CN110618124A - Method for detecting content of tyramine in aquatic product based on azo coupling reaction and surface enhanced resonance Raman scattering - Google Patents
Method for detecting content of tyramine in aquatic product based on azo coupling reaction and surface enhanced resonance Raman scattering Download PDFInfo
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- CN110618124A CN110618124A CN201910875403.3A CN201910875403A CN110618124A CN 110618124 A CN110618124 A CN 110618124A CN 201910875403 A CN201910875403 A CN 201910875403A CN 110618124 A CN110618124 A CN 110618124A
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- DZGWFCGJZKJUFP-UHFFFAOYSA-N Tyramine Natural products NCCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229960003732 tyramine Drugs 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000006149 azo coupling reaction Methods 0.000 title claims abstract description 28
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 26
- DZGWFCGJZKJUFP-UHFFFAOYSA-O tyraminium Chemical compound [NH3+]CCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-O 0.000 title claims abstract 20
- 239000000243 solution Substances 0.000 claims abstract description 102
- 238000001514 detection method Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 26
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 tyramine derivative azo compound Chemical class 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000000523 sample Substances 0.000 claims abstract description 16
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001228 spectrum Methods 0.000 claims abstract description 11
- 239000006228 supernatant Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 241000251468 Actinopterygii Species 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 229960004050 aminobenzoic acid Drugs 0.000 claims abstract description 8
- 239000012488 sample solution Substances 0.000 claims abstract description 6
- 235000013372 meat Nutrition 0.000 claims abstract description 5
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 51
- 239000010931 gold Substances 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002211 L-ascorbic acid Substances 0.000 claims description 5
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000012417 linear regression Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 6
- 235000019688 fish Nutrition 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
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- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical group NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 230000000035 biogenic effect Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000007336 electrophilic substitution reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- SFLSHLFXELFNJZ-QMMMGPOBSA-N (-)-norepinephrine Chemical compound NC[C@H](O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-QMMMGPOBSA-N 0.000 description 1
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000019695 Migraine disease Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 206010047139 Vasoconstriction Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
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- PRQROPMIIGLWRP-BZSNNMDCSA-N chemotactic peptide Chemical compound CSCC[C@H](NC=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@H](C(O)=O)CC1=CC=CC=C1 PRQROPMIIGLWRP-BZSNNMDCSA-N 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 235000021107 fermented food Nutrition 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 238000001871 ion mobility spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 206010027599 migraine Diseases 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229960002748 norepinephrine Drugs 0.000 description 1
- SFLSHLFXELFNJZ-UHFFFAOYSA-N norepinephrine Natural products NCC(O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
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- 235000014102 seafood Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
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- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4077—Concentrating samples by other techniques involving separation of suspended solids
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/02—Food
- G01N33/12—Meat; Fish
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Medicinal Chemistry (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for detecting the content of tyramine in aquatic products based on azo coupling reaction and surface enhanced resonance Raman scattering, which is characterized by comprising the steps of adding trichloroacetic acid solution into fresh fish meat for homogenate, oscillating at room temperature, centrifuging to obtain supernatant, repeatedly extracting residues by trichloroacetic acid solution, combining the supernatants, fixing the volume and filtering by a membrane to obtain a sample solution to be detected; adding NaNO2Adding the solution into a mixed solution obtained by dissolving p-aminobenzoic acid in HCl solution, reacting, and rapidly adding Na under stirring2CO3Carrying out tyramine azo coupling reaction on the solution and tyramine solution to obtain tyramine derived azo compoundA step of solution; the method comprises the steps of mixing a tyramine derivative azo compound solution and an Au @ Ag NPs solution in proportion, carrying out spectrum detection, and calculating the content of tyramine in a sample to be detected according to the linear relation between the tyramine concentration and the characteristic peak signal intensity.
Description
Technical Field
The invention relates to a method for detecting the content of tyramine in an aquatic product, in particular to a method for detecting the content of tyramine in an aquatic product based on azo coupling reaction and surface enhanced resonance Raman scattering.
Background
Tyramine (1-hydroxy-4-ethylamine benzene) belongs to one of biogenic amines and is a degradation product of microbial activity. It is present in fermented foods, beverages, meats, fish, seafood and dairy products. The high-concentration tyramine has great harm to human health, can promote peripheral vasoconstriction, stimulate heart rhythm, increase blood sugar concentration, eliminate norepinephrine in nervous system, and cause migraine. Therefore, it is important to establish a rapid and sensitive tyramine determination method. At present, various methods are established at home and abroad for quantitatively determining the content of tyramine in various foods, and the methods comprise high performance liquid chromatography, capillary electrophoresis and enzyme biosensor methods which are combined with different detection technologies, wherein an HPLC method is the most common method. While these methods have good selectivity and detection limits, they tend to require long times, complex sample pre-treatment and expensive instrumentation. Therefore, the development of a simple and high-sensitivity rapid tyramine detection method is of great significance.
The azo coupling reaction is carried out by reacting amines (-NH) under strong acid and low temperature2) The material is treated with HNO2Oxidized diazonium salt (-N [ identical to ] N)+) The chemical reaction of electrophilic substitution mutual coupling with phenols, aniline and some heterocyclic compounds in alkaline or neutral solution to produce azo molecule. The diazo component is sulfanilic acid molecule, and the diazonium salt ion is used as electrophilic reagent to attack the most nucleophilic site (electron density is strongest) on the coupling molecule, so as to obtain the azo compound with nitrogen-nitrogen double bond (-N = N-) structure. According to the mechanism of the azo reaction, in generalThe diazonium salt ion in this case preferentially attacks the para positions of the phenolic hydroxyl group and the aromatic amino group, but if the para position is occupied, electrophilic substitution occurs in the ortho positions of the hydroxyl group and the amino group.
Surface Enhanced Raman Scattering (SERS) is a fast, extremely sensitive spectroscopic technique with wide application in analytical chemistry, biomedicine and food safety fields. Silver, gold, and copper metal nanoparticles are the most commonly used SERS substrates. Core-shell nanoparticles such as silver-plated gold colloids (Au @ Ag NPs) are widely used in SERS constructions due to their unique Local Surface Plasmon Resonance (LSPR) properties. SERS is an ultrasensitive vibrational spectroscopy technique for molecules adsorbed on or near metal nanostructures, each molecule has its unique vibrational fingerprint information, and the sensitivity of SERS can be further improved by selecting an appropriate excitation wavelength to match the electronic transition state of the target molecule, i.e., SERRS. At present, no relevant research report about a method for detecting the content of tyramine in aquatic products based on azo coupling reaction and surface enhanced resonance Raman scattering is published at home and abroad.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for detecting the content of tyramine in an aquatic product based on azo coupling reaction and surface enhanced resonance Raman scattering, which is simple, quick and high in sensitivity.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for detecting the content of tyramine in an aquatic product based on azo coupling reaction and surface enhanced resonance Raman scattering comprises the following steps:
(1) sample processing
Adding trichloroacetic acid (TCA) solution into fresh fish meat, homogenizing, performing oscillation extraction at room temperature, centrifuging, collecting supernatant, repeatedly extracting the residue with trichloroacetic acid solution for 1 time, mixing the supernatants to desired volume, and filtering with 0.22 μm filter membrane to obtain sample solution to be measured;
(2) tyramine azo coupling reaction
Under the conditions of magnetic stirring and ice-water bath, adding 5 percent by mass of NaNO2Solutions ofAdding the mixture into an equal volume of a mixture prepared by mixing p-aminobenzoic acid (PABA) according to a mass-to-volume ratio of 0.9 g: dissolving 100 mL of the aqueous solution in a mixed solution obtained by dissolving the aqueous solution in 0.12M HCl solution, reacting for 0.5-1min, and rapidly adding NaNO into the reaction solution under stirring2The equal volume of the solution is 6-10% of Na by mass fraction2CO3Solution and 2 times NaNO2Reacting tyramine solution in the volume of the solution for 0.5-1min to obtain azo compound solution derived from tyramine;
(3) synthesis of Au @ Ag NPs
A. 0.25mL of 10-1HAuCl of M4Mixing the solution with 100 mL of deionized water, heating to boil, quickly adding 1.0mL of 1% sodium citrate solution under vigorous magnetic stirring, keeping the solution boiling for 30 minutes under stirring, cooling to room temperature, filtering through a 0.22 mu m filter membrane to obtain a gold nanoparticle suspension (Au NPs) with the particle size of 30-40 nm, and storing at 4 ℃;
B. placing the gold nanoparticle suspension (Au NPs) with the particle size of 30-40 nm synthesized in the step A into a conical flask, and adding the gold nanoparticle suspension (Au NPs) with the concentration of 10 under magnetic stirring-1 M in L-ascorbic acid, with continued stirring, at a concentration of 10 drops/min-3 AgNO of M3Adding the solution into the mixed solution until the color of the solution changes from wine red to bright orange, namely synthesizing Au @ Ag NPs suspension original solution, and concentrating to 1/6-1/2 of the original volume to obtain Au @ Ag NPs solution, wherein the Au nanoparticle suspension, the L-ascorbic acid solution and the AgNO solution3The volume ratio of the solution is 10: 1.5: 3.5;
(4) SERRS sample preparation
Mixing the tyramine derivative azo compound solution prepared in the step (2) with the Au @ Ag NPs solution prepared in the step (3) according to the volume ratio of (2-1): and (1) mixing the components according to the proportion, dripping the mixture on a quartz plate, placing the mixture under a Raman microscope for spectrum detection to obtain SERRS characteristic peak signal intensity, establishing a linear relation between the tyramine concentration and the characteristic peak signal intensity by adopting a linear regression method, and calculating the content of tyramine in the sample to be detected according to the linear relation between the tyramine concentration and the characteristic peak signal intensity.
The step (1) is specifically as follows: taking 10 g of fresh fish, adding 20mL of trichloroacetic acid solution with the concentration of 5wt%, homogenizing for 2min, oscillating and extracting for 30 min at room temperature, centrifuging at 8000r/min and 4 ℃ for 10 min, taking supernate, repeatedly extracting residues with 20mL of trichloroacetic acid solution with the concentration of 5wt% for 1 time, combining the supernate, fixing the volume to 50mL, and filtering with a 0.22 mu m filter membrane to obtain a sample solution to be detected.
Na as described in step (2)2CO3The mass fraction of the solution was 8%.
The concentration method in the step (3) comprises the following steps: taking a certain volume of Au @ AgNPs suspension original solution, centrifuging for 5min at 8000r/min, carefully removing a certain amount of supernatant, and oscillating on an oscillator for 2min to enable the Au @ AgNPs to be suspended uniformly, thus obtaining the Au @ AgNPs solution with the expected concentration multiple.
And (4) concentrating the mixture in the step (3) until the volume is 1/4 times.
The tyramine derivative azo compound solution in the step (4) and the A @ Ag NPs solution are mixed according to the volume ratio of 1: 4, and mixing.
Compared with the prior art, the invention has the advantages that: the invention discloses a method for detecting the tyramine content in aquatic products based on azo coupling reaction and surface enhanced resonance Raman scattering for the first time, because good SERS signals can not be obtained by directly detecting tyramine, Raman signals can be indirectly detected by other methods such as azo coupling reaction and the like. When the concentration of tyramine is in the range of 100 to 0.1mg/L, the concentration is 1245cm-1The intensity of the Raman peak corresponding to the calibration curve established at the characteristic peak of the optical fiber has good linear relation (R)2= 0.9835), a limit of detection (LOD) of 0.01mg/L, normalized recovery between 95.0% and 97.5%, indicating very good reproducibility and accuracy of the method. Furthermore, the proposed method is simple and fast within 5 minutes.
In conclusion, the invention combines the chemical derivatization method-azo coupling and SERRS method based on the high selectivity and sensitivity of SERS technology and the maximum absorption position of azo molecules falling in the visible region, and establishes a simple, rapid and high-sensitivity quantitative tyramine analysis method.
Drawings
FIG. 1 is a process for the synthesis of tyramine-derived azo compounds;
FIG. 2 is a TEM image of Au @ Ag NPs;
FIG. 3 is a graph showing UV absorption spectra of Au @ Ag NPs, 100mg/L tyramine-derived azo compounds, mixtures of azo compounds with Au @ Ag NPs, and Au NPs;
FIG. 4 is a schematic representation of the SERRS detection principle of tyramine-derived azo compounds;
FIG. 5 is a SERRS spectrum of tyramine derived azo compounds at different concentration multiples of Au @ Ag NPs;
FIG. 6 shows tyramine-derived azo compounds at 1245cm for different concentrations of Au @ Ag NPs-1Processing the characteristic peak intensity value;
FIG. 7 shows the difference Na2CO3SERRS spectra of tyramine-derived azo compounds at concentration;
FIG. 8 shows the difference of Na2CO3Characteristic peak intensity value of tyramine derived azo compound at 1245 cm-1 under concentration;
FIG. 9 is a SERRS spectrum at different mixing ratios of tyramine derivative azo compounds to Au @ Ag NPs;
FIG. 10 is a graph showing the characteristic peak intensity values at 1245 cm-1 for different tyramine-derived azo compounds mixed with Au @ Ag NPs;
FIG. 11 is a SERRS spectrum of a derivatized azo compound at various tyramine concentrations;
FIG. 12 shows the 1245cm concentration of azo compounds derivatized at different tyramine concentrations-1And processing the characteristic peak intensity value.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Detailed description of the preferred embodiments
1. Materials and instruments
Materials: fresh mackerel and salted fish are purchased from Ningbo Lolin market. After purchase, the samples were stored at-80 ℃ until use. The skin and bones were removed and only the back muscles were retained as experimental material.
Reagent: para aminobenzoic acid (PABA, C)6H7NO3S > 99.8%), silver nitrate (AgNO)399.9%), sodium nitrite (NaNO)2Not less than 99 percent), hydrochloric acid (HCl, 36.46 percent) and sodium carbonate (Na)2CO399.8% or more) and sodium citrate (98%) were purchased from national pharmaceutical chemicals, ltd (shanghai, china). Tyramine hydrochloride (C)8H11NO & HCl, 98%), chloroauric acid (HAuCl)498%), L-ascorbic acid (99%) and 4-mercaptobenzoic acid (4 MBA, 99%) were purchased from Sigma-Aldrich (Shanghai, China). Deionized water was used during the experiment and all reagents were of analytical reagent grade.
The instrument comprises the following steps: XploRA ONE high sensitivity raman spectrometer (shanghai, china); JEM-2100F Transmission Electron microscope (Tokyo, Japan); d-7PC UV spectrophotometer (Nanjing, China).
Setting instrument parameters: the Raman spectrometer used silicon wafers (Si) at 520 cm before each test-1The peak was instrumentally corrected as a reference peak. If no special description is provided, the surface enhanced Raman spectrum is collected, the laser wavelength is 785 nm, the laser intensity is set to be 50%, the power is 120 mW, the power is 50 multiplied by an eyepiece, the exposure time is 60 s, and the detected spectral ranges are all 200 to 3500 cm-1Resolution of 1cm-1. The parameter settings are kept consistent in the sample detection process, and each sample is repeated at least 3 times to obtain an accurate Raman spectrum result.
2. A method for rapidly detecting the content of tyramine in an aquatic product based on azo coupling reaction and SERRS comprises the following steps:
(1) sample processing method
Taking 10 g of fresh fish meat, adding 20mL of 5wt% trichloroacetic acid (TCA) solution, homogenizing for 2min, extracting at room temperature under shaking for 30 min, centrifuging at 8000r/min and 4 deg.C for 10 min, and collecting supernatant. Repeatedly extracting the residue with 20mL of 5wt% TCA solution for 1 time, mixing the supernatants, diluting to a constant volume of 50mL, and filtering with 0.22 μm filter membrane to obtain a sample solution to be detected;
(2) tyramine azo coupling reaction
Under the conditions of magnetic stirring and ice-water bath, adding 5 percent by mass of NaNO2The solution was added to an equal volume of a solution prepared from para-aminobenzoic acid (PABA) in a mass to volume ratio of 0.9 g: dissolving 100 mL of the aqueous solution in a mixed solution obtained by dissolving the aqueous solution in 0.12M HCl solution, reacting for 0.5-1min, and rapidly adding NaNO into the reaction solution under stirring2The mass fraction of the solution with the same volume is 8 percent of Na2CO3Solution and 2 times NaNO2Reacting tyramine solution in the volume of the solution for 0.5-1min to obtain azo compound solution derived from tyramine; as shown in FIG. 1, tyramine molecules contain a phenolic group and can therefore be converted to the corresponding azo molecule by reaction with a diazo compound. The affinity of the phenolic compounds to Au @ Ag NPs is weak, so that the SERS signal is greatly reduced. In order to improve the affinity of phenolic compounds and Au @ Ag NPs, tyramine is converted into corresponding azo molecules through azo coupling reaction, so that high-sensitivity detection of SERS is realized. FIG. 1 is a schematic view of the azo reaction process. Briefly, NaNO2With HC1 to nitrous acid (HNO)2) Amino (-NH) groups of para-aminobenzoic acid (PABA) molecules under low temperature and strong acidic conditions2) With HNO2Acting to form diazonium positive ion (-N is identical to N)+) then-N.ident.N under basic conditions+Then serving as an electrophilic reagent to attack tyramine so as to generate a corresponding azo molecule;
(3) synthesis of Au @ Ag NPs
A. 0.25mL of 10-1HAuCl of M4Mixing the solution with 100 mL of deionized water, heating to boil, quickly adding 1.0mL of 1% sodium citrate solution under vigorous magnetic stirring, keeping the solution boiling for 30 minutes under stirring, cooling to room temperature, filtering through a 0.22 mu m filter membrane to obtain a gold nanoparticle suspension (AuNPs) with the particle size of 30-40 nm, and storing at 4 ℃;
B. suspending the gold nanoparticles with the particle size of 30-40 nm synthesized in the step A10 mL of the solution (Au NPs) was placed in a conical flask and 1.5mL of 10 concentration solution was added under magnetic stirring-1M in L-ascorbic acid, 3.5 mL at a concentration of 10 at a rate of 1 drop/min with continued stirring-3AgNO of M3Adding the solution into the mixed solution, changing the color of the Au @ Ag NPs from wine red to bright orange with the addition of silver nitrate, namely synthesizing an Au @ Ag NPs suspension original solution with the Ag shell thickness of 7nm, and concentrating to 1/4 of the original volume to obtain the Au @ Ag NPs solution, wherein the concentration step is as follows: taking a certain volume of Au @ AgNPs suspension original solution, centrifuging for 5min at 8000r/min, carefully removing a certain amount of supernatant, and oscillating on an oscillator for 2min to enable the Au @ AgNPs to be suspended uniformly, thus obtaining Au @ AgNPs solution with an expected concentration multiple;
the morphology of the resulting Au @ Ag NPs was determined by transmission electron microscopy. Fig. 2 shows a TEM image of a core-shell structure with spherical geometry. The TEM images clearly show an Ag shell thickness of 7 nm. FIG. 3 shows UV absorption spectra of Au NPs and Au @ Ag NPs. Initially, the gold nanoparticles had a maximum absorbance at 520 nm. 3.5 mL of AgNO were added with stirring3After being added into Au NPs, Ag is gradually attached to the surface of the Au NPs to generate Au @ Ag NP, so that two different plasma absorption peaks at 400nm and 500nm are observed in an ultraviolet absorption spectrogram;
(4) SERRS sample preparation
Mixing the tyramine derivative azo compound solution prepared in the step (2) and the Au @ Ag NPs solution prepared in the step (3) according to a volume ratio of 1: 4, then dropping 3 mu L of the mixed solution on a quartz plate, placing the mixed solution under a Raman microscope for spectral detection to obtain the signal intensity of a characteristic peak SERRS, establishing a linear regression model between the tyramine concentration and the characteristic peak intensity by adopting a linear regression method, and calculating the content of tyramine in the sample to be detected according to the linear relation between the tyramine concentration and the characteristic peak intensity. FIG. 4 is a schematic diagram of the detection principle of SERRS of tyramine-derived azo compounds.
Second, analysis of comparison results
Optimizing the detection condition of tyramine SERRS: design of single factor experiment: au @ Ag NPs suspension concentrate multiple (2X, 4X, 6X, 8X, 10X), Na2CO3The concentration (2%, 4%, 6%, 8%, 10%) and the sample mixing ratio (2: 1, 1: 1, 1: 4, 1: 6, 1: 10) influence factors on the SERRS signal, and a three-factor three-level orthogonal experiment was designed.
1. Single factor test
In order to obtain a good SERRS spectrum, the concentration times of the Au @ Ag NPs suspension stock solution are optimized. And performing SERRS detection on the Au @ Ag NPs under different concentration times. Experimental results indicate that too high a concentration factor may result in aggregation of the nanoparticles, such that the substrate does not bind sufficiently to the molecule being detected, resulting in a reduction or attenuation of the SERRS signal. FIG. 5 shows SERRS spectra at different Au @ Ag NPs concentration factors and 1245cm shown in FIG. 5-1Peak intensity value of (c). As shown in fig. 6, the SERRS signal strength first increases and then decreases. At 4-fold concentration, the SERRS signal reached maximum intensity, indicating that the Au @ Ag NPs and tyramine-derived azo compound were efficiently mixed.
Since the coupling reaction between the diazonium salt and the phenol is usually carried out in a weakly basic medium, Na is used2CO3Adjusting the pH value of the reaction solution to Na2CO3Is optimized. As shown in FIGS. 7 and 8, Na was obtained2CO3The optimum mass concentration of (2) is 8%.
And finally, optimizing the mixing ratio of the tyramine derivative azo compound solution to the Au @ Ag NPs solution according to the ratio of 2: 1,1: 1,1: 4,1: 6 and 1: the detection of SERRS was performed at 5 different ratios of 10. As shown in fig. 9 and 10, when the mixing ratio of the two is 1: at 1, the obtained SERRS signal is strongest.
2. Quadrature test
Based on the above single-factor experiment, the suspension of Au @ Ag NPs was concentrated by multiple times (2 ×, 4 ×, 6 ×), and Na2CO3Three-factor three-level orthogonal experiments were designed with mass concentrations (6%, 8%, 10%) and mixing ratios (2: 1, 1: 1, 1: 4) of tyramine-derived azo compound solution to Au @ Ag NPs solution. By analyzing the K values in Table 1, it can be concluded that the Au @ Ag NPs concentration factor and the mixing ratio have an influence on the SERRS signalThe sound is loud. Obtaining the concentration times and Na of Au @ Ag NPs through an orthogonal test result2CO3The optimum conditions for concentration and mixing ratio were 4 times, 8 wt% and 1: and 4, verifying the optimal conditions obtained by the single-factor test. Comparing the results of two experiments, determining the optimal conditions that the concentration multiple of the Au @ Ag NPs suspension original solution is 4 times, and Na2CO3The mass concentration is 8 percent, and the mixing proportion is 1: 4.
TABLE 1 orthogonal test results Table
。
Third, sensitivity and accuracy of SERRS detection of tyramine
Au @ Ag NPs is a common SERS substrate, and is introduced into the detection of tyramine-derived azo compounds in order to improve the sensitivity of tyramine-derived azo compounds. The SERRS spectrum and RR spectrum of the resulting tyramine-derived azo compound differ due to adsorption of molecules or functional groups of the tyramine-derived azo compound to the metal surface. From SERRS spectrogram, the strongest characteristic peak can be observed to appear at 1245cm-1Here, this is due to the stretching vibration of C-C in the benzene ring. At 1473cm-1The characteristic peak at (a) is related to the stretching vibration of-N = N-. In addition, 1352cm-1The characteristic peak belongs to the bending vibration of C-C-H in the benzene ring. At 1120 and 1591cm-1The characteristic peak at (A) may be related to C-N stretching vibration and C-H bending vibration in the phenolic ring.
After mixing the Au @ Ag NPs with tyramine derived azo compounds, significant colloidal aggregation was observed visually, which induced an increase in SERRS signal. As shown in fig. 11, SERRS intensities of all characteristic peaks vary with concentration. As shown in FIG. 12, when the concentration of tyramine is in the range of 100 to 0.1mg/L, it is at 1245cm-1The characteristic peak has good linear relation with the corresponding Raman peak intensity, the obtained linear regression equation is y =2089.55x +264.60, and the correlation coefficientR 2 = 0.9835. The limit of detection (LOD) of the method was determined to be 0.01mg/L based on the signal-to-noise ratio.
To verify the accuracy of the resulting standard curve, recovery experiments were performed by preparing three samples at different concentrations in the linear range. As shown in table 2, the spiked recovery was between 95% and 97.5% and reproducibility of SERRS detection was achieved (RSD < 10%). Through recovery rate and precision tests, the method has good repeatability and accuracy.
TABLE 2 recovery and prediction experiments using Raman peak intensities
。
Fourth, method verification
Table 3 compares the SERRS method with the method of detecting tyramine that has been commonly used in recent years. The detection limit of the SERRS method is similar to that of other measuring methods through table data comparison. Compared with other tyramine detection methods with the defects of high cost equipment, long sample processing time and the like, the SERRS method combined with azo coupling reaction has the advantages of simplicity, convenience, rapidness, low detection limit and the like. The SERRS method was validated by HPLC method. Table 4 shows the results of the two detection methods. Compared with HPLC, the developed method is faster and simpler, and can achieve satisfactory qualitative and quantitative purposes. The SERRS method is therefore an economical and efficient method for measuring tyramine in food products.
TABLE 3 comparison of several common tyramine content determination methods
The UPLC method reference, the HS-SPME-MIR-IMS method reference, and the SERRS method are as described in the above example.
[1] Zhang H , Yin C , Xu L , et al. An improved determination method for tyramine in foods using ultra-high performance liquid chromatography withbenzylamine as internal standard[J]. International Journal of Food Science & Technology, 2019。
[2] Parchami R , Kamalabadi M , Alizadeh N . Determination of biogenic amines in canned fish samples using head-space solid phasemicroextraction based on nanostructured polypyrrole fiber coupled to modifiedionization region ion mobility spectrometry[J]. Journal of Chromatography A, 2017, 1481:37-43。
Table 4 compares the results of the two methods
。
From the above, the invention develops the method for detecting the tyramine content in the food based on the azo coupling reaction and the surface enhanced resonance Raman scattering, the method utilizes the azo coupling reaction of the tyramine to form a bridge between Au @ Ag NPs and the tyramine, and the method has the advantages of universality, high selectivity, simplicity, convenience and rapidness. Tyramine was converted to the corresponding azo molecule by diazonium ion preparation with PABA, followed by SERRS testing. The SERRS detection conditions of tyramine are optimized through an orthogonal test, the optimization result is that the concentration multiple of Au @ Ag NPs suspension original solution is 4 times, and Na is adopted2CO3The mass concentration is 8%, and the mixing ratio of the tyramine derivative azo compound to the Au @ Ag NPs is 1: 4. when the concentration of tyramine ranges from 100 to 0.1mg/L, the characteristic peak is 1245cm-1The corresponding Raman peak intensity has good linear relation (R) with the corresponding tyramine concentration2= 0.9835). The obtained limit of detection (LOD) is 0.01mg/L, and the recovery rate of the spiked sample is between 95.0% and 97.5%, which shows that the method has very good repeatability and accuracy. In addition, the azo coupling reaction can be completed within 5 minutes, showing the advantage of simple and rapid process. The developed method offers the advantage of simplicity, rapidity and high sensitivity for the detection of tyramine compared to previously reported methods.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (7)
1. A method for detecting the content of tyramine in aquatic products based on azo coupling reaction and surface enhanced resonance Raman scattering is characterized by comprising the following steps:
(1) sample processing
Adding trichloroacetic acid solution into fresh fish meat, homogenizing, performing oscillation extraction at room temperature, centrifuging, collecting supernatant, repeatedly extracting the residue with trichloroacetic acid solution for 1 time, mixing the supernatants to desired volume, and filtering with 0.22 μm filter membrane to obtain sample solution to be measured;
(2) tyramine azo coupling reaction
Under the conditions of magnetic stirring and ice-water bath, adding 5 percent by mass of NaNO2Adding the solution into an equal volume of a solution prepared by mixing p-aminobenzoic acid according to the mass-to-volume ratio of 0.9 g: dissolving 100 mL of the aqueous solution in a mixed solution obtained by dissolving the aqueous solution in 0.12M HCl solution, reacting for 0.5-1min, and rapidly adding NaNO into the reaction solution under stirring2The equal volume of the solution is 6-10% of Na by mass fraction2CO3Solution and 2 times NaNO2Reacting tyramine solution in the volume of the solution for 0.5-1min to obtain azo compound solution derived from tyramine;
(3) synthesis of Au @ Ag NPs
A. 0.25mL of 10-1HAuCl of M4Mixing the solution with 100 mL of deionized water, heating to boil, quickly adding 1.0mL of 1% sodium citrate solution under vigorous magnetic stirring, keeping the solution boiling for 30 minutes under stirring, cooling to room temperature, filtering through a 0.22 mu m filter membrane to obtain a gold nanoparticle suspension with the particle size of 30-40 nm, and storing at 4 ℃;
B. placing the gold nanoparticle suspension with the particle size of 30-40 nm synthesized in the step A into a conical flask, and adding the gold nanoparticle suspension with the concentration of 10 under magnetic stirring-1M in L-ascorbic acid, with continued stirring, at a concentration of 10 drops/min-3AgNO of M3Adding the solution into the mixed solution until the color of the solution changes from wine red to bright orange, namely synthesizing Au @ Ag NPs suspension original solution, and concentrating the solution to 1/6-1/2 of the original volume to obtain Au @ Ag NPs solution, wherein the gold nanoparticle solutionL-ascorbic acid solution and AgNO3The volume ratio of the solution is 10: 1.5: 3.5;
(4) SERRS sample preparation
Mixing the tyramine derivative azo compound solution prepared in the step (2) with the Au @ Ag NPs solution prepared in the step (3) according to the volume ratio of (2-1): and (1) mixing the components according to the proportion, dripping the mixture on a quartz plate, placing the mixture under a Raman microscope for spectrum detection to obtain SERRS characteristic peak signal intensity, establishing a linear relation between the tyramine concentration and the characteristic peak signal intensity by adopting a linear regression method, and calculating the content of tyramine in the sample to be detected according to the linear relation between the tyramine concentration and the characteristic peak signal intensity.
2. The method for detecting the tyramine content in the aquatic product based on the azo coupling reaction and the surface enhanced resonance Raman scattering according to claim 1, wherein the method comprises the following steps: the step (1) is specifically as follows: taking 10 g of fresh fish, adding 20mL of trichloroacetic acid solution with the concentration of 5wt%, homogenizing for 2min, oscillating and extracting for 30 min at room temperature, centrifuging at 8000r/min and 4 ℃ for 10 min, taking supernate, repeatedly extracting residues with 20mL of trichloroacetic acid solution with the concentration of 5wt% for 1 time, combining the supernate, fixing the volume to 50mL, and filtering with a 0.22 mu m filter membrane to obtain a sample solution to be detected.
3. The method for detecting the tyramine content in the aquatic product based on the azo coupling reaction and the surface enhanced resonance Raman scattering according to claim 1, wherein the method comprises the following steps: na as described in step (2)2CO3The mass fraction of the solution was 8%.
4. The method for detecting the tyramine content in the aquatic product based on the azo coupling reaction and the surface enhanced resonance Raman scattering according to claim 1, wherein the method comprises the following steps: the preparation method of the gold nanoparticles in the step (3) is as follows: 0.25mL of 10-1HAuCl of M4The solution was mixed with 100 mL of deionized water and heated to boiling, then 1.0mL of 1% strength by mass sodium citrate solution was added rapidly under vigorous magnetic stirring, and the mixture was stirredKeeping the solution boiling for 30 minutes, cooling to room temperature, filtering through a 0.22 mu m filter membrane to obtain gold nanoparticles with the particle size of 30-40 nm, and storing at 4 ℃.
5. The method for detecting the tyramine content in the aquatic product based on the azo coupling reaction and the surface enhanced resonance Raman scattering according to claim 1, wherein the method comprises the following steps: the concentration method in the step (3) comprises the following steps: taking a certain volume of Au @ AgNPs suspension original solution, centrifuging for 5min at 8000r/min, carefully removing a certain amount of supernatant, and oscillating on an oscillator for 2min to enable the Au @ AgNPs to be suspended uniformly, thus obtaining the Au @ AgNPs solution with the expected concentration multiple.
6. The method for detecting the tyramine content in the aquatic product based on the azo coupling reaction and the surface enhanced resonance Raman scattering according to claim 5, wherein the method comprises the following steps: and (4) concentrating the mixture in the step (3) until the volume is 1/4 times.
7. The method for detecting the tyramine content in the aquatic product based on the azo coupling reaction and the surface enhanced resonance Raman scattering according to claim 1, wherein the method comprises the following steps: the tyramine derivative azo compound solution in the step (4) and the A @ AgNPs solution are mixed according to the volume ratio of 1: 4, and mixing.
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