CN117092085A - Preparation of flexible transparent patch type substrate film based on enhanced Raman spectrum technology and detection of pesticide residue - Google Patents
Preparation of flexible transparent patch type substrate film based on enhanced Raman spectrum technology and detection of pesticide residue Download PDFInfo
- Publication number
- CN117092085A CN117092085A CN202210506540.1A CN202210506540A CN117092085A CN 117092085 A CN117092085 A CN 117092085A CN 202210506540 A CN202210506540 A CN 202210506540A CN 117092085 A CN117092085 A CN 117092085A
- Authority
- CN
- China
- Prior art keywords
- film
- detection
- substrate film
- solution
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 54
- 238000001514 detection method Methods 0.000 title claims abstract description 47
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000001237 Raman spectrum Methods 0.000 title claims description 6
- 238000005516 engineering process Methods 0.000 title claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920001721 polyimide Polymers 0.000 claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 30
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 30
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 27
- 239000000523 sample Substances 0.000 claims abstract description 24
- 239000004642 Polyimide Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 239000000575 pesticide Substances 0.000 claims abstract description 12
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 17
- 239000002356 single layer Substances 0.000 claims description 16
- 238000001069 Raman spectroscopy Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 9
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 230000002708 enhancing effect Effects 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229920005575 poly(amic acid) Polymers 0.000 claims description 4
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 claims description 3
- 108010039627 Aprotinin Proteins 0.000 claims description 3
- 229960004405 aprotinin Drugs 0.000 claims description 3
- ZPNFWUPYTFPOJU-LPYSRVMUSA-N iniprol Chemical compound C([C@H]1C(=O)NCC(=O)NCC(=O)N[C@H]2CSSC[C@H]3C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@H](C(N[C@H](C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=4C=CC(O)=CC=4)C(=O)N[C@@H](CC=4C=CC=CC=4)C(=O)N[C@@H](CC=4C=CC(O)=CC=4)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C)C(=O)NCC(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CSSC[C@H](NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CCC(O)=O)NC(=O)[C@H](C)NC(=O)[C@H](CO)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CC=4C=CC=CC=4)NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](CCCCN)NC(=O)[C@H](C)NC(=O)[C@H](CCCNC(N)=N)NC2=O)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CSSC[C@H](NC(=O)[C@H](CC=2C=CC=CC=2)NC(=O)[C@H](CC(O)=O)NC(=O)[C@H]2N(CCC2)C(=O)[C@@H](N)CCCNC(N)=N)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(O)=O)C(=O)N2[C@@H](CCC2)C(=O)N2[C@@H](CCC2)C(=O)N[C@@H](CC=2C=CC(O)=CC=2)C(=O)N[C@@H]([C@@H](C)O)C(=O)NCC(=O)N2[C@@H](CCC2)C(=O)N3)C(=O)NCC(=O)NCC(=O)N[C@@H](C)C(O)=O)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@H](C(=O)N[C@@H](CC=2C=CC=CC=2)C(=O)N[C@H](C(=O)N1)C(C)C)[C@@H](C)O)[C@@H](C)CC)=O)[C@@H](C)CC)C1=CC=C(O)C=C1 ZPNFWUPYTFPOJU-LPYSRVMUSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 8
- 235000013399 edible fruits Nutrition 0.000 abstract description 6
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 5
- 235000021478 household food Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 44
- 239000010410 layer Substances 0.000 description 18
- 241000220225 Malus Species 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000007790 scraping Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 6
- PZBPKYOVPCNPJY-UHFFFAOYSA-N 1-[2-(allyloxy)-2-(2,4-dichlorophenyl)ethyl]imidazole Chemical compound ClC1=CC(Cl)=CC=C1C(OCC=C)CN1C=NC=C1 PZBPKYOVPCNPJY-UHFFFAOYSA-N 0.000 description 4
- UNZSJASIKFONPS-UHFFFAOYSA-N C(C)(=O)N(C)C.[N].[N] Chemical compound C(C)(=O)N(C)C.[N].[N] UNZSJASIKFONPS-UHFFFAOYSA-N 0.000 description 4
- 239000005795 Imazalil Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229960002125 enilconazole Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000021016 apples Nutrition 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- -1 silver ions Chemical class 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 208000017701 Endocrine disease Diseases 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 206010019629 Hepatic adenoma Diseases 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000021022 fresh fruits Nutrition 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100001224 moderate toxicity Toxicity 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004557 single molecule detection Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 235000013311 vegetables Nutrition 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to a preparation method of an enhanced substrate film for detecting pesticide residues on fruit surfaces, which is high in stability, can realize on-site timely detection and belongs to the field of food safety detection. The method comprises the following steps: 1. preparing a high-transparency flexible polyimide film; 2. preparing silver nitrate and sodium borohydride solution; 3. preparing a probe molecule solution; 4. preparing polyimide in-situ grown nano silver reinforced substrate film; 5. performing multipoint scanning to enhance the consistency of the substrate; 6. the common pesticides in fruits and vegetables are selected and dripped on the surfaces of apple peels, the prepared basement membrane is tightly attached to the apple peels, and the pesticide residue detection limit is detected, so that the accuracy of the prepared enhanced basement data can be determined, and whether trace pesticide residue detection can be realized or not can be determined. The invention is efficient and quick, has low preparation cost, realizes in-situ and in-time detection, and is widely applied to the field of household food safety detection.
Description
Technical Field
The invention discloses a preparation method of a flexible transparent and portable patch type enhanced substrate film, relates to the field of detection of pesticide residues in foods, and particularly relates to the field of detection of surface enhanced Raman spectrum of pesticide residues in fruits.
Background
The problem of pesticide residue has become one of the hot challenges in the food safety field. The development of agricultural industrialization depends on pesticides, antibiotics, hormones and other exogenous substances. However, improper use of pesticides can lead to pesticide residues in agricultural products exceeding standards, affecting human health, for example, affecting human metabolic functions, causing obesity and endocrine disorders, and severely causing toxic death. Therefore, the effective detection of pesticide residues in food has long-term significance for human development and health continuation.
Tricyclazole is a protective triazole fungicide with strong systemic property, which is widely applied to rice and fruits and vegetables. It has strong anti-scouring ability, very little effect on common washing, long residual period and moderate toxicity to human and livestock. Therefore, the related regulation is also made in GB 2763-2014 "maximum residual quantity of pesticides in food", and the maximum residual quantity of tricyclazole in food is 2mg/kg. Imazalil is a systemic bactericide, and merchants can use imazalil to replace fruit wax to be coated on the surfaces of apples, so that the surfaces of the apples are glossy and the shelf life is prolonged, but the intake of imazalil by human bodies can increase the probability of suffering from hepatic adenoma diseases of the human beings, so that the imazalil is very necessary to detect.
At present, a plurality of detection methods at home and abroad exist, wherein the relatively mature detection means comprise an enzyme inhibition method, and the method has high sensitivity and short detection time. The method has the defects of single detection type, can only detect organophosphorus and carbamate pesticides, and belongs to single-residue detection. Thin layer chromatography, also known as thin layer chromatography, is a technique that utilizes different physicochemical properties of the components in a sample to separate them. The disadvantage is that the sensitivity is not high. Liquid chromatography is to separate the solvent in the stationary phase and the mobile phase. The method has the defects of high instrument price, complex operation and long sample pretreatment time. In addition, infrared spectrometry is also available, but modeling is difficult. The ultraviolet visible spectrum has little spectrum information and weak characteristics. The traditional analysis method has long analysis period and lag result, and many fresh fruit and vegetable products are difficult to wait until the detection result comes out to be marketed, and most of the cases are that the detection result does not come out and agricultural products are eaten in the bellies of consumers. Therefore, the rapid screening of pesticide residues and the on-site instant detection are important.
Surface Enhanced Raman Spectroscopy (SERS) can generate a local plasma resonance effect when a laser light source is incident on the surface of noble metals such as gold and silver based on a Raman scattering effect, the intensity is enhanced by an order of magnitude, and the research on a molecular structure is achieved at a trace level. Compared with gas chromatographic columns and liquid chromatographic columns, the method has the advantages of simple operation, short time consumption, low cost, no need of extractant and no environmental pollution phenomenon, can reach a single-molecule detection state, and many scientists focus on SERS (surface enhanced Raman scattering) detection means. However, the method has not been developed in the field of pesticide residue detection due to the poor reproducibility of the enhanced substrate and the limitation of the detection environment.
Therefore, the prepared flexible transparent plastic has high flexibility, high transparency and good stability, the patch type portable SERS substrate film has great significance to the field of food safety.
Disclosure of Invention
The invention aims to provide a method for detecting pesticide residues on the surfaces of fruits and vegetables on site in time. The enhanced basement membrane with convenient carrying and stable signals is prepared, so that the on-site detection of food pesticide residues is realized. The invention has low cost, high detection speed, simple sample treatment and stable detection result.
The flexible high-transparency polyimide silver base film (PI@Ag) prepared by the invention can meet the requirement of detecting substances in different shapes. Because the PI@Ag film is high in transparency and can be directly coated on a detected object, the on-site rapid detection meeting different scenes is realized.
For this purpose, the technical scheme of the invention is as follows:
step one, obtaining a fruit skin sample, and cleaning the fruit skin sample by using an absolute ethanol solution;
step two, preparing a high-transparency flexible polyimide film;
step three, preparing silver nitrate solution;
step four, preparing a reducing agent sodium borohydride solution;
step five, preparing nano silver particles;
step six, preparing probe molecule 1,4 benzene dithiol ethanol solution
Step seven, taking the sample film of the step two, soaking the sample film in the solution of the step three, taking out and drying the sample film, soaking the sample film in the solution of the step four, washing the sample film with ethanol, drying the sample film at room temperature, and repeating the steps to prepare PI@Ag single-layer and multi-layer nano silver substrate films respectively;
step eight, uniformly dripping 1-3 mL of the solution prepared in the step six on the PI@Ag substrate prepared in the step six, naturally volatilizing, and carrying out Raman spectrum detection, wherein the detection range is 200-2000 cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The laser power is 10mW; the laser wavelength is 532nm; collecting time is 20s, obtaining a SERS image of the probe molecules, comparing the intensity change of characteristic peaks through multi-point scanning, and comparing and enhancing the consistency of the substrate.
Step nine, selecting common pesticides in fruits and vegetables, dripping 1-3 mL of the common pesticides on apple peel in the step one, tightly attaching a PI@Ag single-layer or multi-layer nano silver substrate prepared in the step seven on the apple peel, testing a surface enhanced Raman signal of the common pesticides, comparing the surface enhanced Raman signal with a traditional dripping glass slide, and detecting pesticide residue detection limit.
The first step of selecting the fruit skin is to randomly select apples in a supermarket, pour a proper amount of absolute ethyl alcohol, and wipe the surface of the apple skin clean by using a cotton swab.
The preparation method of the high-transparency flexible polyimide film comprises the following steps: polymerization reaction is carried out in a three-neck flask under the protection of nitrogen at the temperature of 0-10 ℃.3 to 10g of nitrogen-nitrogen dimethylacetamide and 0.5 to 1.3g of bistrifluoromethyl diamine biphenyl are put in, after diamine is completely dissolved, 1 to 2g hexafluoro-diphthalic anhydride is added in, and after stirring for 4 to 12 hours, transparent polyamide acid with 20 to 30 percent of solid content is prepared. Scraping a 500 mu m PI film by a film scraping rod, putting the PI film into a vacuum heating furnace, heating the PI film by a program, continuously heating the PI film at 80 ℃ for 1-2 h,150 ℃ for 1-2 h,200 ℃ for 1-2 h,250 ℃ for 1-2 h, naturally cooling the PI film, and taking the PI film out.
The preparation method of the silver nitrate solution in the third step comprises the following steps: 0.2 to 0.6g of silver nitrate is taken and dissolved in 100mL of ultrapure water, 0.5 to 1.5g of polyvinylpyrrolidone is added, and the mixture is stirred for 20 to 30 minutes at room temperature to prepare silver nitrate solution with the concentration range of 0.01 to 0.05 mol/L.
The preparation method of the sodium borohydride reducing agent solution comprises the following steps: 0.05 to 0.15g of sodium borohydride is taken and dissolved in 100mL of ultrapure water, and the mixture is stirred for 1 to 10 minutes to prepare a reducing agent solution which is prepared at present.
The preparation method of the nano silver particles comprises the following steps: firstly, rapidly pouring the silver nitrate solution prepared in the step three into the water solution prepared in the step four, wherein the volume ratio is 1:1, and carrying out light-shielding reaction for 2 hours.
The preparation method of the probe molecule 1, 4-benzene dithiol ethanol solution comprises the following steps: dissolving 0.01-0.05g of 1, 4-benzene dithiol in 100mL of absolute ethanol, and preparing concentration gradient from 10 -3 ～10 -10 mol/L probe molecule solution.
The preparation method of the PI@Ag single-layer and multi-layer nano silver substrate film comprises the steps of soaking a polyimide transparent film subjected to ultrasonic cleaning in a silver nitrate aqueous solution, standing for 1-10 min, and drying. The polyimide transparent film turns yellow to indicate silver nanoparticle formation when immersed in an aqueous sodium borohydride solution to undergo a severe reduction reaction (note the effect of concentration gradients). Taking out the PI film, soaking and washing the PI film with absolute ethyl alcohol, washing away sodium borohydride residues and boric acid radicals coated on the surfaces of silver particles for 1min, taking out the PI film, and drying the PI film in a vacuum oven for 5-10 min to prepare the PI@Ag single-layer nano silver substrate film. The PI@Ag single-layer nano silver base film successfully prepared by the method is continuously soaked in a silver nitrate aqueous solution for 1-10 min, then soaked in a sodium borohydride aqueous solution, nano silver particles grow on the surface in situ, the surface of the polyimide transparent film is deepened in yellow, the two layers of nano silver base films are successfully prepared, and the multi-layer nano silver base film can be prepared by repeating the experiment.
The pesticide in the step nine is tricyclazole and aprotinin.
Compared with the prior art, the method has the following advantages:
1) The invention adopts the polymer film with the three-dimensional structure as the substrate, can adjust the hot spot density, wherein the enrichment effect of the porous structure can promote the adsorption of target molecules on the substrate film, provides a good platform for fixing nano particles, and can effectively solve the problem of enhancing the intensity stability of the Raman spectrum
2) The transparent flexible polyimide film prepared by adopting the fluorine-containing monomer has excellent high temperature resistance. The film has high light transmittance and good bending performance. Compared with the traditional silicon sheet type substrate, the method has lower manufacturing cost, can meet the detection of samples with different shapes and sizes, realizes the timely detection of pesticide residues on fruits and vegetables, and shortens the time cost.
3. The invention adopts nano silver as surface enhancement, effectively improves the sensitivity of Raman detection, reduces the detection limit, saves the cost and is easy to popularize.
4. The reinforced substrate film prepared by the invention has the advantages of convenient carrying, convenient use and high stability.
Drawings
Fig. 1 is a schematic picture of detecting tricyclazole pesticide residues on the surface of apple peel by attaching the enhanced substrate prepared by the invention on the basis of a surface enhanced Raman technology;
fig. 2 is a graph of a raman intensity stability test of probe molecule 1, 4-benzenedithiol on pi@ag monolayer nano-silver substrate;
fig. 3 is a graph showing the effect of pi@ag substrate layer number on raman intensity.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples, but the present invention is not limited to the following examples, and fig. 1 is a schematic diagram of the present invention for detecting pesticide residues.
Example 1
(1) The specific preparation process of the nano silver particles comprises the following steps: the liquid phase reduction method is adopted, sodium borohydride is used as a reducing agent, silver nitrate is used as a precursor, and PVP is used as a dispersing agent. Firstly, 0.51g (3 mM) of silver nitrate and 1.5g of PVP are poured into 100ml of deionized water, and the mixture is fully stirred to complex silver ions and N atoms on PVP chains, and then 0.1g of 100ml of sodium borohydride aqueous solution is quickly poured into the mixture to react for 2 hours in a dark place, and the solution gradually changes from colorless to dark brown.
(2) The preparation process of the flexible transparent polyimide film comprises the following steps: the polymerization reaction was carried out in a three-necked flask at 5℃under the protection of nitrogen. 15g of nitrogen-nitrogen dimethylacetamide and 1.92g of bistrifluoromethyl diamine biphenyl were added, and after diamine was dissolved, 2.66g of hexafluoro-diphthalic anhydride was added and stirred for 6 hours to prepare a transparent polyamic acid with a solid content of 25%. Scraping 500 mu m polyimide film by a film scraping rod, putting the polyimide film into a vacuum heating furnace, heating the polyimide film to 80 ℃ for 1h,150 ℃ for 1h,200 ℃ for 1h,250 ℃ for 2h, naturally cooling the polyimide film, and taking the polyimide film out.
(3) The preparation process of the polyimide film surface in-situ grown nano silver particle reinforced substrate film comprises the following steps: taking 20mL of silver nitrate solution with the concentration of 0.03mol/L, and stirring for 30min at room temperature to prepare a silver raw solution for later use; 0.1g of sodium borohydride is dissolved in 100mL of ultrapure water and stirred for 5min to prepare a reducing agent solution, and the reducing agent solution is prepared at present. And (3) soaking the polyimide transparent film in a silver nitrate solution for 5min, taking out and naturally drying, then soaking in a reducing agent sodium borohydride solution for 5min, taking out and washing the polyimide film by using absolute ethyl alcohol, taking out after washing sodium borohydride residues and borate coated on the surfaces of silver particles for 1min, and drying in a vacuum oven for 10min to prepare the single-layer reinforced substrate film.
(4) As the 1, 4-benzene dithiol has double active groups and a larger Raman scattering cross section, the 1, 4-benzene dithiol is selected as a test for detecting and enhancing the stability of the basement membrane. Firstly, 0.014g of 1, 4-benzene dithiol is dissolved in 100mL of absolute ethanol solution to be dispersed uniformly, and the solution is diluted to prepare the solution with the concentration of 1 multiplied by 10 -10 mol/L of the liquid to be measured. 1mL of probe molecule to-be-detected liquid is taken and evenly dripped on a single-layer transparent flexible polyimide reinforced substrate film with the length of 1 multiplied by 1cm, and is dried at room temperature and then is put into a detection chamber of a Raman spectrometer for detection, and the probe molecule is shown in 1617cm in FIG. 2 -1 The Raman signal intensity of twenty points is randomly distributed, the wave number belongs to the characteristic peak of ring stretching vibration, and the reinforced substrate film prepared by the invention has good stability and provides data basis for improving the reliability of pesticide residue detection data.
Example 2
(1) The specific preparation process of the nano silver particles is as follows: the liquid phase reduction method is adopted, sodium borohydride is used as a reducing agent, silver nitrate is used as a precursor, and PVP is used as a dispersing agent. Firstly, 0.51g (3 mM) of silver nitrate and 1.5g of PVP are poured into 100ml of deionized water, and the mixture is fully stirred to complex silver ions and N atoms on PVP chains, and then 0.1g of 100ml of sodium borohydride aqueous solution is quickly poured into the mixture to react for 2 hours in a dark place, and the solution gradually changes from colorless to dark brown.
(2) The preparation process of the flexible transparent polyimide film comprises the following steps: the polymerization reaction was carried out in a three-necked flask at 5℃under the protection of nitrogen. 15g of nitrogen-nitrogen dimethylacetamide and 1.92g of bistrifluoromethyl diamine biphenyl were added, and after diamine was dissolved, 2.66g of hexafluoro-diphthalic anhydride was added and stirred for 6 hours to prepare a transparent polyamic acid with a solid content of 25%. Scraping 500 mu m polyimide film by a film scraping rod, putting the polyimide film into a vacuum heating furnace, heating the polyimide film to 80 ℃ for 1h,150 ℃ for 1h,200 ℃ for 1h,250 ℃ for 2h, naturally cooling the polyimide film, and taking the polyimide film out.
(3) The preparation process of the polyimide film surface in-situ grown nano silver particle reinforced substrate film comprises the following steps: taking 20mL of silver nitrate solution with the concentration of 0.03mol/L, and stirring for 30min at room temperature to prepare a silver raw solution for later use; 0.1g of sodium borohydride is dissolved in 100mL of ultrapure water and stirred for 5min to prepare a reducing agent solution, and the reducing agent solution is prepared at present. And (3) soaking the polyimide transparent film in a silver nitrate solution for 5min, taking out and naturally drying, then soaking in a reducing agent sodium borohydride solution for 5min, taking out and washing the polyimide film by using absolute ethyl alcohol, taking out after washing sodium borohydride residues and boric acid radicals coated on the surfaces of silver particles for 1min, and drying in a vacuum oven for 10min to prepare the single-layer reinforced substrate film. The single-layer reinforced substrate film successfully prepared by using the method is continuously soaked in a silver nitrate aqueous solution for 5min, then soaked in a sodium borohydride aqueous solution, nano silver particles grow on the surface in situ, and the surface yellow of the polyimide transparent film is deepened, which indicates that the double-layer reinforced substrate film is successfully prepared.
(4) 0.01g of bactericide pesticide tricyclazole is taken and added into 100mL of ultrapure water to be mixed uniformly, and the pesticide residue to be measured liquid with the concentration of 0.05ppm is prepared after dilution. And slowly dripping 1mL of pesticide residue to be detected on the surface of the apple peel treated by the absolute ethyl alcohol, and drying at room temperature. And tightly attaching the prepared double-layer reinforced substrate film to apple peel after pesticide residues are dripped, and placing the apple peel in a detection chamber of a Raman spectrometer for detection. The double-layer reinforced substrate film prepared by the method can realize on-site in-situ detection and can accurately detect trace level.
Example 3
(1) The specific preparation process of the nano silver particles is as follows: the liquid phase reduction method is adopted, sodium borohydride is used as a reducing agent, silver nitrate is used as a precursor, and PVP is used as a dispersing agent. Firstly, 0.51g (3 mM) of silver nitrate and 1.5g of PVP are poured into 100ml of deionized water, and the mixture is fully stirred to complex silver ions and N atoms on PVP chains, and then 0.1g of 100ml of sodium borohydride aqueous solution is quickly poured into the mixture to react for 2 hours in a dark place, and the solution gradually changes from colorless to dark brown.
(2) The preparation process of the flexible transparent polyimide film comprises the following steps: the polymerization reaction is carried out in a three-neck flask under the protection of nitrogen at the temperature of 0-10 ℃.15g of nitrogen-nitrogen dimethylacetamide and 1.92g of bistrifluoromethyl diamine biphenyl are put in, after diamine is dissolved, 2.66g of hexafluoro-diphthalic anhydride is added, and after stirring for 6 hours, transparent polyamide acid with a solid content of 25% is prepared. Scraping the polyimide film with the thickness of 500 mu m by a film scraping rod, putting the polyimide film into a vacuum heating furnace, heating the polyimide film to 80 ℃ for 1h,150 ℃ for 1h,200 ℃ for 1h and 250 ℃ for 2h, and naturally cooling the polyimide film to room temperature to take the polyimide film out.
(3) The preparation process of the polyimide film surface in-situ grown nano silver particle reinforced substrate film comprises the following steps: taking 20mL of silver nitrate solution with the concentration of 0.03mol/L, and stirring for 30min at room temperature; 0.1g of sodium borohydride is dissolved in 100mL of ultrapure water and stirred for 5min to prepare a reducing agent solution, and the reducing agent solution is prepared at present. And (3) soaking the polyimide transparent film in a silver nitrate solution for 5min, taking out and naturally drying, then soaking in a reducing agent sodium borohydride solution for 5min, taking out and washing the polyimide film with absolute ethyl alcohol, washing sodium borohydride residues and boric acid radicals coated on the surfaces of silver particles for 1min, taking out, and drying in a vacuum oven for 10min to prepare the single-layer reinforced substrate film. The single-layer reinforced substrate film successfully prepared by using the method is continuously soaked in a silver nitrate aqueous solution for 5min, then soaked in a sodium borohydride aqueous solution, nano silver particles grow on the surface in situ, the surface of the polyimide transparent film is deepened in yellow, and the method proves that the double-layer reinforced substrate film is successfully prepared.
(4) And respectively dissolving 0.02g of aprotinin and.01g of tricyclazole in 10mL of dichloromethane, uniformly mixing the two pesticide residue to be detected solutions in a ratio of 1:1, dripping 1mL of pesticide residue mixture on the surface of apple peel, tightly attaching the prepared double-layer enhanced substrate film to the apple peel after the dichloromethane on the surface of the apple peel is completely volatilized, and detecting in a detection chamber of a Raman spectrometer. The reinforced substrate prepared by the method can effectively distinguish mixed pesticide residues.
Comparative example 1
(1) Soaking a flexible transparent polyimide substrate film in silver nitrate solution with the concentration of 0.03mol/L for 5min, taking out, naturally drying, soaking in sodium borohydride reducing agent with the concentration of 0.03mol/L for 5min, taking out, soaking and washing the film with absolute ethyl alcohol, washing sodium borohydride residues and boric acid radicals coated on the surfaces of silver particles for 1min, taking out, and placing in a vacuum oven for drying for 10min to prepare the single-layer reinforced substrate film. The single-layer reinforced substrate film successfully prepared by using the method is continuously soaked in silver nitrate aqueous solution for 5min, then is soaked in sodium borohydride aqueous solution for 5min after being dried, nano silver particles grow on the surface in situ, the surface of the polyimide transparent film is deepened in yellow, the double-layer reinforced substrate film is successfully prepared, and three-layer and four-layer reinforced substrate films can be continuously prepared by repeating the experiment
(2) Firstly, 0.014g of 1, 4-benzene dithiol is dissolved in 100mL of absolute ethanol solution to be dispersed uniformly, and the solution is diluted to prepare the solution with the concentration of 1 multiplied by 10 -4 mol/L of the liquid to be measured. 1mL of probe molecule to-be-detected liquid is respectively dripped on a single-layer, double-layer, three-layer and four-layer polyimide reinforced substrate film with the surface of 1 multiplied by 1em for silver growth, and the polyimide reinforced substrate film is dried at room temperature and then is placed into a detection chamber of a Raman spectrometer for detection, and FIG. 3 shows that the double-layer reinforced substrate film has good reinforcing effect and small background interference.
Claims (8)
1. The preparation method of the flexible transparent patch type substrate film based on the enhanced Raman spectrum technology and the detection of pesticide residues is characterized by comprising the following steps:
step one: preparing a flexible transparent polyimide film;
step two: preparing a nano silver particle reinforced substrate film on the surface of the film in situ;
step three: enhancing the stability detection of the substrate film on the probe molecule 1, 4-benzene dithiol;
step four: and the detection of pesticide residues on the surfaces of the apple peels by the substrate film is enhanced.
2. The method of claim 1, wherein the step of preparing a flexible transparent polyimide comprises: selecting fluorine-containing monomer bis (trifluoromethyl) diamine biphenyl and hexafluoro-diphthalic anhydride in N 2 And (3) carrying out polymerization reaction under the condition of atmosphere and low temperature to prepare a polyamic acid (PAA) solution, and then carrying out temperature programming dehydration to obtain the transparent flexible polyimide film.
3. The method for preparing the surface-enhanced Raman substrate film by growing nano silver particles on the surface of the polyimide film in situ in the second step, as claimed in claim 1, is characterized in that:
(1) dissolving 0.2-0.6 g of silver nitrate into 100mL of ultrapure water, adding 0.5-1.5 g of polyvinylpyrrolidone, and stirring at room temperature for 20-30 min to prepare a silver nitrate solution for later use;
(2) dissolving 0.05-0.15 g sodium borohydride in 100mL ultrapure water, stirring for 1-10 min to prepare a reducer solution, and preparing at present;
(3) soaking the polyimide transparent film prepared in the claim 2 in the silver nitrate solution for 1-10 min, taking out and naturally drying, soaking in the reducing agent sodium borohydride solution for 1-10 min, washing away sodium borohydride residues and boric acid radicals coated on the silver surface by using absolute ethyl alcohol, and drying at room temperature to prepare a PI@Ag single-layer silver nanoparticle substrate film;
(4) and (3) repeating the step (3) to prepare the PI@Ag multilayer silver nanoparticle substrate film.
4. The method according to claim 1, wherein the stability of pi@ag base film is tested in step three using a thiol-containing probe molecule 1,4 benzenedithiol, wherein:
(1) dissolving 1, 4-benzene dithiol in absolute ethanol to prepare solution with concentration gradient from 10 -3 ～10 -10 mol/L; respectively soaking PI@Ag basement membrane in probe molecules for 1-10 min, then drying at room temperature, and independently placing the basement membrane in a sample bag for standby;
(2) using co-polymerizationFocal Raman spectrum with detection range of 200-2000 cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The laser power is 10mW; the laser wavelength is 532nm; the acquisition time was 20s.
5. The method of claim 1, wherein the detection of pesticide residues by the substrate film is enhanced in the fourth step, wherein: and (3) soaking the PI@Ag substrate film in an aqueous pesticide solution with the concentration gradient of 0.01 ppm-100 ppm for 1-10 min, taking out and drying at room temperature.
6. The method of manufacture of claim 2, wherein: the polymerization reaction temperature is 0-10 ℃, the reaction time is 4-12 h, the programmed heating step lasts for 1-2 h at 80 ℃, for 1-2 h at 150 ℃, for 1-2 h at 200 ℃ and for 1-2 h at 250 ℃, and then the product is naturally cooled to room temperature and taken out.
7. The method of claim 4, wherein: and (3) selecting 10-30 points randomly, wherein the range of the selected points in the multi-point scanning in the step (2) is 5 multiplied by 5 mu m.
8. The method of manufacture of claim 5, wherein: the pesticide is selected from one or two of tricyclazole and aprotinin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210506540.1A CN117092085A (en) | 2022-05-11 | 2022-05-11 | Preparation of flexible transparent patch type substrate film based on enhanced Raman spectrum technology and detection of pesticide residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210506540.1A CN117092085A (en) | 2022-05-11 | 2022-05-11 | Preparation of flexible transparent patch type substrate film based on enhanced Raman spectrum technology and detection of pesticide residue |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117092085A true CN117092085A (en) | 2023-11-21 |
Family
ID=88768559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210506540.1A Pending CN117092085A (en) | 2022-05-11 | 2022-05-11 | Preparation of flexible transparent patch type substrate film based on enhanced Raman spectrum technology and detection of pesticide residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117092085A (en) |
-
2022
- 2022-05-11 CN CN202210506540.1A patent/CN117092085A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | Ultrasensitive and quantitative detection of paraquat on fruits skins via surface-enhanced Raman spectroscopy | |
| Zhu et al. | Multi-branched gold nanostars with fractal structure for SERS detection of the pesticide thiram | |
| CN103526291B (en) | Surface enhanced raman scattering substrate and its preparation method and application | |
| Li et al. | Au-coated ZnO nanorods on stainless steel fiber for self-cleaning solid phase microextraction-surface enhanced Raman spectroscopy | |
| Kim et al. | Low-cost, high-performance plasmonic nanocomposites for hazardous chemical detection using surface enhanced Raman scattering | |
| CN106093001A (en) | Poly-dopamine silver particles poly-DOPA amine type surface enhanced raman spectroscopy substrate and preparation method thereof | |
| Evyapan et al. | Improving the selectivity of a free base tetraphenylporphyrin based gas sensor for NO2 and carboxylic acid vapors | |
| Wang et al. | Semi-sacrificial template growth-assisted self-supporting MOF chip: A versatile and high-performance SERS sensor for food contaminants monitoring | |
| TWI612288B (en) | A heavy metal detecting device and the fabricating method thereof | |
| Gao et al. | Photothermal-induced partial Leidenfrost superhydrophobic surface as ultrasensitive surface-enhanced Raman scattering platform for the detection of neonicotinoid insecticides | |
| Bai et al. | Construction of flexible, transparent and mechanically robust SERS-active substrate with an efficient spin coating method for rapid in-situ target molecules detection | |
| CN109342400B (en) | Application of semiconductor compound in identification and identification of origin of wine | |
| Bai et al. | Controllable assembly of high sticky and flexibility surface-enhanced Raman scattering substrate for on-site target pesticide residues detection | |
| CN117092085A (en) | Preparation of flexible transparent patch type substrate film based on enhanced Raman spectrum technology and detection of pesticide residue | |
| Tonezzer et al. | Optical sensing properties of CoTPP thin films deposited by glow-discharge-induced sublimation | |
| Liu et al. | New rapid detection method of total chlorogenic acids in plants using SERS based on reusable Cu2O–Ag substrate | |
| CN108411285B (en) | Quick green synthesis of graphene oxide modified popcorn-shaped silver SERS composite structure | |
| Lu et al. | Responsive photonic hydrogel for colorimetric detection of formaldehyde | |
| Muthukumar et al. | Optochemical ammonia gas sensing properties of meso-substituted porphyrin derivatives immobilized Nafion film on glass slide | |
| Zhang et al. | Ultrasensitive detection of pectin based on the decarboxylation reaction and surface-enhanced Raman spectroscopy | |
| Acikbas et al. | Optical Characterization of an N, N′-Dicyclohexyl-3, 4: 9, 10-Perylene bis (Dicarboximide) Langmuir–Blodgett Film for the Determination of Volatile Organic Compounds | |
| Li et al. | Preparation and application of highly sensitive myclobutanil sensor based on molecularly imprinted photonic crystals | |
| CN115849726A (en) | Surface-enhanced Raman scattering composite substrate and preparation method and application thereof | |
| CN114674804A (en) | Erasable SERS substrate for detecting pesticide and preparation method and application thereof | |
| Yin et al. | Pyrimidin-2-amine derivative-grafted cellulose ratiometric fluorescent probe for pH detection in extremely acidic media |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |