CN116448742A - Nanometer sensing paper for visually detecting sulfite as well as preparation method and application thereof - Google Patents
Nanometer sensing paper for visually detecting sulfite as well as preparation method and application thereof Download PDFInfo
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- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 235000013305 food Nutrition 0.000 claims abstract description 11
- 238000007641 inkjet printing Methods 0.000 claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 239000000523 sample Substances 0.000 claims description 46
- 238000001514 detection method Methods 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 15
- 230000000007 visual effect Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007853 buffer solution Substances 0.000 claims description 12
- 239000012086 standard solution Substances 0.000 claims description 12
- 238000007639 printing Methods 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000012488 sample solution Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910020820 NaAc-HAc Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 102000004316 Oxidoreductases Human genes 0.000 claims description 3
- 108090000854 Oxidoreductases Proteins 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000003278 mimic effect Effects 0.000 claims 1
- 239000002778 food additive Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 235000013373 food additive Nutrition 0.000 abstract description 2
- 239000005452 food preservative Substances 0.000 abstract 1
- 235000019249 food preservative Nutrition 0.000 abstract 1
- 235000013405 beer Nutrition 0.000 description 12
- 235000014101 wine Nutrition 0.000 description 9
- 235000021055 solid food Nutrition 0.000 description 8
- 235000013399 edible fruits Nutrition 0.000 description 6
- 239000007850 fluorescent dye Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 238000005375 photometry Methods 0.000 description 3
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- NWWWHCCHHJQISH-UHFFFAOYSA-N 2h-chromene-2-carbonitrile Chemical compound C1=CC=C2C=CC(C#N)OC2=C1 NWWWHCCHHJQISH-UHFFFAOYSA-N 0.000 description 1
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000006499 Flammulina velutipes Species 0.000 description 1
- 235000016640 Flammulina velutipes Nutrition 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- WIKZKBCBKLFMSZ-UHFFFAOYSA-N chromen-2-one;quinoline Chemical compound N1=CC=CC2=CC=CC=C21.C1=CC=C2OC(=O)C=CC2=C1 WIKZKBCBKLFMSZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000011869 dried fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001006 microwave--polyol method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/04—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and forming images of the material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
Abstract
The invention discloses nano sensing paper for quickly and visually detecting sulfite of a food additive and a preparation method thereof. The manufacturing method of the nano sensing paper comprises the following steps: configuration of cobalt ferrite nanoparticles (CoFe) 2 O 4 NPs); coFe using nanomaterial inkjet printing technique 2 O 4 NPs are deposited onto the surface of a paper substrate and CoFe is immobilized with a silylating agent 2 O 4 NCs is the nano sensing paper. The method for detecting the food preservative sulfite by using the nano sensing paper comprises the following steps of: and manufacturing a standard colorimetric card of the sulfite, and detecting the sulfite in the sample to be detected according to the standard colorimetric card. The invention providesThe provided nano sensing paper has the characteristics of simple preparation, low cost, high response speed, high sensitivity and selectivity, can visually detect the sulfite in the food sample, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of nanotechnology and analysis and detection, and particularly relates to nano sensing paper for visually detecting sulfite as well as a preparation method and application thereof.
Background
Sulfite is a widely used food additive, and can be used as bleaching agent, preservative, color retention agent and bulking agent for preserving and preserving preserved fruits, dried fruits, biscuits, cans, sausage, wines and the like. However, long-term ingestion of excessive sulfite by human body can affect the growth and development of human body, and can induce the occurrence of diseases such as asthma and anaphylactic reaction, and the limit standard of sulfite is definitely regulated in GB/T2760-2014 national food safety Standard-food additive use Standard, so that the sulfite detection technology which has rapid and simple development, low cost, sensitivity and strong selectivity has important significance in the food safety field.
Sulfite is an oxyacid salt contained in the structureThe acid radical ion is Sulfite (SO) 3 2- ) The sulfite detection is actually that of sulfite ions (SO 3 2- ) And (5) detecting. The traditional sulfite ion detection methods comprise pararosaniline hydrochloride photometry, distillation method, iodometry, chromatography and the like, and most of the methods need expensive equipment, complex experimental operation and long-time analysis, so that the real-time monitoring requirement on a target object cannot be met. In recent years researchers have developed rapid detection of SO using fluorescent probe technology 3 2- Is designed and synthesized by a new method such as Zhu Sasa and the like based on the coumarin quinoline 3 2- Ratio fluorescent probe (Zhu Sasa, new SO) 3 2- /N 2 H 4 /F - Synthesis of fluorescent Probe and study of spectral Property [ D ]]The university of Hunan, 2013, sheffian et al also designed and synthesized a benzopyran nitrile-based SO 3 2- Fluorescent probe (ZL 201710413814.1). Although the fluorescent probes have the advantages of high sensitivity, good selectivity, rapid detection and the like, the fluorescent probes have complex preparation process, certain toxicity and are used for detecting SO 3 2- In the process of the emergency food safety event, professional instruments and equipment and professional experimental analysts are still required, and the actual requirement of the emergency food safety event on-site rapid detection cannot be met.
In view of the technical background, the invention provides the nano sensing paper for visually detecting the sulfite and the preparation method thereof, and the nano sensing paper is utilized to realize simple, rapid and visual detection of the sulfite in food samples and wine samples, so that the actual requirements of real-time monitoring in the food safety field can be met.
Disclosure of Invention
The invention aims to provide a nano sensing paper for visually detecting sulfite, which consists of 0.5-2% of cobalt ferrite nano particles (CoFe 2 O 4 NPs), filter paper and 3% -10% of 3-aminopropyl triethoxysilane.
Preferably, the cobalt ferrite nanoparticle (CoFe 2 O 4 NPs) is smaller than220nm, has good monodispersity in water phase and has excellent catalytic activity of the simulated oxidase.
The second object of the present invention is to provide a method for preparing the nano sensing paper for visually detecting sulfite, which comprises the following steps:
(1) Cobalt ferrite nanoparticle (CoFe) 2 O 4 NPs) are ultrasonically dispersed into a mixed solution of water and ethanol to form CoFe 2 O 4 NPs colloidal solution;
(2) CoFe obtained in the step (1) 2 O 4 NPs colloid solution is ink, printing liquid drop parameters are debugged, and a plurality of 1.5x4cm printing systems are utilized to print on round Whatman No.1 filter paper 2 Naturally placing, and cutting the round filter paper into a plurality of 1.5X4cm pieces after the ink dries 2 Rectangular paper strips;
(3) And (3) immersing the rectangular paper strip obtained in the step (2) into a 3-aminopropyl triethoxysilane (APTS) aqueous solution, immersing, and drying at 80 ℃ to obtain the nano sensing paper.
Preferably, the volume ratio of water to ethanol in the water and ethanol mixed solution in the step (1) is 1:1 to 1:3, a step of; coFe 2 O 4 The mass fraction of the NPs colloid solution is 0.5% -2%.
Preferably, in the process of printing the nano sensing paper by using the nano material ink-jet printing system in the step (2), the driving voltage is +/-20 v- +/-50 v, and the droplet size is 40-60 μm.
The third object of the invention is to provide a method for visually detecting sulfite by using the nano sensing paper, which comprises the following steps:
(1) Preparation of detection Sulfite (SO) 3 2- ) Standard color chart of (2)
Preparing SO with different concentrations 3 2- Standard solution, the nano sensing paper of claim 1 or 2 is fixed on a rectangular black card with the length of 6cm multiplied by 20cm, and the standard solution is prepared according to SO 3 2- The standard solution concentration is from small to large, and 100 mu L SO is added on the nanometer sensing paper in sequence 3 2- Standard solution, 100. Mu.L of 3,3',after the reaction of 5,5' -tetramethyl benzidine ethanol solution and 300 mu L of 0.2mol/LNaAc-HAc buffer solution for 5 minutes, the tan nano sensing paper strips can be visually changed into blue with different depths, after natural airing, the chromaticity value of the nano sensing paper is measured by a colorimeter, and sulfite (SO 3 2- ) Standard color chart of (c);
(2) Detection of Sulfite (SO) in sample to be tested 3 2- ) Concentration of (2)
And (3) simultaneously dripping 100 mu L of the sample solution to be detected, 100 mu L of the 3,3', 5' -tetramethyl benzidine ethanol solution and 300 mu L of the 0.2mol/LNaAc-HAc buffer solution on the blank nano sensing paper, reacting for 5 minutes to find that the tan nano sensing paper strip turns blue, and comparing with the sulfite standard color chart manufactured in the step (1) after naturally airing to obtain the semi-quantitative concentration of the sulfite in the sample to be detected.
Preferably, the concentration of the 3,3', 5' -tetramethyl benzidine ethanol solution in the step (1) is 24-36 mmol/L, and the pH value of the NaAc-HAc buffer solution is 4.0-5.8.
Preferably, the method detects SO 3 2- The concentration range of (C) is 0-15.0 mmol/L, and the detection limit is 0.1mmol/L.
The fourth object of the invention is to provide the application of the nano sensing paper in visual detection of sulfite in solid food.
The fifth object of the invention is to provide the application of the nano sensing paper in visual detection of sulfite in wine samples.
The beneficial effects of the invention are as follows:
(1) The nano sensing paper provided by the invention has the advantages of simple composition, stable performance, low cost, simple and convenient manufacturing method, easiness in realizing batch production and convenience in popularization.
(2) Compared with the existing sulfite detection method, the nano sensing paper provided by the invention does not need to use a large instrument, can accurately and rapidly carry out semi-quantitative detection on the sulfite, can rapidly distinguish whether the sulfite in an actual sample exceeds the standard by visually detecting the color change of the nano sensing paper, has the characteristics of simple operation, low detection cost and portability, is very suitable for the actual requirement of on-site rapid detection in the food safety field, and has good application prospect.
(3) The invention provides a visual and colorimetric detection SO of nano sensing paper 3 2- The concentration range of (C) is 0-15.0 mmol/L, and the detection limit is 0.1mmol/L.
Drawings
FIG. 1 example 1 cobalt ferrite nanoparticle (CoFe 2 O 4 NPs) transmission electron microscopy images
FIG. 2 example 1 cobalt ferrite nanoparticle (CoFe 2 O 4 NPs) XRD pattern
FIG. 3 photo of nanosensory paper made in example 1 and example 4
FIG. 4 example 4 cobalt ferrite nanoparticle (CoFe 2 O 4 NPs) transmission electron microscopy images
FIG. 5 Sulfite (SO) produced in example 5 3 2- ) Standard color chart of (2)
FIG. 6 detection of Sulfite (SO) by nanosensory paper 3 2- ) Schematic of the principle of (a)
FIG. 7 colorimetric photograph of the visual detection of sulfite in alcoholic samples with nanosensory paper of example 6
Note that: a is a beer sample, b is a sample obtained by adding a standard sulfite solution into the beer sample
FIG. 8 example 7 colorimetric photograph of a nanosensory paper for visual detection of sulfite in a solid state food sample
Detailed Description
The invention is further described in connection with the following detailed description, in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand. The following examples are given solely for the purpose of illustration and not limitation, and although the invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that variations and equivalents may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1 preparation method of nanosensory paper for visually detecting sulfite
(1) Preparing cobalt ferrite nano particles (CoFe) with mass fraction of 1% 2 O 4 NPs) colloidal solution: 10mg of cobalt ferrite nanocluster with the average particle size of 30nm prepared by a microwave polyol method is taken, and 10mL of cobalt ferrite nanocluster with the volume ratio of 1:2, and ultrasonically dispersing until the solution is brown transparent.
(2) Printing nano sensing paper: the cobalt ferrite nanoparticle (CoFe) of the step (1) 2 O 4 NPs) colloid solution is ink, the printing liquid drop parameters are adjusted, the driving working voltage is controlled to be between-40V and 20V, the liquid drop size is about 43 mu m, and 6 pieces of 1.5x4cm are printed on Whatman No.1 filter paper by utilizing a nano material ink-jet printing system 2 Naturally placing the nano-ink, and cutting the round filter paper into 6 rectangular paper strips after the nano-ink is dried;
(3) Fixing nano sensing paper: immersing the rectangular paper strip manufactured in the step (2) into a 3-aminopropyl triethoxysilane (APTS) aqueous solution with the mass fraction of 5%, immersing for 10 minutes, and drying at 80 ℃ to obtain 6 pieces of nano sensing paper.
Cobalt ferrite nanoparticle (CoFe) used in example 1 2 O 4 NPs) and X-ray diffraction (XRD) patterns, as shown in fig. 1 and 2. As can be seen from fig. 1, cobalt ferrite nanoparticles (CoFe 2 O 4 NPs) is made of CoFe 2 O 4 The small nanocrystalline is self-assembled to form loose cluster spherical particles, the average particle diameter is about 30nm, and the monodispersity is good. The diffraction peak position of the spinel structure is matched with the diffraction peak of the standard spectrum (JCPDS 22-1086) as can be seen from FIG. 2.
FIG. 3 is a nano-sensing paper made in example 1, as can be seen from FIG. 3, under this condition CoFe 2 O 4 NPs are uniformly deposited on the surface of paper substrate, and APTS can well deposit CoFe 2 O 4 NPs are stable on paper substrates.
Since the nanosensory paper prepared in example 1 shows good performance, the inventors changed the concentration of raw materials and printing parameters on the basis of example 1, and further observed the performance of the nanosensory paper prepared, and obtained the following examples:
example 2 preparation method 2 of nanosensory paper for visually detecting sulfite
The steps for preparing the nano sensing paper for visually detecting sulfite according to the embodiment are the same as those of the embodiment 1, and the difference is that: the volume ratio of water to ethanol in the water and ethanol mixed solution is 1:3, a step of; coFe 2 O 4 The mass fraction of the NPs colloid solution is 2%; the mass fraction of the aqueous solution of 3-aminopropyl triethoxysilane (APTS) is 10%.
Example 3 preparation method 3 of nanosensory paper for visually detecting sulfite
The steps for preparing the nano sensing paper for visually detecting sulfite according to the embodiment are the same as those of the embodiment 1, and the difference is that: the volume ratio of water to ethanol in the water and ethanol mixed solution is 1:1, a step of; coFe 2 O 4 The mass fraction of the NPs colloid solution is 0.5%; the mass fraction of the aqueous solution of 3-aminopropyl triethoxysilane (APTS) is 3%.
Example 4 preparation method 4 of nanosensory paper for visually detecting sulfite
The steps for preparing the nano sensing paper for visually detecting sulfite according to the embodiment are the same as those of the embodiment 1, and the difference is that: cobalt ferrite nanoparticles (CoFe 2 O 4 NPs) with an average particle diameter of 200nm, and the transmission electron microscope characterization of the NPs is shown in fig. 4, and it can be seen from fig. 4 that the microscopic morphology of the cobalt ferrite nano-particles is also loose cluster spherical particles and is monodisperse; the volume ratio of water to ethanol in the water and ethanol mixed solution is 1:2; coFe 2 O 4 The mass fraction of the NPs colloidal solution is 1%; in the process of printing the nano sensing paper by utilizing the nano material ink-jet printing system, the driving working voltage is controlled to be-25V-50V, and the droplet size is about 60 mu m; the mass fraction of the aqueous solution of 3-aminopropyl triethoxysilane (APTS) is 5%.
Example 5 application of nanosensory paper in visual detection of sulfite
The application of the nano sensing paper prepared in the embodiment 1 in the visual detection of sulfite comprises the following steps:
(1) Preparation of detection Sulfite (SO) 3 2- ) Standard color chart of (2)
Firstly, SO with the concentration of 0mmol/L, 0.2mmol/L, 0.6mmol/L, 1.8mmol/L, 3.6mmol/L, 7.2mmol/L and 15.0mmol/L is prepared 3 2- A standard solution; then 7 pieces of the nano sensing paper prepared in the embodiment 1 are sequentially fixed on rectangular black cards with the length of 6cm multiplied by 20 cm; then 100 mu L of 36mmol/LTMB ethanol solution and 300 mu L of 0.2mol/L NaAc-HAc buffer solution are dripped into the 1 st nano-sensing paper, and the rest 6 nano-sensing papers are dripped into the 1 st nano-sensing paper according to SO 3 2- The standard solution concentration is from small to large, respectively and simultaneously dripping 100 mu LSO 3 2- After the reaction of the standard solution, 100 mu LTMB ethanol solution and 300 mu L of 0.2mol/LNaAc-HAc buffer solution for 5 minutes, the tan nano sensing paper strips can be visually changed into blue with different depths, after the natural airing, the chromaticity value of the nano sensing paper is measured by a colorimeter, and finally Sulfite (SO) is simulated in software by using the chromaticity value 3 2- ) Standard color chart of (c).
(2) Detection of Sulfite (SO) in sample to be tested 3 2- ) Concentration of (2)
Taking 100 mu L of sulfite sample with unknown concentration, simultaneously dripping 100 mu L of 36mmol/LTMB ethanol solution and 300 mu L of 0.2mol/L NaAc-HAc buffer solution on the blank sensing paper prepared in the embodiment 1, reacting for 5 minutes, changing the tan nano sensing paper strip into blue, naturally airing, and contrasting the sulfite (SO 3 2- ) The semi-quantitative concentration of sulfite in the sample to be detected can be obtained by the standard colorimetric card.
FIG. 5 shows the Sulfite (SO) produced in example 5 3 2- ) According to the standard colorimetric card of (2), the graph shows that SO with different concentrations is added dropwise 3 2- When the standard solution (0 mmol/L, 0.2mmol/L, 0.6mmol/L, 1.8mmol/L, 3.6mmol/L, 7.2mmol/L and 15.0 mmol/L) is used, the nano sensing paper has obvious color change and changes into blue with different shades until the color is faded, SO the SO can be changed by visual sensing paper color change 3 2- Concentration ofSemi-quantitative detection is performed.
FIG. 6 is a schematic diagram of the visual detection of sulfite by the nano-sensing paper prepared by the invention, due to cobalt ferrite nano-particles (CoFe 2 O 4 NPs) have the property of simulating oxidase and can efficiently catalyze enzyme substrates, namely 3,3', 5' -tetramethyl benzidine (TMB) and dissolved oxygen (O) 2 ) The color reaction occurs, which causes the nano-sensing paper to change from tan to deep blue, but when sulfite is contained in the sample to be measured, sulfite ions (SO 3 2- ) Can consume the dissolved oxygen in the solution to reduce TMB oxidation products, reduce the color change of the nano sensing paper to cause SO 3 2- The larger the concentration is, the smaller the color change of the nano sensing paper is, so that the sulfite concentration can be quickly and visually detected through the color response of the nano sensing paper to the sample to be detected.
Example 7 application of nanosensory paper in visual detection of sulfite in wine samples
The application of the nano sensing paper prepared in the embodiment 1 to visually detect sulfite in an alcoholic sample comprises the following steps:
(1) Preparing a beer sample solution: the purchased wine was filtered through a 0.45 μm filter, and the filtrate was collected and diluted 1-fold with 0.1mmol/LEDTA solution for use.
(2) Taking 100 mu L of beer sample solution, 100 mu L of 36mmol/LTMB ethanol solution and 300 mu L of 0.2mol/LNaAc-HAc buffer solution, simultaneously dripping the beer sample solution, the buffer solution onto the blank sensing paper prepared in the example 1, reacting for 5 minutes to see that the nano sensing paper has color response to a sample to be detected, naturally airing, and comparing with sulfite (SO 3 2- ) The semi-quantitative concentration of sulfite in the wine to be measured can be obtained by the standard color chart.
In this example, colorimetric detection was performed on a beer sample (sample a) and a sample obtained by adding a standard sulfite solution to the beer sample (sample b) using a nanosensory paper, and the color change of the sensor paper is shown in fig. 7.
In order to verify the reliability of the nano sensing paper for visually detecting the sulfite in the wine sample, the detection method of the sulfite in the national standard, namely the pararosaniline hydrochloride photometry, is adopted to accurately measure the beer sample and the beer sample obtained after the standard is added, and the detection result is shown in the table 1. The nano sensing paper can be found to be consistent with the measurement result of the national standard method by comparison, which shows that the nano sensing paper provided by the invention can be applied to semi-quantitative detection of wine samples.
National food safety standards-food additive usage standards (GB 2760-2014) specify a maximum usage limit of 1.6mmol/L (10.0 mg/kg) of sulfite in beer, when the sulfite in the actual sample exceeds the standard, the nano sensing paper has obvious color change, as shown in a sample b, so that the nano sensing paper provided by the invention can be used in the actual sample of the wine.
Table 1 comparison table of sulfite detection results in beer samples using national standard method and nano-sensing paper, respectively
In the table 1, sample a is a beer sample, and sample b is a sample obtained by adding a standard sulfite solution into sample a;
(2) the background value, the standard addition value and the detection value of the samples a and b in the table 1 are all detected by adopting a pararosaniline hydrochloride photometry.
Example 8 application of nanosensory paper in visual detection of sulfite in solid food sample
The method for visually detecting sulfite in solid food samples by using the nano sensing paper prepared in the embodiment 1 comprises the following steps:
(1) Preparing a solid food sample solution: crushing the purchased preserved fruits and flammulina velutipes, accurately weighing, putting into a beaker, adding 50mL of 0.1mmol/L EDTA solution, performing ultrasonic treatment for 30min, filtering the solution with a 0.45 mu m filter membrane, collecting filtrate, and storing in a refrigerator at 4 ℃ for later use.
(2) 100. Mu.L of solid food sample solution, 100. Mu.L of 36mmol/LTMB ethanol solution and 300. Mu.L of 0.2mol/LNaAc-HAc buffer solution were taken and simultaneously dropped on the blank sensor paper prepared in example 1 to react for 5 minutesThe nanometer sensing paper can be seen to have color response to the sample to be detected, and after the nanometer sensing paper is naturally dried, the nanometer sensing paper is controlled by sulfite (SO 3 2- ) The semi-quantitative concentration of the sulfite in the solid food sample to be detected can be obtained by the standard color chart.
In this example, colorimetric detection was performed on the preserved fruit sample (sample a) and the preserved fruit sample (sample b) respectively using a nano sensor paper, and the color change of the sensor paper is shown in fig. 7. In this example, colorimetric detection was performed on the preserved fruit sample (sample a) and the preserved fruit sample (sample b) respectively using a nano sensor paper, and the color change of the sensor paper is shown as 8 pictures. The graph shows that the sulfite in the solid food sample has obvious color change on the nano sensing paper, so that the nano sensing paper provided by the invention can be used for detecting the sulfite in the solid food sample.
Claims (10)
1. The nanometer sensing paper for visually detecting sulfite is characterized by comprising 0.5-2% of cobalt ferrite nanometer particles (CoFe 2 O 4 NPs), filter paper and 3% -10% of 3-aminopropyl triethoxysilane.
2. The nanosensory paper of claim 1, wherein the cobalt ferrite nanoparticle (CoFe 2 O 4 NPs) is less than 220nm, has good monodispersity in the water phase, and has excellent catalytic activity of the mimic oxidase.
3. The method for preparing the nano sensing paper for visually inspecting the sulfite as claimed in claim 1 or 2, comprising the following steps:
(1) Cobalt ferrite nanoparticle (CoFe) 2 O 4 NPs) are ultrasonically dispersed into a mixed solution of water and ethanol to form CoFe 2 O 4 NPs colloidal solution;
(2) CoFe obtained in the step (1) 2 O 4 NPs colloid solution is ink, printing liquid drop parameters are adjusted, and a nanomaterial ink-jet printing system is utilized to print on round Whatman No.1 filter paperPrinting a plurality of 1.5x4cm 2 Naturally placing, and cutting the round filter paper into a plurality of 1.5x4cm after the ink is dried 2 Rectangular paper strips;
(3) And (3) immersing the rectangular paper strip obtained in the step (2) into a 3-aminopropyl triethoxysilane (APTS) aqueous solution, immersing, and drying at 80 ℃ to obtain the nano sensing paper.
4. The method for preparing the nano sensing paper for visually inspecting the sulfite as claimed in claim 3, wherein the volume ratio of water to ethanol in the mixed solution of water and ethanol in the step (1) is 1:1 to 1:3, a step of; coFe 2 O 4 The mass fraction of the NPs colloid solution is 0.5% -2%.
5. The method for preparing the nano sensing paper for visually inspecting the sulfite as claimed in claim 3, wherein in the process of printing the nano sensing paper by using the nano material ink-jet printing system in the step (2), the driving voltage is +/-20 v- +/-50 v, and the droplet size is 40-60 μm.
6. The method for visually inspecting sulfite of nano sensing paper according to claim 1 or 2, comprising the steps of:
(1) Preparation of detection Sulfite (SO) 3 2- ) Standard color chart of (2)
Preparing SO with different concentrations 3 2- Standard solution, the nano sensing paper of claim 1 or 2 is fixed on a rectangular black card with the length of 6cm multiplied by 20cm, and the standard solution is prepared according to SO 3 2- The standard solution concentration is from small to large, and 100 mu LSO is added on the nanometer sensing paper in sequence 3 2- Standard solution, 100 mu L of 3,3', 5' -tetramethyl benzidine ethanol solution and 300 mu L of 0.2mol/LNaAc-HAc buffer solution, after 5 minutes, the tan nano sensing paper strip can be visually inspected to be changed into blue with different shades, after natural airing, the chromaticity value of the nano sensing paper is measured by a colorimeter, and Sulfite (SO) is simulated in software by using the chromaticity value 3 2- ) Standard colorimetric(s) of (2)A card;
(2) Detection of Sulfite (SO) in sample to be tested 3 2- ) Concentration of (2)
And (3) simultaneously dripping 100 mu L of sample solution to be detected, 100 mu L of 3,3', 5' -tetramethyl benzidine ethanol solution and 300 mu L of 0.2mol/LNaAc-HAc buffer solution on the blank nano sensing paper, reacting for 5 minutes to find that the tan nano sensing paper strip turns blue, and comparing with the sulfite standard color chart manufactured in the step (1) after naturally airing to obtain the semi-quantitative concentration of the sulfite in the sample to be detected.
7. The method for visually inspecting sulfite of nano sensing paper according to claim 6, wherein the concentration of 3,3', 5' -tetramethylbenzidine ethanol solution in the step (1) is 24-36 mmol/L, and the pH value of NaAc-HAc buffer solution is 4.0-5.8.
8. The method for visually inspecting sulfite on nano sensing paper according to claim 2, wherein the method detects SO 3 2- The concentration range of (C) is 0-15.0 mmol/L, and the detection limit is 0.1mmol/L.
9. Use of the nanosensory paper of claim 1 or 2 for visual detection of sulphite in solid state food.
10. Use of the nanosensory paper of claim 1 or 2 for visual detection of sulfite in an alcoholic sample.
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