CN115845811A - Chitosan photonic crystal microsphere for detecting hexavalent chromium ions and preparation method thereof - Google Patents
Chitosan photonic crystal microsphere for detecting hexavalent chromium ions and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 81
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 79
- 239000004038 photonic crystal Substances 0.000 title claims abstract description 75
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000017 hydrogel Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010382 chemical cross-linking Methods 0.000 claims abstract description 4
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011651 chromium Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 description 12
- 230000000171 quenching effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008384 inner phase Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000008385 outer phase Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 208000017169 kidney disease Diseases 0.000 description 1
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000007694 nephrotoxicity Effects 0.000 description 1
- 231100000417 nephrotoxicity Toxicity 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Abstract
The invention relates to the technical field of detection methods, in particular to a chitosan photonic crystal microsphere for detecting hexavalent chromium ions and a preparation method thereof. The invention provides a preparation method of chitosan photonic crystal microspheres, which comprises the steps of firstly preparing photonic crystal microspheres by emulsifying, drying and calcining silicon dioxide nanoparticles, then soaking the photonic crystal microspheres in a chitosan hydrogel solution, adding glutaraldehyde after fully soaking, carrying out chemical crosslinking curing on chitosan and glutaraldehyde in gaps in the silicon dioxide photonic crystal microspheres, and stripping to obtain the chitosan photonic crystal microspheres with chitosan filled inside. According to the invention, chitosan is encapsulated in the photonic crystal microspheres, the microspheres can provide a larger specific surface area, and the photonic crystals can generate a photon forbidden band effect, so that the fluorescence signal effect of chitosan for detecting chromium is enhanced, and the chitosan photonic crystal microspheres have high sensitivity for detecting hexavalent chromium ions.
Description
Technical Field
The invention relates to the technical field of detection methods, in particular to a chitosan photonic crystal microsphere for detecting hexavalent chromium ions and a preparation method thereof.
Background
Chromium is one of the heavy metals, which is present in the aqueous environment in the form of trivalent and hexavalent chromium. Hexavalent chromium has nephrotoxicity and carcinogenic effects and can cause acute or chronic kidney injury, while trivalent chromium is considered harmless. Therefore, the detection of hexavalent chromium ions in water environments is a very important means for preventing the occurrence of kidney diseases. At present, methods for detecting hexavalent chromium include atomic absorption spectrometry, ion chromatography, electrochemical analysis, inductively coupled plasma mass spectrometry, chemiluminescence, and the like. Although these methods are sensitive, they are complicated in steps, high in cost, bulky in detection instrument, and slow in detection speed. The existing research shows that the fluorescent probe not only has high sensitivity and high selectivity, but also is simple to operate and can be used for in-situ monitoring of chromium. However, most of the fluorescent probes in the prior art are complex in synthesis method, and the detection of hexavalent chromium ions is less. Therefore, a product which is simple in preparation method, strong in sensitivity and high in selectivity and is applied to detecting hexavalent chromium ions needs to be developed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of chitosan photonic crystal microspheres, which comprises the step of chemically crosslinking chitosan and glutaraldehyde in gaps in silicon dioxide photonic crystal microspheres to prepare the chitosan photonic crystal microspheres with chitosan filled inside.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of chitosan photonic crystal microspheres, which is characterized by comprising the following steps:
s1, preparing silicon dioxide photonic crystal microspheres by emulsifying, drying, cleaning and calcining silicon dioxide nano particles;
s2, soaking the silica photonic crystal microspheres in a chitosan hydrogel solution, adding glutaraldehyde, performing chemical crosslinking and curing on chitosan and glutaraldehyde in gaps in the silica photonic crystal microspheres, and peeling to obtain the chitosan photonic crystal microspheres with chitosan filled inside.
Preferably, in step S1, the specific method of emulsification is: the silicon dioxide nano-particles are configured into a silicon dioxide nano-particle aqueous solution, the silicon dioxide nano-particle aqueous solution is used as an internal phase solution, the dimethyl silicone oil is used as an external phase solution, and then a micro-fluidic device is used for preparing the silicon dioxide nano-particle emulsion drop.
More preferably, the flow rates of the inner phase solution and the outer phase solution in the respective channels of the microfluidic device are 2mL/h and 6mL/h, respectively.
Preferably, in the step S1, the drying is carried out for 8 to 10 hours at a temperature of between 60 and 70 ℃ and then for 2 to 3 hours at a temperature of between 80 and 90 ℃.
Preferably, in step S1, the calcination is performed by first raising the temperature from room temperature to 800-900 ℃ for 3-4 hours and continuing calcination for 4-5 hours, and then lowering the temperature from 800-900 ℃ to room temperature for 3-4 hours.
Preferably, the particle size of the silica photonic crystal microsphere is 150-300 μm.
Preferably, in step S2, the concentration of the chitosan hydrogel solution is 1% to 6% (w/v).
Preferably, in the step S2, the concentration of the glutaraldehyde solution is 1-10% (w/v), and the mass ratio of the glutaraldehyde to the chitosan is (0.05-1): 1.
Preferably, in step S2, the soaking time is 10min to 3h.
The invention also provides application of the chitosan photonic crystal microsphere prepared by the preparation method in detection of hexavalent chromium ions.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of chitosan photonic crystal microspheres, which comprises the steps of firstly preparing photonic crystal microspheres by emulsifying, drying and calcining silicon dioxide nanoparticles, then soaking the photonic crystal microspheres in a chitosan hydrogel solution, adding glutaraldehyde after fully soaking, carrying out chemical crosslinking curing on chitosan and glutaraldehyde in gaps in the silicon dioxide photonic crystal microspheres, and stripping to obtain the chitosan photonic crystal microspheres with chitosan filled inside. According to the invention, chitosan is filled in the photonic crystal microspheres, the preparation method is simple and convenient, and the porous structure in the microspheres can provide a larger specific surface area, so that the filled chitosan has more sensitive detection; in addition, the photonic crystal can generate a photon forbidden band effect and can enhance the acquisition of a fluorescence signal, so that the fluorescence signal effect of the chitosan for detecting the hexavalent chromium ions is enhanced, and the chitosan photonic crystal microsphere has high sensitivity for detecting the hexavalent chromium ions.
Drawings
FIG. 1 is a schematic diagram of a synthetic route of a chitosan photonic crystal microsphere;
FIG. 2 is a scanning electron micrograph of the silica photonic crystal microspheres of example 1;
FIG. 3 is a scanning electron micrograph of the chitosan photonic crystal microspheres of example 1;
FIG. 4 is a fluorescence quenching graph of silica photonic crystal microspheres of example 1 in solutions of chromium ions of different concentrations;
FIG. 5 is a fluorescence quenching diagram of the silica photonic crystal microspheres of example 1 in different metal ion solutions.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, and is not intended to limit the present invention. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 preparation of Chitosan Photonic Crystal microspheres for detecting hexavalent chromium ions
The process for preparing the chitosan photonic crystal microspheres is shown in figure 1, and the specific steps are as follows:
(1) And (3) synthesis of the silica photonic crystal microspheres:
20 percent (w/v) of silicon dioxide nanoparticle aqueous solution is filled into an injector to be used as inner phase solution, the injector filled with dimethyl silicone oil (500 cs) is used as outer phase solution, two injectors are fixed on a micro-flow pump (LSP 01-1A, baoding Lange constant flow pump company Limited), the inner phase solution and the outer phase solution are respectively led into an inner phase pipe orifice and an outer phase pipe orifice of a PE capillary micro-flow control device through the micro-flow pump, the micro-flow control device is used for controlling the flow rate (the inner phase solution is 2mL/h, and the outer phase solution is 6 mL/h), and micro-droplets with uniform size, namely silicon dioxide nanoparticle emulsion droplets, are obtained at the convergence part of two phase outlets.
The collected silica nanoparticle emulsion droplets were placed in a 65 ℃ oven overnight (16 h), the next day the temperature was adjusted to 85 ℃ and held for 2h to ensure complete evaporation of water. And repeatedly cleaning with normal hexane to remove the excessive dimethyl silicone oil on the emulsion droplets, collecting the emulsion droplets in a crucible, and cleaning for five times to ensure that no residual silicone oil exists. And finally, transferring the cleaned emulsion droplets to a muffle furnace for calcination, heating to 800 ℃ from 30 ℃ for 3h, continuously calcining for 4h, cooling to 30 ℃ from 800 ℃ for 3h, and finally obtaining the firm silicon dioxide photonic crystal microspheres after calcination.
The result of the analysis of the silicon dioxide photonic crystal microsphere by a scanning electron microscope is shown in fig. 2, the microsphere is formed by self-assembling a plurality of nano particles with uniform sizes, the stacking morphology is a microsphere with the particle size of 250 μm, three-dimensionally intercommunicated nano network gaps are formed on the surface and inside, and the porous structure can provide a larger specific surface area.
(2) Preparing the chitosan photonic crystal microspheres:
2g of chitosan was dissolved in 100ml of 2% (v/v) glacial acetic acid solution and stirred overnight to prepare a homogeneous chitosan hydrogel solution. Then dividing the prepared silicon dioxide photonic crystal microspheres into a plurality of groups, wherein each group comprises 10 microspheres, adding each group of microspheres into a 200 mu L tube, adding 50 mu L of 2% (w/v) chitosan hydrogel solution into the tube, soaking for 2h, then adding 10 mu L of 5% (w/v) glutaraldehyde aqueous solution, uniformly vibrating, standing for 10min to ensure that the chitosan and the glutaraldehyde are chemically crosslinked and cured in gaps in the silicon dioxide photonic crystal microspheres, soaking the obtained hydrogel microspheres in water, and peeling off residual hydrogel on the surface by using tweezers to obtain the chitosan photonic crystal microspheres.
Scanning electron microscope analysis is carried out on the chitosan photonic crystal microspheres, and the result is shown in figure 3, and the holes of the microspheres are filled with chitosan potting adhesive.
Example 2 preparation of Chitosan photonic crystal microspheres for detecting hexavalent chromium ions
The preparation method is the same as example 1, except that the chitosan hydrogel solution in step (2) is adjusted from 2% to 3% to prepare the chitosan photonic crystal microspheres.
Example 3 preparation of Chitosan photonic crystal microspheres for detecting hexavalent chromium ions
The preparation method is the same as example 1, except that the chitosan hydrogel solution in step (2) is adjusted from 2% to 4% to prepare the chitosan photonic crystal microspheres.
Example 1 characterization of the Properties of Chitosan Photonic Crystal microspheres for the detection of hexavalent chromium ions
1. Characterization of sensitivity of chitosan photonic crystal microspheres to hexavalent chromium ions
Preparing 100 mu L of hexavalent chromium ion solution to be tested with different concentrations (0 mu M, 1 mu M, 3 mu M, 5 mu M, 10 mu M, 20 mu M, 30 mu M, 50 mu M, 100 mu M, 300 mu M, 1000 mu M, 3000 mu M and 10000 mu M), and recording the fluorescence intensity before reaction as F 0 Adding hexavalent chromium ion solutions to be tested with different concentrations into 13 tubes with 200 μ L, adding 10 chitosan photonic crystal microspheres of example 1, recording the fluorescence intensity after 1min of reaction as F, calculating the fluorescence quenching efficiency before and after the reaction, wherein the Fluorescence Quenching Efficiency (FQE) can be FQE = (F) 0 -F)/F 0 And calculating by using a formula.
The fluorescence quenching efficiency of the chitosan photonic crystal microspheres to chromium ion solutions with different concentrations is shown in fig. 4, the chitosan photonic crystal microspheres have an obvious fluorescence quenching effect on hexavalent chromium ion solutions, and the quenching degree gradually increases and is regularly changed along with the increase of the concentration of the hexavalent chromium ions. When the concentration reaches more than 100 mu M, the fluorescence quenching rate reaches more than 70 percent.
The fluorescence quenching efficiency of the chitosan photonic crystal microspheres in examples 2 and 3 is tested by adopting the method, and the chitosan concentration in example 3 is high, and the quenching effect is better.
2. Selective identification and characterization of chitosan photonic crystal microspheres on hexavalent chromium ions
100 μ L of different ions (Zn) were formulated 2+ 、Ce 3+ 、Hg 2+ 、PO3 4 -、Co 2+ 、Pb 2+ 、Mg 2+ 、Cr 3+ 、Co 2+ 、Fe 3+ 、Mn 2+ 、Ca 2+ 、NO- 2 、Cu 2+ 、Cd 2+ 、AL 3+ ) Recording the fluorescence intensity of the solution to be tested before reaction as F 0 Respectively adding different ion solutions to be tested with the concentration of 1mM into 16 tubes with the volume of 200 mu L, respectively adding 10 chitosan photonic crystal microspheres of example 1, recording the fluorescence intensity after 1min of reaction as F, and calculating the fluorescence intensity ratio F/F before and after the reaction 0 。
The fluorescence quenching efficiency of the chitosan photonic crystal microspheres to different ion solutions is shown in fig. 5, the fluorescence quenching efficiency of most ions is equal to 1, the chitosan photonic crystal microspheres cannot quench most ion solutions, and the chitosan photonic crystal microspheres are proved to quench hexavalent chromium ion solutions through characterization 1, which indicates that the chitosan photonic crystal microspheres have strong selectivity when being applied to detection of hexavalent chromium ions.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principles and spirit of the invention, and these embodiments are still within the scope of the invention.
Claims (9)
1. A preparation method of chitosan photonic crystal microspheres is characterized by comprising the following steps:
s1, preparing silicon dioxide photonic crystal microspheres by emulsifying, drying, cleaning and calcining silicon dioxide nano particles;
and S2, fully soaking the silica photonic crystal microspheres in a chitosan hydrogel solution, adding glutaraldehyde, performing chemical crosslinking and curing on chitosan and glutaraldehyde in gaps in the silica photonic crystal microspheres, and stripping to obtain the chitosan photonic crystal microspheres with chitosan filled inside.
2. The preparation method of the chitosan photonic crystal microspheres of claim 1, wherein in the step S1, the specific method of emulsification is as follows: the method comprises the steps of configuring silicon dioxide nanoparticles into a silicon dioxide nanoparticle aqueous solution, taking the silicon dioxide nanoparticle aqueous solution as an internal phase solution, taking dimethyl silicone oil as an external phase solution, and preparing silicon dioxide nanoparticle emulsion drops by using a microfluidic device.
3. The preparation method of the chitosan photonic crystal microspheres of claim 1, wherein in the step S1, the drying is performed by drying at 60-70 ℃ for 12-18 h, and then drying at 80-90 ℃ for 2-3 h.
4. The preparation method of the chitosan photonic crystal microspheres of claim 1, wherein in the step S1, the calcination is performed by heating from room temperature to 800-900 ℃ for 3-4 hours, continuously calcining for 4-5 hours, and then cooling from 800-900 ℃ to room temperature for 3-4 hours.
5. The method for preparing the chitosan photonic crystal microspheres according to claim 1, wherein the particle size of the silica photonic crystal microspheres is 150-300 μm.
6. The method for preparing the chitosan photonic crystal microspheres of claim 1, wherein in the step S2, the concentration of the chitosan hydrogel solution is 1-6% (w/v).
7. The preparation method of the chitosan photonic crystal microspheres of claim 1, wherein the concentration of the glutaraldehyde solution in step S3 is 1-10% (w/v), and the mass ratio of glutaraldehyde to chitosan is (0.05-1): 1.
8. The preparation method of the chitosan photonic crystal microsphere of claim 1, wherein in the step S2, the soaking time is 10min to 3h.
9. The chitosan photonic crystal microsphere prepared by the preparation method of any one of claims 1 to 8 is applied to the detection of hexavalent chromium ions.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102380335A (en) * | 2011-09-15 | 2012-03-21 | 东南大学 | Core-shell hydrogel colloid crystal microballoon, its preparation method and its purpose |
CN104437395A (en) * | 2014-11-03 | 2015-03-25 | 中国科学院过程工程研究所 | Acid-resistant magnetic chitosan microspheres as well as preparation method and application thereof |
CN106040114A (en) * | 2016-05-24 | 2016-10-26 | 华中科技大学 | Hydrogel photonic crystal microspheres, and preparation method and application thereof |
CN110550636A (en) * | 2019-09-03 | 2019-12-10 | 陕西科技大学 | preparation method of chitosan packaged photonic crystal |
CN112107547A (en) * | 2020-10-16 | 2020-12-22 | 温州医科大学附属第二医院(温州医科大学附属育英儿童医院) | Hydrogel microsphere with photo-thermal responsiveness and preparation method and application thereof |
CN112220759A (en) * | 2020-10-16 | 2021-01-15 | 温州医科大学附属第二医院(温州医科大学附属育英儿童医院) | Preparation of antibacterial hydrogel drug-loaded microspheres and application of antibacterial hydrogel drug-loaded microspheres in cell amplification |
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- 2022-12-07 CN CN202211560610.8A patent/CN115845811B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102380335A (en) * | 2011-09-15 | 2012-03-21 | 东南大学 | Core-shell hydrogel colloid crystal microballoon, its preparation method and its purpose |
CN104437395A (en) * | 2014-11-03 | 2015-03-25 | 中国科学院过程工程研究所 | Acid-resistant magnetic chitosan microspheres as well as preparation method and application thereof |
CN106040114A (en) * | 2016-05-24 | 2016-10-26 | 华中科技大学 | Hydrogel photonic crystal microspheres, and preparation method and application thereof |
CN110550636A (en) * | 2019-09-03 | 2019-12-10 | 陕西科技大学 | preparation method of chitosan packaged photonic crystal |
CN112107547A (en) * | 2020-10-16 | 2020-12-22 | 温州医科大学附属第二医院(温州医科大学附属育英儿童医院) | Hydrogel microsphere with photo-thermal responsiveness and preparation method and application thereof |
CN112220759A (en) * | 2020-10-16 | 2021-01-15 | 温州医科大学附属第二医院(温州医科大学附属育英儿童医院) | Preparation of antibacterial hydrogel drug-loaded microspheres and application of antibacterial hydrogel drug-loaded microspheres in cell amplification |
Non-Patent Citations (1)
Title |
---|
CHEN DH等: ""Speciation of chromium in environmental water samples using chitosan-modified ordered mesoporous silica as solid phase extraction material and determination by inductively coupled plasma optical emission spectrometry"", ATOMIC SPECTROSCOPY, vol. 29, no. 5, pages 165 - 171 * |
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