CN109679650A - Chlorogenic acid carbon dots and preparation method thereof, chlorogenic acid carbon dots doping and its preparation method and application - Google Patents

Chlorogenic acid carbon dots and preparation method thereof, chlorogenic acid carbon dots doping and its preparation method and application Download PDF

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CN109679650A
CN109679650A CN201811463628.XA CN201811463628A CN109679650A CN 109679650 A CN109679650 A CN 109679650A CN 201811463628 A CN201811463628 A CN 201811463628A CN 109679650 A CN109679650 A CN 109679650A
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chlorogenic acid
carbon dots
acid carbon
doping
preparation
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CN109679650B (en
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陈志俊
张馨月
李淑君
刘守新
李坚
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Northeast Forestry University
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    • C09K11/65Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/16Coating with a protective layer; Compositions or apparatus therefor
    • GPHYSICS
    • G01MEASURING; TESTING
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    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6439Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks

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Abstract

The invention discloses a kind of chlorogenic acid carbon dots, the partial size of the carbon dots is 1-4nm, and maximum fluorescence excitation wavelength is 340nm, and launch wavelength 420-570nm is prepared by the way that chlorogenic acid to be dissolved in methanol solvate.Also disclose a kind of chlorogenic acid carbon dots doping and preparation method thereof, comprising: 1) chlorogenic acid carbon dots solution or chlorogenic acid carbon dots are mixed with poly-vinyl alcohol solution, obtain chlorogenic acid carbon dots doping coating solution;2) film process are carried out to chlorogenic acid carbon dots doping coating solution, obtains chlorogenic acid carbon dots doping.Chlorogenic acid carbon dots pattern of the invention is preferable, and partial size is smaller and is evenly distributed, and preparation method raw material is cheap and easily-available, and method is simple and easy, and does not need the additionally processing such as heating or microwave, and quantum yield is high.Chlorogenic acid carbon dots doping prepared by the present invention is safe and nontoxic, easy to use, has preferable application in terms of food fresh keeping, metal ion detection and food spoilage.

Description

Chlorogenic acid carbon dots and preparation method thereof, chlorogenic acid carbon dots doping and preparation method thereof And application
Technical field
The present invention relates to a kind of chlorogenic acid carbon dots and preparation method thereof, and are adulterated by chlorogenic acid carbon dots prepared by the carbon dots Film and preparation method thereof and its application in terms of food fresh keeping, metal ion detection and food spoilage, belong to carbon Quantum dot preparation and applied technical field.
Background technique
Chlorogenic acid is a kind of plant polyphenol, is primarily present in the plants such as honeysuckle, coffee bean, is honeysuckle One of main antibacterial, antiviral effective pharmaceutical component, have extensive antibacterial and anti-inflammation functions.It is because having good inoxidizability With antibiotic property and studied be applied to field of food preservation.The water solubility of chlorogenic acid is poor, and solubility is only 4% in 25 DEG C of water, Solubility is larger in hot water, but chlorogenic acid has unstability, is unable to high temperature and long-time heating.Therefore, chlorogenic acid is water-soluble Property largely limits its application.
Currently, applying chlorogenic acid in field of food preservation mainly by chlorogenic acid and other functional additives or solvent Mixing, is made antistaling agent, and prepare chlorogenic acid carbon dots solution, not only has excellent antioxygenic property, there are also antibacterial action and Its unique optical property, and then film is made, and applied and do not had been reported that but in field of food preservation.
Carbon quantum dot (also referred to as carbon dots) is the Novel Carbon Nanomaterials with photoluminescent property, and size is minimum, and partial size usually exists 10 nanometers in Xu in 2004 etc. when using gel electrophoresis preparative separation nanotube hereinafter, chance on, and had Sun with 2006 It prepares.Compared with other quantum dots, carbon dots have excellent fluorescence property, also have that low molecular weight, partial size be small, bio-compatible Property good, nontoxic, environmentally friendly, good catalytic the advantages that, and prepare carbon dots raw material it is plentiful, cheap.
It has been developed that the method for many synthesis carbon quantum dots, including arc discharge method, laser corrode method, electrochemistry is closed Cheng Fa, chemical oxidization method, combustion method, hydrothermal synthesis method, microwave process for synthesizing, template etc..Currently, using it is more be chemical conjunction Cheng Fa, hydrothermal synthesis method and microwave process for synthesizing.These methods are required under certain inert gas environment, are carried out to reactant The processing modes such as heating and/or microwave, could synthesize carbon quantum dot, preparation method is more complex.
Summary of the invention
The purpose of the present invention is according to problem of the existing technology, provide a kind of chlorogenic acid carbon dots and preparation method thereof. Chlorogenic acid carbon dots pattern of the invention is preferable, and partial size is smaller and is evenly distributed, and preparation method raw material is cheap and easily-available, and method is simply easy Row, and the additionally processing such as heating or microwave is not needed, quantum yield is high.The present invention also provides the chlorogenic acids prepared by the carbon dots Carbon dots doping and preparation method thereof, chlorogenic acid carbon dots doping prepared by the present invention is safe and nontoxic, easy to use, in food Fresh-keeping, metal ion detection and food spoilage detection etc. have preferable application.
According to an aspect of the invention, there is provided a kind of chlorogenic acid carbon dots, the partial size of the carbon dots is 1-4nm, maximum Fluorescence exciting wavelength is 340nm, launch wavelength 420-570nm.
Chlorogenic acid carbon dots pattern of the invention is preferable, and partial size is smaller and is evenly distributed.
According to another aspect of the present invention, provide the preparation method of above-mentioned chlorogenic acid carbon dots, by chlorogenic acid with it is organic Solvent contact is made.
According to certain embodiments of the present invention, the ratio between the quality of the chlorogenic acid and the volume of organic solvent are 10 μ g: (0.5-2) mL, preferably 10 μ g:1mL.
According to the preferred embodiment of the present invention, the organic solvent includes alcohol, preferably methanol, ethyl alcohol or propyl alcohol, more Preferably methanol.
According to the preferred embodiment of the present invention, the time of the chlorogenic acid and organic solvent exposure is 0.5-2h, preferably For 1h, temperature is 20-40 DEG C, preferably 25-30 DEG C.
According to some embodiments of the present invention, the chlorogenic acid carbon dots preparation method the following steps are included:
(1) by chlorogenic acid and organic solvent exposure, chlorogenic acid carbon dots solution is made;
(2) product handling system is carried out to the chlorogenic acid carbon dots solution that step (1) obtains, obtains the biomass nitrogen-doped carbon Point.
According to another aspect of the present invention, a kind of chlorogenic acid carbon dots doping fluorescent film, including above-mentioned green original are additionally provided Sour carbon dots.
According to another aspect of the present invention, a kind of preparation method of above-mentioned chlorogenic acid carbon dots doping is additionally provided, is wrapped It includes:
1) by above-mentioned chlorogenic acid carbon dots or chlorogenic acid carbon dots solution and dispersant, it is molten to obtain chlorogenic acid carbon dots doping Liquid;
2) film process are carried out to chlorogenic acid carbon dots doping coating solution, obtains chlorogenic acid carbon dots doping.
According to certain embodiments of the present invention, the dispersing agent includes poly-vinyl alcohol solution.
According to some embodiments of the present invention, for the preparation method of the poly-vinyl alcohol solution, there is no particular limitation. Some specific embodiments according to the present invention, the poly-vinyl alcohol solution can be prepared via a method which: by 3g polyvinyl alcohol It is dissolved in 80mL, 80-100 DEG C, in preferably 90 DEG C of hot water, stirs 2h, obtained clear solution is poly-vinyl alcohol solution.
According to the preferred embodiment of the present invention, the chlorogenic acid carbon dots and the mass ratio of the poly-vinyl alcohol solution are (0.1-1): 100, preferably (0.3-0.6): 100, more preferably 0.5:100.
For the film process in step 2), there is no particular limitation, is using method known to those skilled in the art It can.In some specific embodiments, the film process may include following steps: the chlorogenic acid carbon dots are adulterated coating solution It pours into be formed in film container and there is certain thickness liquid level, stand, volatilize to solvent, drying and forming-film.
Since during film process, chlorogenic acid carbon dots adulterate the organic solvent volatilization in coating solution, therefore this hair The chlorogenic acid carbon dots doping of bright preparation is safe and nontoxic, easy to use, in food fresh keeping, metal ion detection and food spoilage Detection etc. has preferable application.
According to another aspect of the present invention, the chlorogenic acid carbon dots or chlorogenic acid carbon dots doping are additionally provided in food The application of fresh-keeping aspect.
According to some embodiments of the present invention, the application includes: that will contain the chlorogenic acid carbon dots or chlorogenic acid carbon dots The solution of doping is applied to fresh-keeping food surface, with fresh-keeping to its.
Preferred embodiment in accordance with the present invention, can be by above-mentioned containing the chlorogenic acid carbon dots or chlorogenic acid carbon dots doping Solution is applied to fresh-keeping food surface, after solvent volatilization, is formed one layer in food surface and is contained chlorogenic acid carbon dots Film, by the film to food fresh keeping.
According to certain embodiments of the present invention, the food fresh keeping is preferably fruit freshness preserving.
According to another aspect of the present invention, above-mentioned chlorogenic acid carbon dots doping is additionally provided in terms of metal ion detection Application.
According to some embodiments of the present invention, the application include: the chlorogenic acid carbon dots doping is immersed in it is to be checked It surveys in object solution and is taken out after a period of time, it is dry;Then the chlorogenic acid carbon dots doping impregnated by ultraviolet light irradiation, with It whether detects in the examined object containing metal ion and the species of metal ion contained.
According to a particular embodiment of the invention, the application may include following steps:
1) sample solution of different metal ions is prepared;
2) multiple chlorogenic acid carbon dots dopings are separately immersed in the sample solution of different metal ions, are taken after 10min Out, it spontaneously dries;
3) the chlorogenic acid carbon dots doping for impregnating different metal ions sample solution is irradiated by ultraviolet lamp respectively, is obtained The chlorogenic acid carbon dots doping sample image of the sample containing different metal ions;
4) chlorogenic acid carbon dots doping is immersed in examined object solution, is taken out after 10min, spontaneously dried;
5) the chlorogenic acid carbon dots doping for impregnating examined object solution is irradiated by ultraviolet lamp respectively, is obtained containing to be checked The chlorogenic acid carbon dots for surveying object adulterate film image;
6) image that step 5) obtains is compared with the sample image of step 3), with determine in examined object whether Contain metal ion and the species of metal ion contained.
According to another aspect of the present invention, the chlorogenic acid carbon dots doping is additionally provided in food spoilage context of detection Application.
According to certain embodiments of the present invention, the food spoilage detection is preferably the rotten detection of dairy produce.
Preferred embodiment in accordance with the present invention, the application include: the chlorogenic acid carbon dots doping is immersed in it is to be checked It surveys in object solution and is taken out after a period of time, it is dry;Then the chlorogenic acid carbon dots doping impregnated by ultraviolet light irradiation, with Detect whether the examined object goes bad.
According to a particular embodiment of the invention, the application may include following steps:
1) it prepares respectively and contains H+And OH-Solution;
2) chlorogenic acid carbon dots doping is placed on to top in the sample bottle of the solution containing step 1);
3) pass through ultraviolet lamp distinguish irradiating step 2) chlorogenic acid carbon dots doping, obtain sample image;
4) chlorogenic acid carbon dots doping is placed on top in the sample bottle containing examined object solution;
5) pass through ultraviolet lamp irradiating step 4) chlorogenic acid carbon dots doping, obtain the chlorogenic acid carbon dots containing examined object Adulterate film image;
6) image that step 5) obtains is compared with the sample image of step 3), to determine whether examined object becomes Matter.
Detailed description of the invention
Fig. 1 is the TEM figure of chlorogenic acid carbon dots prepared by embodiment 1.
Fig. 2 is the TEM figure of single chlorogenic acid carbon dots prepared by embodiment 1.
Fig. 3 is the uv absorption spectra (a) of chlorogenic acid carbon dots prepared by embodiment 1 and the emission spectrum of maximum wavelength (b) and excitation spectrum (c) figure.
Fig. 4 is emission spectrum of the chlorogenic acid carbon dots of the preparation of embodiment 1 under different excitation wavelengths.
Fig. 5 is the infrared spectrum of chlorogenic acid carbon dots prepared by embodiment 1.
Fig. 6 is the XPS figure of chlorogenic acid carbon dots prepared by embodiment 1.
Fig. 7 is the SEM figure of polyvinyl alcohol film prepared by comparative example 1.
Fig. 8 is the cross-section diagram of polyvinyl alcohol film prepared by comparative example 1.
Fig. 9 is the SEM figure of chlorogenic acid carbon dots doping prepared by embodiment 2.
Figure 10 is the cross-section diagram of chlorogenic acid carbon dots doping prepared by embodiment 2.
Figure 11 is clearance rate figure of the chlorogenic acid carbon dots solution to DPPH of the preparation of embodiment 1.
Figure 12 is clearance rate figure of the chlorogenic acid carbon dots doping to DPPH of the preparation of embodiment 2.
Figure 13 is the chlorogenic acid carbon dots that embodiment 2 is smeared on blank, the poly-vinyl alcohol solution of surface smearing comparative example 1 and surface The picture that the banana of doping coating solution changes over time.
Figure 14 is the image of 1-9 chlorogenic acid carbon dots doping in the UV lamp in embodiment 5.
Figure 15 is the image of 1-4 chlorogenic acid carbon dots doping in the UV lamp in embodiment 6.
Figure 16 is the image of No. 5 chlorogenic acid carbon dots dopings in the UV lamp in embodiment 6.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below:
Embodiment 1
0.1mg chlorogenic acid is added in 10mL anhydrous methanol solvent, ultrasonic dissolution obtains clear solution, as green original Sour carbon dots solution (CA-CDs).
The chlorogenic acid carbon dots solution is added dropwise on carbon film, after room temperature is dried, is used under the acceleration voltage of 200KV JEM-2100 transmission electron microscope (JEOL Ltd., Tokyo, Japan) carries out transmission electron microscope characterization to it, as a result such as Fig. 1,2 It is shown.
From figure 1 it appears that chlorogenic acid carbon dots are uniformly distributed, appearance approximation is spherical in shape, partial size 1-4nm.From Fig. 2 In it can be seen that chlorogenic acid carbon dots spacing of lattice be 0.21nm.
By the chlorogenic acid carbon dots solution be added four-way cuvette in, by LS-55 Fluorescence Spectrometer (PerkinElmer, Inc., Waltham, USA) Fluorescent Characterization is carried out to it, as a result as shown in Figure 3-4.
Fig. 3 is the uv absorption spectra (a) of chlorogenic acid carbon dots and the emission spectrum (b) and excitation spectrum of maximum wavelength (c) figure, as seen from Figure 3, uv absorption spectra comply fully with the spectrogram of chlorogenic acid standard items, the maximum of chlorogenic acid carbon dots Excitation wavelength is 340nm, at this time in emission spectrum maximum emission peak at 440nm.
Fig. 4 is the emission spectrum under the different excitation wavelengths of chlorogenic acid carbon dots, as seen from Figure 4, with excitation wavelength Increase to 480nm from 280nm, the maximum peak position of emission spectrum moves to from 568nm from 428nm, and apparent red shift, and peak has occurred Value is gradually reduced.
The chlorogenic acid carbon dots solution is placed and is dried in a vacuum drying oven (0.1MPa, 40 DEG C, for 24 hours), Obtain chlorogenic acid carbon dots powder.
IR Characterization is carried out to the chlorogenic acid carbon dots with ATR method, as a result as shown in Figure 5.As shown in figure 5, in 3300cm-1 Place is-OH flexural vibrations peak, 1287cm-1For the stretching vibration peak of C-O-C.The stretching vibration peak of C=O is in 1700cm-1Locate body It is existing, 1595cm-1,1514cm-1And 1439cm-1It is the vibration peak on aromatic rings, 1381cm-1It is the stretching vibration peak of C-O.
XPS PHI 5700 (Physical Electronics, America) characterization, knot are carried out to the chlorogenic acid carbon dots Fruit is as shown in Figure 6.As shown in fig. 6, there are two kinds of Elements Cs and O (C/O=66.7:33.3) in chlorogenic acid carbon dots.
Comparative example 1
3g polyvinyl alcohol is dissolved in 80mL hot water at a temperature of 90 °C, 2h is stirred, obtained clear solution is poly- Glycohol solution;The poly-vinyl alcohol solution is poured into glass guide channel, liquid level is formed, is stood, is volatilized, be dried to naturally to solvent Film takes off film and obtains the polyvinyl alcohol film with a thickness of 60 ± 5mm.
The polyvinyl alcohol film is fixed on sample stage, Electronic Speculum (SEM) Quanta 200 is scanned to it (Philips-FEICo., The Netherlands) characterization, as a result as shown in Figure 7;It separately is quenched to break with liquid nitrogen and observes section, as a result As shown in Figure 8.
Using the mechanical performance of universal testing machine test polyvinyl alcohol film, the results are shown in Table 1.
Embodiment 2
3g polyvinyl alcohol is dissolved in 80mL hot water at a temperature of 90 °C, 2h is stirred, obtained clear solution is poly- Glycohol solution;Chlorogenic acid carbon dots solution 10mL prepared by embodiment 1 is added drop-wise in poly-vinyl alcohol solution, chlorogenic acid carbon is obtained Point doping coating solution;Chlorogenic acid carbon dots doping coating solution is poured into glass guide channel, liquid level is formed, stands, to solvent nature Volatilization, drying and forming-film take off film and obtain the chlorogenic acid carbon dots doping with a thickness of 50 ± 5mm.
The chlorogenic acid carbon dots doping is fixed on sample stage, Electronic Speculum (SEM) Quanta 200 is scanned to it (Philips-FEICo., The Netherlands) characterization, as a result as shown in Figure 9;It separately is quenched to break with liquid nitrogen and observes section, as a result As shown in Figure 10.
As is seen in figs 7-10, chlorogenic acid carbon dots doping of the invention, is all smooth surface with polyvinyl alcohol film.This hair Bright chlorogenic acid carbon dots doping, compared with polyvinyl alcohol film, similar section proves that chlorogenic acid carbon dots and polyvinyl alcohol film are mixed That closes is very uniform.
Using the mechanical performance of universal testing machine test chlorogenic acid carbon dots doping, the results are shown in Table 1.
As can be seen from Table 1, chlorogenic acid carbon dots doping of the invention, performance close to polyvinyl alcohol film, be a kind of stabilization, It is transparent, the film with good mechanical performance.
Table 1
Embodiment 3
It prepares DPPH solution (4mg/10mL dehydrated alcohol).To 1mL concentration be respectively 0.00078125,0.0015625, 0.003125, divide in the chlorogenic acid carbon dots solution of 0.00625,0.0125,0.025,0.05,0.1,0.2,0.4 and 0.8mg/ml Not Jia Ru 3mL DPPH solution, using 1mL water as control, thereto be added 3mL DPPH solution.Light is divided using UV, visible light Degree meter measurement absorbance value at 517nm, is calculated the chlorogenic acid carbon dots solution of each concentration to the clear of DPPH using formula (1) Except rate, as a result as shown in figure 11.
Clearance rate (%)=(AC-A0)/AC*100% (1)
In formula, AC is the absorbance of control group solution;
A0 is the absorbance of chlorogenic acid carbon dots solution.
As seen from Figure 11, with the increase of chlorogenic acid carbon dots concentration, free radical scavenging activity is gradually risen, and is in concentration DPPH free radical scavenging activity reaches 95% or more when 0.1mg/mL, and radicals scavenging effect is very good.
It configures DPPH solution (4mg/10mL dehydrated alcohol).Chlorogenic acid carbon dots doping prepared by embodiment 2 (2x4cm2) be put into DPPH solution, every half an hour measurement absorbance value at 517nm, calculated using formula (1) To DPPH clearance rate, as a result as shown in figure 12.
As seen from Figure 12, free clearance rate reaches 85% to chlorogenic acid carbon dots doping after 2.5h in being placed in DPPH More than, radicals scavenging effect is comparatively fast preferable.
Embodiment 4
By 18 bananas, three groups are equally divided into, first group is blank, second group of polyethylene in surface smearing comparative example 1 Alcoholic solution, third group adulterate coating solution in the chlorogenic acid carbon dots that embodiment 2 is smeared on surface.All bananas are placed on identical conditions Under (23 DEG C of room temperature), daily the same time shoot banana picture, as a result as shown in figure 13.
As seen from Figure 13, with the growth of time, blank group banana surface stain has smeared poly-vinyl alcohol solution Banana black splotch increases, and smeared chlorogenic acid carbon dots doping coating solution banana skin at the 5th day also without black splotch And the phenomenon that blackening, it is closest with original state.It proves that the antioxygenic property of chlorogenic acid carbon dots doping is very good, has to food Preferable fresh-keeping effect.
Embodiment 5
1) it prepares respectively and contains potassium ion, sodium ion, calcium ion, magnesium ion, aluminum ions sample solution;
2) the chlorogenic acid carbon dots doping for taking 7 embodiments 2 to prepare, label 1-7, No. 1 is blank, No. 2 be immersed in from In sub- water, No. 3-7 be separately immersed in step 1) containing potassium ion, sodium ion, calcium ion, magnesium ion, aluminum ions sample solution In, it takes out, spontaneously dries after 10min;
3) it is irradiated respectively by ultraviolet lamp and impregnated 1-7 chlorogenic acid carbon dots doping, obtain 1-7 sample image;
4) deep-fried twisted dough sticks bought from dining room and market are separately immersed in deionized water, soak are taken to be placed in sample bottle, Label is respectively 8-9 solution;
5) chlorogenic acid carbon dots doping is immersed in 8-9 solution, is taken out after 10min, spontaneously dried;
6) the chlorogenic acid carbon dots doping for impregnating 8-9 solution is irradiated by ultraviolet lamp respectively, obtains 8-9 image;
7) image that step 6) obtains is compared with the sample image of step 3), with determine in examined object whether Contain metal ion and the species of metal ion contained.
1-9 image is as shown in figure 14, and No. 1 blank film issues blue-fluorescence in the UV lamp, and is immersed in 2-6 ion Film in solution does not have fluorescence, the fluorescence enhancement of No. 7 aluminium ion solution, the film fluorescence enhancement in No. 8 and No. 9 deep-fried twisted dough sticks solution, with 7 Number aluminium ion effect is consistent, it was demonstrated that contains aluminium ion in deep-fried twisted dough sticks.Compared to No. 8 and No. 9 fluorescence intensities, No. 8 fluorescence is weak, it was demonstrated that from The deep-fried twisted dough sticks that dining room is bought are less compared to the aluminium ion that the deep-fried twisted dough sticks that market is bought contain, healthier.
Embodiment 6
1) HCl and NH is prepared respectively3`H2O solution, marked as 1-2;
2) the chlorogenic acid carbon dots doping for taking 5 embodiments 2 to prepare, label 1-5, No. 1 is placed on HCl solution sample bottle In, No. 2 are placed in deionized water sample bottle, and No. 3 are placed on NH3`H2In O solution example bottle, No. 4 are placed on expired rotten ox In milk sample bottle, No. 5 are placed on the lime-preserved egg for cutting half;
3) pass through ultraviolet lamp distinguish irradiating step 2) 1-5 chlorogenic acid carbon dots doping, obtain 1-5 image, as a result As shown in figures 15-16.
Figure 15 is the photo of chlorogenic acid carbon dots doping at different conditions under ultraviolet light irradiation.(1) in HCl, (2) in deionized water, (3) are in NH3H2In O, (4) are in rotten milk.As seen in Figure 15, (1) is compared (2) (3) can be seen that chlorogenic acid carbon dots doping fluorescence enhancement under alkaline condition, the chlorogenic acid carbon dots doping fluorescence of (4) Become strong, illustrates that rotten milk can release alkaline gas, can detect whether milk goes bad by the method.
Figure 16 is to be placed on chlorogenic acid carbon dots doping on the lime-preserved egg for cutting half, with the photo of ultraviolet light irradiation.It is logical Crossing Figure 16 can be seen that compared with Figure 15 (3), and the fluorescence of chlorogenic acid carbon dots doping is the same, very by force, it was demonstrated that lime-preserved egg is to use alkali Property solution it is processed.
Any numerical value mentioned in the present invention, if between any minimum and any highest value be there are two The interval of unit then includes each all values for increasing a unit from minimum to peak.For example, if stating one kind The value of the state-variables such as the amount of component, or temperature, pressure, time is 50-90, in the present specification it means that specific List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to 0.1,0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side The all possible combinations of formula, the numerical value between cited minimum and peak are considered to have disclosed.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair It is bright to can be extended to other all methods and applications with the same function.

Claims (10)

1. a kind of chlorogenic acid carbon dots, which is characterized in that the partial size of the carbon dots is 1-4nm, and maximum fluorescence excitation wavelength is 340nm, launch wavelength 420-570nm.
2. the preparation method of chlorogenic acid carbon dots according to claim 1, including chlorogenic acid and organic solvent exposure are made.
3. preparation method according to claim 2, which is characterized in that the quality of the chlorogenic acid and the volume of organic solvent The ratio between be 10 μ g:(0.5-2) mL, preferably 10 μ g:1mL.
4. preparation method according to claim 2 or 3, which is characterized in that the organic solvent includes alcohol, preferably first Alcohol, ethyl alcohol or propyl alcohol.
5. any one in a kind of chlorogenic acid carbon dots doping, including chlorogenic acid carbon dots described in claim 1 or claim 2-4 The chlorogenic acid carbon dots of item method preparation.
6. the preparation method of chlorogenic acid carbon dots doping according to claim 5, comprising:
1) the chlorogenic acid carbon dots for preparing any one of chlorogenic acid carbon dots described in claim 1 or claim 2-4 method With dispersant, chlorogenic acid carbon dots doping coating solution is obtained;
2) film process are carried out to chlorogenic acid carbon dots doping coating solution, obtains chlorogenic acid carbon dots doping.
7. preparation method according to claim 6, which is characterized in that the dispersing agent includes poly-vinyl alcohol solution.
8. chlorogenic acid carbon dots doping is in food fresh keeping side described in chlorogenic acid carbon dots described in claim 1 or claim 5 The application in face.
9. application of the chlorogenic acid carbon dots doping described in claim 5 in terms of detecting metal ion.
10. application of the chlorogenic acid carbon dots doping described in claim 5 in terms of detecting food spoilage.
CN201811463628.XA 2018-12-03 2018-12-03 Chlorogenic acid carbon dot and preparation method thereof, chlorogenic acid carbon dot doped film and preparation method and application thereof Active CN109679650B (en)

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