CN114214062A - Preparation method of fluorine-doped silicon quantum dots and application of fluorine-doped silicon quantum dots in detection of carmine - Google Patents

Preparation method of fluorine-doped silicon quantum dots and application of fluorine-doped silicon quantum dots in detection of carmine Download PDF

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CN114214062A
CN114214062A CN202111619965.5A CN202111619965A CN114214062A CN 114214062 A CN114214062 A CN 114214062A CN 202111619965 A CN202111619965 A CN 202111619965A CN 114214062 A CN114214062 A CN 114214062A
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China
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silicon quantum
fluorine
doped silicon
quantum dots
carmine
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CN202111619965.5A
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Inventor
昝明辉
董文飞
柳裕禄
宋明轩
安帅
吴再辉
刘莹
贾明正
王东
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Zhengzhou Zhongke Biomedical Engineering Technology Research Institute
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Zhengzhou Zhongke Biomedical Engineering Technology Research Institute
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Priority to CN202111619965.5A priority Critical patent/CN114214062A/en
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Priority to CN202210306810.4A priority patent/CN114702954B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/617—Silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention belongs to the field of silicon quantum dots, and particularly relates to a preparation method of fluorine-doped silicon quantum dots and application of the fluorine-doped silicon quantum dots in detection of carmine. The method comprises the following steps: carrying out hydrothermal reaction on 3-aminopropyltriethoxysilane and levofloxacin in water at 180-220 ℃, then carrying out dialysis treatment on the obtained reaction liquid, and drying to obtain fluorine-doped silicon quantum dots; the amount of 3-aminopropyltriethoxysilane used is 0.1-2 g/0.1-2 mL. According to the preparation method of the fluorine-doped silicon quantum dot, the obtained blue fluorescence emission silicon quantum dot has high luminous intensity, shows a specific fluorescence quenching characteristic to carmine, and can realize the specific and sensitive detection of the carmine.

Description

Preparation method of fluorine-doped silicon quantum dots and application of fluorine-doped silicon quantum dots in detection of carmine
Technical Field
The invention belongs to the field of silicon quantum dots, and particularly relates to a preparation method of fluorine-doped silicon quantum dots and application of the fluorine-doped silicon quantum dots in detection of carmine.
Background
Carmine is a commonly used synthetic food pigment, belonging to a strongly acidic dye. Excessive carmine has been shown to have serious carcinogenic and mutagenic effects, and the use of carmine in any food product is banned in the united states, canada, denmark, norway, and many other countries. In many countries it is approved as an additive and has strict usage levels in certain food products, such as beverages, candies and pickles. In china, the use of carmine in the food industry is limited to frozen beverages, jams, beverages, candies, cakes, syrups, preserves and cans. In order to ensure the health of the consumer, it is important to establish a simple, fast, sensitive and accurate method for the efficient detection of carmine in food products.
Methods for detecting carmine include chromatography, colorimetry, electrochemical methods, and the like, however, these methods suffer from certain disadvantages, such as long sample pretreatment time, expensive reagents required, long run time, and low sensitivity.
Disclosure of Invention
The invention aims to provide a preparation method of fluorine-doped silicon quantum dots, which can realize the fluorescence detection of carmine and has the characteristics of good specificity and high sensitivity.
The second purpose of the invention is to provide the application of the fluorine-doped silicon quantum dots obtained by the method in the detection of carmine.
In order to realize the purpose, the preparation method of the fluorine-doped silicon quantum dot adopts the technical scheme that:
a preparation method of fluorine-doped silicon quantum dots comprises the following steps: carrying out hydrothermal reaction on 3-aminopropyltriethoxysilane and levofloxacin in water at 180-220 ℃, then carrying out dialysis treatment on the obtained reaction liquid, and drying to obtain fluorine-doped silicon quantum dots; the dosage of the levofloxacin corresponding to 0.1-2 mL of 3-aminopropyltriethoxysilane is 0.1-2 g.
According to the preparation method of the fluorine-doped silicon quantum dot, the obtained blue fluorescence emission silicon quantum dot has high luminous intensity, shows a specific fluorescence quenching characteristic to carmine, and can realize the specific and sensitive detection of the carmine.
In order to further improve the reaction efficiency, the amount of water used is preferably 10mL per 0.1-0.2 mL of 3-aminopropyltriethoxysilane.
In order to better take the conversion rate of raw materials and the yield of products into consideration, the time of the hydrothermal reaction is preferably 6-10 hours or 8-10 hours; more preferably 7-9 h; further preferably 8 hours.
For better purification of the fluorine-doped silicon quantum dots, preferably, the dialysis treatment is performed in water, and the cut-off molecular weight of the dialysis treatment is 500-2000 Da. Further preferably, the cut-off molecular weight of the dialysis treatment is 1000 Da.
In order to further optimize the purification effect, the dialysis treatment time is preferably 40-60 h; more preferably 48-60 h.
To better preserve the structure of the silicon quantum dots and reduce damage, preferably, the drying is freeze-drying.
The fluorine-doped silicon quantum dot is applied to the detection of carmine.
The fluorine-doped silicon quantum dots are applied to detection of carmine, and have the advantages of low detection limit, accurate and reliable detection and the like.
In order to more efficiently realize the specific monitoring of the carmine, preferably, the content of the carmine is detected by a fluorescence method by utilizing the fluorescence quenching characteristic of the carmine on the fluorine-doped silicon quantum dots.
To further enhance the detection effect, the excitation wavelength at the time of detection is preferably 375 nm.
Drawings
FIG. 1 is a graph showing the optical properties and characteristics of fluorine-doped silicon quantum dots prepared in example 1 of the present invention;
FIG. 2 is a graph showing the results of rapid detection of carmine using fluorine-doped silicon quantum dots in Experimental example 2 of the present invention;
fig. 3 is a comparison graph of ion interference in rapid detection of carmine by using fluorine-doped silicon quantum dots prepared in example 1 of the present invention.
Detailed Description
The following will further illustrate the practice of the present invention with reference to specific examples.
First, the specific embodiment of the preparation method of fluorine doped silicon quantum dots
Example 1
The preparation method of the fluorine-doped silicon quantum dot comprises the following steps:
(1) 0.3g of levofloxacin is weighed and added into 10ml of ultrapure water, after ultrasonic treatment is carried out until the levofloxacin is completely dissolved, 0.1ml of 3-Aminopropyltriethoxysilane (APTES) is added, after full mixing, the mixture is placed into a 100ml of polytetrafluoroethylene reaction kettle to react for 8h at 200 ℃.
(2) Cooling the reaction solution obtained in the step (1) to room temperature, dialyzing in water for 48h by using a dialysis bag (1000Da), and finally obtaining a solid product through freeze drying.
Example 2
The preparation method of the fluorine-doped silicon quantum dot in the embodiment is different from the embodiment 1 in that:
in the step (1), the dosage of the levofloxacin is 0.1g, and the dosage of the APTES is 1 ml. The temperature of the hydrothermal reaction is 180 ℃ and the time is 7 h.
Example 3
The preparation method of the fluorine-doped silicon quantum dot in the embodiment is different from the embodiment 1 in that:
in the step (1), the dosage of the levofloxacin is 2g, and the dosage of the APTES is 2 ml. The temperature of the hydrothermal reaction is 180 ℃ and the time is 9 h.
Second, the detailed description of the application of the fluorine-doped silicon quantum dots is given in the experimental examples below.
Third, Experimental example
Experimental example 1
This experimental example tests the fluorescence optical properties of the fluorine-doped silicon quantum dots obtained in example 1 in water, and the results are shown in fig. 1A and B.
As can be seen from FIGS. 1A and B, the maximum excitation light wavelength of the fluorine-doped silicon quantum dots is 375nm, and the maximum emission peak is 475nm (blue fluorescence).
The characterization results of the fluorine-doped silicon quantum dots are shown in fig. 1C and D, and FT-IR and XPS spectra together prove the existence of Si element and the successful doping of F element into the silicon quantum dots.
Experimental example 2 fluorescent silicon quantum dots for detection of carmine
mu.L of carmine solutions of different concentrations (concentrations of 0,1,3,5,10,20,30,40,50,60,70,80,90,100,120,130,140,150,160,170,180,190, 200. mu. mol/L, respectively) were added to 3mL of fluorine doped silicon quantum dot solution (concentration of 0.1mg/mL) and allowed to stand for 3 minutes. Then, the excitation wavelength was set at 375nm, and the mixed solution was tested for fluorescence intensity value, the result of which is shown in FIG. 2.
As can be seen from fig. 2, the fluorescence intensity of the silicon quantum dots gradually decreases with the increase of the carmine concentration. Meanwhile, the figure shows that a good linear relation exists between the fluorescence intensity of the silicon quantum dots and the carmine concentration, and the detection limit of the fluorine-doped silicon quantum dots to the carmine is calculated to be 0.18 mu mol/L. The mechanism of quenching associated with this is presumed to be the Internal Filter Effect (IFE) mechanism.
Experimental example 3 fluorescence method for detecting specificity
With reference to the method of experimental example 2, the fluorescence response behavior of the fluorine-doped silicon quantum dot solution and other interferent solutions was tested. Interferent (NaCl) Na+,(KCl)K+,(CaCl2)Ca2+,(MgCl2)Mg2+,(Pb(NO3)2)Pb2+,(Ba(NO3)2)Ba2+,(C4H6O4Zn)Zn2+,(NiCl)Ni+,(CdH8N2O10)Cd2+,(AlCl3)Al3+,(MnCl2)Mn2+，(NaNO2)NO2 -,(NaNO3)NO3 -,(C2H3NaO2)CH3COO-,(NaF)F-,(NaCl)Cl-,(NaBr)Br-,(NaI)I-,(Na2SO3)SO3 2-,(Na2SO4)SO4 2-The concentrations of glucose, sucrose and cysteine were 1mmol/L, and the results are shown in FIG. 3.
As can be seen from FIG. 3, only carmine has a strong quenching effect on the fluorescence of the silicon quantum dot solution in the presence of the corresponding interferents, while other interferents have no significant effect on the fluorescence intensity.
According to the experimental results, the blue fluorescence-emitting silicon quantum dots can be prepared by the method of the embodiment, and the carmine can be specifically and sensitively detected by utilizing the characteristic of quenching the fluorescence of the carmine.

Claims (10)

1. A preparation method of fluorine-doped silicon quantum dots is characterized by comprising the following steps: carrying out hydrothermal reaction on 3-aminopropyltriethoxysilane and levofloxacin in water at 180-220 ℃, then carrying out dialysis treatment on the obtained reaction liquid, and drying to obtain fluorine-doped silicon quantum dots; the dosage of the levofloxacin corresponding to 0.1-2 mL of 3-aminopropyltriethoxysilane is 0.1-2 g.
2. The method of claim 1, wherein the amount of water used per 0.1-0.2 mL of 3-aminopropyltriethoxysilane used is 10 mL.
3. The method for preparing fluorine-doped silicon quantum dots according to claim 1, wherein the hydrothermal reaction time is 6-10h or 8-10 h.
4. The method for preparing fluorine-doped silicon quantum dots according to claim 1, wherein the dialysis treatment is performed in water, and the cut-off molecular weight of the dialysis treatment is 500-2000 Da.
5. The method of claim 4, wherein the dialysis treatment has a molecular weight cut-off of 1000 Da.
6. The method for preparing fluorine-doped silicon quantum dots according to claim 4 or 5, wherein the dialysis treatment time is 40-60h or 48-60 h.
7. The method of any one of claims 1 to 5, wherein the drying is freeze drying.
8. Application of the fluorine-doped silicon quantum dot prepared by the preparation method of claim 1 in detection of carmine.
9. The use of claim 8, wherein the content of carmine is detected by a fluorescence method by utilizing the fluorescence quenching property of the carmine on the fluorine-doped silicon quantum dots.
10. The use according to claim 9, wherein the excitation wavelength at detection is 375 nm.
CN202111619965.5A 2021-12-23 2021-12-23 Preparation method of fluorine-doped silicon quantum dots and application of fluorine-doped silicon quantum dots in detection of carmine Pending CN114214062A (en)

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CN115093848A (en) * 2022-08-11 2022-09-23 郑州中科生物医学工程技术研究院 Yellow fluorescent silicon quantum dot and preparation method and application thereof

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WO2009051016A1 (en) * 2007-10-17 2009-04-23 Konica Minolta Medical & Graphic, Inc. Silicon quantum dots and biological labeling agent using the same
US9209352B2 (en) * 2011-11-30 2015-12-08 University Of Washington Through Its Center For Commercialization Surface-passivated silicon quantum dot phosphors
CN105372221B (en) * 2015-12-09 2018-07-24 吉林化工学院 A method of detecting carmine content in beverage using fluorescence quenching method
CN105969346B (en) * 2016-05-25 2018-05-08 中国科学院武汉物理与数学研究所 A kind of method that microwave method prepares the fluorescence silicon quantum dot of fluorine doped
CN107474821A (en) * 2016-06-07 2017-12-15 上海交通大学 A kind of Silica-coated quantum dot and preparation method thereof
CN107325814B (en) * 2017-06-22 2018-11-09 东南大学 A kind of fluorescence silicon nano dots and the preparation method and application thereof
KR20190004607A (en) * 2017-07-04 2019-01-14 국방과학연구소 Silicon quantum dots-baesd explosive taggant detection sensors and manufacturing method of size-selective silicon quantum dots

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CN115093848A (en) * 2022-08-11 2022-09-23 郑州中科生物医学工程技术研究院 Yellow fluorescent silicon quantum dot and preparation method and application thereof
CN115093848B (en) * 2022-08-11 2023-10-20 郑州中科生物医学工程技术研究院 Yellow fluorescent silicon quantum dot and preparation method and application thereof

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Application publication date: 20220322