CN114956048B - Carbon material for detecting iron ions as well as synthesis method and application thereof - Google Patents
Carbon material for detecting iron ions as well as synthesis method and application thereof Download PDFInfo
- Publication number
- CN114956048B CN114956048B CN202210513097.0A CN202210513097A CN114956048B CN 114956048 B CN114956048 B CN 114956048B CN 202210513097 A CN202210513097 A CN 202210513097A CN 114956048 B CN114956048 B CN 114956048B
- Authority
- CN
- China
- Prior art keywords
- carbon material
- iron ions
- solution
- polyethyleneimine
- aldehyde group
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- 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
-
- 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"
- G01N2021/6439—Measuring 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
Abstract
The invention relates to the technical field of fluorescent nano materials, in particular to a carbon material for detecting iron ions, a synthesis method and application thereof, wherein the carbon material for detecting iron ions comprises the following steps of S1: measuring and dissolving an aldehyde group-containing carbon quantum dot solution into water to obtain an aldehyde group-containing carbon quantum dot aqueous solution; s2: weighing polyethyleneimine, then dissolving the polyethyleneimine into ethanol with the volume concentration of 95% to obtain a polyethyleneimine-containing solution, adding the polyethyleneimine-containing solution into an aqueous solution containing aldehyde group carbon quantum dots, and carrying out mutual reaction to obtain an assembled carbon material which is a pale yellow solution; s3: dialyzing the pale yellow solution prepared in the step S2 to obtain a primary product filtrate; s4: and filtering the primary product filtrate by a filter membrane to remove large particles, and freeze-drying to obtain yellow powder, namely the carbon material N-CQDs, wherein the yellow powder selectively responds to iron ions, and only the iron ions can quench the fluorescence of the carbon quantum dots.
Description
Technical Field
The invention belongs to the technical field of fluorescent nano materials, and particularly relates to a carbon material for detecting iron ions, a synthesis method and application thereof.
Background
Iron is one of the most abundant heavy metals in the earth, and the content in the crust is 5-10%, although the emission of iron ions is not limited in the current 'industrial' three wastes 'emission test standard', excessive iron ions can cause the water body to be reddish orange and become turbid, and the dissolved oxygen in the water body is rapidly reduced, so that the water body is biologically dead and severely polluted. After industrial wastewater and domestic sewage are injected into a water body, the content of organic matters in the water is gradually increased and reacts with iron ions, so that the normal valence conversion and circulation of the iron ions are affected. And FeS is finally formed and deposited on the water bottom through a series of reaction iron ions, and the water body is black under the combined action of other factors. And then, because of the circulation of the atmospheric water body, volatile organic compounds and H in the water 2 S and NH 3 The substances are diffused into the atmosphere, so that the water body becomes odorous.
Meanwhile, iron ions are an indispensable part of human body and can participate in the processes of cell metabolism, electron transfer, oxygen transport, enzyme catalysis, DNA, RNA synthesis and the like in the human body, but excessive or insufficient Fe 3+ Can lead to imbalance of cellular environment and induce diseases such as anemia, cancer, mental deterioration, diabetes, etc.
Conventional methods for detecting iron ions include atomic absorption spectrometry, inductively coupled plasma mass spectrometry (ICP-MS), spectrophotometry, and stripping voltammetry, which have high sensitivity and multiple detection capabilities, but complicated sample preparation processes and high-cost, high-time detection processes limit their application in many practical cases.
In recent years, research on Carbon Quantum Dots (CQDs) has rapidly progressed, and compared with organic dyes and conventional semiconductor quantum dots, carbon Quantum Dots (CQDs) have been developed as a very promising fluorescent probe because they have many unique advantages including good solubility in aqueous solutions, low toxicity, good biocompatibility and environmental friendliness, and good sensitivity and selectivity, etc. In addition, carbon quantum dots have been widely used in a wide range of fields such as bioimaging, catalysis, and sensors. Previous studies have demonstrated that both surface functionalization/passivation and heteroatom doping can improve the performance of CQDs in such applications.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. For this purpose, the invention proposes a carbon material for detecting iron ions, and a synthesis method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
in a first aspect, the present invention provides a method for synthesizing a carbon material for detecting iron ions, including the steps of:
s1: measuring and dissolving an aldehyde group-containing carbon quantum dot solution into water to obtain an aldehyde group-containing carbon quantum dot aqueous solution;
s2: weighing polyethyleneimine, then dissolving the polyethyleneimine into ethanol with the volume concentration of 95% to obtain a polyethyleneimine-containing solution, adding the polyethyleneimine-containing solution into an aqueous solution of aldehyde-group-containing carbon quantum dots, and carrying out mutual reaction to obtain an assembled carbon material which is a pale yellow solution;
s3: dialyzing the pale yellow solution prepared in the step S2 to obtain a primary product filtrate;
s4: filtering the primary product filtrate by a filter membrane to remove large particles, and freeze-drying to obtain yellow powder, namely the carbon material N-CQDs.
Preferably, in step S1, the amount of water is 20mL.
Preferably, in step S2, the amount of ethanol having a volume concentration of 95% is 20mL.
Preferably, in the step S2, the solution containing polyethyleneimine is added into the solution containing the aldehyde group carbon quantum dots, and then the reaction is carried out for 6 to 12 hours at normal temperature.
Preferably, in step S4, the pore size of the filtration membrane is less than or equal to 0.22. Mu.m.
Compared with the prior art, the carbon quantum dot prepared by the method has high specificity and selectively responds to iron ions, and only Fe 3+ The fluorescent light of the carbon quantum dots can be quenched, and the fluorescent light has good light stability in the extreme environment of mixing other metal ions, strong acid and strong alkali, and meanwhile, the fluorescent light is very good in time stability, and the reaction is completed within 1min, so that the N-CQDs can rapidly complete the reaction on Fe under severe conditions 3+ Is detected.
Preferably, in the step S2, the dosage ratio of the polyethyleneimine to the solution of the carbon quantum dots containing aldehyde groups is (0.85-0.96 g): (10-200. Mu.L).
Preferably, the dialysis specific operation steps are as follows: the pale yellow solution is put into a dialysis bag and dialyzed for 24 to 72 hours, and the raw materials are removed.
Further preferably, the dialysis bag has a molecular weight cut-off of 1200Da.
Preferably, in step S1, the solution of carbon quantum dots containing aldehyde groups is prepared by the following steps:
s101: the volume ratio is 1:2, 50% glutaraldehyde and ethanol with the volume concentration of 95% are mixed to obtain a mixture;
s102: putting the mixture into an autoclave, and performing heating treatment to obtain a primary product;
s103: dissolving the initial product into ethanol with the volume concentration of 95% to obtain an aldehyde group-containing carbon quantum dot solution, wherein the aldehyde group-containing carbon quantum dot solution is yellowish.
Further preferably, the amount of ethanol having a volume concentration of 95% in step S103 is 2.4 to 5mL.
Further preferably, the autoclave is a polytetrafluoroethylene-lined autoclave (50 mL).
Preferably, in step S101, the volume ratio is 1:2, and glycerol is also added after 50% glutaraldehyde and ethanol with the volume concentration of 95% are mixed, and the volume ratio is 1:2, and the dosage ratio of ethanol with the volume concentration of 95 percent to glycerin is (1.2-2.5 mL): (2.4-5 mL): (0.01-0.3 mL).
Preferably, the heating treatment is carried out under the conditions that the heating temperature is 120-180 ℃ and the heating time is 90-300 min.
In a second aspect, the present invention provides a carbon material for detecting iron ions, which is prepared by the synthesis method of the carbon material for detecting iron ions according to the first aspect.
In a third aspect, the present invention provides a use of a carbon material for detecting iron ions as described in the second aspect for detecting iron ions.
Compared with the prior art, the invention has the beneficial effects that:
(1) The carbon material N-CQDs provided by the invention has very high specificity and selectively responds to iron ions, and only Fe 3+ Fluorescence of the carbon quantum dots can be quenched, and under the condition of sigma=3, the carbon quantum dots provided by the invention are Fe 3+ Is 0.18 μm, which is much lower than other fluorescent probes based on carbon materials.
(2) The carbon material N-CQDs provided by the invention still have good light stability in the extreme environment of mixing other metal ions.
(3) The carbon material N-CQDs provided by the invention has very good time stability, the fluorescence quenching rate of the N-CQDs is greatly reduced within the pH range of 4-10, and the reaction is completed within 1min, which indicates that the N-CQDs can rapidly complete the reaction of Fe under severe conditions 3+ Is detected.
Drawings
FIG. 1 is a perspective electron microscope view of the carbon material N-CQDs provided by the invention;
FIG. 2 is an infrared spectrum of the carbon material N-CQDs provided by the invention;
FIG. 3 shows the addition of Fe to the carbon material N-CQDs of the present invention 3+ Fluorescence intensity versus time for front and rear N-CQDs;
FIG. 4 shows the addition of Fe to the carbon material N-CQDs of the present invention 3+ Fluorescence intensity vs. pH profile for front and rear N-CQDs;
FIG. 5 is a view of Fe of N-CQDs of carbon material according to the present invention 3+ Gradient concentration-fluorescence intensity plot;
FIG. 6 shows fluorescence quenching rate-Fe of the carbon material N-CQDs according to the present invention 3+ A concentration map;
FIG. 7 shows the addition of Hg alone to the N-CQDs solution of carbon materials according to the present invention 2+ 、Cd 2+ 、Zn 2+ 、K + 、Na + 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Fe 2+ 、Ba 2+ 、Mg 2+ 、Mn 2+ 、Ca 2+ 、Ag + Or Cr 3+ A change pattern of fluorescence intensity of the sample before and after the solution of the plasma metal ions;
FIG. 8 shows the addition of Hg alone to N-CQDs of carbon materials according to the present invention 2+ 、Cd 2+ 、Zn 2+ 、K + 、Na + 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Fe 2+ 、Ba 2+ 、Mg 2+ 、Mn 2+ 、Ca 2+ 、Ag + Or Cr 3+ The fluorescence intensity of the sample changes before and after the plasma metal ion, and Hg is added respectively 2+ 、Cd 2+ 、Zn 2+ 、K + 、Na + 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Fe 2+ 、Ba 2+ 、Mg 2+ 、Mn 2+ 、Ca 2+ 、Ag + Or Cr 3+ Fe of plasma metal ion 3+ A graph of the change in fluorescence intensity of the sample before and after the solution of (a).
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment of the invention provides a carbon material for detecting iron ions, which is characterized in that: the method comprises the following steps:
s1: weighing 10 mu L of the solution of the carbon quantum dot containing the aldehyde group, and dissolving the solution into 20mL of water to obtain an aqueous solution of the carbon quantum dot containing the aldehyde group;
the aldehyde group-containing carbon quantum dot solution is prepared through the following steps:
s101: the volume ratio is 1:2 with ethanol with a volume concentration of 95%, followed by the addition of glycerol, to obtain a mixture, wherein the volume ratio is 1:2, the dosage ratio of glutaraldehyde 50%, ethanol with volume concentration of 95% and glycerin is 1.2mL:2.4mL:0.01mL;
s102: placing the mixture into an autoclave, and obtaining a primary product under the conditions that the heating temperature is 120 ℃ and the heating time is 90 min;
s103: dissolving the initial product into 2.4mL of ethanol with volume concentration of 95% to obtain an aldehyde group-containing carbon quantum dot solution, wherein the aldehyde group-containing carbon quantum dot solution is yellowish;
s2: weighing polyethyleneimine, then dissolving the polyethyleneimine into 20mL of ethanol with the volume concentration of 95% to obtain a polyethyleneimine-containing solution, adding the polyethyleneimine-containing solution into an aqueous solution of aldehyde-group-containing carbon quantum dots, reacting for 6 hours at normal temperature, and reacting with each other to obtain an assembled carbon material which is a pale yellow solution, wherein the dosage ratio of the polyethyleneimine to the aldehyde-group-containing carbon quantum dots is 0.85 g/10 mu L;
s3: putting the pale yellow solution prepared in the step S2 into a dialysis bag, dialyzing for 24 hours, and removing raw materials to obtain a primary product filtrate;
s4: filtering the primary product filtrate by a 0.22 mu m filter membrane, removing large particles, and freeze-drying to obtain yellow powder, namely the carbon material N-CQDs.
Example 2
The embodiment of the invention provides a carbon material for detecting iron ions, which is characterized in that: the method comprises the following steps:
s1: measuring 100 mu L of the solution of the carbon quantum dot containing the aldehyde group, and dissolving the solution into 20mL of water to obtain an aqueous solution of the carbon quantum dot containing the aldehyde group;
the aldehyde group-containing carbon quantum dot solution is prepared through the following steps:
s101: the volume ratio is 1:2 with ethanol having a volume concentration of 95%, followed by the addition of glycerol (glycerol in an amount of 0.2 mL) to give a mixture, wherein the volume ratio is 1:2, the dosage ratio of glutaraldehyde 50% to ethanol with a volume concentration of 95% is 1.5mL:3mL;
s102: placing the mixture into an autoclave, and obtaining a primary product under the conditions that the heating temperature is 150 ℃ and the heating time is 180 min;
s103: dissolving the initial product into 5mL of ethanol with the volume concentration of 95% to obtain an aldehyde group-containing carbon quantum dot solution, wherein the aldehyde group-containing carbon quantum dot solution is yellowish;
s2: weighing polyethyleneimine, then dissolving the polyethyleneimine into 20mL of ethanol with volume concentration of 95% to obtain a polyethyleneimine-containing solution, adding the polyethyleneimine-containing solution into an aqueous solution of aldehyde-group-containing carbon quantum dots, reacting for 6 hours at normal temperature, and reacting with each other to obtain an assembled carbon material which is a pale yellow solution, wherein the dosage ratio of the polyethyleneimine to the aldehyde-group-containing carbon quantum dots is 0.96g: 100. Mu.L;
s3: putting the pale yellow solution prepared in the step S2 into a dialysis bag, dialyzing for 48 hours, and removing raw materials to obtain a primary product filtrate;
s4: filtering the primary product filtrate by a 0.22 mu m filter membrane, removing large particles, and freeze-drying to obtain yellow powder, namely the carbon material N-CQDs.
Example 3
The embodiment of the invention provides a carbon material for detecting iron ions, which is characterized in that: the method comprises the following steps:
s1: 200 mu L of the solution containing the aldehyde group carbon quantum dots is measured and dissolved in 20mL of water to obtain an aqueous solution containing the aldehyde group carbon quantum dots;
the aldehyde group-containing carbon quantum dot solution is prepared through the following steps:
s101: the volume ratio is 1:2 with ethanol having a volume concentration of 95%, followed by the addition of glycerol (glycerol in an amount of 0.3 mL) to give a mixture, wherein the volume ratio is 1:2, the dosage ratio of glutaraldehyde 50% to ethanol with a volume concentration of 95% is 2.5mL:5mL;
s102: placing the mixture into an autoclave, and obtaining a primary product under the conditions that the heating temperature is 180 ℃ and the heating time is 300 min;
s103: dissolving the initial product into 5mL of ethanol with the volume concentration of 95% to obtain an aldehyde group-containing carbon quantum dot solution, wherein the aldehyde group-containing carbon quantum dot solution is yellowish;
s2: weighing polyethyleneimine, then dissolving the polyethyleneimine into 20mL of ethanol with volume concentration of 95% to obtain a polyethyleneimine-containing solution, adding the polyethyleneimine-containing solution into an aqueous solution of aldehyde-group-containing carbon quantum dots, reacting for 12 hours at normal temperature, and reacting with each other to obtain an assembled carbon material which is a pale yellow solution, wherein the dosage ratio of the polyethyleneimine to the aldehyde-group-containing carbon quantum dots is 0.96g: 200. Mu.L;
s3: and (3) filling the pale yellow solution prepared in the step (S2) into a dialysis bag, dialyzing for 72h, and removing the raw materials. Obtaining a primary product filtrate;
s4: filtering the primary product filtrate by a 0.22 mu m filter membrane, removing large particles, and freeze-drying to obtain yellow powder, namely the carbon material N-CQDs.
Test case
In the above examples, example 2 is a preferred example, and in order to further illustrate the beneficial effects of the present invention, performance tests were performed using the carbon material N-CQDs prepared in example 2:
1. carbon material N-CQDs morphology test
The morphology test is carried out on the carbon material N-CQDs, and as can be seen from the perspective electron microscope image of fig. 1, the aldehyde group-containing Carbon Quantum Dots (CQDs) and PEI react with each other through active groups, so that the novel carbon material N-CQDs is assembled, and therefore, the assembly body contains a plurality of carbon quantum dots and is in a uniform distribution state.
2. Carbon material N-CQDs infrared test
The morphology test of the carbon material N-CQDs is carried out, and the infrared spectrogram of FIG. 2 shows that the carbon material N-CQDs is in 3421cm -1 The peaks appear due to N-H and O-H stretching vibrations; 2957cm -1 And 2852cm -1 is-CH in PEI 2 Is a stretching vibration peak of (2); at 1710cm -1 The peak of (C=O) is a characteristic absorption peak at 1587cm -1 The presence of the peak indicates the presence of-CONH-, and the infrared spectrum further indicates that PEI successfully crosslinks to the aldehyde group-containing CQDs, indicating that the aldehyde group-containing carbon quantum dots and polyethyleneimine form carbon material N-CQDs.
3. Effect of pH and incubation time on fluorescence quenching Rate of carbon Material N-CQDs
Incubation time performance test was performed on carbon material N-CQDs, pH performance test was performed on carbon material N-CQDs at the same time, and Fe was added as shown in FIG. 3 3+ Fluorescence intensity vs. time graphs of front and rear N-CQDs and Fe addition of FIG. 4 3+ The fluorescence intensity-pH diagram of the front and rear N-CQDs shows that the fluorescence intensity of the N-CQDs is not greatly changed within the range of pH 4-10, and the fluorescence intensity of the N-CQDs can be obviously changed within 1min when the pH is smaller than 4 or higher than 10, because the amine group and the carboxyl group of the N-CQDs are widely protonated and deprotonated; in the pH range of 4 to 10, fe 3+ The fluorescence quenching rate of N-CQDs is greatly reduced, and the reaction is completed within 1min, which shows that the fluorescence probe can rapidly complete the reaction of Fe under severe conditions 3+ Is detected; thus, the optimal experimental conditions were: N-CQDs were dissolved with ultra-pure water at pH=7 for Fe detection 3+ In this case, only 1min of incubation was required.
4. Fluorescence characteristic and linear range of carbon material N-CQDs applied to iron ion detection
(1) Determination of detection limit of iron ions
3800. Mu.L of ultrapure water, 100. Mu.L of a carbon material N-CQDs solution (15 mg/mL) and 100. Mu.L of Fe of different concentrations were mixed 3+ Mixing to obtain Fe 3+ The total volume of the sensing system was kept at 4mL, and the final concentration of the carbon material N-CQDs solution was 0.375mg/mL.
After 1min of reaction at room temperature, fluorescence spectra were recorded at an excitation wavelength of 320 nm.
Fluorescence quenching rate (1-F/F) 0 ) With Fe 3+ A linear regression equation was established between the concentrations. 30. Mu.M of different metal ions (Pb) was added to a 0.375mg/mL solution of carbon material N-CQDs 2+ 、Cd 2+ 、Cr 3+ 、Zn 2+ 、Cu 2+ 、Mn 2+ 、Ca 2+ 、Mg 2+ 、Ba 2+ 、Ni 2 + 、Fe 2+ 、Hg 2+ 、Ag + 、K + And Na (Na) + ) Testing carbon materials N-CQDs vs. Fe 3+ Is selected from the group consisting of (1). Testing the anti-interference performance of the carbon material N-CQDs, and adding 30 mu M Fe 3+ And 15 metal ion solutions having a concentration of 30. Mu.M were added to the carbon material N-CQDs solution.
The detection limit (Limit of detection, LOD) is one of the important parameters for measuring the sensitivity of a fluorescent probe, and is defined as the minimum concentration or minimum amount of a substance to be detected from a sample by a specific analysis method within a given confidence, and is calculated according to equation 1.
Equation 1:
wherein:
sigma-signal to noise ratio, which is typically 3;
s-blank standard deviation;
n—slope of standard curve.
(2) Detection step of iron ions
Filtering lake water from artificial lake of mountain school area of Guangdong university of Pharmacology with 0.22 μm microporous membrane, centrifuging at 8000rpm for 10min, removing particulates, adding 3.8mL water sample into water sample containing 100 μl carbon material N-CQDs (15 mg/mL) and 100 μl Fe with different concentrations 3+ In the mixture of (5. Mu.M, 10. Mu.M and 15. Mu.M), the total volume was 4mL, and the fluorescence intensity was obtained by the test, and each experiment was performed in triplicate.
According to the fluorescence quenching rate and Fe 3+ Linear square of concentrationThe recovery rates of 5.1. Mu.M, 15.6. Mu.M and 19.6. Mu.M were found to be 101.75%, 103.90% and 98.23%, respectively, with a Relative Standard Deviation (RSD) of 0.7-2.1%, indicating that the carbon material N-CQDs are useful for detecting Fe in a practical sample 3+ Still has higher sensitivity and good performance, and achieves the purpose of detecting Fe in the actual environment 3+ Is effective in (1).
From FIG. 5 Fe 3+ As can be seen from the gradient concentration-fluorescence intensity plot, when Fe was added to the N-CQDs solution (15 mg/mL) respectively 3+ The fluorescence intensity of N-CQDs gradually decreases at the gradient concentration, indicating that the fluorescence of N-CQDs is relative to Fe 3+ The concentration change is very sensitive.
From FIG. 6, fluorescence quenching rate-Fe 3+ The concentration chart shows that fluorescence quenching rate and Fe 3+ The concentration is in a good linear relation within the range of 1-22 mu M, and the linear equation is 1-F/F 0 ＝0.02565C Fe 3+ 0.05318, linear correlation is good, correlation coefficient (R 2 ) 0.9950.
5. Selective and anti-interference performance of carbon material N-CQDs applied to iron ion detection
The respective addition of Hg-only from the carbon material N-CQDs solution of FIG. 7 2+ 、Cd 2+ 、Zn 2+ 、K + 、Na + 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Fe 2+ 、Ba 2+ 、Mg 2+ 、Mn 2+ 、Ca 2+ 、Ag + Or Cr 3+ The change pattern of fluorescence intensity of the sample before and after the solution of the plasma metal ion and FIG. 8 are respectively obtained by adding Hg-only solution of carbon material N-CQDs 2+ 、Cd 2+ 、Zn 2+ 、K + 、Na + 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Fe 2+ 、Ba 2+ 、Mg 2 + 、Mn 2+ 、Ca 2+ 、Ag + Or Cr 3+ The fluorescence intensity of the sample changes before and after the plasma metal ion, and Hg is added respectively 2+ 、Cd 2+ 、Zn 2+ 、K + 、Na + 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Fe 2+ 、Ba 2+ 、Mg 2+ 、Mn 2+ 、Ca 2+ 、Ag + Or Cr 3+ Fe of plasma metal ion 3+ A graph of the change in fluorescence intensity of the sample before and after the solution of (a); as can be seen from comparison, when Fe 3+ Respectively with Hg 2+ 、Cd 2+ 、Zn 2+ 、K + 、Na + 、Cu 2+ 、Ni 2+ 、Pb 2 + 、Fe 2+ 、Ba 2+ 、Mg 2+ 、Mn 2+ 、Ca 2+ 、Ag + Or Cr 3+ When the N-CQDs exist simultaneously, the fluorescence of the N-CQDs solution sample is obviously reduced, fluorescence quenching is generated, and the N-CQDs have obvious anti-interference performance to Fe 3+ Has good selectivity in detection.
Compared with the prior art, the carbon material N-CQDs prepared by adopting the embodiment 2 has higher specificity and selectivity to respond to iron ions compared with CDs fluorescent probes, N, P-CQDs fluorescent probes, N, S-CQDs fluorescent probes, CDs fluorescent probes and CDs fluorescent probes, and only Fe 3+ Fluorescence of the carbon quantum dots can be quenched; in the case of σ=3, fe 3+ LOD of 0.18 mu M, which is much lower than other fluorescent probes based on carbon materials; the light stability is still good in the extreme environment of mixing other metal ions; the time stability is very good, the fluorescence quenching rate of the N-CQDs is greatly reduced within the pH range of 4-10, and the reaction is completed within 1min, which indicates that the N-CQDs can rapidly complete the reaction on Fe under severe conditions 3+ Is detected.
In the description of the present invention, a number means one or more, a number means two or more, and greater than, less than, exceeding, etc. are understood to not include the present number, and above, below, within, etc. are understood to include the present number. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The synthesis method of the carbon material for detecting iron ions is characterized by comprising the following steps: the method comprises the following steps:
s1: measuring and dissolving an aldehyde group-containing carbon quantum dot solution in water to obtain an aldehyde group-containing carbon quantum dot aqueous solution;
s2: weighing polyethyleneimine, then dissolving the polyethyleneimine into ethanol with the volume concentration of 95% to obtain a polyethyleneimine-containing solution, adding the polyethyleneimine-containing solution into an aqueous solution containing aldehyde group carbon quantum dots, reacting for 6-12 h at normal temperature, and reacting with each other to obtain an assembled carbon material which is a pale yellow solution; the dosage ratio of the polyethyleneimine to the aldehyde group-containing carbon quantum dot solution is (0.85-0.96 g): (10-200. Mu.L);
s3: dialyzing the pale yellow solution prepared in the step S2 to obtain a primary product filtrate;
s4: filtering the primary product filtrate by a filter membrane to remove large particles, and freeze-drying to obtain yellow powder, namely the carbon material N-CQDs.
2. The method for synthesizing a carbon material for detecting iron ions according to claim 1, wherein: in step S3, the dialysis comprises the steps of: and (3) filling the pale yellow solution prepared in the step (S2) into a dialysis bag, dialyzing for 24-72 h, and removing the raw materials.
3. The method for synthesizing a carbon material for detecting iron ions according to claim 1, wherein: in the step S4, the pore size of the filtering membrane is less than or equal to 0.22 mu m.
4. The method for synthesizing a carbon material for detecting iron ions according to claim 1, wherein: in the step S1, the aldehyde group-containing carbon quantum dot solution is prepared by the following steps:
s101: mixing glutaraldehyde 50% and ethanol with a volume concentration of 95% to obtain a mixture; the volume ratio of the glutaraldehyde to the ethanol with the volume concentration of 95% is 1:2;
s102: putting the mixture into an autoclave, and performing heating treatment to obtain a primary product;
s103: dissolving the initial product into ethanol with the volume concentration of 95% to obtain an aldehyde group-containing carbon quantum dot solution, wherein the aldehyde group-containing carbon quantum dot solution is yellowish.
5. The method for synthesizing a carbon material for detecting iron ions according to claim 4, wherein: in the step S101, after 50% glutaraldehyde and 95% ethanol by volume concentration are mixed, glycerol is also added, and the dosage ratio of 50% glutaraldehyde, 95% ethanol by volume concentration and glycerol is (1.2-2.5 mL): (2.4-5 mL): (0.01-0.3 mL).
6. The method for synthesizing a carbon material for detecting iron ions according to claim 4, wherein: in step S102, the heating treatment is performed under the conditions that the heating temperature is 120-180 ℃ and the heating time is 90-300 min.
7. A carbon material for detecting iron ions, characterized in that: a carbon material for detecting iron ions according to any one of claims 1 to 6.
8. Use of the carbon material for detecting iron ions according to claim 7 for detecting iron ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210513097.0A CN114956048B (en) | 2022-05-12 | 2022-05-12 | Carbon material for detecting iron ions as well as synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210513097.0A CN114956048B (en) | 2022-05-12 | 2022-05-12 | Carbon material for detecting iron ions as well as synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114956048A CN114956048A (en) | 2022-08-30 |
| CN114956048B true CN114956048B (en) | 2023-10-13 |
Family
ID=82980676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210513097.0A Active CN114956048B (en) | 2022-05-12 | 2022-05-12 | Carbon material for detecting iron ions as well as synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114956048B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386376B (en) * | 2022-10-27 | 2022-12-20 | 广东药科大学 | Nano platinum composite material based on carbon quantum dot assembly and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102973948A (en) * | 2012-12-03 | 2013-03-20 | 上海交通大学 | Method for preparing drug carrier based on magnetic carbon quantum dot/chitosan composite microsphere |
| CN108192601A (en) * | 2018-01-04 | 2018-06-22 | 中北大学 | A kind of functionalization inorganic fluorescent microsphere of nitrogen-doped carbon quantum dot and preparation method thereof |
| CN109111917A (en) * | 2018-07-23 | 2019-01-01 | 中国科学院合肥物质科学研究院 | A kind of crosslinking carbon quantum dot nanosphere fluorescence probe material and the preparation method and application thereof |
-
2022
- 2022-05-12 CN CN202210513097.0A patent/CN114956048B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102973948A (en) * | 2012-12-03 | 2013-03-20 | 上海交通大学 | Method for preparing drug carrier based on magnetic carbon quantum dot/chitosan composite microsphere |
| CN108192601A (en) * | 2018-01-04 | 2018-06-22 | 中北大学 | A kind of functionalization inorganic fluorescent microsphere of nitrogen-doped carbon quantum dot and preparation method thereof |
| CN109111917A (en) * | 2018-07-23 | 2019-01-01 | 中国科学院合肥物质科学研究院 | A kind of crosslinking carbon quantum dot nanosphere fluorescence probe material and the preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Development of nitrogen‑doped carbon quantum dots as fluorescent probes for highly selective and sensitive detection of the heavy‑ion Fe3+;Rui Liu等;《Carbon Letters》;全文 * |
| N-doped carbon quantum dots as fluorescent probes for highly selective and sensitive detection of Fe3+ ions;Xiangyi Deng等;《Particuology》;第41卷;全文 * |
| Study on luminescence mechanism of nitrogen-doped carbon quantum dots with different fluorescence properties and application in Fe3+ detection;Caimei Liang等;《J Nanopart Res》;第23卷;全文 * |
| Surface chemistry-dependent antibacterial and antibiofilm activities of polyamine-functionalized carbon quantum dots;Peili Li等;《Journal of Materials Science》;第55卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114956048A (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114956048B (en) | Carbon material for detecting iron ions as well as synthesis method and application thereof | |
| Wang et al. | A dual-emission fluorescence sensor constructed by encapsulating double carbon dots in zeolite imidazole frameworks for sensing Pb2+ | |
| CN111690405B (en) | Fluorescent carbon dot, preparation method thereof and application thereof in copper ion detection | |
| CN109307665B (en) | Method for detecting Fe by using fluorescent carbon quantum dots3+Method (2) | |
| CN115386371B (en) | Blue fluorescent quantum dot preparation method and application of blue fluorescent quantum dot as glutathione detection probe | |
| CN115138369B (en) | Molybdenum trioxide composite material and preparation method and application thereof | |
| CN113773834A (en) | Nitrogen and sulfur co-doped carbon quantum dot and preparation method and application thereof | |
| CN109439321B (en) | Carbon quantum dot using silkworm excrement as raw material, preparation method and application thereof | |
| CN113201335B (en) | Enhanced fluorescent carbon dot, preparation method and application in cadmium ion detection | |
| Mohandoss et al. | Nitrogen and sulfur co-doped photoluminescent carbon dots for highly selective and sensitive detection of Ag+ and Hg2+ ions in aqueous media: Applications in bioimaging and real sample analysis | |
| CN109097026B (en) | Nano flower-shaped Al-MOF fluorescent probe material and preparation method and application thereof | |
| CN111879746B (en) | Fluorescent chemical sensor and preparation method and application thereof | |
| CN110907589B (en) | Visible Cu detection based on GQDs photocatalysis2+Method (2) | |
| CN113462386A (en) | Blue iron ion carbon quantum dot and preparation method and application thereof | |
| CN112357913B (en) | Fluorescence reduction graphene oxide and preparation method and application thereof | |
| CN108192603B (en) | Nitrogen oxide-doped carbon dot fluorescent probe for formaldehyde detection and preparation method thereof | |
| Xiang et al. | Synthesis of Carbon dots from Biomass Chenpi for the Detection of Hg 2 | |
| CN116333732B (en) | Nitrogen-doped carbon dot, preparation method thereof and Fe3+Application in detection | |
| CN113092565B (en) | Arsenite radical detection method based on electrochemiluminescence effect | |
| CN115926789B (en) | Preparation and application of pH-responsive N, S co-doped graphene quantum dot | |
| CN115820248A (en) | Method for preparing carbon quantum dots by utilizing landfill leachate membrane concentrated solution and method for detecting palladium ions by utilizing carbon quantum dots | |
| CN116622371B (en) | Preparation method of novel carbon quantum dot fluorescent probe based on magnolia officinalis, product and application thereof | |
| CN116790248B (en) | Zinc-nitrogen doped carbon dot and preparation method and application thereof | |
| CN113416541B (en) | Polymer carbon dot fluorescent probe for ppb level aniline detection and preparation method thereof | |
| CN113999674B (en) | CDs synthesis method and H detection method by using CDs 2 O 2 Is a method of (2) |
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 |