CN114148999A - Double-channel fluorescent probe Blood-CDs and preparation method and application thereof - Google Patents

Double-channel fluorescent probe Blood-CDs and preparation method and application thereof Download PDF

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CN114148999A
CN114148999A CN202111502290.6A CN202111502290A CN114148999A CN 114148999 A CN114148999 A CN 114148999A CN 202111502290 A CN202111502290 A CN 202111502290A CN 114148999 A CN114148999 A CN 114148999A
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鲍光明
范青
袁厚群
王小莺
邓科
李思涵
刘思依
蔡欣如
夏义凡
李伟
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Abstract

The invention discloses a dual-channel fluorescent probe Blood-CDs and a preparation method and application thereof3+And Hg2+Has high selectivity and sensitivity. The fluorescence of the two-channel fluorescent probe Blood-CDs prepared by the invention can be changed by Fe in an aqueous medium3+And Hg2+Quenching, and has higher selectivity and sensitivity; further, FCan selectively recover Fe3+Quenched fluorescence, Al3+Can selectively recover Hg2+Quenched fluorescence. Therefore, the dual-channel fluorescent probe Blood-CDs can be used for distinguishing Fe3+And Hg2+In particular for livestockFe in animal feed or environmental water sample3+And Hg2+Quantitative detection and identification.

Description

Double-channel fluorescent probe Blood-CDs and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a dual-channel fluorescent probe Blood-CDs, and a preparation method and application thereof.
Background
With the rapid development of the breeding industry, the livestock and poultry breeding wastewater containing heavy metal ions is discharged in a large amount, so that the heavy metal ions enter soil, water and even atmosphere. Subsequently, these heavy metal ions migrate through the food chain to grains, forage, etc., causing serious degradation in the quality and safety of animal products, posing a threat to human health.
Fe3+As an important component of hemoglobin, it is involved in various metabolic processes of the body, but Fe is present in the body3+Deficiency or excess can lead to physical disorders and even diseases such as renal failure, anemia, heart disease, liver damage, etc. Therefore, a highly selective, highly sensitive method was developed for quantitative monitoring of Fe in an environment3+Is very necessary.
Hg2+One of the heavy metal ions considered to be strongly toxic is due to its characteristics of durability, high biotoxicity, carcinogenicity and difficult biodegradability. It can invade the human body through the respiratory and digestive tracts and even the skin, causing severe damage to the nervous system, heart, kidneys and many other organs even at low concentrations. Thus, Hg in an environment is monitored2+It is also important.
General Fe3+And Hg2+Detection methods include inductively coupled plasma mass spectrometry, electrochemical methods, and atomic absorption spectrometry. Although these methods have certain advantages in terms of sensitivity and multi-element detection capability, they are too complex and time consuming and laborious. Therefore, other methods have been developed to overcome these disadvantages, and fluorescence spectroscopy has attracted much attention due to its low cost, fast analysis speed, high selectivity and sensitivity, and easy operation. Carbon Dots (CDs) are a new carbon material with unique properties, including simple preparation, high fluorescence intensity, low toxicity, high stability, good water solubility and biocompatibility and the like, and are widely used in the fields of ion and small molecule detection, biological imaging and the like. At present, carbon dot probes for detecting various metal ions have been reported, but since they generate the same signal, the detection of metal ions cannot be distinguished.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a dual-channel fluorescent probe Blood-CDs and a preparation method and application thereof, and the following technical scheme is specifically adopted:
a dual-channel fluorescent probe Blood-CDs is prepared from chicken Blood and trisodium citrate dihydrate by hydrothermal method.
The fluorescence of the two-channel fluorescent probe Blood-CDs can be Fe in an aqueous medium3+And Hg2+Quenching, and has higher selectivity and sensitivity; further, F-Can selectively recover Fe3+Quenched fluorescence, Al3+Can selectively recover Hg2+Quenched fluorescence.
Therefore, the invention also provides a dual-channel fluorescent probe Blood-CDs in Fe3+And Hg2+Application in the field of detection, preferably, in the detection of Fe in livestock feed or environmental water samples3+And Hg2+The use of (1). Through research, the two-channel fluorescent probe Blood-CDs is used for Fe3+And Hg2+The detection of (2) shows good wide-range linear characteristics of 0-100. mu.M and 0-120. mu.M, respectively. And calculating that the dual-channel fluorescent probe Blood-CDs is opposite to Fe3+The detection limit of (a) is 0.23. mu.M,for Hg2+The detection limit of (2) is 0.17 mu M, and the detection recovery rate is high.
The invention also provides a preparation method of the double-channel fluorescent probe Blood-CDs, which comprises the following steps: mixing chicken blood and trisodium citrate dihydrate, performing hydrothermal reaction for 1 day at 180 ℃ to obtain a dark brown solution, centrifuging, filtering with a filter membrane to remove large particles, collecting supernatant, performing dialysis for 1 day to remove small particles, and finally performing freeze-drying collection, wherein the ratio of the chicken blood to the trisodium citrate dihydrate is 1 mL: 10 mg.
Preferably, the hydrothermal process is carried out in a polytetrafluoroethylene autoclave having a specification of 50 mL.
The centrifugation conditions were: centrifuge at 11000rpm for 12 minutes.
The filter membrane specification is 0.22 μm.
And (4) dialyzing by adopting a dialysis membrane, wherein the specification of the dialysis membrane is 1000 Da.
The invention has the beneficial effects that: the dual-channel fluorescent probe Blood-CDs prepared by the invention shows Fe in the presence of p-Fe in an aqueous medium3+And Hg2+High selectivity and sensitivity to Fe3+And Hg2+The detection of (2) shows the characteristics of wide linear range, respectively 0-100 mu M and 0-120 mu M, for Fe3+The detection limit of (2) to Hg is 0.23. mu.M2+The detection limit of (2) was 0.17. mu.M. In addition, the probe pair Fe3+And Hg2+Has a fluorescence quenching reaction, and F-Can selectively recover Fe3+Quenched fluorescence, Al3+Can specifically recover from Hg2+Quenched fluorescence. Therefore, the dual-channel fluorescent probe Blood-CDs can be used for distinguishing Fe3+And Hg2+Especially for detecting Fe in livestock feed or environmental water samples3+And Hg2+Quantitative detection and identification.
Drawings
FIG. 1(a) is a TEM and HRTEM image of a two-channel fluorescent probe Blood-CDs according to the present invention; FIG. 1(b) shows the particle size distribution of a two-channel fluorescent probe Blood-CDs; FIG. 1(c) is an XRD pattern of a two-channel fluorescent probe Blood-CDs; FIG. 1(d) is a FT-IR diagram of a two-channel fluorescent probe Blood-CDs;
FIG. 2(a) is an XPS survey of two-channel fluorescent probes Blood-CDs according to the present invention; FIG. 2(b) is a high resolution spectrum of C1 s; FIG. 2(c) is a high resolution spectrum of N1 s; FIG. 2(d) is a high resolution O1s spectrum;
FIG. 3(a) is a photograph showing the ultraviolet absorption and fluorescence spectra of the Blood-CDs of the two-channel fluorescent probe of the present invention, and photographs taken under sunlight (left) and under a 365nm ultraviolet lamp (right); FIG. 3(b) is the fluorescence emission spectrum of the dual-channel fluorescent probe Blood-CDs at different excitation wavelengths;
FIG. 4(a) is the 7-day fluorescence intensity of the two-channel fluorescent probe Blood-CDs of the present invention; FIG. 4(b) shows fluorescence intensities of two-channel fluorescent probe Blood-CDs at different pH values;
FIG. 5(a) shows M in example 5 of the present inventionn+Fluorescence pictures of @ Blood-CDs under UV lamp (365 nm); FIG. 5(b) shows Mn+Fluorescence intensity change of @ Blood-CDs under 449nm wavelength excitation; FIG. 5(c) shows Mn+@ Blood-CDs at 449nm wavelength excitation and Hg respectively2+Change in fluorescence intensity in the presence/absence of the compound; FIG. 5(d) is Mn+@ Blood-CDs at 449nm wavelength excitation and Fe respectively3+Change in fluorescence intensity in the presence/absence of the compound;
FIG. 6(a) shows the concentration of Hg in the solution containing the two-channel fluorescent probe Blood-CDs of the present invention2+(0-120. mu.M) fluorescence spectrum; FIG. 6(b) shows Hg2+F of (A)0A change curve of the/F value; FIG. 6(c) shows two-channel fluorescent probe Blood-CDs containing different concentrations of Fe3+(0-100. mu.M) fluorescence spectrum; FIG. 6(b) shows Fe3+F of (A)0A change curve of the/F value;
FIG. 7 shows the two-channel fluorescent probes Blood-CDs and Hg of the present invention2+@ Blood-CDs and Fe3+The fluorescence lifetime curve of @ Blood-CDs;
FIG. 8 shows the two-channel fluorescent probes Blood-CDs and Hg of the present invention2+@ Blood-CDs and Fe3+The ultraviolet absorption spectrum of @ Blood-CDs;
FIG. 9(a) shows the two-channel fluorescent probes Blood-CDs and Hg of the present invention2+@Blood-CDs、Al3+@Blood-CDs-Hg2 +And F-@Blood-CDs-Hg2+Photograph under ultraviolet lamp; FIG. 9(b) shows two-channel fluorescent probes Blood-CDs and Hg2+@Blood-CDs、Al3+@Blood-CDs-Hg2+And F-@Blood-CDs-Hg2+Fluorescence spectrum under 370nm excitation; FIG. 9(c) shows two-channel fluorescent probes Blood-CDs and Fe3+@Blood-CDs、F-@Blood-CDs-Fe3+And Al3+@Blood-CDs-Fe3+Photograph under ultraviolet lamp; FIG. 9(d) shows two-channel fluorescent probes Blood-CDs and Fe3+@Blood-CDs、F-@Blood-CDs-Fe3+And Al3+@Blood-CDs-Fe3+Fluorescence spectrum under 370nm excitation;
FIG. 10(a) shows a two-channel fluorescent probe Blood-CDs and Al of the present invention3+@ Blood-CDs and F-Picture of @ Blood-CDs under 365nm ultraviolet lamp; FIG. 10(b) shows a two-channel fluorescent probe Blood-CDs, Al3+@ Blood-CDs and F-Fluorescence spectra of @ Blood-CDs at an excitation wavelength of 370 nm;
FIG. 11(a) shows the two-channel fluorescent probes Blood-CDs and Hg of the present invention2+@ Blood-CDs and Al3+@Blood-CDs-Hg2+Ultraviolet-visible absorption spectrum of (a); FIG. 11(b) shows two-channel fluorescent probes Blood-CDs and Fe3+@ Blood-CDs and F-@Blood-CDs-Fe3+Ultraviolet-visible absorption spectrum of (a);
FIG. 12 shows the preparation process of the dual-channel fluorescent probe Blood-CDs and the dual-channel fluorescent probe Blood-CDs vs Fe3+And Hg2+The process of detection and identification of (1).
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, aspects and effects of the present invention.
The chemicals and instruments used in the present invention:
chemical products:
the chicken blood is from chicken bought in the local market of Nanchang city of Jiangxi province of China. The chemicals were obtained from Aladdin Chemicals, Inc. (China), except that trisodium citrate dihydrate was obtained from West Long chemical reagent (China). The aqueous solution of metal ions is prepared from the chloride or nitrate thereof.
The instrument comprises the following steps:
observing the morphology and structure of Blood-CDs in a FEI Tecnai G2F 20 high resolution Transmission Electron Microscope (TEM);
x-ray diffraction (XRD) patterns were measured on a D8 ADVANCE diffractometer with Cu-ka radiation (λ 1.5406 nm);
measuring a Fourier transform infrared (FT-IR) spectrum on a Perkinelmer spectrum-II Fourier transform infrared spectrometer;
measuring X-ray photoelectron spectroscopy (XPS) on a Thermo ESCALAB 250XI electron spectrometer;
recording the fluorescence spectra on an INESA 970CRT fluorescence spectrophotometer;
the UV-visible absorption spectrum was measured in a Gold Spectrum lab 54 UV-visible spectrophotometer.
Example 1
Preparing a double-channel fluorescent probe Blood-CDs:
5mL of chicken Blood and 50mg of trisodium citrate dihydrate are mixed, transferred to a 50mL polytetrafluoroethylene autoclave, reacted at 180 ℃ for 1 day to obtain a dark brown solution, centrifuged at 11000rpm for 12 minutes, filtered through a 0.22-micron filter membrane to remove large particles, the supernatant is collected, dialyzed through a 1000Da dialysis membrane for one day to remove small particles, Blood-CDs are collected by freeze-drying, and finally the Blood-CDs are dispersed in water to prepare a 0.25mg/mL solution.
The process for preparing the dual-channel fluorescent probe Blood-CDs of the invention is shown in FIG. 12, and the fluorescence of the dual-channel fluorescent probe Blood-CDs can be changed by Fe in the aqueous medium3+And Hg2+Quenching, and has higher selectivity and sensitivity; adding F-Can selectively recover Fe3+Quenched fluorescence, addition of Al3+Can selectively recover Hg2+Quenched fluorescence.
Example 2
Determination of the characterization of the two-channel fluorescent probe Blood-CDs:
as shown in fig. 1(a), the morphology and size of Blood-CDs, which is a uniform dispersion of individual particles, was analyzed by Transmission Electron Microscopy (TEM) and high resolution TEM images showed sharp lattice edges with a pitch of 0.21nm, which is consistent with the lattice pitch of graphitic carbon (100).
As shown in FIG. 1(b), Blood-CDs have a particle size distribution of 3.5 to 6.5nm and an average particle size of about 4.9 nm.
As shown in fig. 1(c), the X-ray diffraction (XRD) pattern has a broad diffraction peak at 23 ° 2 θ, which is caused by the disordered carbon atoms and the interlayer spacing of the graphite structure.
As shown in FIG. 1(d), Fourier transform infrared spectroscopy (FT-IR) revealed 3453cm-1、3274cm-1And 2965--1The absorption peaks of (a) correspond to the tensile vibrations of O-H, N-H and C-H, respectively; 1591cm-1Corresponds to asymmetric tensile vibration of C ═ O; 1394-doped 1441cm-1Several absorption peaks of (a) correspond to tensile vibrations of C ═ C and C — O; 1079cm-1And 1282-1305cm-1Corresponds to the tensile vibration of C-N; 1157-1194cm-1Corresponds to the stretching vibration of C-O.
As shown in fig. 2(a), X-ray photoelectron spectroscopy (XPS) showed three distinct peaks of 285.34eV, 400.07eV and 531.86eV, corresponding to C1s, N1s and O1s, respectively, and the calculated contents of carbon, nitrogen and oxygen were 66.18%, 12.40% and 20.42%, respectively.
As shown in fig. 2(b), the C1s high resolution spectrum is divided into three peaks centered at 288.01eV, 286.12eV, and 284.80eV, which are assigned to C-O, C-N/C-O and C-C/C-C, respectively.
As shown in FIG. 2(C), the high resolution spectrum of N1s contained only one peak at 399.79eV, corresponding to the C-N functionality.
As shown in fig. 2(d), the O1s high resolution spectrum is divided into two peaks at 532.41eV and 531.21eV, respectively due to C-O and C ═ O.
Example 3
Measuring the optical characteristics of the two-channel fluorescent probe Blood-CDs:
as shown in FIG. 3(a), the aqueous solution of Blood-CDs is pale yellow in sunlight, but emits bright blue fluorescence under ultraviolet irradiation (365 nm). The uv-vis absorption spectrum shows two broad weak absorption peaks at 280nm and 400nm, which are attributed to the C ═ O bond pi-pi transition and C — N bond N-pi transition, respectively, the emission (red) and excitation (blue) spectra of Blood-CDs, indicating that the optimal excitation and emission wavelengths are at 370nm and 449nm, respectively.
As shown in FIG. 3(b), the emission peak of Blood-CDs gradually red-shifted as the excitation wavelength increased from 320nm to 400nm, indicating that Blood-CDs exhibited excitation-dependent Photoluminescence (PL) characteristics, which was calculated to be 13.78% in quantum yield.
As shown in FIG. 4(a), there was no significant change in the fluorescence intensity of Blood-CDs after standing for 7 days, which indicates that the fluorescence of Blood-CDs in an aqueous medium was stable.
As shown in FIG. 4(b), the fluorescence intensity of Blood-CDs was stable in the pH range of 3-7, but decreased in the pH ranges of 1-2 and 8-14, indicating that the optimal conditions for fluorescence detection of Blood-CDs were weakly acidic.
Example 4
Preparing metal ions:
different metal ions (10. mu.L, 0.1M) were added to 2mL of 0.25mg/mL Blood-CDs aqueous solution to obtain Mn+@Blood-CDs(Mn+=Zn2+,Cd2+,Na+,Mg2+,K+,Ag+,Fe2+,Pb2+,Ni2+,Co2+,Fe3+,Hg2+)。
Example 5
Detection capability of the two-channel fluorescent probe Blood-CDs on the metal ions prepared in example 4:
to an aqueous solution of Blood-CDs was added 500. mu.M each of various metal ions (Na)+、Ag+、K+、Mg2+、Ni2+、Cd2+、Zn2+、Co2+、Fe2+、Pb2+、Hg2+And Fe3+). As shown in FIG. 5(a), Na+、Ag+、K+、Mg2+、Ni2+、Cd2+、Zn2+、Co2+、Fe2+And Pb2+After addition, the Blood-CDs fluorescence intensity changes were negligible. While adding Hg2+And Fe3+Then, the phenomenon of obvious quenching of the fluorescence of the probe can be obviously observed under an ultraviolet lamp by naked eyes, and the fluorescence spectrum further confirms the observation result.
As shown in FIG. 5(b), Zn was added separately2+、Cd2+、Na+Or Mg2+Then, the fluorescence intensity of Blood-CDs at 449nm has no obvious change; separately adding K+、Ag+、Fe2+、Pb2+、Ni2+Or Co2+Then, the fluorescence intensity of Blood-CDs at 449nm is slightly reduced; hg is added2+Or Fe3+Thereafter, the fluorescence intensity of Blood-CDs at 449nm decreased significantly. This shows that the dual-channel fluorescent probe Blood-CDs pair detects Hg2+And Fe3+Exhibit a high degree of selectivity.
In order to prove the potential practical application capability, the probe is also explored for detecting Hg2+Or Fe3+The anti-interference capability of the system. As shown in fig. 5c and 5d, the interference system Mn+@Blood-CDs(Mn+=K+、Na+、Mg2+、Fe2+、Ag+、Zn2+、Cd2+、Pb2+、Co2+And Ni2+) Hg is added separately2+Or Fe3+After that, the luminous intensity is significantly decreased. Indicating that the probe is directed to Hg2+Or Fe3+The detection has good anti-interference performance.
Example 6
Double-channel fluorescent probe Blood-CDs to Hg2+And Fe3+The quantitative detection of (2):
as shown in FIG. 6(a), the Hg is varied2+The fluorescence intensity of Blood-CDs gradually decreased with increasing concentration (0-120. mu.M), as shown in FIG. 6(c), with Fe3+The fluorescence intensity of Blood-CDs gradually decreased with increasing concentration (0-100. mu.M).
The quenching effect was quantitatively analyzed by the standard Stern-Volmer equation: f0/F=Ksv[C]+1
Wherein F and F0Respectively in Hg2+Or Fe3+Fluorescence intensity of Blood-CDs in the presence and absence. KsvIs the Stern-Volmer quench constant. [ C ]]Is Hg2+/Fe3+The concentration of (c). Calculated, Hg2+And Fe3+K ofsvEach 1.62X 104M-1And 1.37X 104M-1. These values indicate that Hg2+And Fe3+Has strong quenching effect on Blood-CDs.
Hg as shown in FIG. 6(b)2+Linear correlation coefficient (R) of2) 0.9978, Fe as shown in FIG. 6(d)3+Linear correlation coefficient (R) of2) 0.9982, indicating the fluorescence intensity of Blood-CDs and Hg2+And Fe3+Has a good linear relationship between the concentrations of (a) and (b). According to the formula LOD of 3 sigma/S, the detection limit of the detection probe for mercury ions is 0.17 mu M and is lower than the limit concentration specified in the national integrated wastewater discharge standard (GB8978-1996), and the detection limit of the detection probe for iron ions is 0.23 mu M and is lower than the maximum allowable concentration in drinking water specified by the United states environmental protection agency.
Example 7
Research on Hg by using dual-channel fluorescent probe Blood-CDs through fluorescence lifetime and ultraviolet-visible absorption spectrum2+And Fe3+The quenching mechanism of (1):
in general, there are two mechanisms for fluorescence quenching, static and dynamic, with and without Hg, respectively2+And Fe3+The luminescence lifetime of Blood-CDs was examined for decay, and the mean lifetime of Blood-CDs was calculated to be 0.712ns, as shown in Table 1. As shown in FIG. 7 and Table 1, Blood-CDs and Hg2+Or Fe3+After the interaction, the results were calculated to be 0.674ns and 0.685ns, respectively, indicating that the fluorescence quenching process is a static quenching process.
TABLE 1
Figure BDA0003402243620000061
Figure BDA0003402243620000071
As shown in FIG. 8, Hg was added to the UV-visible absorption spectrum of Blood-CDs2+Thereafter, the peak at 280nm disappeared, and the peak at 400nm red-shifted. Adding Fe3+Thereafter, a new peak appeared around 300nm, indicating that the surface functional groups (carboxyl or hydroxyl) of Blood-CDs were associated with the analyte (Hg)2+And Fe3+) Coordination occurs between them. These coordination effects change the electronic structure of Blood-CDs, affect the distribution of electrons, accelerate non-radiative recombination, and result in fluorescence quenching of Blood-CDs.
Example 8
Hg distinction by two-channel fluorescent probe Blood-CDs2+And Fe3+Detection of (2):
the synthesized Blood-CDs were tested for Hg as described in examples 6 and 72+And Fe3+Show good performance, however they have the same fluorescence quenching signal.
To distinguish Hg2+And Fe3+In Hg2+@ Blood-CDs and Fe3+@ Blood-CDs in aqueous solution with a series of competing ions. Hg as shown in FIG. 92+Quenching of fluorescence by @ Blood-CDs can be achieved by addition of Al3+Recovery of specificity, and Fe3+Quenching of fluorescence by @ Blood-CDs can be achieved by addition of F-Specificity was restored, while as shown in FIG. 10, only Al was added3+Or F-Has little influence on the fluorescence intensity of Blood-CDs. This indicates that Al3+And F-Hg can be identified by specific recovery of fluorescence quenching2+And Fe3+
As shown in fig. 11, the mechanism leading to the recovery of fluorescence intensity was inferred to be a competitive interaction. It can be seen that for Hg2+@ Blood-CDs system, Al3+Has stronger affinity with Blood-CDs than Hg2+And Blood-CDs; and for Fe3+@ Blood-CDs system, Fe3+And F-Has a stronger affinity than Fe3+And Blood-CDs; these competitive interactionsHg is led2+And Fe3+Removed from the Blood-CDs surface, and fluorescence was recovered.
Example 9
Application of two-channel fluorescent probe Blood-CDs in detection of Hg in pig farm wastewater and pig feed2+And Fe3+
(1) Pretreating a sample of the wastewater of the pig farm: a sample of the pig farm wastewater was filtered through a 0.22 μm filter to remove insoluble residues, and standard concentrations of Hg were added2+(0.4. mu.M, 0.8. mu.M and 1.8. mu.M) or Fe3+(12. mu.M, 24. mu.M and 54. mu.M) were added to the resulting treated water samples, respectively, and then their fluorescence intensities at 449nm were recorded.
(2) Pretreating a pig feed sample: after a pig feed sample is treated by a microwave-assisted acid digestion method, 0.2g of the pig feed sample is weighed into a polytetrafluoroethylene tube, 2mL of a newly prepared mixture of concentrated nitric acid and hydrogen peroxide (1: 1, v/v) is added into the tube, the tube is placed for 10 minutes at room temperature, then the tube is covered, and microwaves are applied for 2-4 minutes at 720W, so that the sample is completely dissolved. Subsequently, the mixture was filtered through a 0.22 μm filter, and the resulting solution was made up to 10mL with water to obtain a sample solution. Standard concentration of Hg2+(0.4. mu.M, 0.8. mu.M and 1.8. mu.M) or Fe3+(12. mu.M, 24. mu.M and 54. mu.M) were added to the sample solutions, respectively, and then their fluorescence intensities at 449nm were recorded.
The results of the measurement are shown in Table 1, Hg2+The recovery rate of the Fe is 95.72-105.38 percent3+The recovery rate of (A) was 99.18-103.17%, the recovery rate was good and the RSD value was satisfactory. It can be seen that Blood-CDs quantitatively monitor Hg in pig farm wastewater and pig feed2+And Fe3+The concentration shows great potential.
TABLE 2 determination of Hg in actual pig farm wastewater and pig feed samples2+And Fe3+Recovery rate of (n ═ 3)
Figure BDA0003402243620000081
While the present invention has been described in considerable detail and with particular reference to a few illustrative embodiments thereof, it is not intended to be limited to any such details or embodiments or any particular embodiments, but it is to be construed as effectively covering the intended scope of the invention by providing a broad, potential interpretation of such claims in view of the prior art with reference to the appended claims. Furthermore, the foregoing describes the invention in terms of embodiments foreseen by the inventor for which an enabling description was available, notwithstanding that insubstantial modifications of the invention, not presently foreseen, may nonetheless represent equivalent modifications thereto.

Claims (9)

1. A dual-channel fluorescent probe Blood-CDs is characterized in that the dual-channel fluorescent probe Blood-CDs is prepared by a hydrothermal method through a mixture of chicken Blood and trisodium citrate dihydrate.
2. The dual channel fluorescent probe Blood-CDs in Fe as claimed in claim 13+And Hg2+Application in the field of detection.
3. The use of claim 2, wherein the dual channel fluorescent probe Blood-CDs is used for detecting Fe in livestock feed or environmental water samples3+And Hg2+The use of (1).
4. Use according to claim 2, wherein the dual channel fluorescent probe Blood-CDs is for Fe3+The detection limit of (2) to Hg is 0.23. mu.M2+The detection limit of (2) was 0.17. mu.M.
5. A preparation method of a dual-channel fluorescent probe Blood-CDs is characterized by comprising the following steps: mixing chicken blood and trisodium citrate dihydrate, performing hydrothermal reaction for 1 day at 180 ℃ to obtain a dark brown solution, centrifuging, filtering with a filter membrane to remove large particles, collecting supernatant, performing dialysis for 1 day to remove small particles, and finally performing freeze-drying collection, wherein the ratio of the chicken blood to the trisodium citrate dihydrate is 1 mL: 10 mg.
6. The method for preparing the dual channel fluorescent probe Blood-CDs according to claim 5, wherein the hydrothermal method is performed in a Teflon autoclave, which has a specification of 50 mL.
7. The method for preparing the dual channel fluorescent probe Blood-CDs according to claim 5, wherein the centrifugation conditions are as follows: centrifuge at 11000rpm for 12 minutes.
8. The method for preparing the dual channel fluorescent probe Blood-CDs as claimed in claim 5, wherein the size of the filter membrane is 0.22 μm.
9. The method for preparing the two-channel fluorescent probe Blood-CDs according to claim 5, wherein the dialysis is performed by using a dialysis membrane having a specification of 1000 Da.
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CN101049156A (en) * 2007-05-10 2007-10-10 武汉工业学院 Method for preparing microcapsule of enzyme hydrolysis object of poultry blood
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CN109110746A (en) * 2018-11-06 2019-01-01 湖南农业大学 It is a kind of using livestock and poultry blood as raw material prepare fluorescent carbon point method and its manufactured fluorescent carbon point
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US9316591B1 (en) * 2015-02-09 2016-04-19 University Of Guelph Biosensor for detection of subclinical ketosis
CN107603611A (en) * 2017-09-17 2018-01-19 西南大学 One kind has Catalyzed Synthesis By Peroxidase active fluoro carbon quantum dot and preparation method thereof
CN109110746A (en) * 2018-11-06 2019-01-01 湖南农业大学 It is a kind of using livestock and poultry blood as raw material prepare fluorescent carbon point method and its manufactured fluorescent carbon point
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