CN116023940B - Yellow-green cellulose-based carbon quantum dot, preparation method and application thereof in detection of chromium (VI) and ascorbic acid - Google Patents

Yellow-green cellulose-based carbon quantum dot, preparation method and application thereof in detection of chromium (VI) and ascorbic acid Download PDF

Info

Publication number
CN116023940B
CN116023940B CN202310034834.3A CN202310034834A CN116023940B CN 116023940 B CN116023940 B CN 116023940B CN 202310034834 A CN202310034834 A CN 202310034834A CN 116023940 B CN116023940 B CN 116023940B
Authority
CN
China
Prior art keywords
carbon quantum
based carbon
ascorbic acid
yellow
cellulose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310034834.3A
Other languages
Chinese (zh)
Other versions
CN116023940A (en
Inventor
张献
李燕峰
周玉莲
卢倩
刘钦泽
王心雨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN202310034834.3A priority Critical patent/CN116023940B/en
Publication of CN116023940A publication Critical patent/CN116023940A/en
Application granted granted Critical
Publication of CN116023940B publication Critical patent/CN116023940B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20Controlling water pollution; Waste water treatment
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention provides a yellow-green cellulose-based carbon quantum dot, a preparation method and application thereof in chromium (VI) and ascorbic acid detection. The preparation method of the carbon quantum dot comprises the following steps: fully dispersing cellulose acetate and p-phenylenediamine in water to obtain a dispersion liquid; and then carrying out hydrothermal reaction, removing sediment and impurities, and freeze-drying to obtain the yellowish green cellulose-based carbon quantum dots. The preparation method of the carbon quantum dots is simple, convenient and feasible, and the raw materials are economical; the prepared carbon quantum dots are N-doped cellulose-based carbon quantum dots (N-CDs) with large Stokes shift. The present invention establishes IFE-based "on-off" fluorescence sensors for monitoring Cr (VI) and Ascorbic Acid (AA) based on Internal Filter Effects (IFE) and the reducibility of ascorbic acid; can be used for analyzing Cr (VI) in industrial wastewater and AA in samples, and has higher sensitivity.

Description

Yellow-green cellulose-based carbon quantum dot, preparation method and application thereof in detection of chromium (VI) and ascorbic acid
Technical Field
The invention relates to the technical field of fluorescent probes, in particular to a yellow-green cellulose-based carbon quantum dot, a preparation method and application thereof in chromium (VI) and ascorbic acid detection.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information has become known to those of ordinary skill in the art.
The economic level of China is continuously improved, the industrial level is greatly improved, and hexavalent chromium (Cr (VI)) is one of the most common heavy metal pollutants which can be detected in industrial wastewater. Along with the continuous improvement of the human living standard, the harm of Cr (VI) to the environment and the body is continuously realized. Chromium ions have two main oxidation states: trivalent chromium (Cr (III)) and hexavalent chromium (Cr (VI)). Among them, cr (III) is a nutrient essential for organisms, and has little research significance because it has a small fluidity, little toxicity, and no harm. Cr (VI) has genetic mutation and cancerogenic action on human body and has great harm to health and environment. Therefore, it is necessary to design a high-sensitivity and rapid-response analysis method and a detector to monitor the Cr (VI) content in water and reduce the risk of substandard Cr (VI) emission in industrial wastewater.
Ascorbic Acid (AA), also known as vitamin C, is an essential substance for maintaining normal physiological functions of the human body and is often used for growth and repair of body tissues. It is essential for the repair and maintenance of collagen, skin, blood vessels, wounds, bones and teeth. Lack of intake of AA can pose a great threat to human health, such as adverse reactions such as anemia and decreased resistance, and serious people can be life-threatening. Quantitative detection of AA is an important content in pharmaceutical analysis, so it is particularly important to detect AA content in foods by a highly sensitive and rapid-response analysis method in order to ensure a sufficient daily intake of AA for the health of people. Although various methods have been used to quantify AA, efforts are still being made to find better methods for determining AA content.
Many analytical methods for accurate detection have been developed in the detection of Cr (VI) and AA, such as colorimetry, electrochemistry, atomic absorption spectrometry, inductively coupled plasma mass spectrometry, high Performance Liquid Chromatography (HPLC) and spectrophotometry. However, the practical application of these detection methods in various fields is hindered by the drawbacks of requiring expensive instruments and complicated sample pretreatment, and the need for environmentally unfriendly chemicals during the detection process. In contrast, the fluorescent probe method has the advantages of simple sample pretreatment, quick response, wide linear dynamic range, small interference and high sensitivity, and can meet the requirements of detection application of various substances in industry. Therefore, it is necessary to develop a nanomaterial-based fluorescence sensor for the simultaneous analytical detection of chromium (VI) and Ascorbic Acid (AA).
The Internal Filter Effect (IFE) is a common means of fluorescence sensing detection and has wide application in various fields. In this system, the excitation wavelength of the fluorophore is required to overlap with the absorption wavelength of the absorber; such radiation shielding causes competition for excitation light, resulting in a decrease in the intensity of fluorescence emission, but this process requires the selection of appropriate fluorescent materials and corresponding absorbers.
Cellulose is the most widely existing substance in nature, is cheap and easy to obtain, is nontoxic, and is environment-friendly in raw materials. The size of the carbon dots formed by doping and forming the main body is difficult to grasp because the cellulose has a high molecular weight. However, the research based on cellulose-based fluorescent carbon dots is less at present, so that the preparation of the cellulose-based fluorescent carbon quantum dots with proper sizes as fluorescent probes is good in prospect of being applied to detection of various substances. Compared with other polymers or traditional semiconductor quantum dots, the carbon quantum dots (CDs) have many advantages, such as good light resistance, high biocompatibility, high photoluminescence adjustability, chemical inertness and the like, and meanwhile, the carbon dots are widely applied to the fluorescence field by the characteristics of good biocompatibility, stable chemical and physical properties, good water solubility, low toxicity, simple synthesis method, good fluorescence performance and the like. The fluorescent probe detection method has the advantages of high analysis sensitivity, strong selectivity, simple and convenient use and the like, and has also received wide attention in the aspect of detecting Cr (VI) and AA. At present, the emission wavelength of the cellulose-based carbon quantum dot is shorter, and the Stokes shift is smaller; and the detection of CDs as fluorescent substances is single, only one substance can be detected, and meanwhile, the detection of 2 substances can be realized relatively little, and the detection of Cr (VI) and AA based on cellulose-based CDs with larger Stokes displacement is not reported yet.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a yellow-green cellulose-based carbon quantum dot, a preparation method and application thereof in chromium (VI) and ascorbic acid detection. The preparation method of the carbon quantum dots is simple, convenient and feasible, and the raw materials are economical; the prepared carbon quantum dots are N-doped cellulose-based carbon quantum dots (N-CDs) with large Stokes shift. The present invention establishes IFE-based "on-off" fluorescence sensors for monitoring Cr (VI) and Ascorbic Acid (AA) based on Internal Filter Effects (IFE) and the reducibility of ascorbic acid; can be used for analyzing Cr (VI) in industrial wastewater and AA in samples, and has higher sensitivity.
The technical scheme of the invention is as follows:
the carbon quantum dots are N-doped carbon quantum dots, and the average particle size of the carbon quantum dots is 5-7nm.
The preparation method of the yellow-green cellulose-based carbon quantum dot comprises the following steps:
fully dispersing cellulose acetate and p-phenylenediamine in water to obtain a dispersion liquid; then carrying out hydrothermal reaction, removing sediment and impurities, and freeze-drying to obtain the yellow-green cellulose-based carbon quantum dots (N-CDs).
According to the invention, the mass ratio of the cellulose acetate to the p-phenylenediamine is preferably 1:0.4 to 1, preferably 1:0.7.
according to a preferred embodiment of the invention, the mass concentration of cellulose acetate in the dispersion is 1 to 5%.
According to the invention, the preferable hydrothermal reaction temperature is 160-210 ℃ and the hydrothermal reaction time is 6-16 h; preferably, the hydrothermal reaction temperature is 180 ℃ and the hydrothermal reaction time is 12 hours.
According to the present invention, a preferred method for removing the precipitate and impurities is as follows: taking supernatant after ultrasonic treatment of reaction liquid obtained by hydrothermal reaction, and then filtering and dialyzing to remove sediment and impurities in the reaction liquid; preferably, the pore size of the filter membrane used for filtration is 0.22. Mu.m; the molecular weight cut-off of the dialysis bag used for dialysis is 1000Da, and the dialysis is carried out for 60-80 hours at room temperature. .
The application of the yellow-green cellulose-based carbon quantum dot in chromium (VI) and ascorbic acid detection.
According to the invention, the method for detecting chromium (VI) by using the yellow-green cellulose-based carbon quantum dots comprises the following steps: adjusting the pH value of the solution to be tested containing Cr (VI) to 6 to obtain a test solution; adding the yellow-green cellulose-based carbon quantum dots, uniformly mixing, and performing fluorescence detection.
Preferably, the pH is adjusted using PBS buffer.
Preferably, the volume ratio of the mass of the yellow-green cellulose-based carbon quantum dot to the test liquid is 0.1-0.5g/mL.
According to the invention, the method for detecting the ascorbic acid by using the yellow-green cellulose-based carbon quantum dots comprises the following steps of: adjusting the pH of the Cr (VI) aqueous solution to 6, adding the yellow-green cellulose-based carbon quantum dots, uniformly mixing, and incubating to form an ascorbic acid detection platform; adding an ascorbic acid sample to be detected, mixing and dispersing uniformly to obtain a test solution, and then carrying out fluorescence detection.
Preferably, the concentration of the aqueous Cr (VI) solution is 70-100. Mu. Mo/L.
Preferably, the pH is adjusted using PBS buffer.
Preferably, the incubation temperature is room temperature and the incubation time is 1-10min.
Preferably, the concentration of the yellow-green cellulose-based carbon quantum dots in the ascorbic acid detection platform is 0.1-0.5g/mL.
The invention has the technical characteristics and beneficial effects that:
1. the invention takes cellulose acetate and p-phenylenediamine as basic raw materials, and synthesizes the fluorescent carbon quantum dots through hydrothermal reaction. The preparation method of the carbon quantum dots is simple, convenient and feasible, has the advantages of economical raw materials and low cost, and is suitable for industrial production. The carbon quantum dots prepared by the invention are N-doped cellulose-based carbon quantum dots (N-CDs) with large Stokes displacement, and emit yellow-green fluorescence under the irradiation of an ultraviolet lamp. In the preparation method of the invention, the proportion of raw materials and the reaction conditions (hydrothermal reaction time and hydrothermal reaction temperature) are important, and if the proportion of raw materials and the reaction conditions are unsuitable, the excellent effect of the invention is not realized.
2. The N-CDs of the present invention have excellent overlapping properties between the fluorescence excitation spectrum position (370 nm) and the ultraviolet absorption spectrum position (361 nm) of Cr (VI), and can be subjected to conditions for generating an Internal Filter Effect (IFE). When the N-CDs are applied to Cr (VI) detection, the Cr (VI) is an absorber, and the ultraviolet absorption peak intensity of the Cr (VI) at 361nm is correspondingly enhanced along with the increase of the concentration of the Cr (VI) in an acidic environment; when Cr (VI) is blended with the N-CDs of the invention and excited at 370nm, a part of excitation waves can be absorbed by the Cr (VI) through an internal filtering effect, and as the concentration of the Cr (VI) increases, the absorption of the excitation waves of the N-CDs is more, so that the fluorescence intensity is weakened or quenched, and the quantitative detection of the Cr (VI) is realized. The color change of the sample to be detected under different Cr (VI) contents can be obviously seen by naked eyes in the fluorescence quenching process, and the Cr (VI) content can be conveniently and rapidly detected qualitatively.
In addition, the present invention detects Cr (VI) in a weakly acidic environment (ph=6), because Cr in a detection environment of ph=6 6+ Will be HCrO 4- And CrO 4 2- The two forms exist, and the detection is more comprehensive and accurate.
3. When the N-CDs are applied to detecting ascorbic acid, firstly, mixing an aqueous solution of Cr (VI) with the yellow-green cellulose-based carbon quantum dots, and incubating to form an ascorbic acid detection platform; in the above detection platform, the fluorescence intensity of N-CDs was quenched. AA is reducing and is capable of reducing Cr (VI) to Cr (III); and the ultraviolet-visible absorption spectrum of Cr (III) is almost not overlapped with the fluorescence excitation spectrum of N-CDs. In the AA detection process, along with the increase of the AA concentration, cr (VI) in a detection platform system is reduced into Cr (III), and the IFE effect between Cr (VI) and N-CDs is weakened, so that fluorescence is recovered, and the purpose of quantitatively detecting the AA is achieved. The color change of the sample to be detected under different AA contents can be obviously seen by naked eyes in the fluorescence recovery process, and the AA content can be conveniently and rapidly detected qualitatively.
4. The invention provides an on-off fluorescent carbon quantum dot which is applied to Cr (VI) and AA detection, and has the advantages of low background interference, high sensitivity, strong anti-interference performance, simple operation method, low cost and universality. The fluorescent carbon quantum dot can be used for analyzing Cr (VI) in industrial wastewater and AA in real fruit samples or other samples; and the detection result shows that the carbon quantum dot has stronger selectivity to Cr (VI) and AA. In the preparation method of the carbon dots, the raw material ratio, the hydrothermal reaction time and the hydrothermal reaction temperature all have influence on whether the carbon dots can be obtained or not, and the particle size and uniformity of the carbon dots, and further have influence on the detection performance, so that the mass ratio of cellulose acetate to p-phenylenediamine is preferably 1:0.7, the hydrothermal reaction temperature is preferably 180 ℃, the hydrothermal reaction time is preferably 12 hours, and the carbon dots formed under the conditions have uniform particle size and small size and have the best detection performance.
Drawings
Fig. 1 is a transmission electron microscope image of the carbon quantum dot prepared in example 1.
Fig. 2 is a fourier infrared spectrum of the carbon quantum dot prepared in example 1; wherein the abscissa is wavelength and the ordinate is transmittance.
FIG. 3 is a graph (a) showing the fluorescence excitation and fluorescence emission spectra of the carbon quantum dots prepared in example 1 and the comparison of the ultraviolet-visible absorption spectra of Cr (VI); a fluorescence excitation spectrum of the carbon quantum dot prepared in example 1, and an ultraviolet-visible absorption spectrum of Cr (VI) and an ultraviolet-visible absorption spectrum of Cr (III) versus (b); wherein the abscissa is wavelength, the left ordinate is absorbance, and the right ordinate is fluorescence intensity.
FIG. 4 is a graph a showing the comparison of fluorescence intensity of carbon quantum dots obtained by varying amounts of p-phenylenediamine in example 2; comparison graph b of fluorescence intensity of carbon quantum dots obtained at different hydrothermal reaction temperatures in example 3; comparison graph c of fluorescence intensity of carbon quantum dots obtained at different hydrothermal reaction times in example 4; in the graph a, the abscissa represents the mass of p-phenylenediamine, and the ordinate represents the fluorescence intensity; in the graph b, the abscissa indicates the hydrothermal reaction temperature, and the ordinate indicates the fluorescence intensity; in the graph c, the abscissa represents the hydrothermal reaction time and the ordinate represents the fluorescence intensity.
FIG. 5a is a fluorescence quenching diagram of the carbon quantum dots prepared in example 1 of test example 1 under the environment of different concentrations of Cr (VI), wherein the illustration is a fluorescence quenching dotted line diagram of the carbon quantum dots at 510nm when the concentration of Cr (VI) is between 0 and 100 mu M; FIG. 5b is a graph showing the linear relationship between the concentration of Cr (VI) at 0.01-40. Mu.M, and the graph showing the color change of the system solution with different Cr (VI) concentrations under sunlight (left) and the graph showing the fluorescence change of the system solution with different Cr (VI) concentrations under an ultraviolet lamp box (right). In the graph a, the abscissa indicates wavelength and the ordinate indicates fluorescence intensity; in the inset of fig. a, the abscissa indicates the concentration and the ordinate indicates the fluorescence intensity; in the graph b, the abscissa indicates the concentration, and the ordinate indicates the fluorescence intensity.
FIG. 6a is a graph showing fluorescence recovery of the carbon quantum dots prepared in example 1 of test example 2 when detecting different amounts of AA, wherein the inset is a graph showing fluorescence quenching dotted lines of the carbon quantum dots at 510nm when the concentration of AA is 0-500. Mu.M; FIG. 6b is a graph showing the linear relationship between AA concentration of 0.1-100. Mu.M, and the graph showing the color change of the system solution with different AA concentration under sunlight (left) and the fluorescence change of the system solution with different AA concentration under ultraviolet lamp box (right). In the graph a, the abscissa indicates wavelength and the ordinate indicates fluorescence intensity; in the inset of fig. a, the abscissa indicates the concentration and the ordinate indicates the fluorescence intensity; in the graph b, the abscissa indicates the concentration, and the ordinate indicates the fluorescence intensity.
FIG. 7 is a graph (a) showing the specificity of the carbon quantum dot prepared in example 1 in test example 3 to Cr (VI) in the presence of different interfering ions, and a graph (b) showing the specificity of the carbon quantum dot prepared in example 1 in test example 4 to AA in the presence of different types of amino acids; in fig. a and b, the ordinate indicates the fluorescence intensity.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
Example 1
A preparation method of a yellow-green cellulose-based carbon quantum dot comprises the following steps:
respectively taking 1g of cellulose acetate and 0.7g of p-phenylenediamine in a beaker, adding 35mL of ultrapure water, fully stirring and carrying out ultrasonic treatment for 40min, transferring the fully dispersed solution into a polytetrafluoroethylene lining of a high-pressure hydrothermal reaction kettle, preheating an oven to 180 ℃ in advance, and putting the mixture into the high-pressure hydrothermal reaction kettle for reaction for 12h. And taking out the reaction kettle after the reaction is finished, cooling to room temperature, taking out the reaction solution, carrying out ultrasonic treatment again for 30min, centrifuging the obtained water-dispersible solution at 9000rpm/30min, taking out supernatant, and filtering through a 0.22 mu m membrane filter. And (3) dialyzing in a dialysis bag with the molecular weight cut-off of 1000Da at room temperature for 72 hours after the filtration is finished, and obtaining the yellowish green cellulose-based carbon quantum dot solution. And finally, placing the dialyzed solution into a freeze dryer for freeze drying to obtain dark brown powder, namely the yellowish green cellulose-based carbon quantum dots (N-CDs).
The yellow-green cellulose-based carbon quantum dot solution prepared in the embodiment is dripped on a copper mesh, placed in a constant temperature incubator for 12 hours, subjected to TEM test, and shown in a TEM chart in FIG. 1, the carbon quantum dots are uniformly distributed, and the average size is 6nm.
The infrared spectrogram of the yellow-green cellulose-based carbon quantum dot prepared in the embodiment is shown in figure 2 and is 3448cm -1 The broad absorption peak as the center is the stretching vibration of O-H and N-H bonds, 2925cm -1 Corresponding to the peak of C-H bond stretching vibration, 1264cm -1 The absorption peak of (C) is Ar-H vibration, and 1516cm -1 And 3006cm -1 The presence of benzene ring structures in N-CDs is demonstrated by the absorption peaks of (C). 1836cm -1 And 1639cm -1 The peaks of (C) correspond to the tensile vibration peaks of the c=o and c=n bonds, respectively. At 1380cm -1 The peak being the center is caused by the stretching vibration of-COOH on the N-CDs surface. The characteristic absorption band of the C-N bond tensile vibration appears at 1181cm -1 Where it is located. 818cm -1 The peak at which corresponds to the tensile vibration peak of the 1, 4-disubstituted Ar-H of the benzene ring. In conclusion, the carbon quantum dot is successfully doped with N element and forms corresponding chemical bonds through infrared spectrum.
The fluorescence excitation (CDs: ex) and fluorescence emission (CDs-Em) spectra of the yellow-green cellulose-based carbon quantum dots prepared in this example, and the ultraviolet-visible absorption spectrum (Cr (VI): abs) of Cr (VI) are shown in fig. 3a, the ultraviolet-visible absorption peak of Cr (VI) is at 361nm, the fluorescence excitation peak position of N-CDs is at 370nm, and the fluorescence emission peak position is at 510 nm; it can be seen that the fluorescence excitation spectrum position of the N-CDs and the ultraviolet absorption spectrum position of Cr (VI) have good overlapping property, and can have the condition of generating an Internal Filter Effect (IFE). The fluorescence excitation spectra (CDs: ex) of the yellow-green cellulose-based carbon quantum dots prepared in this example, and the ultraviolet-visible absorption spectra (Cr (VI): abs.) and (Cr (III): abs.) of Cr (VI) are shown in FIG. 3b, and the ultraviolet-visible absorption peak positions of Cr (III) are located at 446nm and 530nm, and do not significantly overlap with the fluorescence excitation peak (370 nm) of N-CDs, and do not have the condition of IFE occurrence.
Example 2
A method for preparing a yellow-green cellulose-based carbon quantum dot, as described in example 1, except that: the dosage of the p-phenylenediamine is 0.4g,0.5g,0.6g,0.8g,0.9g and 1g respectively; other steps and conditions were consistent with example 1.
The fluorescence emission spectra of the yellow-green cellulose-based carbon quantum dots obtained in example 1 and this example were tested, and the fluorescence intensity at 510nm is shown in fig. 4a, when the mass ratio of cellulose acetate to p-phenylenediamine is 1: at 0.7, the fluorescence intensity of the prepared carbon dots was highest.
Example 3
A method for preparing a yellow-green cellulose-based carbon quantum dot, as described in example 1, except that: the hydrothermal reaction temperature is 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and 210 ℃ respectively, and the hydrothermal reaction time is 10 hours; other steps and conditions were consistent with example 1.
The fluorescence emission spectrum test is carried out on the yellow-green cellulose-based carbon quantum dots obtained in the embodiment, the corresponding fluorescence intensity at 510nm is shown in fig. 4b, and the fluorescence intensity of the carbon dots prepared at the hydrothermal reaction temperature of 180 ℃ is the highest.
Example 4
A method for preparing a yellow-green cellulose-based carbon quantum dot, as described in example 1, except that: the hydrothermal reaction time is 6, 8, 10, 14 and 16 hours respectively; other steps and conditions were consistent with example 1.
Fluorescence emission spectra of the yellow-green cellulose-based carbon quantum dots obtained in example 1 and this example were tested, and the fluorescence intensity at 510nm was the highest for the carbon dots prepared at 12h hydrothermal time, as shown in fig. 4 c.
Test example 1
Sensitivity detection of the yellow-green cellulose-based carbon quantum dots prepared in example 1 to Cr (VI):
first, in order to demonstrate the feasibility of Cr (VI) detection by the yellow-green cellulose-based carbon quantum dots (N-CDs) prepared in example 1, cr (VI) was added at different concentrations during the detection to form a control. Preparing a PBS solution containing Cr (VI) with the concentration of 0-100 mu M and the pH value of=6, and obtaining a test solution; N-CDs prepared in example 1 (N-CDs concentration in the system was 0.3 mg/mL) were added, and the color of the solution at various concentrations of Cr (VI) and the degree of fluorescence quenching were visually observed. Finally, after standing for 4min, carrying out fluorescence spectrophotometry analysis on the mixed solution under the excitation wavelength of 370nm, and comparing the change of fluorescence intensity.
As shown in fig. 5a, N-CDs (0.3 mg/mL) showed good fluorescence quenching with increasing Cr (VI) concentration in the test solution in a weakly acidic environment at ph=6; and by sorting the fluorescence intensity at 510nm (FIG. 5a inset), it can be seen that the final degree of quenching of N-CDs is 93.2% at a concentration of 0-100. Mu.M; when the concentration of Cr (VI) in the test solution reaches 70 mu M, the fluorescence quenching degree of the system can reach 87.3 percent; the concentration of Cr (VI) is continuously increased, the quenching degree of the system is less in change, and when the concentration of Cr (VI) reaches 100 mu M, the fluorescence quenching degree of the system can finally reach 93.2 percent. As can be seen from FIG. 5b, the concentration of Cr (VI) exhibits a good linear relationship at 0.01 to 40. Mu.M, the linear correlation coefficient R 2 = 0.9954. FIG. 5b shows the color change of the system solution under sunlight (left) with increasing Cr (VI) concentration; and a system solution fluorescence change graph under an ultraviolet lamp box (right) along with the increase of the concentration of Cr (VI). The color of the system solution gradually changes from light yellow to dark yellow and finally changes to dark brown along with the increase of the concentration of Cr (VI) under sunlight, and the corresponding fluorescence gradually quenches from bright yellow to green, so that the quenching degree reaches the maximum at 100 mu M. In summary, N-CDs (0.3 mg/mL) can have a good response to Cr (VI) concentrations in the range of 0 to 100. Mu.M.
Test example 2
Sensitivity detection of the yellow-green cellulose-based carbon quantum dots prepared in example 1 to ascorbic acid:
as can be seen from FIG. 6a of test example 1, when the concentration of Cr (VI) in the test solution reaches 70. Mu.M, the fluorescence quenching degree of the system can reach 87.3%, while the concentration of Cr (VI) is continuously increased, and the quenching degree of the system is changed slightly, so that the composition of Cr (VI) with the concentration of 70. Mu.M and N-CDs is selected to detect the ascorbic acid platform to detect AA. The specific method comprises the following steps: preparing a Cr (VI) containing PBS solution with the Cr (VI) concentration of 70 mu M and the pH=6, adding N-CDs prepared in the example 1 (the N-CDs concentration in the system is 0.3 mg/mL), and incubating for 4min at room temperature to form an ascorbic acid detection platform; AA (concentration of AA in the system is 0-500 mu M) is then added, and the color and fluorescence recovery degree of the solution under different concentrations of AA are observed by naked eyes. Finally, after standing for 4min, carrying out fluorescence spectrophotometry analysis on the mixed solution under the excitation wavelength of 370nm, and comparing the change of fluorescence intensity.
As shown in fig. 6a, the fluorescence recovery was very good with increasing AA concentration; and by arranging the fluorescence intensity at 510nm (fig. 6a inset), it can be seen that the final recovery degree of the fluorescence intensity of the detection platform can reach 75.16% at the concentration of 0-500 μm. As can be seen from FIG. 5b, the concentration of AA is 0.1-100. Mu.M, which shows a good linear relationship, the linear correlation coefficient R 2 = 0.9942. FIG. 6b is an illustration showing the color change of the system solution under sunlight (left) with increasing AA concentration in the assay platform, respectively; and the fluorescence change graph of the system solution under the ultraviolet lamp box (right) along with the increase of the AA concentration. The color of the system solution under sunlight gradually changes from dark brown to dark yellow and finally changes to light yellow along with the increase of the AA concentration, the corresponding fluorescence gradually recovers from a dark yellow-green fluorescence quenching state to bright yellow-green fluorescence, and the recovery degree of the fluorescence reaches the maximum at the AA concentration of 500 mu M. In conclusion, the detection platform provided by the invention can respond well to the AA with the concentration of 0-500 mu M.
Test example 3
The specificity of the yellow-green cellulose-based carbon quantum dots prepared in example 1 to Cr (VI) and ascorbic acid was measured as follows:
preparing PBS solution with pH=6 containing different metal or nonmetal interference ions (the different metal or nonmetal interference ions are selected from one of the following ions: al 3+ 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Cr 3+ 、Na + 、Ni 3+ 、Pb 2+ 、Zn 2+ 、Cl - 、SO 4 2- 、NO 3 - (concentration: 350. Mu.M), fe 2+ (concentration: 210. Mu.M), fe 3+ 、Cr 6+ (concentration: 70 μm)), a test solution was obtained; N-CDs prepared in example 1 (N-CDs concentration in the system was 0.3 mg/mL) were added, and after standing at room temperature for 4min, the mixed solution was subjected to fluorescence spectrophotometry at an excitation wavelength of 370 nm.
The results are shown in FIG. 7a, and it can be seen from FIG. 7a that, in addition to Fe 2+ (fluorescence intensity decrease ratio 19.15%), fe 3+ (fluorescence intensity decrease rate 34%) and Cu 2+ In addition to (fluorescence intensity decrease rate 26.48%), only Cr (VI) (fluorescence intensity decrease rate 86.5%) caused a significant decrease in fluorescence intensity. The concentration of Cr (VI) in the leather industrial wastewater is obviously higher than that of Fe 2+ 、Fe 3+ And Cu 2+ So their interference is negligible. In conclusion, the method has good selectivity for detecting Cr (VI) in wastewater (such as leather industrial wastewater).
Test example 4
In order to avoid false positives during the detection process, the prepared detection ascorbic acid platform is very important for the specific detection of Ascorbic Acid (AA). Therefore, the invention selects different interference substances such as different types of amino acids possibly contained in fruits for interference experiments. The test method is as follows: preparing a Cr (VI) containing PBS solution with the Cr (VI) concentration of 70 mu M and the pH=6, adding N-CDs prepared in the example 1 (the N-CDs concentration in the system is 0.3 mg/mL), and incubating for 4min at room temperature to form an ascorbic acid detection platform; AA (concentration of AA in the system is 100 mu M), and interfering substances such as different types of amino acids (selected from one of L-phenylalanine (L-Phe), L-alanine (L-Ala), glutamic acid (Glu), leucine (Leu), L-tryptophan (L-Trp), serine methyl ester hydrochloride (Ser), L-norvaline (L-Cbz), L-histidine (L-His), uric Acid (UA) and Citric Acid (CA) are added, wherein the concentration of the interfering substances in the system is 500 mu M). After standing for 4min, the mixed solution was subjected to fluorescence spectrophotometry at an excitation wavelength of 370 nm.
The results are shown in FIG. 7 b. As a result, it was found that at concentrations above 5 times that of AA, the interference effect of other interfering substances on the detection platform was almost negligible. Only citric acid gives some fluorescence recovery (15.9%) to the detection system, but this is a small degree of recovery relative to AA (55%), so that the detection process is not affected when AA is detected.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The application of the yellow-green cellulose-based carbon quantum dot in chromium (VI) and ascorbic acid detection is characterized in that the carbon quantum dot is an N-doped carbon quantum dot, and the average particle size of the carbon quantum dot is 5-7nm;
the preparation method of the yellow-green cellulose-based carbon quantum dot comprises the following steps:
fully dispersing cellulose acetate and p-phenylenediamine in water to obtain a dispersion liquid; then carrying out hydrothermal reaction, removing sediment and impurities, and freeze-drying to obtain the yellowish green cellulose-based carbon quantum dots;
the hydrothermal reaction temperature is 160-210 ℃.
2. The application of the yellowish green cellulose-based carbon quantum dot in chromium (VI) and ascorbic acid detection according to claim 1, wherein the mass ratio of cellulose acetate to p-phenylenediamine is 1:0.4 to 1.
3. The use of the yellowish green cellulose-based carbon quantum dot according to claim 1 in chromium (VI) and ascorbic acid detection, wherein the mass concentration of cellulose acetate in the dispersion is 1-5%.
4. The application of the yellowish green cellulose-based carbon quantum dot in chromium (VI) and ascorbic acid detection according to claim 1, wherein the hydrothermal reaction time is 6-16 h.
5. Use of the yellowish green cellulose-based carbon quantum dot according to claim 1 in the detection of chromium (VI) and ascorbic acid, characterized in that the method for removing the precipitate and impurities is as follows: taking supernatant after ultrasonic treatment of reaction liquid obtained by hydrothermal reaction, and then filtering and dialyzing to remove sediment and impurities in the reaction liquid; the pore diameter of the filter membrane used for filtration is 0.22 mu m; the molecular weight cut-off of the dialysis bag used for dialysis is 1000Da, and the dialysis is carried out for 60-80 hours at room temperature.
6. The use of the yellow-green cellulose-based carbon quantum dots in the detection of chromium (VI) and ascorbic acid according to claim 1, wherein the method for detecting chromium (VI) by the yellow-green cellulose-based carbon quantum dots comprises the steps of: adjusting the pH value of the solution to be tested containing Cr (VI) to 6 to obtain a test solution; adding the yellow-green cellulose-based carbon quantum dots, uniformly mixing, and performing fluorescence detection.
7. Use of the yellowish green cellulose-based carbon quantum dot according to claim 6 for the detection of chromium (VI) and ascorbic acid, characterized in that the pH is adjusted using PBS buffer.
8. The application of the yellow-green cellulose-based carbon quantum dot in chromium (VI) and ascorbic acid detection according to claim 6, wherein the volume ratio of the mass of the yellow-green cellulose-based carbon quantum dot to the test solution is 0.1-0.5g/mL.
9. The use of the yellow-green cellulose-based carbon quantum dots in the detection of chromium (VI) and ascorbic acid according to claim 1, wherein the method for detecting ascorbic acid by the yellow-green cellulose-based carbon quantum dots comprises the steps of: adjusting the pH of the Cr (VI) aqueous solution to 6, adding the yellow-green cellulose-based carbon quantum dots, uniformly mixing, and incubating to form an ascorbic acid detection platform; adding an ascorbic acid sample to be detected, mixing and dispersing uniformly to obtain a test solution, and then carrying out fluorescence detection.
10. Use of the yellowish green cellulose-based carbon quantum dot according to claim 9 in the detection of chromium (VI) and ascorbic acid, comprising one or more of the following conditions:
i. the concentration of the Cr (VI) aqueous solution is 70-100 mu mo/L;
ii. The pH was adjusted using PBS buffer;
iii, the incubation temperature is room temperature, and the incubation time is 1-10 min;
iv, in the ascorbic acid detection platform, the concentration of the yellow-green cellulose-based carbon quantum dots is 0.1-0.5g/mL.
CN202310034834.3A 2023-01-10 2023-01-10 Yellow-green cellulose-based carbon quantum dot, preparation method and application thereof in detection of chromium (VI) and ascorbic acid Active CN116023940B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310034834.3A CN116023940B (en) 2023-01-10 2023-01-10 Yellow-green cellulose-based carbon quantum dot, preparation method and application thereof in detection of chromium (VI) and ascorbic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310034834.3A CN116023940B (en) 2023-01-10 2023-01-10 Yellow-green cellulose-based carbon quantum dot, preparation method and application thereof in detection of chromium (VI) and ascorbic acid

Publications (2)

Publication Number Publication Date
CN116023940A CN116023940A (en) 2023-04-28
CN116023940B true CN116023940B (en) 2023-11-24

Family

ID=86070385

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310034834.3A Active CN116023940B (en) 2023-01-10 2023-01-10 Yellow-green cellulose-based carbon quantum dot, preparation method and application thereof in detection of chromium (VI) and ascorbic acid

Country Status (1)

Country Link
CN (1) CN116023940B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116606649B (en) * 2023-05-22 2024-04-12 齐鲁工业大学(山东省科学院) Red luminous cellulose-based carbon quantum dot, preparation method and application thereof in malachite green detection

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108456519A (en) * 2018-07-06 2018-08-28 大连工业大学 A kind of N doping fluorescent carbon quantum dot and preparation method thereof
CN108774519A (en) * 2018-05-29 2018-11-09 安徽师范大学 A kind of application using mung bean shell as carbon quantum dot of carbon source and preparation method thereof and in detecting ascorbic acid
CN108929672A (en) * 2018-05-29 2018-12-04 安徽师范大学 It is a kind of using shrimp shell as carbon quantum dot of carbon source and preparation method thereof and detection ascorbic acid in application
CN113861970A (en) * 2021-09-29 2021-12-31 东北林业大学 Preparation method of cellulose-based carbon dots and application of cellulose-based carbon dots in blue light resistant field
CN114540022A (en) * 2022-03-25 2022-05-27 齐鲁工业大学 Preparation of cellulose-based carbon quantum dot and application of cellulose-based carbon quantum dot in uric acid detection

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108774519A (en) * 2018-05-29 2018-11-09 安徽师范大学 A kind of application using mung bean shell as carbon quantum dot of carbon source and preparation method thereof and in detecting ascorbic acid
CN108929672A (en) * 2018-05-29 2018-12-04 安徽师范大学 It is a kind of using shrimp shell as carbon quantum dot of carbon source and preparation method thereof and detection ascorbic acid in application
CN108456519A (en) * 2018-07-06 2018-08-28 大连工业大学 A kind of N doping fluorescent carbon quantum dot and preparation method thereof
CN113861970A (en) * 2021-09-29 2021-12-31 东北林业大学 Preparation method of cellulose-based carbon dots and application of cellulose-based carbon dots in blue light resistant field
CN114540022A (en) * 2022-03-25 2022-05-27 齐鲁工业大学 Preparation of cellulose-based carbon quantum dot and application of cellulose-based carbon quantum dot in uric acid detection

Also Published As

Publication number Publication date
CN116023940A (en) 2023-04-28

Similar Documents

Publication Publication Date Title
Pacquiao et al. Highly fluorescent carbon dots from enokitake mushroom as multi-faceted optical nanomaterials for Cr6+ and VOC detection and imaging applications
CN108384539B (en) Green fluorescent carbon quantum dot, and preparation method and application thereof
CN108083256A (en) The preparation method of high fluorescence property fluorescent carbon quantum dot and its in Cr(VI)Application in detection
CN116023940B (en) Yellow-green cellulose-based carbon quantum dot, preparation method and application thereof in detection of chromium (VI) and ascorbic acid
CN108485661B (en) Preparation method and application of fluorescent carbon quantum dots
CN110082329B (en) Bromelain-coated fluorescent platinum nanocluster and preparation method and application thereof
CN110940648B (en) Synthesis method of green fluorescent carbon quantum dots and application of green fluorescent carbon quantum dots in detection of nitrite
CN115161020B (en) Preparation of N self-doped carbon quantum dot and detection method of cadmium and mercury in agricultural products by N self-doped carbon quantum dot
Wu et al. Construction of carbon dots/metal–organic framework composite for ratiometric sensing of norfloxacin
CN114540022B (en) Preparation of cellulose-based carbon quantum dot and application of cellulose-based carbon quantum dot in uric acid detection
CN111793494B (en) High-water-solubility fluorescent carbon dot and preparation method and application thereof
CN114456806A (en) Near-infrared fluorescent nano probe capable of identifying palladium ions as well as preparation method and application thereof
CN113429960A (en) Can be used for trace Cu2+Carbon quantum dot composite UiO-66 derivative for ion detection
CN113933274A (en) Ratiometric fluorescent molecularly imprinted chitosan gel ball based on europium-doped carbon dots, and preparation method and application thereof
CN111141710B (en) Rapid detection method of metallic mercury
CN112705195A (en) Functional material for degrading and determining tetracycline, preparation method and application
LU502866B1 (en) Iodine-doped Carbon Quantum Dots and Preparation Method and Application Thereof
CN115260509B (en) Boric acid functionalization-based multi-emission metal organic framework compound Eu-MOF and application thereof in gallic acid detection
CN115326764A (en) Preparation method of nitrogen-phosphorus-codoped red fluorescent carbon dots and detection method of nitrogen-phosphorus-codoped red fluorescent carbon dots on malachite green
CN114965413A (en) Method for detecting ferulic acid by using nitrogen-doped carbon dots
Seritti et al. Production of hydrophobic fluorescent organic matter by the marine diatom Phaeodactylum tricornutum
CN114540014B (en) Fluorescent silicon nano-particles and preparation method and application thereof
CN116606649B (en) Red luminous cellulose-based carbon quantum dot, preparation method and application thereof in malachite green detection
CN112986198A (en) Sensor based on arginine fluorescent carbon quantum dots and preparation method and application thereof
CN112577935B (en) Mercury ion detection test paper and use method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant