CN113933284B - Surface enhanced Raman rapid detection of natural anthraquinone dye in silk based on silver nano sol - Google Patents
Surface enhanced Raman rapid detection of natural anthraquinone dye in silk based on silver nano sol Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 47
- 239000004332 silver Substances 0.000 title claims abstract description 47
- 239000001000 anthraquinone dye Substances 0.000 title claims abstract description 41
- 238000001514 detection method Methods 0.000 title abstract description 14
- 238000001069 Raman spectroscopy Methods 0.000 title description 10
- 238000000034 method Methods 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 37
- 238000011282 treatment Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000001237 Raman spectrum Methods 0.000 claims description 26
- 238000007605 air drying Methods 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 238000004043 dyeing Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000010354 integration Effects 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 8
- 238000001228 spectrum Methods 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 6
- SYHGEUNFJIGTRX-UHFFFAOYSA-N methylenedioxypyrovalerone Chemical compound C=1C=C2OCOC2=CC=1C(=O)C(CCC)N1CCCC1 SYHGEUNFJIGTRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229930182559 Natural dye Natural products 0.000 abstract description 24
- 239000000978 natural dye Substances 0.000 abstract description 24
- 239000000758 substrate Substances 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 abstract description 6
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 30
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 25
- 238000011065 in-situ storage Methods 0.000 description 24
- 239000004106 carminic acid Substances 0.000 description 19
- 235000012730 carminic acid Nutrition 0.000 description 19
- 238000004611 spectroscopical analysis Methods 0.000 description 16
- DGQLVPJVXFOQEV-NGOCYOHBSA-N carminic acid Chemical compound OC1=C2C(=O)C=3C(C)=C(C(O)=O)C(O)=CC=3C(=O)C2=C(O)C(O)=C1[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O DGQLVPJVXFOQEV-NGOCYOHBSA-N 0.000 description 10
- 229940114118 carminic acid Drugs 0.000 description 10
- 241000123069 Ocyurus chrysurus Species 0.000 description 9
- 229940080423 cochineal Drugs 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000007447 staining method Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000001972 Gardenia jasminoides Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 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
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 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 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 210000002268 wool Anatomy 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
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- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention provides a method for rapidly detecting natural anthraquinone dye in silk based on surface enhanced Raman spectroscopy of silver nano sol based on silver nano sol, which takes silver nano sol prepared by a glycol solvothermal method as a substrate, takes dyed silk as a carrier, takes natural anthraquinone dye in the silk as a research object, and utilizes HF steam to pretreat the dyed silk to rapidly detect the natural dye on the dyed silk. The method has high detection precision, short detection time and simple operation, and provides a rapid, cheap, simple and sensitive analysis and detection method for realizing the detection of the natural anthraquinone dye.
Description
Technical Field
The invention relates to the field of analysis and detection of natural dyes, in particular to a method for rapidly detecting natural anthraquinone dyes in silk by using a surface enhanced Raman spectrum based on silver nano sol.
Background
Before the advent of synthetic dyes, all dyes were obtained from natural sources. Natural dyes are generally derived from plants, animals or shellfish, and their identification is a challenging task due to their potential sources of diversity, similar chemical structures, etc. In recent decades, detection and identification of dyes in historical and archaeological textiles have been attracting more and more attention in the fields of cultural heritage and protective practice, and dye analysis has become one of the most explanatory and reliable methods for understanding social and scientific developments in different cultures and historic periods. Traditional methods for detecting natural dyes such as chromatography are expensive in equipment, require long detection times and require specialized personnel to operate; spectroscopic methods such as ultraviolet-visible spectrum and fluorescence spectroscopy are all lossy analysis methods, and have poor sensitivity, easily interfered spectra, easily overlapped spectra and the like, and have certain limitations in the detection of natural dyes.
Raman spectroscopy is a scattering spectrum that reflects the characteristic structure of molecules, but raman scattering effects are a very weak process, so raman signals are very weak, and raman spectroscopy studies on surface-adsorbed species almost always use some enhancement effect. Surface Enhanced Raman Spectroscopy (SERS) refers to the adsorption of molecules onto the surface of certain nanoscale roughened metals (e.g., gold, silver, copper) to increase the raman signal of the adsorbed species by geometric factors, which is suitable for the identification and screening of natural dyes in dyed silk.
The success of SERS application depends on the development and preparation of the substrate, the most used substrate in the field of natural dye analysis being nano-silver colloid prepared by the Lee-Meisel method, obtained by reduction of silver nitrate using sodium citrate. M.V.The yellow gardenia dye in wool and silk is identified by using the nano silver colloid prepared by the Lee-Meisel method; and B, identifying anthraquinone dye in the archaeological sample by using nano silver colloid prepared by using a Lee-Meisel method by Silvia. The preparation method of the nano silver colloid provided by the Lee-Meisel method is simple in process and has important significance in the field of dye identification, however, the silver colloid prepared by the method is nonuniform in particle size and shape and greatly influenced by synthesis conditions, and the application of the silver colloid solution is limited to a certain extent due to the fact that the silver colloid solution is easy to agglomerate and sink. Thus, a surface pull against natural dyesThe synthesis of the nano silver colloid substrate with quick identification, high yield, good repeatability and good stability of the Mannheim spectrum is necessary.
Disclosure of Invention
The invention aims to provide a method for rapidly detecting natural anthraquinone dyes in silk based on surface enhanced Raman spectrum of silver nano sol, which provides a rapid, low-cost, simple, convenient and accurate analysis and detection method for detecting anthraquinone natural dyes.
The invention provides a method for rapidly detecting natural anthraquinone dye in silk by surface enhanced Raman spectroscopy based on silver nano sol, which comprises the following steps:
(1) Synthesizing and post-treating silver nano sol;
(2) Collecting Raman spectrum of natural anthraquinone dye standard substance, and establishing a spectrum chart library of natural anthraquinone dye standard substance;
(3) Preprocessing modern dyed silk with known natural anthraquinone dye components, collecting Raman spectrum, and comparing the pretreated silk with the spectrogram of the corresponding natural anthraquinone dye standard substance obtained in the step (2); adjusting pretreatment parameters of modern dyed silk until the spectrogram of the known natural anthraquinone dye in the modern dyed silk is compared with the spectrogram of the corresponding natural anthraquinone dye standard product obtained in the step (2);
(4) And (3) preprocessing the silk of the real cultural relic to be detected and collecting Raman spectrum by adopting the preprocessing parameters finally adjusted in the step (3), and comparing the silk with a spectrogram of a natural anthraquinone dye standard substance to obtain dye components.
As a preferred embodiment of the present invention, the step (1) includes the steps of:
1.1 Respectively weighing silver nitrate and polyvinylpyrrolidone;
1.2 Respectively dissolving the weighed silver nitrate and polyvinylpyrrolidone in an ethylene glycol solvent to prepare solutions, and then mixing the solutions;
1.3 Transferring the mixed solution into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a heating device with preset reaction temperature, taking out the reaction kettle after reacting for a certain time under non-stirring, and cooling the reaction kettle to room temperature to obtain silver nano sol mother liquor;
1.4 Centrifuging the silver nano sol mother liquor in batches, and removing supernatant to obtain a precipitate; dispersing the precipitate in ultrapure water or absolute ethyl alcohol to obtain uniform silver nano sol dispersion liquid. .
Further, the mass ratio of the silver nitrate to the polyvinylpyrrolidone is between 0.05 and 0.6, and the concentration of the silver nitrate in the final mixed solution in the step 1.2) is between 0.0025 and 0.01g/mL; the concentration of polyvinylpyrrolidone is 0.005-0.05g/mL; in the step 1.3), the reaction temperature of a preset heating device is 140-180 ℃, the reaction time is 2-8 hours, and in the step 1.4), the concentration of sediment in the silver nano sol dispersion liquid is 0.1-0.5g/mL.
In the step (2), as a preferable scheme of the invention, the specific steps are as follows: firstly, dripping the silver nano sol processed in the step (1) on a clean glass slide, dripping a natural anthraquinone dye standard substance after natural air drying, and collecting Raman spectrum after natural air drying to obtain a spectrogram of the natural anthraquinone dye standard substance;
changing the type of natural anthraquinone dye and repeating the steps; establishing a spectrum library of each natural anthraquinone dye standard substance;
wherein, the concentration of the silver nano sol is 0.1-0.5g/mL, and the dosage is 1 mu L; the concentration of the natural anthraquinone dye standard substance is 1m mol/L, the dosage is 1 mu L, and the solvent is absolute ethyl alcohol.
As a preferable scheme of the invention, the specific steps of the step (3) are as follows: placing modern dyed silk in an HF reaction chamber for pretreatment for proper time, taking out, air-drying, dripping the treated silver nano sol, naturally air-drying, and collecting Raman spectrum; adjusting pretreatment parameters of modern dyed silk until the spectrogram of the known natural anthraquinone dye in the modern dyed silk is compared with the spectrogram of the corresponding natural anthraquinone dye standard product obtained in the step (2); wherein, the dosage of the modern dyed silk is at least one fiber, and the length is 1-2 mm.
As a preferred embodiment of the invention, in step (3), the treatment time of modern dyed silk in an HF reaction chamber is 0 to 30 minutes.
As a preferred embodiment of the present invention, in the step (3), the amount of the silver nanosol is 1. Mu.L.
In the step (4), as a preferable scheme of the invention, the specific steps are as follows: and (3) adopting the finally adjusted pretreatment parameters in the step (3), placing the silk of the real cultural relics to be detected in an HF reaction chamber for treatment, taking out, air-drying, then dripping the treated nano silver colloid, naturally air-drying, and then carrying out Raman spectrum acquisition to obtain dyeing component results.
As a preferred embodiment of the present invention, in steps (2) - (4), the raman spectrum acquisition parameters are set as follows: excitation wavelength 532nm, energy 1%, scanning range 400-1800cm -1 Integration time 10s, integration three times.
Compared with the prior art, the invention has the following advantages:
according to the method, a nucleating agent is not used, stirring is not used, the silver nano material is prepared by adopting a polyol solvothermal method to perform airtight reaction in a heating device with preset temperature, the preparation method is simple, the steps are few, the efficiency is high, the cost is low, and the high-quality silver nano material can be prepared in a fixed time. The silver nano material prepared by the method is quasi-spherical nano particles, has uniform particle size, less impurities, good repeatability and good stability.
The invention constructs the detection method of the natural anthraquinone dye in the dyed silk, and applies the surface enhanced Raman spectrum to the detection precision of the natural anthraquinone dye in the dyed silk, and has the advantages of short detection time and simple operation.
Drawings
Fig. 1 is a 120KV TEM image of a nano silver paste prepared by using a glycol solvothermal method.
FIG. 2 is 10 -7 SERS spectra of M alizarin standard and 10 -3 Common raman spectrum of M alizarin standard.
FIG. 3 is a diagram of example 1 at 10 -3 SERS spectra of M alizarin standard solutions are shown as 470, 585, 629, 658, 675, 811, 895, 1011, 1044, 1153, 1182, 1202, 1259, 1289, 1316, 1420, 1452, 1470, 1494, 1550, 1578, 1598cm -1 SERS characteristic peaks as alizarin standards.
FIG. 4 (A) contains HF in situ treatments 0, 10, 15,20. SERS spectra of the Xinjiang madder dyed fibers for 25 min and 30 min; (B) SERS spectra of Xinjiang madder dyed fibers treated in situ for 10min with HF are shown at 462, 550, 626, 653, 689, 815, 962, 996, 1017, 1035, 1070, 1156, 1249, 1333, 1401, 1442, 1478, 1585cm -1 Comparing the SERS characteristic peaks of the natural dye extracted by HF in situ treatment on the fiber dyed with xinjiang madder with the characteristic peaks of the alizarin standard in fig. 3, it can be obtained that the natural dye present on the fiber dyed with xinjiang madder is alizarin (due to the influence of factors such as dyeing method, HF treatment, etc., a few wave number deviations are considered reasonable).
FIG. 5 is a diagram of example 2 at 10 -3 SERS spectra of M carminic acid standard solution are shown in 461, 559, 662, 677, 694, 801, 1067, 1134, 1205, 1297, 1429, 1619cm -1 SERS characteristic peaks as carminic acid standards.
The SERS spectra of cochineal dyed fibers comprising HF in situ treatments 0, 10, 15, 20, 25, 30min in fig. 6 (a); (B) SERS spectra of cochineal dyed fibers treated in situ for 10min with HF are shown at 456, 767, 997, 1037, 1076, 1225, 1324, 1443, 1571, 1632cm -1 The SERS characteristic peaks of the natural dye extracted by HF in situ treatment on the cochineal dyed fiber are compared with the characteristic peaks of the carminic acid standard in FIG. 5, and it can be obtained that the natural dye present on the cochineal dyed fiber is carminic acid (due to the influence of factors such as dyeing method, HF treatment, etc., a few wave number shifts are considered reasonable).
FIG. 7 is a diagram of example 2 at 10 -3 SERS spectrum of M lac standard solution is marked as 438, 527, 591, 651, 804, 860, 909, 1012, 1061, 1101, 1132, 1198, 1293, 1326, 1463, 1522cm in the figure -1 SERS characteristic peaks as lac acid standard.
FIG. 8 is a SERS spectrum of a shellac dyed fiber comprising HF in situ treatments 0, 10, 15, 20, 25, 30min in (A); (B) SERS spectra of Violet beetle dyed fibers treated in situ for 10min with HF are shown at 453, 655, 818, 850, 1009, 1053, 1096, 1194, 1226, 1282、1328、1462、1571cm -1 Comparing the SERS characteristic peak of the natural dye extracted by HF in-situ treatment on the lac dyeing fiber with the characteristic peak of the lac acid standard in fig. 7, it can be obtained that the natural dye existing on the lac dyeing fiber is lac acid (due to the influence of factors such as dyeing method, HF treatment, etc., the deviation of a few wave numbers is considered reasonable).
FIG. 9 is a chart of SERS spectra of cultural relic fibers (No. YP 0044) from Xinjiang ying plate after in-situ HF treatment for 10min, labeled 450, 659, 960, 1015, 1035, 1075, 1156, 1327, 1405cm -1 It was shown that YP0044 contained alizarin on the fiber (few wave number shifts were considered reasonable due to the influence of factors such as staining method, HF treatment, etc.).
FIG. 10 is a chart of SERS spectra of a Xinjiang nutrient dish unearthed cultural relic fiber (No. YP 0049) after in-situ HF treatment for 10min, labeled 467, 631, 659, 992, 1019, 1034, 1065, 1154, 1269, 1324, 1473cm -1 It was shown that YP0049 contained alizarin on the fiber (few wave number shifts were considered reasonable due to the influence of factors such as staining method, HF treatment, etc.).
FIG. 11 is a chart of SERS spectra of Chinese wind brocade (number 2016-18-24) measured by HF in situ treatment for 10min, labeled 455, 658, 1055, 1193, 1312cm -1 The 2016-18-24 fiber was shown to contain carminic acid (a few wave number shifts are considered reasonable due to factors such as dyeing methods, HF treatment, etc.).
Detailed Description
The invention provides a method for rapidly detecting natural dye in silk by surface enhanced Raman spectrum based on silver nano sol. The following examples of the present invention will be described in detail, which give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the examples described below.
Example 1:
0.0932g of silver nitrate and 0.6897g of polyvinylpyrrolidone are weighed; respectively dissolving in 10ml of ethylene glycol solvent, transferring the solution obtained by ultrasonic mixing of the two into a reaction kettle for sealing, placing into a preset oven at 160 ℃, taking out (without stirring in the process) after reacting for 2 hours, and cooling to room temperature to obtain silver nano sol mother liquor; centrifuging the silver nano sol mother liquor in batches at 6000rpm, and removing the supernatant to obtain a precipitate. After repeating the centrifugal separation process for 4-5 times, dispersing the precipitate in ultrapure water or absolute ethyl alcohol to obtain silver nano sol with the concentration of 0.5g/mL; the TEM characterization diagram of the material is shown in figure 1, and the prepared silver nano-form is complete and the particle size is average.
Dropping 1 mu L of the treated silver nano sol on a clean glass slide, and dropping 10 after natural air drying -7 M (FIG. 2) and 10 -3 M (FIG. 3) ethanol solution of natural dye alizarin standard substance, and Raman spectrum acquisition (10) after natural air drying -7 The M alizarin standard was used to evaluate the properties of the base material). The raman spectrum acquisition parameters are set as follows: excitation wavelength 532nm, energy 1%, scanning range 400-1800cm -1 Integration time 10s, integration three times.
Selecting 1316cm -1 Calculating AEF:
calculated aef=1.22×10 5 。
470, 585, 629, 658, 675, 811, 895, 1011, 1044, 1153, 1182, 1202, 1259, 1289, 1316, 1420, 1452, 1470, 1494, 1550, 1578, 1598cm marked in fig. 3 -1 SERS characteristic peaks as alizarin standards.
And (3) putting modern dyed silk (dyed by madder in Xinjiang) with the length of about 2mm into an HF reaction chamber, respectively treating for 0, 10, 15, 20, 25 and 30min, taking out, air-drying, dripping the treated silver nano sol, and naturally air-drying and then collecting Raman spectra (shown in figure 4). Wherein, the SERS spectrum of the Xinjiang madder dyed fiber containing HF in-situ treatment for 0, 10, 15, 20, 25, 30min is shown in FIG. 4 (A); FIG. 4 (B) is a SERS spectrum of the fiber dyed from Xinjiang madder treated in situ for 10min with HF, 462, 550, 626, 653, 689, 815, 962, 996, 1017, 1035, 1070, 1156, 1249, 1333, 1401, 1442, 1478, 1585cm-1 being the SERS characteristic peak of the natural dye extracted from the fiber dyed from Xinjiang madder treated in situ with HF, compared with the characteristic peak of the alizarin standard in FIG. 3, and it can be obtained that the natural dye present on the fiber dyed from Xinjiang madder is alizarin (due to the influence of factors such as dyeing method, HF treatment, etc., a few wave number shifts are considered reasonable).
Example 2:
the raman substrate material was the silver nanosol synthesized and treated in example 1.
Dropping 1 mu L of the treated silver nano sol on a clean glass slide, and dropping 10 after natural air drying -3 An ethanol solution of the M natural dye carminic acid standard was naturally air-dried and then subjected to Raman spectrum acquisition (FIG. 5). The raman spectrum acquisition parameters are set as follows: excitation wavelength 532nm, energy 1%, scanning range 400-1800cm -1 Integration time 10s, integration three times.
461, 559, 662, 677, 694, 801, 1067, 1134, 1205, 1297, 1429, 1619cm as indicated in the figure -1 SERS characteristic peaks as carminic acid standards.
And (3) putting the modern dyed silk (cochineal dyeing) with the thickness of about 2mm into an HF reaction chamber, respectively treating for 0, 10, 15, 20, 25 and 30min, taking out, air-drying for a period of time, dripping the treated silver nano sol, and naturally air-drying and then collecting Raman spectra (figure 6). The SERS spectra of cochineal dyed fibers comprising HF in situ treatments 0, 10, 15, 20, 25, 30min in fig. 6 (a); FIG. 6 (B) is a SERS spectrum of cochineal dyed fiber treated in situ with HF for 10min, labeled 456, 767, 997, 1037, 1076, 1225, 1324, 1443, 1571, 1632cm -1 The SERS characteristic peaks of the natural dye extracted by HF in situ treatment on the cochineal dyed fiber are compared with the characteristic peaks of the carminic acid standard in FIG. 5, and it can be obtained that the natural dye present on the cochineal dyed fiber is carminic acid (due to the influence of factors such as dyeing method, HF treatment, etc., a few wave number shifts are considered reasonable).
Example 3:
the raman substrate material was the silver nanosol synthesized and treated in example 1.
Dripping 1 mu L of treated nano silver colloid on a clean slide, and dripping 10 after natural air drying -3 And (3) naturally air-drying an ethanol solution of the M natural dye lac acid standard substance, and then collecting Raman spectrum (figure 7). The raman spectrum acquisition parameters are set as follows: excitation wavelength 532nm, energy 1%, scanning range 400-1800cm -1 Integration time 10s, integration three times.
438, 527, 591, 651, 804, 860, 909, 1012, 1061, 1101, 1132, 1198, 1293, 1326, 1463, 1522cm marked in the figure -1 SERS characteristic peaks as lac acid standard.
And (3) putting modern dyed silk (lac worm dyeing) with the thickness of about 2mm into an HF reaction chamber, respectively treating for 0, 10, 15, 20, 25 and 30min, taking out, air-drying for a period of time, dripping the treated silver nano sol, and naturally air-drying and then collecting Raman spectra (figure 8). SERS spectra of lac-stained fibers comprising HF in situ treatments 0, 10, 15, 20, 25, 30min in fig. 8 (a); FIG. 8 (B) is a SERS spectrum of a Violet-stained fiber treated in situ with HF for 10min, labeled 453, 655, 818, 850, 1009, 1053, 1096, 1194, 1226, 1282, 1328, 1462, 1571cm -1 Comparing the SERS characteristic peak of the natural dye extracted by HF in-situ treatment on the lac dyeing fiber with the characteristic peak of the lac acid standard in fig. 7, it can be obtained that the natural dye existing on the lac dyeing fiber is lac acid (due to the influence of factors such as dyeing method, HF treatment, etc., the deviation of a few wave numbers is considered reasonable).
Example 4:
combining examples 1-3; the treatment in the HF reaction chamber is determined to be 10min, and the Raman spectrum acquisition parameters are set as follows: excitation wavelength 532nm, energy 1%, scanning range 400-1800cm -1 Integration time 10s, integration three times.
In the embodiment, the dye components in the silk of the real ancient cultural relics are identified, and the Raman substrate material is the silver nano sol synthesized and processed in the embodiment 1.
Taking ancient cultural relic silk with the length of about 2 mm: cultural relic fibers (numbers YP0044 and YP 0049) and Chinese on Xinjiang ying plateBrocade (number 2016-18-24), after being placed in an HF reaction chamber for 10min, the mixture is taken out, and after being air-dried for a period of time, the treated silver nano sol is dripped on the mixture, and after natural air-drying, raman spectrum collection is carried out (figures 9-11). As shown in FIG. 9, the SERS spectrum of the cultural relic fiber (No. YP 0044) unearthed by Xinjiang ying dish after HF in-situ treatment for 10min is shown as 450, 659, 960, 1015, 1035, 1075, 1156, 1327 and 1405cm -1 It was shown that YP0044 contained alizarin on the fiber (few wave number shifts were considered reasonable due to the influence of factors such as staining method, HF treatment, etc.). As shown in FIG. 10, the cultural relic fiber (No. YP 0049) of Xinjiang ying plate is subjected to in-situ HF treatment for 10min to obtain SERS spectrogram, and 467, 631, 659, 992, 1019, 1034, 1065, 1154, 1269, 1324 and 1473cm are marked in the image -1 It was shown that YP0049 contained alizarin on the fiber (few wave number shifts were considered reasonable due to the influence of factors such as staining method, HF treatment, etc.). As shown in FIG. 11, the SERS spectrum of Chinese brocade (number 2016-18-24) measured by HF in-situ treatment for 10min is shown as 455, 658, 1055, 1193, 1312cm -1 The 2016-18-24 fiber was shown to contain carminic acid (a few wave number shifts are considered reasonable due to factors such as dyeing methods, HF treatment, etc.).
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (2)
1. A method for rapidly detecting natural anthraquinone dye in silk by surface enhanced Raman spectroscopy based on silver nano sol is characterized by comprising the following steps: the method comprises the following steps:
(1) Synthesizing and post-treating silver nano sol;
(2) Collecting Raman spectrum of natural anthraquinone dye standard substance, and establishing a spectrum chart library of natural anthraquinone dye standard substance;
(3) Preprocessing modern dyed silk with known natural anthraquinone dye components, collecting Raman spectrum, and comparing the pretreated silk with the spectrogram of the corresponding natural anthraquinone dye standard substance obtained in the step (2); adjusting pretreatment parameters of modern dyed silk until the spectrogram of the known natural anthraquinone dye in the modern dyed silk is compared with the spectrogram of the corresponding natural anthraquinone dye standard product obtained in the step (2);
(4) Preprocessing and Raman spectrum acquisition are carried out on silk of the real cultural relics to be detected by adopting the preprocessing parameters finally adjusted in the step (3), and the preprocessing parameters are compared with a spectrogram of a natural anthraquinone dye standard substance to obtain dye components;
the step (1) comprises the following steps:
1.1 Respectively weighing silver nitrate and polyvinylpyrrolidone;
1.2 Respectively dissolving the weighed silver nitrate and polyvinylpyrrolidone in an ethylene glycol solvent to prepare solutions, and then mixing the solutions;
1.3 Transferring the mixed solution into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a heating device with preset reaction temperature, taking out the reaction kettle after reacting for a certain time under non-stirring, and cooling the reaction kettle to room temperature to obtain nano silver colloid mother liquor;
1.4 Centrifuging the nanometer silver colloid mother liquor in batches, and removing supernatant to obtain precipitate; dispersing the precipitate in ultrapure water or absolute ethyl alcohol to obtain uniform nano silver colloid dispersion liquid;
the mass ratio of the silver nitrate to the polyvinylpyrrolidone is between 0.05 and 0.6, and the concentration of the silver nitrate in the final mixed solution in the step 1.2 is 0.0025 to 0.01g/mL; the concentration of polyvinylpyrrolidone is 0.005-0.05g/mL; in the step 1.3), the reaction temperature of a preset heating device is 140-180 ℃, the reaction time is 2-8 hours, and in the step 1.4), the concentration of sediment in the nano silver colloid dispersion liquid is 0.1-0.5g/mL;
in the step (2), the specific steps are as follows:
firstly, dripping the silver nano sol processed in the step (1) on a clean glass slide, dripping a natural anthraquinone dye standard substance after natural air drying, and collecting Raman spectrum after natural air drying to obtain a spectrogram of the natural anthraquinone dye standard substance;
changing the type of natural anthraquinone dye and repeating the steps; establishing a spectrum library of each natural anthraquinone dye standard substance;
wherein, the concentration of the silver nano sol is 0.1-0.5g/mL, and the dosage is 1 mu L; the concentration of the natural anthraquinone dye standard substance is 1m mol/L, the dosage is 1 mu L, and the solvent is absolute ethyl alcohol;
the specific steps of the step (3) are as follows: placing modern dyed silk in an HF reaction chamber for pretreatment for proper time, taking out, air-drying, dripping the treated silver nano sol, naturally air-drying, and collecting Raman spectrum; adjusting pretreatment parameters of modern dyed silk until the spectrogram of the known natural anthraquinone dye in the modern dyed silk is compared with the spectrogram of the corresponding natural anthraquinone dye standard product obtained in the step (2); wherein, the dosage of the modern dyed silk is at least one fiber, and the length is 1-2 mm;
in the step (3), the treatment time of the modern dyed silk in an HF reaction chamber is 0-30 minutes;
in the step (3), the concentration of the silver nano sol is 0.5g/mL, and the dosage is 1 mu L;
in the step (4), the specific steps are as follows: and (3) adopting the finally adjusted pretreatment parameters in the step (3), placing the silk of the real cultural relics to be detected in an HF reaction chamber for treatment, taking out, air-drying, then dripping the treated silver nano sol, naturally air-drying, and then carrying out Raman spectrum acquisition to obtain dyeing component results.
2. The method for rapidly detecting natural anthraquinone dyes in silk based on surface enhanced Raman spectroscopy of silver nano sol as set forth in claim 1, wherein the method is characterized in that: in the steps (2) - (4), the raman spectrum acquisition parameters are set as follows: excitation wavelength 532nm, energy 1%, scanning range 400-1800cm -1 Integration time 10s, integration three times.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102085574A (en) * | 2009-12-04 | 2011-06-08 | 深圳先进技术研究院 | Water-dispersible silver nanometer particles and preparation method thereof |
| CN102313785A (en) * | 2011-08-04 | 2012-01-11 | 中粮生物化学（安徽）股份有限公司 | Analysis method of citric acid fermentation aqueous solution |
| CN107685156A (en) * | 2017-10-11 | 2018-02-13 | 中国科学院合肥物质科学研究院 | The preparation method of silver nanocubes |
| CN107914022A (en) * | 2017-11-16 | 2018-04-17 | 中国计量大学 | A kind of preparation method of the nano silver wire with surface Raman enhancement effect |
| CN108181293A (en) * | 2017-12-15 | 2018-06-19 | 上海海洋大学 | The Surface enhanced Raman spectroscopy method of pigment in a kind of quick detection beverage |
| CN112098390A (en) * | 2020-09-16 | 2020-12-18 | 燕山大学 | Surface enhanced Raman scattering substrate and preparation method thereof |
| CN112285092A (en) * | 2020-10-29 | 2021-01-29 | 浙江大学 | Safflower dyeing rapid detection method based on surface enhanced Raman spectroscopy |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7362431B2 (en) * | 2005-08-11 | 2008-04-22 | The Metropolitan Museum Of Art | Non-invasive identification of fluorescent dyes in historic textiles by matrix transfer-surface enhanced Raman scattering |
-
2021
- 2021-10-12 CN CN202111188109.9A patent/CN113933284B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102085574A (en) * | 2009-12-04 | 2011-06-08 | 深圳先进技术研究院 | Water-dispersible silver nanometer particles and preparation method thereof |
| CN102313785A (en) * | 2011-08-04 | 2012-01-11 | 中粮生物化学（安徽）股份有限公司 | Analysis method of citric acid fermentation aqueous solution |
| CN107685156A (en) * | 2017-10-11 | 2018-02-13 | 中国科学院合肥物质科学研究院 | The preparation method of silver nanocubes |
| CN107914022A (en) * | 2017-11-16 | 2018-04-17 | 中国计量大学 | A kind of preparation method of the nano silver wire with surface Raman enhancement effect |
| CN108181293A (en) * | 2017-12-15 | 2018-06-19 | 上海海洋大学 | The Surface enhanced Raman spectroscopy method of pigment in a kind of quick detection beverage |
| CN112098390A (en) * | 2020-09-16 | 2020-12-18 | 燕山大学 | Surface enhanced Raman scattering substrate and preparation method thereof |
| CN112285092A (en) * | 2020-10-29 | 2021-01-29 | 浙江大学 | Safflower dyeing rapid detection method based on surface enhanced Raman spectroscopy |
Non-Patent Citations (3)
| Title |
|---|
| 基于表面增强拉曼光谱快速鉴定和分析纺织品文物中天然染料的研究;陈磊;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第6期);正文第10-73页 * |
| 球形银纳米粒子的制备及其表面增强拉曼活性研究;李东;《长春大学学报》;第27卷(第2期);正文第21页 * |
| 陈磊.基于表面增强拉曼光谱快速鉴定和分析纺织品文物中天然染料的研究.《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》.2019,(第6期),正文第10-73页. * |
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