm, 450nm, 540nm
The fluorescence intensity change that each response point forms front and back is surveyed, realizes the detection to the type and/or concentration of antibiotic in solution to be measured.
9. detection method according to claim 8, characterized by comprising:
Respectively by solution and a series of marks containing various concentration antibiotic containing different carbon quantum dot-metal ion complex
Quasi- solution is mixed to form multiple response points, and detects each response point with the excitation wavelength of 360nm, 450nm, 540nm and form front and back
Fluorescence intensity change, thus establish fluorescence intensity change-antibiotic concentration standard fit curve；
Solution containing different carbon quantum dot-metal ion complex is mixed to form with the solution to be measured containing antibiotic multiple
Response point, and the fluorescence intensity change that each response point forms front and back is detected with the excitation wavelength of 360nm, 450nm, 540nm, later
Detection data and the standard fit curve control will be obtained, to measure the content of antibiotic in solution to be measured.
10. according to the method described in claim 9, it is characterized in that specifically comprising the following steps:
(1) by solution and a series of marks containing various concentration antibiotic containing different carbon quantum dot-metal ion complex
Quasi- solution is mixed to form multiple response points, reads the fluorescence intensity in each response point by Fluorescence Scanner and is denoted as F0, and with
The excitation wavelength of 360nm, 450nm, 540nm detect the fluorescence intensity change that each response point forms front and back, pass through Fluorescence Scanner
It reads the fluorescence intensity after response point is formed and is denoted as F1；
(2) fluorescence intensity of front and back is formed to each response point that the Fluorescence Scanner in step (1) is read by normalized
Variation carries out digitized processing, i.e. (F1-F0)/F0, and then obtain fluorescence intensity change-antibiotic of the antibiotic of various concentration
Concentration standard matched curve；
(3) solution containing different carbon quantum dot-metal ion complex is mixed to form with the solution to be measured containing antibiotic
Multiple response points, and the fluorescence intensity change that each response point forms front and back is detected with the excitation wavelength of 360nm, 450nm, 540nm,
By Fluorescence Scanner read the fluorescence intensity change go forward side by side digitized processing, later with the standard fit curve control,
The type and/or concentration of antibiotic in solution to be measured are determined according to the degree of agreement of the two；
Preferably, the Fluorescence Scanner includes sepectrophotofluorometer；Preferably, the antibiotic includes Tetracyclines, quinoline
Any one in promise ketone, beta-lactam and aminoglycosides or two or more combinations.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117488A (en) * | 2018-02-07 | 2019-08-13 | 中国科学院宁波材料技术与工程研究所 | Near-infrared antibiotic fluorescence probe detection reagent, preparation method and application |
| CN110618125A (en) * | 2019-08-28 | 2019-12-27 | 江苏大学 | Preparation method and application of fluorescent paper-based sensor |
| CN111624184A (en) * | 2020-06-05 | 2020-09-04 | 深圳职业技术学院 | Fluorescent array sensor based on silicon quantum dots and preparation method and application thereof |
| CN113791058A (en) * | 2021-09-15 | 2021-12-14 | 南京大学 | Sensor array and detection device for detecting antibiotics and formed by LOMF (low-temperature multi-aperture membrane) |
| CN116023939A (en) * | 2022-12-21 | 2023-04-28 | 宁波慈溪生物医学工程研究所 | Metal doped carbon quantum dot, colorimetric sensing solution, colorimetric array sensor, preparation method of colorimetric array sensor and method for detecting biological mercaptan |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104694121A (en) * | 2015-01-30 | 2015-06-10 | 常州大学 | Preparation method of europium-doped carbon quantum dot composite material |
| CN104845619A (en) * | 2015-05-25 | 2015-08-19 | 广西师范学院 | Rapid synthesis method for high-quantum-yield fluorescent carbon dots |
| CN106675558A (en) * | 2017-01-16 | 2017-05-17 | 华南农业大学 | Carbon quantum dot/Eu<3+>/mesoporous alumina composite luminescent material and preparation and application thereof |
| CN106947475A (en) * | 2017-03-30 | 2017-07-14 | 皖西学院 | Al in fluorescent carbon quantum dot preparation method and its detection water3+Ion application |
| CN107227152A (en) * | 2016-03-25 | 2017-10-03 | 中国科学院宁波材料技术与工程研究所 | With near infrared emission fluorescent carbon point of translation function and preparation method thereof up and down |
| CN107300544A (en) * | 2017-06-16 | 2017-10-27 | 安徽师范大学 | A kind of detection method of ferrous ion |
-
2017
- 2017-12-27 CN CN201711445375.9A patent/CN109975253B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104694121A (en) * | 2015-01-30 | 2015-06-10 | 常州大学 | Preparation method of europium-doped carbon quantum dot composite material |
| CN104845619A (en) * | 2015-05-25 | 2015-08-19 | 广西师范学院 | Rapid synthesis method for high-quantum-yield fluorescent carbon dots |
| CN107227152A (en) * | 2016-03-25 | 2017-10-03 | 中国科学院宁波材料技术与工程研究所 | With near infrared emission fluorescent carbon point of translation function and preparation method thereof up and down |
| CN106675558A (en) * | 2017-01-16 | 2017-05-17 | 华南农业大学 | Carbon quantum dot/Eu<3+>/mesoporous alumina composite luminescent material and preparation and application thereof |
| CN106947475A (en) * | 2017-03-30 | 2017-07-14 | 皖西学院 | Al in fluorescent carbon quantum dot preparation method and its detection water3+Ion application |
| CN107300544A (en) * | 2017-06-16 | 2017-10-27 | 安徽师范大学 | A kind of detection method of ferrous ion |
Non-Patent Citations (5)
| Title |
|---|
| SHAN SUN 等: "Applying Carbon Dots-Metal Ions Ensembles as a Multichannel", 《ANALYTICAL CHEMISTRY》 * |
| 于永丽 等: "基于NaGdF4:Eu纳米粒子的荧光猝灭测定痕量Cu2+", 《光谱学与光谱分析》 * |
| 王文 等: "有机相CdTe量子点/铕/聚甲基丙烯酸甲酯复合体系的发光性质", 《应用化学》 * |
| 薛霏 等: "CdSe与CdSe/ZnS量子点合成及稀土掺杂", 《功能材料》 * |
| 魏伟 等: "碳量子点合成及其在食品检测中的应用", 《食品科学》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117488A (en) * | 2018-02-07 | 2019-08-13 | 中国科学院宁波材料技术与工程研究所 | Near-infrared antibiotic fluorescence probe detection reagent, preparation method and application |
| CN110117488B (en) * | 2018-02-07 | 2022-04-19 | 中国科学院宁波材料技术与工程研究所 | Near-infrared antibiotic fluorescent probe detection reagent, preparation method and application thereof |
| CN110618125A (en) * | 2019-08-28 | 2019-12-27 | 江苏大学 | Preparation method and application of fluorescent paper-based sensor |
| CN111624184A (en) * | 2020-06-05 | 2020-09-04 | 深圳职业技术学院 | Fluorescent array sensor based on silicon quantum dots and preparation method and application thereof |
| CN113791058A (en) * | 2021-09-15 | 2021-12-14 | 南京大学 | Sensor array and detection device for detecting antibiotics and formed by LOMF (low-temperature multi-aperture membrane) |
| CN116023939A (en) * | 2022-12-21 | 2023-04-28 | 宁波慈溪生物医学工程研究所 | Metal doped carbon quantum dot, colorimetric sensing solution, colorimetric array sensor, preparation method of colorimetric array sensor and method for detecting biological mercaptan |
| CN116023939B (en) * | 2022-12-21 | 2023-12-19 | 宁波慈溪生物医学工程研究所 | Metal doped carbon quantum dot, colorimetric sensing solution, colorimetric array sensor, preparation method of colorimetric array sensor and method for detecting biological mercaptan |
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